Chelating Metal-Organic Frameworks and Their Polymer-Composites For Water Remediation

CHELATING METAL-ORGANIC
FRAMEWORKS AND THEIR POLYMER-
COMPOSITES FOR WATER
REMEDIATION
MARÍA CALLES GARCÍA
Di ec o es:
D . Robe o Fe nandez de Luis
D . Vik o Pe enko
2025
(cc) 2025 Ma ía Calles Ga cía (cc by-nc-sa 4.0)
CHELATING METAL-ORGANIC
FRAMEWORKS AND THEIR POLYMER-
COMPOSITES FOR WATER
REMEDIATION
MARÍA CALLES GARCÍA
Supe iso s:
D . Robe o Fe nandez de Luis
D . Vik o Pe enko
2025
©2025 MARÍA CALLES GARCÍA

Table o Con en s
Abs ac .................................................................................................. i
Resumen ...............................................................................................
1. Chap e 1: In oduc ion .................................................................... 1
1.1. Wa e and en i onmen al emedia ion ......................................................... 1
1.2. Me al-O ganic F amewo ks Chemis y ....................................................... 10
1.2.1. Clus e s ............................................................................................ 13
1.2.2. Linke s ............................................................................................. 16
1.3. Syn hesis o MOFs ..................................................................................... 18
1.4. Func ionalisa ion s a egies o Z (IV)MOFs o hea y me als abso p ion ... 22
1.5. Polyme and Polyme composi es o wa e emedia ion ........................... 28
1.6. Polyme @MOF composi e ......................................................................... 33
1.7. Objec i es and s uc u e o he hesis ........................................................ 39
1.8. Re e ences ................................................................................................. 41
2. Chap e 2: Ma he ials and Cha ac e isa ion ................................. 61
2.1. Chemicals .................................................................................................. 61
2.2. Cha ac e isa ion echniques....................................................................... 63
2.2.1. X- ay Sca e ing Techniques ............................................................ 63
2.2.2. Neu on Sca e ing Techniques ........................................................ 67
2.3. The mog a ime ic analysis (TGA) ............................................................ 69
2.4. P o on Nuclea Magne ic Resonance ........................................................ 71
2.5. Magne oelas ic esonance ......................................................................... 72
2.6. Gas Adso p ion/Deso p ion Iso he ms ....................................................... 73
2.7. Ze a Po en ial ............................................................................................. 75
2.8. Scanning Elec on Mic oscopy (SEM) ........................................................ 77
2.9. In a ed Spec oscopy (IR) ......................................................................... 78
2.10. X- ay Pho oelec on Spec oscopy (XPS) .................................................. 80
2.11. High Pe o mance Liquid Ch oma og aphy (HPLC) coupled wi h UV- isible
de ec ion ............................................................................................................... 81
2.12. Induc i ely Coupled Plasma A omic Emission Spec oscopy (ICP-AES) 82
2.13. Adso p ion Expe imen s and Models ...................................................... 83
2.13.1. Kine ic models ................................................................................ 83
2.13.2. Iso he m models ............................................................................ 85
2.14. Re e ences ............................................................................................. 88
Chap e 3: Syn hesis o C4 Dica boxylic Acids MOFs ...................... 93
3.1. In oduc ion ................................................................................................ 93
3.2. Syn hesis and Cha ac e isa ion ................................................................. 96
3.3. Applica ion o C4MOFs ............................................................................. 118
3.3.1. Abso p ion o phenolic compounds ................................................ 118
3.3.2. Wa e ha es ing ............................................................................ 121
3.3.3. Hea y me al adso p ion sc eening ................................................. 123
3.4. Conclusions ............................................................................................. 132
3.5. Re e ences ............................................................................................... 135
Chap e 4: Hyb id Biopolyme @MOF 3D-Sponges o Remo al o
he “Big Fi e” Hea y Me als ........................................................... 139
4.1. In oduc ion .............................................................................................. 140
4.2. Expe imen al p ocedu e ........................................................................... 143
4.2.1. Syn hesis o BCM-1 ....................................................................... 143
4.2.2. Syn hesis o SPICHI@BCM-1 sponges ......................................... 143
4.3. Resul s and discussion ............................................................................ 144
4.3.1. Cha ac e iza ion o BCM-1 and SPICHI@BCM-1 sponges ............ 144
4.3.2. Func ional Cha ac e isa ion ........................................................... 155
4.4. Conclusions ............................................................................................. 185
4.5. Re e ences ............................................................................................... 187
Chap e 5: PVDF@MOF Memb ane o Hea y Me al Cap u e ........ 195
5.1. In oduc ion ..................................................................................... 195
5.2. Expe imen al p ocedu e ..................................................................... 197
5.2.1. Syn hesis o BCM-5 ....................................................................... 197
5.2.2. PVDF-HFP@BCM-5 memb anes p ocessing ................................ 198
5.3. Resul s and discussion ...................................................................... 199
5.3.1. Cha ac e iza ion o BCM-5 ............................................................. 199
5.3.2. Cha ac e iza ion o PVDF-HFP@BCM-5 memb anes ................... 207
5.3.3. Func ional Cha ac e isa ion ........................................................... 217
5.4. Conclusions ..................................................................................... 237
5.5. Re e ences ...................................................................................... 239
Chap e 6: Conclusions and Fu u e ends ..................................... 245
2.1. Conclusions ............................................................................................. 245
2.2. Fu u e ends ............................................................................................ 247
A. Annex ............................................................................................ 251
A.1. Educa ion .................................................................................................... 251
A.2. Publica ions ................................................................................................. 251
A.2.1. Pa o he Thesis ........................................................................ 251
A.2.2. O he Publica ions ....................................................................... 252
A.3. Con ibu ion o con e ences......................................................................... 252
A.4. T aining cou ses and o he con ibu ions ..................................................... 252
A.5. Resea ch s ays ............................................................................................ 253
Resumen
ii
c is alog á icos conduce al colapso de la es uc u a cúbica hacia un empaque amien o
hexagonal. En conjun o, se demues a que an o la uncionalidad quelan e del
enlazado como su disposición espacial den o de la es uc u a c is alina inal in luyen
de mane a c í ica en las ciné icas de adso ción y en las capacidades hacia iones
me álicos, con aminan es o gánicos y apo de agua. En el ma co de es e capí ulo se
encuen a un a ículo en p epa ación.
Una ez sin e izados los C4-MOFs, es os se inco po a on en dos ipos de ma ices
polimé icas: una mezcla biobasada de β–qui osano y aislado p o eico de soja
(SPICHI) (Capí ulo 4), y un políme o sin é ico luo inado, PVDF-HFP (Capí ulo 5).
El Capí ulo 4 de alla cómo se ob u ie on esponjas idimensionales compues as
MOF/políme o median e la in eg ación de uno de los C4-MOFs desc i os (BCM-1) en
una ma iz biopolimé ica de p o eína de soja y qui ina. Es a esponja mul i uncional
p esen a g an es abilidad mecánica, al a pe meabilidad y una amplia a inidad química,
capaces de elimina los cinco me ales pesados más ele an es. Median e
expe imen os de imagen de neu ones y mic oscopía elec ónica de ba ido se
e idenció la es uc u a po osa 3D in e conec ada desde escala mac omé ica has a
mic omé ica, mien as que los análisis SAXS con i ma on, a escala nanomé ica, la
in eg ación homogénea de BCM-1 como nanopa ículas casi monodispe sas (~50 nm)
en la ed polimé ica SPICHI. Los es udios de adso ción mos a on e iciencias
supe io es al 90% pa a la mayo ía de los me ales pesados obje i o, con e ec os
siné gicos pa a Cd(II) y As(III), y capacidades de e ención ac ecen adas con la ca ga
de MOF. Aun cuando se iden i ica on lige as limi aciones en e a oxianiones (As(V),
C (VI)) a baja concen ación de MOF, un mayo con enido del mismo mejo ó el
endimien o gene al del compues o. Es e abajo, p esen ado en el Capí ulo 4,
e ue za el po encial de los compues os biopolíme o–MOF como pla a o mas
e sá iles an o es uc u al como uncionalmen e pa a la eliminación e icien e de
di e sos iones me álicos pesados (Calles, M.; Salaza , H.; B i o, S.; Tomchuk, O.;
Ma ins, P. M.; P adhan, A.; Cássio F.; Lance os-Mendez, S.; de la Caba, K.; Gue e o,
P.; Pe enko, V.; Fe nández de Luis, R., Hyb id Biopolyme /Me al–O ganic F amewo k
3D-Sponges Towa ds he Cap u e o he ‘Big Fi e’ Hea y Me als, Chem. Eng. J. 2025,
524, 169442. h ps://doi.o g/10.1016/j.cej.2025.169442).

Resumen
iii
El Capí ulo 5 desc ibe el diseño de un MOF de ci conio uncionalizado con g upos
ioles (BCM-5), sin e izado empleando ácido dime cap osuccínico (DMSA), e
in eg ado en una memb ana je á quicamen e po osa de PVDF-HFP median e una
es a egia de lixi iación salina. Es e en oque conse a los si ios ac i os del MOF y
mejo a su accesibilidad, a o eciendo la coo dinación ue e y selec i a con me ales
blandos pesados como Hg(II), Pb(II) y Cd(II). Los análisis es uc u ales y
espec oscópicos con i ma on la conse ación de la c is alinidad y la accesibilidad de
los g upos uncionales en la memb ana. Las memb anas compues as PVDF-
HFP@BCM-5 mos a on un endimien o de adso ción sob esalien e, con capacidades
muy supe io es a las de sus componen es indi iduales, e idenciando un e ec o
siné gico de i ado de la dispe sión op imizada del MOF y de la in e conec i idad de
po os en la ma iz polimé ica, que acili a la di usión de con aminan es. Los análisis
pos -adso ción (XRD, FTIR y XPS) con i ma on un mecanismo de quimioso ción
basado en la coo dinación de los me ales pesados con g upos iol y ca boxilo. Es e
capí ulo p esen a una es a egia e sá il pa a desa olla memb anas compues as
MOF@PVDF-HFP obus as y uncionales que no solo man ienen, sino que incluso
mejo an, el endimien o de BCM-5 en la cap u a de me ales pesados en aguas
con aminadas (Calles, M.; Rosales, M.; Ma ins, P. M.; Lance os-Mendez, S.;
Pe enko, V.; Fe nández de Luis, R., Zi conium(IV)-Succime Me al-O ganic
F amewo k Func ionalized PVDF-HFP Memb anes o Hea y-Me als Cap u e, 2025,
Chemis y Eu opean Jou nal, e e ees).
En conjun o, es e abajo p esen a una es a egia de allada pa a el diseño de MOFs
con uncionalidad quelan e y sus compues os políme o@MOF, o ien ada a mejo a la
e iciencia global de eliminación de me ales óxicos de medios acuosos. Al in eg a
adso ben es de al o endimien o en ma ices es ables y uncionales, es os esul ados
con ibuyen al desa ollo de ma e iales de nue a gene ación pa a la
descon aminación del agua y la p o ección ambien al sos enible.
In oduc ion
9
Chap e 1
In oduc ion
1
Chap e 1
In oduc ion
1.1. Wa e and en i onmen al emedia ion
The apid indus ialisa ion o a ious coun ies wo ldwide o e he las cen u y has led
o signi ican en i onmen al challenges, pa icula ly ega ding he quali y and
a ailabili y o eshwa e esou ces.1 As a consequence o an h opogenic ac i i ies, a
wide ange o pollu an s, including pe sis en o ganic pollu an s (POPs) such as
polychlo ina ed biphenyls (PCBs), polycyclic a oma ic hyd oca bons (PAHs), dioxins,
and o ganochlo ine pes icides,2 along wi h pha maceu icals,3 mic oplas ics,4 and oxic
ino ganic species such as hea y me als and me alloids,5 ha e been and con inue o
be eleased in o aqua ic en i onmen s. Al hough wa e moni o ing agencies ha e
shi ed he ocus o wa e pollu ion o con aminan s o eme ging conce n, also known
as o e e chemicals, hea y me als con inue o ep esen one o he mos signi ican
ec o s o con amina ion in many egions wo ldwide.6
Since ancien imes, hea y me als ha e been known o be one o he mos haza dous
classes o con aminan s.7 In ac , hey a e de ined by egula o y bodies as p io i y
con aminan s due o hei pe sis ence, mobili y and oxici y,8–10 along wi h hei
endency o bioaccumula e h ough he ood chain.11 Unlike o ganic pollu an s, which
unde go na u al deg ada ion, hea y me als such as me cu y, lead, cadmium,
ch omium, and a senic, among o he s, emain s able inde ini ely in he en i onmen .
The oxicological p o ile o hea y me als p esen s signi ican public heal h conce ns
e en a ace concen a ions.12 These elemen s demons a e he capaci y o dis up
mul iple physiological sys ems e en a e p olonged exposu e o ppb concen a ions.
The e a e widely documen ed impac s o hea y me als on neu ological unc ions, enal
pe o mance and immune sys em in eg i y.9,13 In addi ion, he ecological implica ions
o hea y me als ex end beyond he e ec s o hei di ec oxici y. Hea y me als can
Chap e 1
2
al e he balance o an aqua ic ecosys em by a ec ing p ima y p oduce s, dis up ing
p eda o -p ey ela ionships and educing biodi e si y. As species ha se e as
indica o s o ecosys em heal h, ish popula ions demons a e measu able
bioaccumula ion pa e ns ha sp ead con amina ion e ec s h oughou ood chains,
ul ima ely impac ing human consume s h ough die a y exposu e.14
Focusing on hei sou ces, hea y me als a e in oduced in o aqua ic en i onmen s
(Fig. 1.1) p ima ily h ough indus ial ac i i ies such as mining, elec opla ing
p ocesses, he ag icul u al applica ion o pes icides and e ilise s, he manu ac u e o
elec onics, and he p oduc ion o ba e ies.15 All o hem con ibu e o he elease o
con en ional hea y me als, bu also o he elease o highly aluable elemen s, such
as some o he ones lis ed as c i ical aw elemen s by he Eu opean Commission (e.g.
Co, Ni o REE).16
Figu e 2.1. Hea y me al pollu ion sou ces.
In egions wi hou adequa e was ewa e ea men in as uc u e, hese sou ces o
me al pollu ion c ea e di ec exposu e haza ds o ulne able popula ions. I is
impo an o poin ou ha , in addi ion o an h opogenic ac i i ies, hea y me als' en y
in o wa e bodies can also a ise om he na u al wea he ing o ocks con aining
speci ic mine alogic associa ions. The global a senic con amina ion c isis is a clea

In oduc ion
3
example o his scena io. In many egions wo ldwide, such as no he n Chile, some
a eas o he Uni ed S a es, o India, he le els o a senic in d inking wa e a e
consis en ly abo e he Wo ld Heal h O ganisa ion's (WHO) sa e y guidelines, pu ing
millions o people wo ldwide a se ious isk.16,17 Fo ins ance, in no he n Chile, mo e
han 250,000 esiden s we e exposed o a senic concen a ions o 860 µg/L be ween
1958 and 1970, leading o ele a ed incidences o bladde , lung, and skin cance s.18 In
he Uni ed S a es, namely in Cali o nia, esiden s ha e aced p olonged a senic
con amina ion in g oundwa e , esul ing in inc eased cance and ca dio ascula
isks.19 Simila ly, in India, he s a e o Biha is se e ely a ec ed, wi h o e 10 million
people consuming wa e wi h a senic le els exceeding he WHO limi o 10 µg/L, and
concen a ions in some dis ic s eaching up o 724 µg/L, causing widesp ead heal h
p oblems including skin lesions and a ious cance s.20 Table 1.1 summa ises he
p incipal an h opogenic and na u al sou ces o hea y me als, oge he wi h he ypical
concen a ion anges epo ed in con amina ed na u al and was ewa e s.21–27
Table 2.1. Main sou ces and c i ical concen a ions o hea y me als in con amina ed Wa e s.
Me al
Main sou ces o con amina ion
Typical concen a ions in
con amina ed wa e s*
A senic
(As)
Na u al (wea he ing o a senic-bea ing
mine als, olcanism); a senical
pes icides; me al smel ing22
10–500 µg/L22 (WHO
guideline: 10 µg/L)21
Cadmium
(Cd)
Elec onics indus y (ba e ies,
semiconduc o s); pigmen s; phospha e
e ilize s26
1–50 µg/L26 (WHO guideline: 3
µg/L)21
Lead (Pb)
Mining and smel ing; leaded uel
(his o ical); old wa e pipes26
10–100 µg/L26 (WHO guideline:
10 µg/L)21
Me cu y
(Hg)
A isanal and illegal gold mining
(amalgams); chlo -alkali indus y; coal
combus ion25
0.5–50 µg/L24 (WHO guideline: 6
µg/L)21
Ch omium
(C )
Tanne ies; elec opla ing; pigmen and
s ainless-s eel p oduc ion24
10–300 µg/L27 (WHO guideline:
50 µg/L)21
Nickel
(Ni)
Me al e ining; s ainless s eel
p oduc ion; ba e ies26
20–200 µg/L26 (WHO guideline:
70 µg/L)21
Coppe
(Cu)
Mining; coppe plumbing; pes icides and
ungicides26
50–2000 µg/L26 (WHO guideline:
2000 µg/L)21
Zinc (Zn)
Gal aniza ion; e ilize s; me allu gical
e luen s26
100–5000 µg/L (no WHO
guideline; ~3000 µg/L o en used
as e e ence)26
*Values ep esen ypical anges epo ed in pollu ed na u al and was ewa e s; hey may a y
depending on egion and speci ic ac i i y.
Chap e 1
4
This o e iew highligh s he s ong link be ween speci ic human ac i i ies and hea y
me al pollu ion, wi h concen a ions exceeding he WHO guidelines.
In mos cases, cu en emedia ion echnologies a e based on he con en ional
physico-chemical (p ecipi a ion, coagula ion– loccula ion, ion exchange, o
elec ochemical me hods), biological (mic obial bioso p ion, bioaccumula ion, o
enzyma ic deg ada ion) and abso p ion/memb ane echnologies applied in he
di e en s ages o he was e o indus ial wa e ea men plan s. Al hough he
combina ion o all hese ea men s eps has been e ealed as highly unc ional unde
speci ic condi ions, hey ace signi ican limi a ions ha es ic hei b oade
applica ion.28 Con en ional app oaches, including ion exchange, chemical
p ecipi a ion, memb ane il a ion, and e e se osmosis, o en equi e subs an ial
capi al in es men , ope a ional cos s and ene gy inpu s. These ac o s limi hei
accessibili y in places wi h limi ed esou ces o isola ed a eas lacking con en ional
was ewa e ea men acili ies.29 Fu he mo e, hese echnologies o en p oduce
seconda y was e p oduc s o wa e s eams ha demand addi ional ea men s. B ines
gene a ed by desalina ion and memb ane- il a ion p ocesses, as well as me al-laden
sludges om con en ional p ecipi a ion and coagula ion ea men s, exempli y his
challenge. The sa e disposal o hese concen a ed me allic esidues equi es
specialised me hods o p e en e-con amina ion o en i onmen al sys ems.30 Despi e
i s c i ical impo ance o ensu ing he o e all sus ainabili y o wa e ea men , he
managemen o hese seconda y was e s eams o en ecei es insu icien a en ion in
echnology de elopmen .
Among all he emedia ion echnologies men ioned, adso p ion s ands ou as a
pa icula ly a ac i e app oach due o i s inhe en simplici y, cos -e ec i eness,
ope a ional lexibili y, and po en ial o adso ben egene a ion and euse.31 Adso p ion
can ope a e unde ambien condi ions wi h minimal in as uc u e equi emen s,
making i accessible o implemen a ion in esou ce-limi ed se ings. Mo eo e , he
design o adso p ion sys ems, combined wi h hei modula scalabili y, allows o
adap a ion o a ying ea men capaci ies and con amina ion le els wi hou
subs an ial modi ica ions o exis ing in as uc u e.32 Howe e , he e ec i eness o
adso p ion echnology is undamen ally dependen on he ca e ul selec ion and design
o adso ben ma e ials ha can be ailo ed o ma ch he speci ic physicochemical
p ope ies o a ge me al con aminan s.33 The success o adso p ion elies on
In oduc ion
5
op imising he in e ac ion mechanisms be ween he adso ben su ace and he me al
species, which a y signi ican ly depending on ac o s such as ionic adius, cha ge
densi y, hyd a ion ene gy, and complexa ion beha iou o di e en me als. Fo
ins ance, so me als like me cu y and lead exhibi a s ong a ini y o sulphu -
con aining unc ional g oups, while ha d me als such as ch omium and aluminium
p e e en ially in e ac wi h oxygen-dono si es.34 This speci ici y equi emen has
d i en ex ensi e esea ch in o he de elopmen o unc ionalized adso ben ma e ials,
including modi ied ac i a ed ca bons, biopolyme -based composi es, a ious po ous
ma e ials and especially me al-o ganic amewo ks (MOFs), each designed o
enhance selec i i y and adso p ion capaci y o pa icula me al con aminan s.35,36
F om a chemical poin o iew, hea y me al con amina ion is highly complex due o
he a ie y o me al specia ion ha is obse ed in na u al wa e s, depending on hei
pH o eV condi ions, jus o men ion wo o he mos impo an pa ame e s. As
illus a ed in Figu e 1.2 o he “big i e” hea y me als, hese me als can be ound in
di e en o ms, om posi i e ions (Pb(II), Cd(II)) o neu al molecules (HgCl2, As(OH)3)
and nega i e complexes (HC O4-, H2AsO4-). The chemical o m has a di ec impac on
en i onmen al mobili y, bioa ailabili y, and in e ac ion wi h po en ial emedia ion
ma e ials.37
Chap e 1
6
Figu e 2.2. a) Hg(II), b) Pb(II), c) Cd(II), d) C (VI), e) As(III) and ) As(V) equilib ium.
Fu he mo e, he in o ma ion p esen ed abo e highligh s he need o e ec i e
ea men s a egies capable o add essing he chemical di e si y o con aminan s. In
eal-wo ld scena ios, con amina ion o en in ol es mul iple me al species
simul aneously, a si ua ion pa icula ly common in indus ial e luen s and acid mine
d ainage. These mul i-me al en i onmen s p esen se e al challenges in e ms o hei
emedia ion due o po en ial syne gis ic e ec s be ween his cock ail o ions o block
In oduc ion
13
amewo ks has led o he ema kable de elopmen o mo e han 100.000 epo ed
MOF s uc u es, each wi h ailo ed p ope ies o speci ic unc ional applica ions.88
1.2.1. Clus e s
A wide ange o me al ions has been employed o MOF-assembly, including ansi ion
me als, lan hanides, and ac inides. Each class o me al p o ides dis inc coo dina ion
geome ies, oxida ion s a es, and speci ically, bonding modes wi h he coo dina ion
g oups o he o ganic linke s ha de ine he esul ing s uc u al building uni . The
connec i i y and geome y o bo h he ino ganic uni s and o ganic linke s de e mine
he amewo k's opology, s abili y, and unc ionali y.86
T ansi ion me als such as Cu(II) and Zn(II) a e widely used in MOF syn hesis due o
hei lexible coo dina ion modes and accessible oxida ion s a es. Lan hanides, in u n,
p o ide unique op ical p ope ies esul ing om hei high coo dina ion numbe s and
shielded 4 o bi als. Howe e , amewo ks based on hese me als o en display limi ed
s abili y unde hyd o he mal o chemically ha sh condi ions.87,88 These limi a ions ha e
s imula ed he pu sui o al e na i e me al nodes wi h g ea e obus ness.91,92
Wi hin his con ex , e a alen me als—pa icula ly Z (IV), H (IV), and Ce(IV)—ha e
eme ged as especially impo an . Thei high cha ge densi y and s ong oxophilici y
enable he o ma ion o du able bonds wi h ca boxyla e linke s, yielding MOFs wi h
excep ional he mal, chemical, and hyd oly ic s abili y.89 The well-de ined coo dina ion
en i onmen o hese M(IV) cen es also acili a es he cons uc ion o highly
connec ed SBUs, which unde pin he syn hesis o ema kably obus and po ous
a chi ec u es.90
Zi conium Clus e s in Z -MOFs
Zi conium clus e s exhibi conside able s uc u al di e si y, wi h hexanuclea (Z 6) and
dodecanuclea (Z 12) uni s being he mos epo ed seconda y building uni s in he
li e a u e. Addi ionally, oc anuclea (Z 8) clus e s, hough less common and o en
a ising om s uc u al diso de , cons i u e ano he no able clus e ype.91,92 This hesis
ocuses speci ically on Z 6 and Z 12 clus e s, as hese a e he s uc u al mo i s ound in

Chap e 1
14
he MOF ma e ials syn hesised and cha ac e ised in his wo k. A summa y o hese
h ee clus e s is p esen ed in Table 1.3.
Table 2.3. Di e en ypes o Z clus e s.
Clus e
Type
Geome y
Connec i i y
Coo dina ion
Si es
Rep esen a i e
MOFs
Z 6
Oc ahed al
3-12
12
(edges)
UiO-66,
MOF-808
Z 12
Bi-
oc ahed al
12-24
24
( a iable modes)
Ca aly ic
amewo ks
Z 8
Cubic
12
12 (edges)
PCN-221,
NPF-200
The Z 6(μ3-O)4(μ3-OH)4 clus e (Fig. 1.5) is he mos common and well-s udied
seconda y building uni (SBU) in zi conium-based me al–o ganic amewo ks (Z -
MOFs). This hexanuclea uni adop s an oc ahed al geome y, in which six Z (IV)
cen es occupy he e ices o a egula oc ahed on. Each clus e p o ides up o wel e
coo dina ion si es, enabling he o ma ion o amewo ks wi h di e se connec i i y,
ypically anging om 3 o 12, depending on he linke con igu a ion and o e all
amewo k symme y.93
Wi hin he clus e , ou μ3-oxo and ou μ3-hyd oxo ligands al e na ely cap he
oc ahed al aces, o ming a highly s able ino ganic co e wi h ema kable esis ance o
hyd olysis. The wel e ca boxyla e coo dina ion si es a e loca ed along he wel e
edges o he oc ahed on, whe e each ca boxyla e ligand usually adop s a μ2-η¹:η¹
coo dina ion mode. This a angemen allows he Z 6 node o ac as a e sa ile
ino ganic connec o capable o suppo ing a wide ange o opologies.94
Se e al s uc u al a ia ions o his clus e ha e been epo ed.95 The s anda d o m,
Z 6O4(OH)4, ea u es mixed oxo/hyd oxo b idges, whe eas he ully dep o ona ed
Z 6O8 e sion exhibi s enhanced cha ge densi y and inc eased chemical s abili y. In
addi ion, de ec i e Z 6 clus e s— esul ing om missing linke s— in oduce addi ional
po osi y and accessible ac i e si es, he eby imp o ing he ma e ial’s chemical
unc ionali y and ca aly ic po en ial.
In oduc ion
15
Figu e 2.5. Rep esen a ion o he Z 6 clus e .
Beyond he Z 6 mo i , la ge zi conium clus e s such as Z 12 (Fig. 1.6) ha e also been
iden i ied. These s uc u es o m h ough he dime isa ion o wo Z 6 oc ahed al uni s,
which a e linked ia addi ional b idging ligands o p oduce a bi-oc ahed al geome y
o educed symme y. The in e clus e dis ance a ies depending on he na u e o he
b idging ligands.96
Ligands wi hin Z 12 clus e s can adop ou dis inc coo dina ion modes: (i) chela ing,
in ol ing biden a e coo dina ion o a single Z cen e; (ii) bel b idging, in which μ₂-
linke s connec wo Z a oms wi hin he same Z 6 uni ; (iii) in e clus e b idging, whe e
linke s span ac oss bo h oc ahed al subuni s; and (i ) inne - ace b idging, occu ing a
he in e ace be ween he wo oc ahed a. This s uc u al di e si y allows Z 12 clus e s
o se e as e sa ile nodes in he design o amewo ks wi h complex h ee-
dimensional opologies.97
Figu e 2.6. Rep esen a ion o he Z 12 clus e .
Z 6O4(OH)4
[Z 6O4(OH)4]2OH6
Chap e 1
16
Ano he impo an mo i is he Z 8O6 clus e , which exhibi s a cubic geome y
undamen ally di e en om he oc ahed al Z 6 s uc u e. In his con igu a ion, eigh Z
a oms occupy he cube e ices, while six μ4-oxo g oups cap he cube aces. Each
edge o he cube hos s a ca boxyla e coo dina ion si e, esul ing in an exclusi e 12-
old connec i i y.98
This high-symme y con igu a ion a ou s he o ma ion o amewo ks wi h he a e
(4,12)-connec ed w opology, cha ac e ised by la ge ca i ies and high po osi y. Due
o i s cubic geome y, he Z 8 clus e is pa icula ly compa ible wi h plana po phy inic
linke s, acili a ing he cons uc ion o highly o de ed, mesopo ous amewo ks wi h
la ge accessible olumes.99
1.2.2. Linke s
The o ganic componen o MOFs o e s ema kable s uc u al di e si y, wi h linke s
anging om simple dica boxyla es o complex mul i opic ligands. The choice o
o ganic linke enables p ecise ailo ing o po e size, shape, and unc ionali y o he
inal MOF by modula ing hei leng h, geome y, and chemical unc ionaliza ion.100. 109
The inc easing complexi y o o ganic linke s has enabled he disco e y o coun less
c ys al s uc u e a ian s in Z -MOFs, each cha ac e ised by di e se po osi y me ics,
su ace a eas, and de ec chemis ies. Among hese, a chi ec u es assembled om
C4-linke s ha e demons a ed ou s anding chemical obus ness, en i onmen ally
benign syn hesis ou es, and mic opo ous en i onmen s, oge he wi h high chemical
and opological di e si y.101
The chemical s uc u e o hese C4 linke s ypically comp ises a igid a oma ic o
alipha ic co e wi h ou ca boxyla e g oups posi ioned symme ically o asymme ically,
o en complemen ed by la e al unc ional g oups (Fig. 1.7). These side g oups,
combined wi h modula ion o syn he ic pa ame e s such as empe a u e, pH, and
modula o concen a ion, guide he c ys allisa ion o Z -MOF-C4 ma e ials in o dis inc
c ys alline phases and opologies.102
In oduc ion
17
Figu e 2.7. Examples o a ious C4 linke s. The linke s employed in his hesis a e highligh ed wi h a
dashed line.
Se e al C4 linke s ha e been ex ensi ely s udied in he li e a u e, leading o Z -MOFs
wi h well-cha ac e ised s uc u es ha illus a e his s uc u al di e si y. F amewo ks
based on aspa ic, ans-aconi ic, uma ic, and b omosuccinic acids ypically
c ys allise in a Pn-3 cubic s uc u e, cha ac e ised by a obus 3D ne wo k wi h small
o mode a e po e sizes and high s abili y. The symme y and posi ioning o he
ca boxyla e g oups a ou he o ma ion o highly connec ed seconda y building uni s
wi h oc ahed al Z 6 nodes.
In con as , MOFs cons uc ed om uma ic and malic acids o en adop an Immm
o ho hombic s uc u e, ea u ing elonga ed po es and aniso opic connec i i y owing
o he mo e lexible o less symme ic linke con o ma ion. Z -MOFs u ilising hiomalic
acid display polymo phism, c ys allising in dis inc s uc u es such as an F23 cubic
phase and a P63/mmm hexagonal phase, whe e he p esence o sulphu a oms
impa s unique binding modes and po en ial unc ionali ies ha in luence bo h c ys al
packing and po e connec i i y.
Fuma ic acid
Succinic acid Malic acid
Mesaconic acid
Me hylsuccinic acid
T ans-aconi ic acid
Thiomalic acid Aspa ic acid Dime cap osuccinic acid
Sulphosuccinic acidB omosuccinic acid Dib omosuccinic acid
Chap e 1
18
F amewo ks based on sul osuccinic acid o m in he I4/m e agonal space g oup,
whe e he sul ona e unc ional g oup con ibu es o al e ed coo dina ion en i onmen s,
inducing he o ma ion o unique po e a chi ec u es wi h po en ial hyd ophilic
cha ac e .
Each o hese c ys alline phases exhibi s dis inc i e s uc u al ea u es: a ia ions in
po e size and shape, connec i i y o nodes, and amewo k dimensionali y. These
di e ences p o oundly impac he physical p ope ies o he MOFs, including gas
adso p ion beha iou , chemical s abili y, and po en ial ca aly ic ac i i y. Thus, by
ca e ully selec ing he C4 linke chemis y and op imising syn he ic condi ions, i is
possible o ailo he c ys alline s uc u e and opological a ie y o Z -MOFs. This
e sa ili y unde pins hei sui abili y in di e se applica ions equi ing p ecise con ol o
po e en i onmen s and amewo k obus ness.
1.3. Syn hesis o MOFs
Thus, he inal amewo k o a MOF, e en when cons uc ed om he same s uc u al
uni s, can in many cases be highly dependen on he speci ic syn hesis condi ions
employed o c ys allise i . In gene al e ms, he syn hesis p ocess aims o p omo e
nuclea ion and c ys al g ow h while minimising he p ecipi a ion o o ma ion o dense
phases.103,104 Below, we will p esen di e en pa ame e s which impac he syn hesis
o MOF samples.
The mos widely employed syn he ic app oach is sol o he mal syn hesis, whe e me al
sal s and o ganic ligands a e hea ed in sealed essels be ween 80 and 200°C,
c ea ing con olled condi ions ha p omo e he sel -assembly o highly c ys alline
amewo k s uc u es.105 The applica ion o his me hod p o ides he he mal ene gy
necessa y o o e come kine ic ba ie s and p omo e he o ma ion o
he modynamically s able c ys alline phases.106 The selec ion o sol en is c i ical as
i in luences he solubili y o eac an s, he coo dina ion en i onmen o me al cen es,
and he empla ing e ec on po e o ma ion.107–109
Hyd o he mal syn hesis is a echnique ha employs wa e as he p ima y sol en and
has p o en e ec i e o he p epa a ion o many hyd oly ically s able MOFs. The high
dielec ic cons an o wa e enables he dissocia ion o me al sal s and enhances ionic

In oduc ion
19
in e ac ions, while i s hyd ogen bonding ne wo k enables hei coope a i e assembly
and s abilisa ion.110 Beyond hese undamen al physicochemical ad an ages, wa e -
based syn hesis ou es align wi h he p inciples o g een chemis y by elimina ing oxic
o ganic sol en s, educing ene gy consump ion, and minimising haza dous was e
gene a ion.111 This app oach has gained inc easing a en ion as he ield mo es owa d
mo e sus ainable and scalable p oduc ion me hods ha a e compa ible wi h indus ial
implemen a ion and en i onmen al egula ions.
Mo eo e , aqueous media p o e pa icula ly compa ible wi h he solubili y
equi emen s o mos me al sal s employed in MOF syn hesis, including zi conium
sal s such as Z Cl4, which eadily dissol e and hyd olyse in wa e o gene a e eac i e
me al species. Simila ly, C4-dica boxylic linke s, including aspa ic acid, uma ic acid,
malic acid and hei de i a i es, exhibi su icien solubili y in wa e , especially unde
con olled pH condi ions whe e dep o ona ion o ca boxyla e g oups enhances hei
dissolu ion. This dual solubili y enables s aigh o wa d mixing o eagen s wi hou
equi ing complex sol en sys ems o solubilising agen s, he eby simpli ying eac ion
p o ocols and acili a ing ep oducibili y. The compa ibili y o bo h me al p ecu so and
o ganic linke s wi h aqueous en i onmen s has he e o e been ins umen al in
enabling milde , mo e sus ainable syn hesis pa hways o Z -C4-MOFs, which we e
p epa ed and s udied in his hesis.
These cha ac e is ics ha e opened he oom o he p og essi e so ening o he
syn hesis and c ys allisa ion o Z -C4-MOFs when employing he p ope eac ion
condi ions. In ac , oom- empe a u e syn hesis o e s ad an ages o he p epa a ion
o kine ically s able phases con aining he mally labile unc ional g oups.112,113 Fo
eaching as e syn hesis imes, mic owa e-assis ed me hods ha e gained popula i y
by educing eac ion imes om days o minu es while main aining excellen p oduc
quali y.114 Mo eo e , elec ochemical syn hesis p o ides p ecise con ol o e me al ion
elease h ough elec ode dissolu ion, while sonochemical me hods employ ul asonic
agi a ion o accele a ed nuclea ion and enable p ecise egula ion o po e a chi ec u e
and amewo k opology.115,116 Mechanochemical syn hesis is a iable,
en i onmen ally iendly app oach ha educes sol en consump ion.117 I o e s
simplici y, high ep oducibili y, and mild eac ion condi ions, while enabling he
p epa a ion o amewo ks ha migh be di icul o syn hesise h ough adi ional
me hods.
Chap e 1
20
I is now well es ablished ha he syn hesis condi ions o MOFs exe a signi ican
in luence on hei inal p ope ies, he eby o e ing oppo uni ies o sys ema ic
op imisa ion o hese ma e ials. In gene al e ms, he c ys allisa ion o MOFs ollows
he gene al ules o c ys allisa ion, being nuclea ion kine ics and c ys al g ow h being
he wo key s eps o he p ocess.
Low eagen concen a ions a ou limi ed nuclea ion and ex ended c ys al g ow h,
esul ing in la ge , well-o de ed, and de ec - ee single c ys als. In con as , high
concen a ions p omo e apid nuclea ion, yielding smalle c ys als wi h a highe densi y
o de ec s and al e ed coo dina ion en i onmen s.118 The me al- o-ligand a io, he
na u e o he sol en o sol en mix u es, and he anionic coun e ions o he ini ial
me al sal s can exe a s ong in luence on he inal amewo k, he me al coo dina ion
en i onmen , and he inco po a ion o sol en molecules o anions in o he MOF
s uc u e 125119 Tempe a u e plays a c ucial ole in nuclea ion and c ys al g ow h a es,
wi h highe empe a u es gene ally p omo ing la ge c ys al sizes.120 Howe e ,
ele a ed empe a u es may lead o amewo k decomposi ion in he mally sensi i e
sys ems.121 The pH o he eac ion medium also in luences he dep o ona ion o
o ganic linke s, me al specia ion, and coo dina ion geome y, which in u n impac he
amewo k opology.122,123 Reac ion ime is a c i ical ac o in he op imisa ion o
c ys allini y and phase pu i y, whe e sho e eac ion imes o en esul in he o ma ion
o smalle c ys als wi h highe su ace a eas, while ex ended eac ion imes p omo e
c ys al g ow h and enhance s uc u al o de ing.124
Syn hesis o Z (IV) MOFs
All he ac o s men ioned abo e gene ally in luence he c ys allisa ion o all ypes o
MOF ma e ials; howe e , he syn hesis o Z -MOFs in oduces an addi ional ac o ha
plays a c ucial ole in con olling hei c ys allisa ion p ocess and he de ec i i y o he
esul ing c ys als: he modula o s.
Modula o s a e compe i i e coo dina ion agen s ha con ol Z -MOF syn hesis by
empo a ily compe ing wi h p ima y ligands o zi conium coo dina ion si es, he eby
egula ing c ys al g ow h, pa icle size, and de ec o ma ion and dis ibu ion wi hin he
amewo k.125 In Z -MOFs, de ec s a e no me ely s uc u al impe ec ions bu
unc ional ea u es ha can be a ionally enginee ed h ough modula ion s a egies.126
In oduc ion
21
The con olled in oduc ion o missing-linke o missing-clus e de ec s has eme ged
as a powe ul ool o ailo ing he p ope ies o Z -based amewo ks, enabling
enhanced po osi y, imp o ed adso p ion pe o mance, and unable ca aly ic ac i i y.127
The e icacy o modula o s in di ec ing Z -MOF c ys allisa ion and de ec enginee ing
depends p ima ily on wo ac o s: he pKa o he acidic g oup and he s uc u al
cha ac e is ics o he subs i uen .128 Monoca boxylic acids wi h lowe pKa alues
(s ong acids) coo dina e mo e weakly o Z 6 clus e s due o hei highe endency o
emain dep o ona ed in solu ion, esul ing in as e ligand exchange kine ics and
educed in e e ence wi h amewo k assembly. Con e sely, modula o s wi h highe
pKa alues (weake acids) bind mo e s ongly o me al nodes, slowing c ys al g ow h
and p omo ing he o ma ion o la ge , mo e o de ed c ys als wi h ewe de ec s. This
compe i ion be ween linke and modula o o coo dina ion o he Z SBUs is key o
e ec i e modula ion, whe e a close ma ch in pKa a ou s la ge and mo e well-de ined
c ys alli es.126 The na u e o he subs i uen also plays a c ucial ole: alipha ic
subs i uen s, such as hose in ace ic o o mic acid, p o ide lexibili y and minimal
s e ic hind ance, while a oma ic subs i uen s, such as hose in benzoic acid, in oduce
π-π in e ac ions and enhanced compa ibili y wi h a oma ic linke s, in luencing c ys al
mo phology and amewo k opology.
Among hese, ace ic acid emains he mos widely employed modula o o Z -MOF
syn hesis due o i s in e media e pKa (~4.76), which p o ides balanced coo dina ion
s eng h ha slows c ys allisa ion and imp o es c ys al quali y wi hou excessi ely
hinde ing amewo k o ma ion. Fo mic acid p o ides s onge coo dina ion o pa icle
size con ol, while benzoic acid o e s be e compa ibili y wi h a oma ic amewo ks.129
Howe e , highe concen a ions ypically yield la ge c ys als and highe de ec
densi ies, some imes e en al e ing he amewo k connec i i y. The inco po a ion o
missing-linke and missing-clus e de ec s can lead o s uc u al eo ganisa ion a he
nanoscale: o ins ance, in UiO-66(H ), high concen a ions o o mic acid modula o
du ing syn hesis p omo e he o ma ion o co ela ed clus e acancy nano egions ha
locally adop an eigh -connec ed eo opology, dispe sed wi hin he pa en wel e-
connec ed cu amewo k. This opological he e ogenei y a ises om he p e e en ial
inclusion o o de ed clus e acancies, which educe he coo dina ion numbe o he
zi conium nodes and induce local s uc u al modi ica ions. Such phenomena
unde sco e he p o ound in luence o modula o concen a ion no only on c ys al
Chap e 1
22
quali y and de ec densi y bu also on he local amewo k connec i i y, highligh ing he
impo ance o ca e ul syn he ic con ol in Z -MOF syn hesis.130
In gene al e ms o Z -MOFs, he use o s onge acid modula o s inc eases phase
di e si y in samples con aining lexible ligands, whe eas highe syn hesis
empe a u es end o educe c ys alli e size and enhance phase selec i i y o igid
ligands.131 Ne e heless, he syn hesis pa ame e space equi es me iculous
explo a ion. A ho ough unde s anding o hese pa ame e s and hei e ec s on MOF
o ma ion mechanisms is essen ial o designing ma e ials wi h p edic able s uc u es
and p ope ies.
1.4. Func ionalisa ion s a egies o Z (IV)MOFs o
hea y me als abso p ion
Syn hesis-induced de ec i i y in Z -MOFs is no only a means o con olling he inal
opology o hese ma e ials bu also p o ides an ideal pla o m o di e se si es o pos -
syn he ic unc ionaliza ion. In gene al, he chemical encoding o hese amewo ks can
be achie ed h ough wo p ima y app oaches ha o e complemen a y ad an ages:
p e-syn he ic unc ionaliza ion, whe e unc ional g oups a e inco po a ed in o he
o ganic linke s be o e amewo k assembly, and pos -syn he ic modi ica ion, whe e
exis ing amewo ks a e chemically modi ied a e syn hesis.132,133
In gene al e ms, he abso p ion o anionic species by Z -MOFs is go e ned by wo
complemen a y mechanisms. Fi s , anionic con aminan s such as ch oma e (C O42-)
o a sena e (AsO43-) can coo dina e di ec ly o unco ela ed and co ela ed de ec i e
posi ions in he Z -oxo clus e s, whe e missing linke s o clus e de ec s expose
unsa u a ed me al si es wi h high a ini y o hese species. This coo dina ion-based
cap u e is pa icula ly e ec i e due o he ha d Lewis acid cha ac e o Z (IV) cen es.
Second, elec os a ic in e ac ions play a c ucial ole when he amewo k inco po a es
ca ionic g oups, mos p o ona ed amines (-NH3+), which a e ei he p esen in he
o ganic linke s o in oduced h ough pos -syn he ic modi ica ion. These posi i ely
cha ged moie ies c ea e an elec oposi i e en i onmen wi hin he po es ha acili a es
he adso p ion o anionic pollu an s, o en achie ing high selec i i y e en in complex
mul i-ionic solu ions.134
In oduc ion
29
biopolyme s—such as ca boxyl (-COOH), hyd oxyl (-OH), amine (-NH2), amide (-CO
NH2), hiol (-SH), and phospha e (-PO43-) g oups— ende s hese ma e ials inhe en ly
unc ional o hea y me al.175,176 No able examples include chi osan, which possesses
abundan amine and hyd oxyl g oups capable o chela ing ha d and bo de line me al
ions such as Pb(II), Cd(II), Cu(II), and Ni(II) h ough coo dina ion and elec os a ic
in e ac ions.177 Algina e, ich in ca boxyl g oups, exhibi s high a ini y o di alen
ca ions like Pb(II), Cu(II), and Zn(II) h ough he o ma ion o s able me al-ca boxyla e
complexes.178 Cellulose and i s de i a i es, bea ing hyd oxyl and ca boxyl g oups,
ha e demons a ed e ec i e adso p ion o C (VI), Hg(II), and As(V).179
Fu he mo e, he su ace chemis y o polyme ic memb anes and il e s can be
modi ied pos -p ocessing, enabling he ancho ing o addi ional me al-chela ing g oups
o he s uc u e o he polyme ic sca old and he eby enhancing o ailo ing hei
adso p ion p ope ies. Pos -syn he ic modi ica ion s a egies include g a ing o
unc ional monome s ia ee- adical polyme isa ion, plasma ea men o in oduce
eac i e g oups, chemical ac i a ion ollowed by coupling eac ions, and laye -by-laye
assembly o unc ional coa ings.180 Fo ins ance, chi osan memb anes modi ied wi h
hiol g oups h ough eac ion wi h hioglycolic acid ha e exhibi ed signi ican ly
enhanced Hg(II) emo al compa ed o unmodi ied chi osan.181 Simila ly, cellulose-
based il e s unc ionalized wi h e hylenediamine e aace ic acid (EDTA) o
die hylene iaminepen aace ic acid (DTPA) ha e demons a ed imp o ed chela ion
capaci y o Pb(II), Cd(II), and Cu(II).182 Polyamide memb anes modi ied wi h ca boxyl,
amine, o phosphona e g oups h ough su ace g a ing ha e shown selec i e
adso p ion owa d a e-ea h elemen s and ansi ion me als.183 These pos -
modi ica ion s a egies allow ine- uning o selec i i y, capaci y, and kine ics wi hou
comp omising he mechanical in eg i y o pe meabili y o he il a ion sys em.
All in all, he chemical di e si y, p ocessabili y, and modi iabili y o polyme s ha e
opened he oom o he de elopmen o wa e il e ing sys ems based on abso p ion
o he emo al o hea y me als, wi h ou s anding chemical and mechanical p ope ies,
as well as good abso p ion pe o mances. Examples o success ul hea y me al
emo al include chi osan-based memb anes achie ing >95% emo al o Pb(II), Cd(II),
and Cu(II) om indus ial was ewa e ,184 algina e beads demons a ing capaci ies o
200-400 mg/g o Pb(II) and Cu(II),185 cellulose nano ibe ae ogels emo ing >99% o
C (VI) and Hg²⁺ om con amina ed wa e ,186 and hiol-modi ied polyac yloni ile ib es

Chap e 1
30
cap u ing Hg2+ wi h adso p ion capaci ies exceeding 1200 mg/g.187 These polyme ic
sys ems o e cos -e ec i e, scalable, and en i onmen ally iendly al e na i es o
con en ional wa e ea men echnologies, b idging he gap be ween labo a o y
esea ch and p ac ical implemen a ion in eal-wo ld emedia ion scena ios.
Bu he e is a pa allel way o modi y he polyme s’ cha ac e is ics in e ms o hei
physicochemical p ope ies and unc ionali y: he design o polyme composi es made
o a mix u e o wo o mo e di e en componen s: polyme ma ix ( he con inuous
phase) and ein o cing ma e ials ( he dispe sed phase). The polyme ma ix, gene ally
a plas ic o esin, ac s as a binding, holding he pa s o he ma e ial oge he . The
ein o cing ma e ials, such as ib es, pa icles o o he ille s, imp o e mechanical
p ope ies and expand hei unc ionali y.188 Combining he low weigh and he
unc ional p ope ies o hese ma e ials allows o he c ea ion o ma e ials wi h ailo ed
p ope ies ha signi ican ly o e come hose o hei indi idual componen s. The
de elopmen o polyme composi es has enabled o modi ica ion o bo h he ma ix
and he ein o cemen in e ms o composi ion, mo phology, dispe sion and in e acial
in e ac ions.189 This lexibili y enables he ob aining o a wide a ie y o composi e
a chi ec u es, including ib e- ein o ced sys ems, pa icle- illed polyme s and
nanocomposi es.190 These ma e ials p esen syne gis ic p ope ies ha allow he
simul aneous op imisa ion o mechanical, he mal, elec ical and chemical p ope ies,
jus o men ion some examples. In ou case s udy, h ee di e en polyme s o
biopolyme s ha e been used:
Poly( inylidene luo ide-co-hexa luo op opylene) (PVDF-HFP) is a he moplas ic
and highly enginee ed luo ina ed copolyme which ep esen s an ad anced e sion
o poly inylidene luo ide (PVDF). I o e s a combina ion o chemical s abili y,
mechanical lexibili y and elec oac i e beha iou .191 The inco po a ion o
hexa luo op opylene uni s (HFP) in o he poly inylidene luo ide (PVDF) main
s uc u e induces al e a ions in he c ys alline s uc u es, inc easing chain mobili y and
enabling he de elopmen o pola β-phases.192 These phases imp o e su ace
pola i y, ionic conduc i i y, hyd ophobici y and solubili y h ough s onge dipole and
elec os a ic in e ac ions.
This polyme se es as an excep ional polyme ic ma ix o hos ing MOFs due o i s
mechanical s eng h, he mal s abili y and chemical compa ibili y, p o iding a s able
In oduc ion
31
and p o ec i e en i onmen o inco po a ed MOFs.193 The componen s can e ain
hei unc ional p ope ies o e ex ended pe iods while he polyme i sel emains low-
cos , non- eac i e, and easily p ocessable, allowing he composi e p ope ies o be
op imised o ob ain ma e ials wi h excellen unc ional ac i i y. The ma e ial's s uc u al
e sa ili y and compa ibili y wi h a wide ange o unc ional ille s ep esen a signi ican
ad an age in he design o nex -gene a ion ma e ials, as i can be modi ied o c ea e
wa e il e s and memb anes wi h enginee ed po ous s uc u es highly e ec i e o
wa e emedia ion and he emo al o hea y me als.194–198
The e a e many p ocessing echniques employed in he p oduc ion o hese
composi es, bu in his hesis, hese ma e ials ha e been syn hesised by sal leaching,
which is a undamen al and widely employed echnique o c ea ing po ous composi e
polyme s uc u es wi h con olled mo phology and in e connec ed po e ne wo ks. This
me hod employs wa e -soluble pa icles ha a e uni o mly dis ibu ed wi hin a polyme
ma ix du ing p ocessing and hen emo ed h ough aqueous ex ac ion, esul ing in
he o ma ion o a h ee-dimensional po ous a chi ec u e wi hin he polyme ma ix.
Sodium chlo ide is he mos commonly used sal due o i s chemical ine ness,
con olled pa icle size a ailabili y, and comple e wa e solubili y.199–202 This echnique
o e s excep ional con ol o e po e size, po osi y, and po e connec i i y by modi ying
he sal pa icle size dis ibu ion, loading pe cen age, and leaching condi ions.
β-chi in is a semi-syn he ic polyme . Chi in is he second mos abundan na u al
polyme a e cellulose and is a linea aminopolysaccha ide composed o β(1-4)-linked
N-ace ylglucosamine uni s, p esen ed in he exoskele ons o a h opods. The
ma e ial's molecula con igu a ion is cha ac e ised by a high numbe o hyd ogen
bonds, which con ibu e o i s mechanical s eng h, chemical s abili y, and biological
unc ionali y.203–205
This polyme exis s na u ally in h ee polymo phic o ms (α, β, and γ), wi h di e en
c ys allini y and mechanical p ope ies and con e ing a high deg ee o e sa ili y on
he polyme . Among hese, α-chi in is he mos abundan and mechanically obus ,
o ming he s uc u al basis o many biological composi es.206 Howe e , β-chi in has a
dis inc a angemen o i s chains, wi h a pa allel con igu a ion whe e all polyme
chains a e o ien ed in he same di ec ion, esul ing in a c ys alline ne wo k ha is mo e
accessible and lexible in compa ison o α.207 This s uc u al con igu a ion con e s
Chap e 1
32
g ea e lexibili y, wa e a ini y, and chemical eac i i y, making β-chi in pa icula ly
sui able as a ma ix o unc ional composi es.
The p esence o hyd oxyl and ace amido g oups along he polyme backbone p o ides
in insic coo dina ion si es o me al ions, while he po ous a chi ec u e esul ing om
chi in's ib illa mo phology acili a es mass anspo and accessibili y o embedded
unc ional ille s. The inco po a ion o hese nanos uc u es enables unc ionali ies
such as an imic obial ac i i y and wa e esis ance, which a e c ucial o biomedical
applica ions and sus ainable packaging. 208 The en i onmen ally bene icial p ope ies
o chi in, oge he wi h i s adap abili y h ough nanoscale s uc u al design and
chemical modi ica ion, highligh i s po en ial as a sus ainable, high-pe o mance
ma e ial o unc ional composi es.
Soy p o ein, a na u al polyme o biopolyme and is ex ac ed om soybeans, is
s uc u ally ich wi h biomolecules composed o unc ional g oups such as hyd oxyl,
ca boxyl, amino, and sul hyd yl moie ies.209 These eac i e si es enable a a ie y o
chemical modi ica ions and c oss-linking s a egies, allowing he c ea ion o h ee-
dimensional polyme ne wo ks wi h ailo ed mechanical p ope ies.210 Fo he
syn hesis o soy p o ein composi es, addi i es such as glyce ol o so bi ol a e o en
employed as plas icise s o imp o e lexibili y and p ocessabili y.211 And o he
p ocessing me hods, soy p o ein composi es gene ally use aqueous o alkaline
en i onmen s, ollowed by cas ing, comp ession moulding, o ex usion.212 In his
hesis, we ha e used he p o ein isola e (SPI). These composi es ep esen a
sus ainable and enewable al e na i e o con en ional polyme s. Thanks o hei
na u al ilm- o ming abili y, biodeg adabili y, and abundance, soy p o eins a e being
mos used as he ma ix in composi e ma e ials, showing posi i e esul s o new
applica ions, such as p oducing po ous sca olds.213 This app oach enables p ecise
con ol o e p o ein con o ma ion and su ace eac i i y and modi ies he ma e ial’s
solubili y, mechanical s eng h, wa e esis ance, and educes mois u e sensi i i y. The
po en ial applica ion a eas o soy p o ein-based composi es a e ex ensi e and
mul idisciplina y.214 Soy p o ein composi es a e a key playe in he de elopmen o
nex -gene a ion sus ainable ma e ials due o hei abili y o une pe o mance h ough
s uc u al and chemical modi ica ion, combined wi h hei low en i onmen al oo p in .
In oduc ion
33
These h ee polyme s demons a e he wide ange o app oaches a ailable o
de eloping high-pe o mance composi e ma e ials, ex ending om syn he ic
luo opolyme s o na u al biopolyme s (Fig.1.9).
Figu e 2.9. Rep esen a ion o PVDF-HFP, β-chi in and soy p o ein isola ed polyme s used in he
hesis, wi h main ad an ages o each polyme .
The complemen a y cha ac e is ics o hese polyme ma ices, anging om di e en
deg ees o hyd ophilici y, c ys allini y, mechanical s eng h, and inhe en me al-binding
unc ionali y, p o ide a e sa ile pla o m o in eg a ion wi h po ous ma e ials.
1.6. Polyme @MOF composi e
The de elopmen o MOF-based composi es a ises om he need o in eg a e MOFs
in o s able ma ices wi hou comp omising hei s uc u e o unc ion.215 MOFs a e
highly p omising ma e ials o he emedia ion o hea y me al-con amina ed wa e due
o hei excep ional adso p ion capabili ies. Howe e , hei main limi a ion is hei
physical o m, as hey a e ob ained as ine powde s ha a e di icul o handle o di ec
applica ion in eal-wo ld en i onmen al scena ios.216–218
To o e come his challenge, MOF composi es ha e been designed o embed hese
ma e ials wi hin suppo i e ma ices ha p ese e hei in insic po osi y and me al-
binding p ope ies. Beyond he me e unc ion o p o iding suppo , hese ma ices,
n
cc
F F F F
H
HH
cc
F F
c
HH
cF
F
c
F
F
F
c
F
c
- Syn he ic
- Hyd ophobic
- Semic is aline
- Flexible
- No in e ac ion wi h me als
- Mechanical suppo
- Na u al
- Hyd ophilic
- Low c is alini y
- Flexible
- In e a ion wi h me als
- Imp o e lexibili y
- Na u al
- Hyd ophilic/Anphiphilic
- Amo ph
- Flexible
- In e a ion wi h me als
- Imp o e me al adso p ion
PVDF-HFP β-qui in Soy p o ein isola ed
-(CH2CF2)x-(CF2-CF(CF3))y- -[C8H13O5N]n- -[NH-CH(R)-CO]n-
Chap e 1
34
composed o unc ional polyme s, can also con ibu e o he o e all adso p ion
pe o mance. In some cases, he esul ing composi es p esen syne gis ic e ec s,
showing be e adso p ion capaci y compa ed o he indi idual componen s alone.219
Building upon es ablished insigh s in o MOF unc ionali ies and polyme ma ix
in eg a ion, Table 1.5 summa ises some s udied PVDF@MOF composi es o hea y
me al adso p ion. This compila ion e lec s he cu en s a e o labo a o y-scale
esea ch, highligh s p omising candida es wi h di e se adso p ion p o iles and
egene a ion po en ials, and unde sco es he exis ing gap owa ds p ac ical ield
applica ions.220–222
Table 2.5. Compa a i e Table o di e en PVDF@MOF composi es.
Ma e ial
Adso p ion
Capaci y
(mg/g)
Adso p ion
Kine ics
(PSO)
(min)
TRC*
So ben
Cos
S&R*
TRL*3
PVDF@MOF-808@Cys
Hg(II): 30
240
No
Medium
Good,
Chemical
3-4
PVDF@β–CD-ZIF-8
Pb(II): 708
Cu(II): 651
120
No
High
Good,
Chemical
4-5
PVDF@Guanidine-
G a ed-NH2-MIL-
101(Fe)
Pb(II): 29
720
No
High
-
3-4
*TRC: Tes ed in Real Condi ions, S&R: S abili y and Regene abili y, TRL: Technology Readiness Le el
Simila ly, he in eg a ion o MOFs wi h biopolyme s has gained conside able a en ion
due o he inhe en ad an ages o na u al polyme s, including biocompa ibili y,
biodeg adabili y, and cos -e ec i eness. Table 1.6 summa ises se e al s udied
biopolyme @MOF composi es o hea y me al adso p ion. The esul ing bio-based
composi es o e a sus ainable al e na i e o syn he ic polyme ma ices while
main aining e icien adso p ion pe o mance and acili a ing ecyclabili y.223–229
Table 2.6. Compa a i e Table o di e en Biopolyme @MOF composi es.
Ma e ial
Adso p ion
Capaci y
(mg/g)
Adso p ion
Kine ics (PSO)
(min)
TRC*
So ben
Cos
S&R*
TRL*
Chi osan@ZIF-67
Pb(II): 5.5
-
No
Medium
Good,
Chemical
3-4
Chi osan@NH2-
MIL-125
Pb(II): 945
40
No
Medium
Good,
Chemical
3-4
Chi osan@MOF-
808
C (VI): 320
20
No
Medium
Good,
Chemical
3-4
CNC@Zn-BTC
Pb(II): 559
30
No
Low
Good,
Chemical
3-4

In oduc ion
35
CHIPEC@UiO-66-
NH2
As(II): 168
As(V): 335
-
No
Medium
Good,
Chemical
3-4
Co-Al-
LDH@CHN/Fe3O4
Pb(II): 559
C (VI): 711
-
No
Medium
High,
Chemical
4-5
Cellulose@ZIF-8
Pb(II): 307
Cd(II): 143
Co(II): 350
Cu(II): 354
Fe(III): 261
30
No
Medium
High,
Chemical
3-4
*TRC: Tes ed in Real Condi ions, S&R: S abili y and Regene abili y, TRL: Technology Readiness Le el
The syn hesis o composi e@MOF can be achie ed h ough a ious me hods, among
hem he mos common a e in-si u polyme isa ion, elec ospinning, physical blending
and sol en cas ing, each o e ing dis inc ad an ages o ailo ing ma e ial s uc u e
and unc ionali y.230 In si u polyme isa ion is a p ocess ha in ol es he g ow h o
polyme chains wi hin he po es o MOF pa icles. This imp o es in e acial adhesion,
enabling polyme chains o pene a e he MOF po es o o m co alen bonds wi h
su ace unc ional g oups. This c ea es a mo e uni o m dis ibu ion h oughou he
polyme ma ix.231,232 Elec ospinning is a echnique ha in ol es a s ong elec ic ield
o d aw a polyme solu ion in o ul a- ine ib es. As he sol en e apo a es, ib es wi h
a high su ace- o- olume a io, con ollable po osi y, and unable mo phology a e
ob ained.233–235 Physical blending o e s ano he e ec i e s a egy by physically
combining MOFs wi h polyme s o c ea e mul i unc ional composi es. I in ol es he
inco po a ion o p e-syn hesised MOFs in o polyme solu ions h ough mechanical
mixing, o e ing scalable p oduc ion wi h adequa e he mal s abili y.236,237 Sol en
cas ing emains he mos s aigh o wa d app oach, whe e MOFs a e dispe sed in a
polyme solu ion ollowed by con olled sol en e apo a ion o yield homogeneous
composi e ilms, a me hod pa icula ly a ou ed o i s simplici y and
ep oducibili y.238,239
In his hesis, wo di e en polyme @MOF composi es ha e been de eloped, using
na u al and syn he ic polyme s as a ma ix and wo di e en syn hesis me hods:
PVDF-HFP@MOF composi e a combina ion o sol en cas ing wi h sal leaching
me hods we e used, whe e MOF, polyme and NaCl (as po e o ming agen ) we e
mixed in a solu ion, moulded and d ied a oom empe a u e (Fig. 1.10). This echnique
allows a well-con olled s uc u e wi h a high su ace a ea, enabling a uni o m
dis ibu ion o he MOF wi hin he ma ix while in oducing in e connec ed po es upon
sal emo al, imp o ing he accessibili y o ac i e si es. I also a oids he use o high
Chap e 1
36
empe a u es o complex equipmen , making i scalable and compa ible wi h
s uc u ally sensi i e MOFs.240
Figu e 2.10. Rep esen a ion o PVDF-HFP@MOF composi e p epa ed by sol en cas ing wi h sal
leaching me hod.
SPICHI@MOF composi e (Soy P o ein-Chi in@MOF): is p epa ed ia aqueous-
phase blending and eeze-d ying o soy p o ein isola e, chi in and he MOF a a high
empe a u e, ollowed by pH adjus men and he addi ion o glyce ol. The esul ing
mix u e is pou ed in o moulds, ozen and eeze-d ied o ob ain he inal composi e
(Fig. 1.11). This me hod a oids he use o ha sh sol en s o e y high empe a u es,
enabling homogeneous dispe sion o he componen s. F eeze-d ying also allows he
o ma ion o highly po ous s uc u es ha a e necessa y o adso p ion
applica ions.241,242 Addi ionally, hese biopolyme s inc ease he me al-binding capaci y
wi h hei unc ional g oups and p ese e he o iginal MOF s uc u e.
Figu e 2.11. Rep esen a ion o SPICHI@MOF composi e.
In oduc ion
37
The inal p ope ies o composi es a e de e mined by he in e ac ions be ween MOFs
and polyme s, such as hyd ogen bonding, elec os a ic o ces, coo dina ion o
co alen bonding.243 These in e ac ions in e e e wi h he dispe sion and adhesion o
MOFs wi hin he polyme ma ix and in luence he ma e ial's mechanical s eng h,
po osi y, and o e all s abili y. The p esence o s ong bonds imp o es he s uc u al
in eg i y, p e en s MOFs om agg ega ion and keeps hei po osi y.244,245 The e o e, a
deep unde s anding o he na u e and s eng h o MOF–polyme in e ac ions is
essen ial o designing composi es wi h speci ic unc ionali ies.
The ema kable pe o mance o MOF-polyme composi es in me al adso p ion can be
a ibu ed o se e al syne gis ic mechanisms ha add ess he limi a ions o indi idual
componen s. Polyme s as a ma ix help us o keep and handle MOF pa icles o he
il a ion, as well as p o ec MOF s uc u es om wa e -induced deg ada ion while
main aining access o ac i e si es.246 This p o ec i e e ec mani es s di e en ly
depending on he polyme 's na u e.
In PVDF-HFP, hyd ophobic and hyd ophilic domains c ea e an op imal en i onmen
o me al adso p ion. The PVDF backbone p o ides hyd ophobic p o ec ion ha
shields MOF c ys als om di ec wa e con ac , p e en ing MOF deg ada ion, while
he HFP co-monome in oduces con olled hyd ophilici y ha acili a es me al ion
anspo .247 Fluo ine a oms in PVDF-HFP gene a e s ong dipoles, which in e ac wi h
me al ca ions h ough ion-dipole o ces, b inging hem in o p oximi y o he MOF
su ace. Despi e he absence o unc ional g oups capable o coo dina ing me als, he
dipola na u e and physical encapsula ion o PVDF-HFP acili a e MOF dispe sion and
ion accessibili y.248 Fu he mo e, i s chemical ine ness con ibu es o s uc u al
in eg i y and long- e m pe o mance in ha sh aqueous en i onmen s, suppo ing
s able and e icien me al adso p ion h oughou ex ended ope a ional pe iods.
On he o he hand, biopolyme s such as chi in and soy p o ein c ea e hyd ophilic
en i onmen s ha acili a e me al ion anspo and o e addi ional binding si es. The
amino g oups in chi in and he di e se unc ional g oups in soy p o ein (ca boxyl,
amino, hyd oxyl, and sul hyd yl g oups) wo k syne gis ically o c ea e a mul i- unc ional
binding ma ix ha complemen s MOF adso p ion si es. P ima y adso p ion occu s a
MOF ac i e si es h ough coo dina ion bonds, ion exchange, and elec os a ic
in e ac ions, while seconda y adso p ion akes place a polyme unc ional g oups.249
Chap e 1
38
In chi in-soy p o ein composi es, he polyme ma ix con ibu es signi ican addi ional
chela ion capaci y h ough mul iple mechanisms: chi in's amino g oups can o m
coo dina ion complexes wi h ansi ion me als, while soy p o ein's di e se amino acid
esidues p o ide sulphu and ni ogen dono a oms ha exhibi s ong a ini y o hea y
me als. The in e ac ions be ween MOF pa icles and biopolyme composi es a e
di e en om hose wi h syn he ic polyme s. In chi in-soy p o ein-MOF sys ems, he
o ma ion o hyd ogen bonds be ween polyme hyd oxyl/amino g oups and MOF
o ganic linke s c ea es a s able egion.250 Fu he mo e, he p o ein componen exhibi s
con o ma ional changes when binding o me al ions, which esul in he exposu e o
p e iously hidden binding si es, imp o ing he selec i i y o he p ocess since i has
he capaci y o adap i s s uc u e o be e accommoda e speci ic me als. In addi ion,
he chi in componen p o ides s uc u al suppo h ough i s c ys alline egions, while
i s amo phous domains add lexibili y.251
Bo h polyme ma ices a e capable o main aining he op imum pa icle dispe sion and
p e en ing he agglome a ion, ensu ing ha MOF po es emain accessible o me al
ions in he adso p ion p ocess.252 This is e y use ul o selec i e me al emo al, as i
keeps he size-selec i e p ope ies o MOF po es while p o iding mechanical
s abili y.253
The me al adso p ion p ocess in MOF–polyme composi es displays a mul i ude o
in e connec ed mechanisms. The p ocess begins wi h he di usion o me al ions om
he solu ion owa ds he composi e su ace un il me al ions mo e deepe in o he
composi e and each he MOF pa icles embedded wi hin he polyme ma ix. The
capaci y o ions o access he ac i e si es o he MOF is signi ican ly in luenced by he
na u e o he polyme -MOF in e ace. In well-in eg a ed composi es, polyme chains
can ac as molecula pa hways ha guide me al ions di ec ly owa ds he MOF
po es.254 The i s binding a ini y wi h me al ions is wi h he unsa u a ed me al si es o
he MOF, ollowed by he unc ional g oups o he MOF’s o ganic linke s, and nex in
a ini y wi h he unc ional g oups o high-a ini y si es on he polyme .255,256
The way me als in e ac wi h he composi e in ol es wo ypes o selec i i y:
he modynamic and kine ic. The modynamic selec i i y depends on he di e en me al
ions and on hei p e e ences o speci ic binding si es, ollowing ends as he I ing-
Williams se ies o ansi ion me als.257 Meanwhile, kine ic selec i i y is in luenced by
In oduc ion
45
(63) Poo khalil, A.; Taye ehsey i, E.; Fa okhzad, H.; Mohsenzadeh, A. Na u al and Syn he ic Zeoli es
o A senic Remo al om Wa e : A Comp ehensi e Re iew o Mechanisms, Pe o mance, and
Fu u e Pe spec i es. Jou nal o Haza dous Ma e ials Ad ances 2025, 19, 100866.
h ps://doi.o g/10.1016/j.hazad .2025.100866.
(64) Yin, X.; Wang, F.; Zheng, Q.; Ning, S.; Chen, L.; Wei, Y. Re iew on Syn hesis o Silica-Based
Hyb id So ben s and Thei Applica ion in Radionuclide Sepa a ion and Remo al ia
Ch oma og aphic Technique. Toxics 2025, 13 (4), 319. h ps://doi.o g/10.3390/ oxics13040319.
(65) Kaushal, A. Regene a ion S udy o Adso ben s Loaded wi h Zinc Me al Ions om Con amina ed
Wa e . In e na ional Jou nal o Hyd ology 2023, 7 (5), 189–192.
h ps://doi.o g/10.15406/ijh.2023.07.00356.
(66) Dha map iya, T. N.; Li, D.; Chung, Y.-C.; Huang, P.-J. G een Syn hesis o Reusable Adso ben s
o he Remo al o Hea y Me al Ions. ACS Omega 2021, 6 (45), 30478–30487.
h ps://doi.o g/10.1021/acsomega.1c03879.
(67) Li, J.; Wang, X.; Zhao, G.; Chen, C.; Chai, Z.; Alsaedi, A.; Haya , T.; Wang, X. Me al–O ganic
F amewo k-Based Ma e ials: Supe io Adso ben s o he Cap u e o Toxic and Radioac i e
Me al Ions. Chem Soc Re 2018, 47 (7), 2322–2356. h ps://doi.o g/10.1039/C7CS00543A.
(68) Li, J.-R.; Kupple , R. J.; Zhou, H.-C. Selec i e Gas Adso p ion and Sepa a ion in Me al–O ganic
F amewo ks. Chem Soc Re 2009, 38 (5), 1477. h ps://doi.o g/10.1039/b802426j.
(69) Jin, E.; Lee, S.; Kang, E.; Kim, Y.; Choe, W. Me al-O ganic F amewo ks as Ad anced Adso ben s
o Pha maceu ical and Pe sonal Ca e P oduc s. Coo d Chem Re 2020, 425, 213526.
h ps://doi.o g/10.1016/j.cc .2020.213526.
(70) Essalmi, S.; Lo i, S.; BaQais, A.; Saadi, M.; A ab, M.; Ai Ahsaine, H. Design and Applica ion o
Me al O ganic F amewo ks o Hea y Me als Adso p ion in Wa e : A Re iew. RSC Ad 2024, 14
(13), 9365–9390. h ps://doi.o g/10.1039/D3RA08815D.
(71) Liu, Y.; Yang, J.; Wu, J.; Jiang, Z.; Zhang, X.; Meng, F. The Applica ion o Mul i unc ional Me al–
O ganic F amewo ks o he De ec ion, Adso p ion, and Deg ada ion o Con aminan s in an
Aqua ic En i onmen . Molecules 2025, 30 (6), 1336.
h ps://doi.o g/10.3390/molecules30061336.
(72) Russo, V.; Hmoudah, M.; B occoli, F.; Iesce, M. R.; Jung, O.-S.; Di Se io, M. Applica ions o
Me al O ganic F amewo ks in Was ewa e T ea men : A Re iew on Adso p ion and
Pho odeg ada ion. F on ie s in Chemical Enginee ing 2020, 2.
h ps://doi.o g/10.3389/ ceng.2020.581487.
(73) Swain, J.; P iyada shini, A.; Panda, S.; Haj a, S.; Das, N.; Vi ekanan han, V.; Mis ewicz, K.;
Saman ay, R.; Joon Kim, H.; Sahu, R. Me al–O ganic F amewo ks: Syn hesis Me hods and
Mul i unc ional Applica ions. Ene gy Technology 2025, 13 (5).
h ps://doi.o g/10.1002/en e.202402354.
(74) Meek, S. T.; G ea house, J. A.; Allendo , M. D. Me al‐O ganic F amewo ks: A Rapidly G owing
Class o Ve sa ile Nanopo ous Ma e ials. Ad anced Ma e ials 2011, 23 (2), 249–267.
h ps://doi.o g/10.1002/adma.201002854.
(75) Li, X.; Yang, X.; Xue, H.; Pang, H.; Xu, Q. Me al–O ganic F amewo ks as a Pla o m o Clean
Ene gy Applica ions. Ene gyChem 2020, 2 (2), 100027.
h ps://doi.o g/10.1016/j.enchem.2020.100027.
(76) Cui, Y.; Li, B.; He, H.; Zhou, W.; Chen, B.; Qian, G. Me al–O ganic F amewo ks as Pla o ms o
Func ional Ma e ials. Acc Chem Res 2016, 49 (3), 483–493.
h ps://doi.o g/10.1021/acs.accoun s.5b00530.
(77) Eddaoudi, M.; Mole , D. B.; Li, H.; Chen, B.; Reineke, T. M.; O’Kee e, M.; Yaghi, O. M. Modula
Chemis y: Seconda y Building Uni s as a Basis o he Design o Highly Po ous and Robus
Me al−O ganic Ca boxyla e F amewo ks. Acc Chem Res 2001, 34 (4), 319–330.
h ps://doi.o g/10.1021/a 000034b.

Chap e 1
46
(78) T anchemon agne, D. J.; Mendoza-Co és, J. L.; O’Kee e, M.; Yaghi, O. M. Seconda y Building
Uni s, Ne s and Bonding in he Chemis y o Me al–O ganic F amewo ks. Chem Soc Re 2009,
38 (5), 1257. h ps://doi.o g/10.1039/b817735j.
(79) Lu, W.; Wei, Z.; Gu, Z.-Y.; Liu, T.-F.; Pa k, J.; Pa k, J.; Tian, J.; Zhang, M.; Zhang, Q.; Gen le III,
T.; Bosch, M.; Zhou, H.-C. Tuning he S uc u e and Func ion o Me al–O ganic F amewo ks ia
Linke Design. Chem. Soc. Re . 2014, 43 (16), 5561–5593.
h ps://doi.o g/10.1039/C4CS00003J.
(80) Kalmu zki, M. J.; Hanikel, N.; Yaghi, O. M. Seconda y Building Uni s as he Tu ning Poin in he
De elopmen o he Re icula Chemis y o MOFs. Sci Ad 2018, 4 (10).
h ps://doi.o g/10.1126/sciad .aa 9180.
(81) Yaghi, O. M.; O’Kee e, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Re icula Syn hesis
and he Design o New Ma e ials. Na u e 2003, 423 (6941), 705–714.
h ps://doi.o g/10.1038/na u e01650.
(82) G opp, C.; Canossa, S.; Wu ke, S.; Gánda a, F.; Li, Q.; Gaglia di, L.; Yaghi, O. M. S anda d
P ac ices o Re icula Chemis y. ACS Cen Sci 2020, 6 (8), 1255–1273.
h ps://doi.o g/10.1021/acscen sci.0c00592.
(83) Kalmu zki, M. J.; Hanikel, N.; Yaghi, O. M. Seconda y Building Uni s as he Tu ning Poin in he
De elopmen o he Re icula Chemis y o MOFs. Sci Ad 2018, 4 (10).
h ps://doi.o g/10.1126/sciad .aa 9180.
(84) Mai, Z.; Liu, D. Syn hesis and Applica ions o Iso e icula Me al–O ganic F amewo ks IRMOFs-
n ( n = 1, 3, 6, 8). C ys G ow h Des 2019, 19 (12), 7439–7462.
h ps://doi.o g/10.1021/acs.cgd.9b00879.
(85) Comlek, Y.; Pham, T. D.; Snu , R. Q.; Chen, W. Rapid Design o Top-Pe o ming Me al-O ganic
F amewo ks wi h Quali a i e Rep esen a ions o Building Blocks. NPJ Compu Ma e 2023, 9
(1), 170. h ps://doi.o g/10.1038/s41524-023-01125-1.
(86) Islamoglu, T.; Ray, D.; Li, P.; Majewski, M. B.; Akpina , I.; Zhang, X.; C ame , C. J.; Gaglia di, L.;
Fa ha, O. K. F om T ansi ion Me als o Lan hanides o Ac inides: Me al-Media ed Tuning o
Elec onic P ope ies o Isos uc u al Me al–O ganic F amewo ks. Ino g Chem 2018, 57 (21),
13246–13251. h ps://doi.o g/10.1021/acs.ino gchem.8b01748.
(87) Bu ch, N. C.; Jasuja, H.; Wal on, K. S. Wa e S abili y and Adso p ion in Me al–O ganic
F amewo ks. Chem Re 2014, 114 (20), 10575–10612. h ps://doi.o g/10.1021/c 5002589.
(88) Bünzli, J.-C. G.; Pigue , C. Lan hanide-Con aining Molecula and Sup amolecula Polyme allic
Func ional Assemblies. Chem Re 2002, 102 (6), 1897–1928. h ps://doi.o g/10.1021/c 010299j.
(89) Ca ka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lambe i, C.; Bo diga, S.; Lille ud, K. P. A
New Zi conium Ino ganic Building B ick Fo ming Me al O ganic F amewo ks wi h Excep ional
S abili y. J Am Chem Soc 2008, 130 (42), 13850–13851. h ps://doi.o g/10.1021/ja8057953.
(90) Eddaoudi, M.; Mole , D. B.; Li, H.; Chen, B.; Reineke, T. M.; O’Kee e, M.; Yaghi, O. M. Modula
Chemis y: Seconda y Building Uni s as a Basis o he Design o Highly Po ous and Robus
Me al−O ganic Ca boxyla e F amewo ks. Acc Chem Res 2001, 34 (4), 319–330.
h ps://doi.o g/10.1021/a 000034b.
(91) Peh, S. B.; Cheng, Y.; Zhang, J.; Wang, Y.; Chan, G. H.; Wang, J.; Zhao, D. Clus e Nuclea i y
Con ol and Modula ed Hyd o he mal Syn hesis o Func ionalized Z 12 Me al–O ganic
F amewo ks. Dal on T ansac ions 2019, 48 (21), 7069–7073.
h ps://doi.o g/10.1039/C8DT05060K.
(92) Koschnick, C.; Te ban, M. W.; F ison, R.; E e , M.; Böhm, F. A.; P ose pio, D. M.; K ause, S.;
Dinnebie , R. E.; Canossa, S.; Lo sch, B. V. Unlocking New Topologies in Z -Based Me al–
O ganic F amewo ks by Combining Linke Flexibili y and Building Block Diso de . J Am Chem
Soc 2023, 145 (18), 10051–10060. h ps://doi.o g/10.1021/jacs.2c13731.
(93) Schube , U. Clus e s wi h a Z 6O8 Co e. Coo d Chem Re 2022, 469, 214686.
h ps://doi.o g/10.1016/j.cc .2022.214686.
In oduc ion
47
(94) Lu, W.; Wei, Z.; Gu, Z.-Y.; Liu, T.-F.; Pa k, J.; Pa k, J.; Tian, J.; Zhang, M.; Zhang, Q.; Gen le III,
T.; Bosch, M.; Zhou, H.-C. Tuning he S uc u e and Func ion o Me al–O ganic F amewo ks ia
Linke Design. Chem. Soc. Re . 2014, 43 (16), 5561–5593.
h ps://doi.o g/10.1039/C4CS00003J.
(95) DeS e ano, M. R.; Islamoglu, T.; Ga ibay, S. J.; Hupp, J. T.; Fa ha, O. K. Room-Tempe a u e
Syn hesis o UiO-66 and The mal Modula ion o Densi ies o De ec Si es. Chemis y o Ma e ials
2017, 29 (3), 1357–1361. h ps://doi.o g/10.1021/acs.chemma e .6b05115.
(96) Van den Eynden, D.; Pok a a h, R.; Ma hew, J. P.; Goossens, E.; De Buysse , K.; De Roo, J.
Fa y Acid Capped, Me al Oxo Clus e s as he Smalles Concei able Nanoc ys al P o o ypes.
Chem Sci 2023, 14 (3), 573–585. h ps://doi.o g/10.1039/D2SC05037D.
(97) Mu ali, M.; Bijani, C.; Da an, J.-C.; Manou y, E.; Poli, R. Ace a e Exchange Mechanism on a Z
12 Oxo Hyd oxo Clus e : Rele ance o Reshaping Z –Ca boxyla e Coo dina ion Adap able
Ne wo ks. Chem Sci 2023, 14 (30), 8152–8163. h ps://doi.o g/10.1039/D3SC02204H.
(98) Feng, D.; Jiang, H.-L.; Chen, Y.-P.; Gu, Z.-Y.; Wei, Z.; Zhou, H.-C. Me al–O ganic F amewo ks
Based on P e iously Unknown Z 8 /H 8 Cubic Clus e s. Ino g Chem 2013, 52 (21), 12661–
12667. h ps://doi.o g/10.1021/ic4018536.
(99) Liu, T.-F.; Feng, D.; Chen, Y.-P.; Zou, L.; Bosch, M.; Yuan, S.; Wei, Z.; Fo dham, S.; Wang, K.;
Zhou, H.-C. Topology-Guided Design and Syn heses o Highly S able Mesopo ous Po phy inic
Zi conium Me al–O ganic F amewo ks wi h High Su ace A ea. J Am Chem Soc 2015, 137 (1),
413–419. h ps://doi.o g/10.1021/ja5111317.
(100) Almeida Paz, F. A.; Klinowski, J.; Vilela, S. M. F.; Tomé, J. P. C.; Ca alei o, J. A. S.; Rocha, J.
Ligand Design o Func ional Me al–O ganic F amewo ks. Chem. Soc. Re . 2012, 41 (3), 1088–
1110. h ps://doi.o g/10.1039/C1CS15055C.
(101) Die cks, C. S.; Yaghi, O. M. The A om, he Molecule, and he Co alen O ganic F amewo k.
Science (1979) 2017, 355 (6328). h ps://doi.o g/10.1126/science.aal1585.
(102) Schaa e, A.; Roy, P.; God , A.; Lippke, J.; Wal z, F.; Wiebcke, M.; Beh ens, P. Modula ed
Syn hesis o Z ‐Based Me al–O ganic F amewo ks: F om Nano o Single C ys als. Chemis y –
A Eu opean Jou nal 2011, 17 (24), 6643–6651. h ps://doi.o g/10.1002/chem.201003211.
(103) Van Vlee , M. J.; Weng, T.; Li, X.; Schmid , J. R. In Si u, Time-Resol ed, and Mechanis ic S udies
o Me al–O ganic F amewo k Nuclea ion and G ow h. Chem Re 2018, 118 (7), 3681–3721.
h ps://doi.o g/10.1021/acs.chem e .7b00582.
(104) Rosi, N. L.; Eddaoudi, M.; Kim, J.; O’Kee e, M.; Yaghi, O. M. Ad ances in he Chemis y o
Me al–O ganic F amewo ks. C ys EngComm 2002, 4 (68), 401–404.
h ps://doi.o g/10.1039/B203193K.
(105) Sud, D.; Kau , G. A Comp ehensi e Re iew on Syn he ic App oaches o Me al-O ganic
F amewo ks: F om T adi ional Sol o he mal o G eene P o ocols. Polyhed on 2021, 193,
114897. h ps://doi.o g/10.1016/j.poly.2020.114897.
(106) Chen, X.-M.; Tong, M.-L. Sol o he mal in Si u Me al/Ligand Reac ions: A New B idge be ween
Coo dina ion Chemis y and O ganic Syn he ic Chemis y. Acc Chem Res 2007, 40 (2), 162–
170. h ps://doi.o g/10.1021/a 068084p.
(107) Li, C.-P.; Du, M. Role o Sol en s in Coo dina ion Sup amolecula Sys ems. Chemical
Communica ions 2011, 47 (21), 5958. h ps://doi.o g/10.1039/c1cc10935a.
(108) Rosi, N. L.; Eddaoudi, M.; Kim, J.; O’Kee e, M.; Yaghi, O. M. Ad ances in he Chemis y o
Me al–O ganic F amewo ks. C ys EngComm 2002, 4 (68), 401–404.
h ps://doi.o g/10.1039/B203193K.
(109) Bu ows, A. D.; Cassa , K.; F iend, R. M. W.; Mahon, M. F.; Rigby, S. P.; Wa en, J. E. Sol en
Hyd olysis and Templa ing E ec s in he Syn hesis o Me al–O ganic F amewo ks.
C ys EngComm 2005, 7 (89), 548. h ps://doi.o g/10.1039/b509460g.
Chap e 1
48
(110) Chen, W.; Du, L.; Wu, C. Hyd o he mal Syn hesis o MOFs. In Me al-O ganic F amewo ks o
Biomedical Applica ions; Else ie , 2020; pp 141–157. h ps://doi.o g/10.1016/B978-0-12-
816984-1.00009-3.
(111) Simon, M.-O.; Li, C.-J. G een Chemis y O ien ed O ganic Syn hesis in Wa e . Chem. Soc. Re .
2012, 41 (4), 1415–1427. h ps://doi.o g/10.1039/C1CS15222J.
(112) Baghe i, A. R.; A amesh, N. Towa ds he Room-Tempe a u e Syn hesis o Co alen O ganic
F amewo ks: A Mini-Re iew. J Ma e Sci 2021, 56 (2), 1116–1132.
h ps://doi.o g/10.1007/s10853-020-05308-9.
(113) Wu, D.; Gu, N.; Yao, J.; Cao, Y.; Wang, L.; Shaki , I.; Sun, Y.; Xu, Y. Recen Ad ances in Room-
Tempe a u e Syn hesis o Co alen O ganic F amewo ks. Chem Sci 2025, 16 (13), 5447–5463.
h ps://doi.o g/10.1039/D5SC00109A.
(114) Oli e Kappe, C. Mic owa e Dielec ic Hea ing in Syn he ic O ganic Chemis y. Chem Soc Re
2008, 37 (6), 1127. h ps://doi.o g/10.1039/b803001b.
(115) Li, C.; Iqbal, M.; Lin, J.; Luo, X.; Jiang, B.; Malg as, V.; Wu, K. C.-W.; Kim, J.; Yamauchi, Y.
Elec ochemical Deposi ion: An Ad anced App oach o Templa ed Syn hesis o Nanopo ous
Me al A chi ec u es. Acc Chem Res 2018, 51 (8), 1764–1773.
h ps://doi.o g/10.1021/acs.accoun s.8b00119.
(116) Głowniak, S.; Szczęśniak, B.; Choma, J.; Ja oniec, M. Recen De elopmen s in Sonochemical
Syn hesis o Nanopo ous Ma e ials. Molecules 2023, 28 (6), 2639.
h ps://doi.o g/10.3390/molecules28062639.
(117) James, S. L.; Adams, C. J.; Bolm, C.; B aga, D.; Collie , P.; F iščić, T.; G epioni, F.; Ha is, K. D.
M.; Hye , G.; Jones, W.; K ebs, A.; Mack, J.; Maini, L.; O pen, A. G.; Pa kin, I. P.; Shea ouse,
W. C.; S eed, J. W.; Waddell, D. C. Mechanochemis y: Oppo uni ies o New and Cleane
Syn hesis. Chem. Soc. Re . 2012, 41 (1), 413–447. h ps://doi.o g/10.1039/C1CS15171A.
(118) Yang, S. J.; Cho, J. H.; Lee, K.; Kim, T.; Pa k, C. R. Concen a ion-D i en E olu ion o C ys al
S uc u e, Po e Cha ac e is ics, and Hyd ogen S o age Capaci y o Me al O ganic F amewo k-
5s: Expe imen al and Compu a ional S udies. Chemis y o Ma e ials 2010, 22 (22), 6138–6145.
h ps://doi.o g/10.1021/cm101943e.
(119) Łuczak, J.; K oczewska, M.; Baluk, M.; Sowik, J.; Mazie ski, P.; Zaleska-Medynska, A.
Mo phology Con ol h ough he Syn hesis o Me al-O ganic F amewo ks. Ad Colloid In e ace
Sci 2023, 314, 102864. h ps://doi.o g/10.1016/j.cis.2023.102864.
(120) De Villenoisy, T.; Ho, N.; Chen, S.; Zheng, X.; So ell, C. C.; Zhang, Y.; Koshy, P. Elucida ing he
Role o Syn hesis Condi ions on Z -MOF P ope ies and Yield. Ma e Chem Phys 2023, 309,
128448. h ps://doi.o g/10.1016/j.ma chemphys.2023.128448.
(121) A in, S.; Khan, M. W.; Haque, E.; Ren, B.; Ou, J. Z. Recen Ad ances in he Tuning o he
O ganic F amewo k Ma e ials – The Selec ions o Ligands, Reac ion Condi ions, and Pos -
Syn hesis App oaches. J Colloid In e ace Sci 2022, 623, 378–404.
h ps://doi.o g/10.1016/j.jcis.2022.05.026.
(122) Long, L.-S. PH E ec on he Assembly o Me al–O ganic A chi ec u es. C ys EngComm 2010,
12 (5), 1354. h ps://doi.o g/10.1039/b921146b.
(123) Guo, H.; Zhu, Y.; Wang, S.; Su, S.; Zhou, L.; Zhang, H. Combining Coo dina ion Modula ion wi h
Acid–Base Adjus men o he Con ol o e Size o Me al–O ganic F amewo ks. Chemis y o
Ma e ials 2012, 24 (3), 444–450. h ps://doi.o g/10.1021/cm202593h.
(124) Łuczak, J.; K oczewska, M.; Baluk, M.; Sowik, J.; Mazie ski, P.; Zaleska-Medynska, A.
Mo phology Con ol h ough he Syn hesis o Me al-O ganic F amewo ks. Ad Colloid In e ace
Sci 2023, 314, 102864. h ps://doi.o g/10.1016/j.cis.2023.102864.
(125) Hou, S.; Liu, F.; Xie, H.; Hanna, S. L.; Id ees, K. B.; Zhang, C.; Wang, X.; Chen, Y.; Li, P.; Fa ha,
O. K. Un eiling he S uc u e–Modula o Rela ionships in Tho ium-Based Me al–O ganic
F amewo k C ys alliza ion. Ino g Chem 2023, 62 (14), 5479–5486.
h ps://doi.o g/10.1021/acs.ino gchem.2c04447.
In oduc ion
49
(126) Chen, F. E.; Pi , T. A.; Okong’o, D. J.; We he bee, L. G.; Fuen es-Ri e a, J. J.; Milne , P. J. A
S uc u e–Ac i i y S udy o A oma ic Acid Modula o s o he Syn hesis o Zi conium-Based
Me al–O ganic F amewo ks. Chemis y o Ma e ials 2022, 34 (7), 3383–3394.
h ps://doi.o g/10.1021/acs.chemma e .2c00241.
(127) Assaad, N.; Sabeh, G.; Hmadeh, M. De ec Con ol in Z -Based Me al–O ganic F amewo k
Nanopa icles o A senic Remo al om Wa e . ACS Appl Nano Ma e 2020, 3 (9), 8997–9008.
h ps://doi.o g/10.1021/acsanm.0c01696.
(128) Gu o , O. V.; He ia, M. G.; Escude o-Adán, E. C.; Sha i , A. Me al–O ganic F amewo k (MOF)
De ec s unde Con ol: Insigh s in o he Missing Linke Si es and Thei Implica ion in he
Reac i i y o Zi conium-Based F amewo ks. Ino g Chem 2015, 54 (17), 8396–8400.
h ps://doi.o g/10.1021/acs.ino gchem.5b01053.
(129) Epley, C. C.; Lo e, M. D.; Mo is, A. J. Cha ac e izing De ec s in a UiO-AZB Me al–O ganic
F amewo k. Ino g Chem 2017, 56 (22), 13777–13784.
h ps://doi.o g/10.1021/acs.ino gchem.7b01801.
(130) Cli e, M. J.; Wan, W.; Zou, X.; Cha e , P. A.; Kleppe, A. K.; Tucke , M. G.; Wilhelm, H.; Funnell,
N. P.; Coude , F.-X.; Goodwin, A. L. Co ela ed De ec Nano egions in a Me al–O ganic
F amewo k. Na Commun 2014, 5 (1), 4176. h ps://doi.o g/10.1038/ncomms5176.
(131) De Villenoisy, T.; Ho, N.; Chen, S.; Zheng, X.; So ell, C. C.; Zhang, Y.; Koshy, P. Elucida ing he
Role o Syn hesis Condi ions on Z -MOF P ope ies and Yield. Ma e Chem Phys 2023, 309,
128448. h ps://doi.o g/10.1016/j.ma chemphys.2023.128448.
(132) Li, B.; Wen, H.; Cui, Y.; Zhou, W.; Qian, G.; Chen, B. Eme ging Mul i unc ional Me al–O ganic
F amewo k Ma e ials. Ad anced Ma e ials 2016, 28 (40), 8819–8860.
h ps://doi.o g/10.1002/adma.201601133.
(133) Ali Akba Raza i, S.; Mo sali, A. Linke Func ionalized Me al-O ganic F amewo ks. Coo d Chem
Re 2019, 399, 213023. h ps://doi.o g/10.1016/j.cc .2019.213023.
(134) Du a, S.; Fajal, S.; Ghosh, S. K. Hea y Me al-Based Toxic Oxo-Pollu an s Seques a ion by
Ad anced Func ional Po ous Ma e ials o Sa e D inking Wa e . Acc Chem Res 2024, 57 (17),
2546–2560. h ps://doi.o g/10.1021/acs.accoun s.4c00348.
(135) Hamisu, A. M.; A i in, A.; Wibowo, A. C. Ca ion Exchange in Me al-O ganic F amewo ks (MOFs):
The Ha d-So Acid-Base (HSAB) P inciple App aisal. Ino ganica Chim Ac a 2020, 511, 119801.
h ps://doi.o g/10.1016/j.ica.2020.119801.
(136) Ma in, R. B. Ha d & So Acids and Bases. In Encyclopedia o Ino ganic and Bioino ganic
Chemis y; Wiley, 2005. h ps://doi.o g/10.1002/9781119951438.eibc0251.
(137) Yoshina i, N.; Kuwamu a, N.; Kojima, T.; Konno, T. De elopmen o Coo dina ion Chemis y wi h
Thiol-Con aining Amino Acids. Coo d Chem Re 2023, 474, 214857.
h ps://doi.o g/10.1016/j.cc .2022.214857.
(138) Te eh, S. Coo dina ion Beha io o Ni 2+ , Cu 2+ , and Zn 2+ in Te ahed al 1-Me hylimidazole
Complexes: A DFT/CSD S udy. Bioino g Chem Appl 2018, 2018, 1–8.
h ps://doi.o g/10.1155/2018/3157969.
(139) Yuan, N.; Gong, X.; Sun, W.; Yu, C. Ad anced Applica ions o Z -Based MOFs in he Remo al
o Wa e Pollu an s. Chemosphe e 2021, 267, 128863.
h ps://doi.o g/10.1016/j.chemosphe e.2020.128863.
(140) Ahmed, I.; Mondol, Md. M. H.; Jung, M.; Lee, G. H.; Jhung, S. H. MOFs wi h B idging o Te minal
Hyd oxo Ligands: Applica ions in Adso p ion, Ca alysis, and Func ionaliza ion. Coo d Chem Re
2023, 475, 214912. h ps://doi.o g/10.1016/j.cc .2022.214912.
(141) Val e de, A.; Payno, D.; Lezama, L.; Laza, J. M.; Wu ke, S.; Fe nández de Luis, R. Mul i a ia e
Func ionaliza ion o UiO‐66 o Pho oca aly ic Wa e Remedia ion. Ad Sus ain Sys 2022, 6 (7).
h ps://doi.o g/10.1002/adsu.202200024.
Chap e 1
50
(142) Ali Akba Raza i, S.; Mo sali, A. Linke Func ionalized Me al-O ganic F amewo ks. Coo d Chem
Re 2019, 399, 213023. h ps://doi.o g/10.1016/j.cc .2019.213023.
(143) Bu igana, M.; Wang, H.; Elm o h No dlande , J.; Yaghi, O. M. Mul i a ia e Me al–O ganic
F amewo k-5 wi h 36 Di e en Linke s. Ino g Chem 2025, 64 (11), 5561–5567.
h ps://doi.o g/10.1021/acs.ino gchem.5c00015.
(144) Chang, C.-K.; Ko, T.-R.; Lin, T.-Y.; Lin, Y.-C.; Yu, H. J.; Lee, J. S.; Li, Y.-P.; Wu, H.-L.; Kang, D.-
Y. Mixed-Linke S a egy o Supp essing S uc u al Flexibili y o Me al-O ganic F amewo k
Memb anes o Gas Sepa a ion. Commun Chem 2023, 6 (1), 118.
h ps://doi.o g/10.1038/s42004-023-00917-2.
(145) He, S.; Wu, L.; Li, X.; Sun, H.; Xiong, T.; Liu, J.; Huang, C.; Xu, H.; Sun, H.; Chen, W.; G e , R.;
Zhang, J. Me al-O ganic F amewo ks o Ad anced D ug Deli e y. Ac a Pha m Sin B 2021, 11
(8), 2362–2395. h ps://doi.o g/10.1016/j.apsb.2021.03.019.
(146) Hou, X.; Chen, B.; Zhai, X.; Gao, X.; Fu, Y.; He, W.; Xiao, X.; Chen, J.; Fu, Y. C ea ing Mul i a ia e
Me al–O ganic F amewo ks wi h Hie a chical S uc u es by Pseudomo phic T ans o ma ion as
Long-Las ing Ca alys o CO 2 Con e sion. ACS Sus ain Chem Eng 2025, 13 (30), 12034–
12045. h ps://doi.o g/10.1021/acssuschemeng.5c03486.
(147) Li, J.-R.; Kupple , R. J.; Zhou, H.-C. Selec i e Gas Adso p ion and Sepa a ion in Me al–O ganic
F amewo ks. Chem Soc Re 2009, 38 (5), 1477. h ps://doi.o g/10.1039/b802426j.
(148) Wang, H.; Liu, Y.; Li, J. Designe Me al–O ganic F amewo ks o Size‐Exclusion‐Based
Hyd oca bon Sepa a ions: P og ess and Challenges. Ad anced Ma e ials 2020, 32 (44).
h ps://doi.o g/10.1002/adma.202002603.
(149) Liu, X.; Oh, M.; Lah, M. S. Size- and Shape-Selec i e Isos uc u al Mic opo ous Me al–O ganic
F amewo ks wi h Di e en E ec i e Ape u e Sizes. Ino g Chem 2011, 50 (11), 5044–5053.
h ps://doi.o g/10.1021/ic200328q.
(150) Chen, B.; Xiang, S.; Qian, G. Me al−O ganic F amewo ks wi h Func ional Po es o Recogni ion
o Small Molecules. Acc Chem Res 2010, 43 (8), 1115–1124. h ps://doi.o g/10.1021/a 100023y.
(151) Rojas, S.; Ho cajada, P. Me al–O ganic F amewo ks o he Remo al o Eme ging O ganic
Con aminan s in Wa e . Chem Re 2020, 120 (16), 8378–8415.
h ps://doi.o g/10.1021/acs.chem e .9b00797.
(152) Zhang, S.; Wang, J.; Zhang, Y.; Ma, J.; Huang, L.; Yu, S.; Chen, L.; Song, G.; Qiu, M.; Wang, X.
Applica ions o Wa e -S able Me al-O ganic F amewo ks in he Remo al o Wa e Pollu an s: A
Re iew. En i onmen al Pollu ion 2021, 291, 118076.
h ps://doi.o g/10.1016/j.en pol.2021.118076.
(153) Rasheed, T.; Hassan, A. A.; Bilal, M.; Hussain, T.; Rizwan, K. Me al-O ganic F amewo ks Based
Adso ben s: A Re iew om Remo al Pe spec i e o Va ious En i onmen al Con aminan s om
Was ewa e . Chemosphe e 2020, 259, 127369.
h ps://doi.o g/10.1016/j.chemosphe e.2020.127369.
(154) Lal, S.; Singh, P.; Singhal, A.; Kuma , S.; Singh Gahlo , A. P.; Gandhi, N.; Kuma i, P. Ad ances
in Me al–O ganic F amewo ks o Wa e Remedia ion Applica ions. RSC Ad 2024, 14 (5),
3413–3446. h ps://doi.o g/10.1039/D3RA07982A.
(155) Lei, Y.; Xie, J.; Quan, W.; Chen, Q.; Long, X.; Wang, A. Ad ances in he Adso p ion o Hea y
Me al Ions in Wa e by UiO-66 Composi es. F on Chem 2023, 11.
h ps://doi.o g/10.3389/ chem.2023.1211989.
(156) Shokouh a , N.; Abou o abi, L.; Mo sali, A. Imp o ing he Capabili y o UiO-66 o C (
<scp> i</Scp> ) Adso p ion om Aqueous Solu ions by In oducing Isonico ina e N -Oxide as
he Func ional G oup. Dal on T ansac ions 2018, 47 (41), 14549–14555.
h ps://doi.o g/10.1039/C8DT03196G.
(157) Abha i, P. S.; Man eghi, F.; Teh ani, Z. Adso p ion o Lead Ions by a G een AC/HKUST-1
Nanocomposi e. Nanoma e ials 2020, 10 (9), 1647. h ps://doi.o g/10.3390/nano10091647.

In oduc ion
51
(158) Huang, L.; Cao, H.; Ma, J.; Wang, X. E icien Remo al o Pb(II) by UiO-66-NH2: A Combined
Expe imen al and Spec oscopic S udies. En i on Nano echnol Moni Manag 2022, 18, 100741.
h ps://doi.o g/10.1016/j.enmm.2022.100741.
(159) KHOSRAVI, A.; RANDJBAR, M.; HABIBPOUR, R. Syn hesis, Cha ac e iza ion, and Applica ion
o ZIF-8 o Remo al o Cd, Ni, and Pb Ions om Aqueous Solu ions: Op imiza ion o he P ocess
by Response Su ace Me hodology (RSM) Based on Cen al Composi e Design (CCD)
Technique. Jou nal o Me als, Ma e ials and Mine als 2023, 33 (2), 88–102.
h ps://doi.o g/10.55713/jmmm. 33i2.1668.
(160) Ahadi, N.; Aska i, S.; Fouladi aja , A.; Akba i, I. Facile Syn hesis o Hie a chically S uc u ed MIL-
53(Al) wi h Supe io P ope ies Using an En i onmen ally-F iendly Ul asonic Me hod o
Sepa a ing Lead Ions om Aqueous Solu ions. Sci Rep 2022, 12 (1), 2649.
h ps://doi.o g/10.1038/s41598-022-06518-8.
(161) Alsho i i, F. T.; El Da awy, S. M.; Ahmed, A. I. Fe/Co-MOF Nanoca alys s: G eene Chemis y
App oach o he Remo al o Toxic Me als and Ca aly ic Applica ions. ACS Omega 2022, 7 (27),
23421–23444. h ps://doi.o g/10.1021/acsomega.2c01770.
(162) Ga ou, M.-A.; Vagena, I.-A.; Lagopa i, N.; Pippa, N.; Gazouli, M.; Pa la ou, E. A. Func ional
MOF-Based Ma e ials o En i onmen al and Biomedical Applica ions: A C i ical Re iew.
Nanoma e ials 2023, 13 (15), 2224. h ps://doi.o g/10.3390/nano13152224.
(163) Yusu , V. F.; Malek, N. I.; Kailasa, S. K. Re iew on Me al–O ganic F amewo k Classi ica ion,
Syn he ic App oaches, and In luencing Fac o s: Applica ions in Ene gy, D ug Deli e y, and
Was ewa e T ea men . ACS Omega 2022, 7 (49), 44507–44531.
h ps://doi.o g/10.1021/acsomega.2c05310.
(164) Swain, J.; P iyada shini, A.; Panda, S.; Haj a, S.; Das, N.; Vi ekanan han, V.; Mis ewicz, K.;
Saman ay, R.; Joon Kim, H.; Sahu, R. Me al–O ganic F amewo ks: Syn hesis Me hods and
Mul i unc ional Applica ions. Ene gy Technology 2025, 13 (5).
h ps://doi.o g/10.1002/en e.202402354.
(165) Jiang, H.-L.; Xu, Q. Po ous Me al–O ganic F amewo ks as Pla o ms o Func ional Applica ions.
Chemical Communica ions 2011, 47 (12), 3351. h ps://doi.o g/10.1039/c0cc05419d.
(166) Czaja, A. U.; T ukhan, N.; Mülle , U. Indus ial Applica ions o Me al–O ganic F amewo ks. Chem
Soc Re 2009, 38 (5), 1284. h ps://doi.o g/10.1039/b804680h.
(167) Ki chon, A.; Feng, L.; D ake, H. F.; Joseph, E. A.; Zhou, H.-C. F om Fundamen als o
Applica ions: A Toolbox o Robus and Mul i unc ional MOF Ma e ials. Chem Soc Re 2018, 47
(23), 8611–8638. h ps://doi.o g/10.1039/C8CS00688A.
(168) Rap opoulou, C. P. Me al-O ganic F amewo ks: Syn he ic Me hods and Po en ial Applica ions.
Ma e ials 2021, 14 (2), 310. h ps://doi.o g/10.3390/ma14020310.
(169) Li, D.; Yada , A.; Zhou, H.; Roy, K.; Thanaseka an, P.; Lee, C. Ad ances and Applica ions o
Me al‐O ganic F amewo ks (MOFs) in Eme ging Technologies: A Comp ehensi e Re iew.
Global Challenges 2024, 8 (2). h ps://doi.o g/10.1002/gch2.202300244.
(170) Sa chanska, G.; Da ido a, S.; Pe o , P. D. Na u al and Syn he ic Polyme s o Biomedical and
En i onmen al Applica ions. Polyme s (Basel) 2024, 16 (8), 1159.
h ps://doi.o g/10.3390/polym16081159.
(171) Deside y, L.; Lano e, M. Polyme s and Plas ics: Types, P ope ies, and Manu ac u ing. In Plas ic
Was e o Sus ainable Asphal Roads; Else ie , 2022; pp 3–28. h ps://doi.o g/10.1016/B978-0-
323-85789-5.00001-0.
(172) Sun, H.; Klok, H.-A.; Zhong, Z. Polyme s om Na u e and o Na u e. Biomac omolecules 2018,
19 (6), 1697–1700. h ps://doi.o g/10.1021/acs.biomac.8b00830.
(173) Shioha a, A.; P ie o-Simon, B.; Voelcke , N. H. Po ous Polyme ic Memb anes: Fab ica ion
Techniques and Biomedical Applica ions. J Ma e Chem B 2021, 9 (9), 2129–2154.
h ps://doi.o g/10.1039/D0TB01727B.
Chap e 1
52
(174) Alkhaldi, H.; Alha hi, S.; Alha hi, S.; AlGhamdi, H. A.; AlZah ani, Y. M.; Mahmoud, S. A.; Amin,
L. G.; Al-Shaalan, N. H.; Bo aie, W. E.; A ia, M. S.; Al-Gah any, S. A.; Aldaleeli, N.; Ghobashy,
M. M.; Sha shi , A. I.; Madani, M.; Da wesh, R.; Abaza, S. F. Sus ainable Polyme ic Adso ben s
o Adso p ion-Based Wa e Remedia ion and Pa hogen Deac i a ion: A Re iew. RSC Ad 2024,
14 (45), 33143–33190. h ps://doi.o g/10.1039/D4RA05269B.
(175) Ali, S.; Zuh a, Z.; Ali, S.; Han, Q.; Ahmad, M.; Wang, Z. Ul a-Deep Remo al o Pb by
Func ionali y Tuned UiO-66 F amewo k: A Combined Expe imen al, Theo e ical and HSAB
App oach. Chemosphe e 2021, 284, 131305.
h ps://doi.o g/10.1016/j.chemosphe e.2021.131305.
(176) DEANS, J.; DIXON, B. Up ake o Pb2+ and Cu2+ by No el Biopolyme s. Wa e Res 1992, 26
(4), 469–472. h ps://doi.o g/10.1016/0043-1354(92)90047-8.
(177) Na a o, R.; Guzmán, J.; Saucedo, I.; Re illa, J.; Guibal, E. Reco e y o Me al Ions by Chi osan:
So p ion Mechanisms and In luence o Me al Specia ion. Mac omol Biosci 2003, 3 (10), 552–
561. h ps://doi.o g/10.1002/mabi.200300013.
(178) To di, P.; Ridi, F.; Samo ì, P.; Bonini, M. Ca ion‐Algina e Complexes and Thei Hyd ogels: A
Powe ul Toolki o he De elopmen o Nex ‐Gene a ion Sus ainable Func ional Ma e ials. Ad
Func Ma e 2025, 35 (9). h ps://doi.o g/10.1002/ad m.202416390.
(179) Aslam, A. A.; Hassan, S. U.; Saeed, M. H.; Kokab, O.; Ali, Z.; Nazi , M. S.; Siddiqi, W.; Aslam, A.
A. Cellulose-Based Adso ben Ma e ials o Wa e Remedia ion: Ha nessing Thei Po en ial in
Hea y Me als and Dyes Remo al. J Clean P od 2023, 421, 138555.
h ps://doi.o g/10.1016/j.jclep o.2023.138555.
(180) Khulbe, K. C.; Feng, C.; Ma suu a, T. The A o Su ace Modi ica ion o Syn he ic Polyme ic
Memb anes. J Appl Polym Sci 2010, 115 (2), 855–895. h ps://doi.o g/10.1002/app.31108.
(181) Mi e zky, P.; Ci elli, A. F. Hg(II) Remo al om Wa e by Chi osan and Chi osan De i a i es: A
Re iew. J Haza d Ma e 2009, 167 (1–3), 10–23. h ps://doi.o g/10.1016/j.jhazma .2009.01.060.
(182) Repo, E.; Wa choł, J. K.; Bha naga , A.; Mudhoo, A.; Sillanpää, M. Aminopolyca boxylic Acid
Func ionalized Adso ben s o Hea y Me als Remo al om Wa e . Wa e Res 2013, 47 (14),
4812–4832. h ps://doi.o g/10.1016/j.wa es.2013.06.020.
(183) VASUDEVAN, T.; DAS, S.; SODAYE, S.; PANDEY, A.; REDDY, A. Po e-Func ionalized Polyme
Memb anes o P econcen a ion o Hea y Me al Ions. Talan a 2009, 78 (1), 171–177.
h ps://doi.o g/10.1016/j. alan a.2008.10.053.
(184) She h, Y.; Dha aska , S.; Khalid, M.; Sonawane, S. An En i onmen F iendly App oach o Hea y
Me al Remo al om Indus ial Was ewa e Using Chi osan Based Bioso ben : A Re iew.
Sus ainable Ene gy Technologies and Assessmen s 2021, 43, 100951.
h ps://doi.o g/10.1016/j.se a.2020.100951.
(185) Wang, S.; Vincen , T.; Fau , C.; Guibal, E. Algina e and Algal-Based Beads o he So p ion o
Me al Ca ions: Cu(II) and Pb(II). In J Mol Sci 2016, 17 (9), 1453.
h ps://doi.o g/10.3390/ijms17091453.
(186) He, X.; Cheng, L.; Wang, Y.; Zhao, J.; Zhang, W.; Lu, C. Ae ogels om Qua e na y Ammonium-
Func ionalized Cellulose Nano ibe s o Rapid Remo al o C (VI) om Wa e . Ca bohyd Polym
2014, 111, 683–687. h ps://doi.o g/10.1016/j.ca bpol.2014.05.020.
(187) Deng, S.; Yu, C.; Liu, X.; Wu, F.; Lin, H.; Liao, J.; Liu, F. E icien and Enhanced Hg2+ Remo al
om Wa e Using a Thio Func ionalized Fib ous Adso ben P epa ed wi h Mic owa e I adia ion:
Ba ch and Fixed-Bed Column S udy. J Clean P od 2020, 267, 122163.
h ps://doi.o g/10.1016/j.jclep o.2020.122163.
(188) Baghe pou , S. Fib e Rein o ced Polyes e Composi es. In Polyes e ; InTech, 2012.
h ps://doi.o g/10.5772/48697.
(189) Kash ipou , M. A.; Meh a, N.; Zhu, J. A Re iew on he Role o In e ace in Mechanical, The mal,
and Elec ical P ope ies o Polyme Composi es. Ad Compos Hyb id Ma e 2018, 1 (3), 415–
439. h ps://doi.o g/10.1007/s42114-018-0022-9.
In oduc ion
53
(190) Balazs, A. C.; Em ick, T.; Russell, T. P. Nanopa icle Polyme Composi es: Whe e Two Small
Wo lds Mee . Science (1979) 2006, 314 (5802), 1107–1110.
h ps://doi.o g/10.1126/science.1130557.
(191) Val e de, A.; de Fe nandez‐de Luis, R.; Salaza , H.; Gonçal es, B. F.; King, S.; Almásy, L.;
K iechbaum, M.; Laza, J. M.; Vilas‐Vilela, J. L.; Ma ins, P. M.; Lance os‐Mendez, S.; Po o, J.
M.; Pe enko, V. I. On The Mul iscale S uc u e and Mo phology o PVDF‐HFP@MOF
Memb anes in The Scope o Wa e Remedia ion Applica ions. Ad Ma e In e aces 2023, 10
(31). h ps://doi.o g/10.1002/admi.202300424.
(192) Wang, F.; F ubing, P.; Wi ges, W.; Ge ha d, R.; Wegene , M. Enhanced Pola iza ion in Mel -
Quenched and S e ched Poly(Vinylidene Fluo ide-Hexa luo op opylene) Films. IEEE
T ansac ions on Dielec ics and Elec ical Insula ion 2010, 17 (4), 1088–1095.
h ps://doi.o g/10.1109/TDEI.2010.5539679.
(193) Val e de, A.; de Fe nandez‐de Luis, R.; Salaza , H.; Gonçal es, B. F.; King, S.; Almásy, L.;
K iechbaum, M.; Laza, J. M.; Vilas‐Vilela, J. L.; Ma ins, P. M.; Lance os‐Mendez, S.; Po o, J.
M.; Pe enko, V. I. On The Mul iscale S uc u e and Mo phology o PVDF‐HFP@MOF
Memb anes in The Scope o Wa e Remedia ion Applica ions. Ad Ma e In e aces 2023, 10
(31). h ps://doi.o g/10.1002/admi.202300424.
(194) Bah ami, S.; Ya ian, M. R.; Naj ak, P.; Dola ya i, L.; Shayani-Jam, H.; Kole , S. D. PVDF-HFP
Based Polyme Inclusion Memb anes Con aining Cyphos® IL 101 and Aliqua ® 336 o he
Remo al o C (VI) om Sul a e Solu ions. Sep Pu i Technol 2020, 250, 117251.
h ps://doi.o g/10.1016/j.seppu .2020.117251.
(195) Zhao, S.; Tao, Z.; Chen, L.; Han, M.; Zhao, B.; Tian, X.; Wang, L.; Meng, F. An An i ouling
Ca echol/Chi osan-Modi ied Poly inylidene Fluo ide Memb ane o Sus ainable Oil-in-Wa e
Emulsions Sepa a ion. F on En i on Sci Eng 2021, 15 (4), 63. h ps://doi.o g/10.1007/s11783-
020-1355-5.
(196) Fan, H.; Peng, Y. Applica ion o PVDF Memb anes in Desalina ion and Compa ison o he VMD
and DCMD P ocesses. Chem Eng Sci 2012, 79, 94–102.
h ps://doi.o g/10.1016/j.ces.2012.05.052.
(197) Hou, D.; Wang, J.; Qu, D.; Luan, Z.; Ren, X. Fab ica ion and Cha ac e iza ion o Hyd ophobic
PVDF Hollow Fibe Memb anes o Desalina ion h ough Di ec Con ac Memb ane Dis illa ion.
Sep Pu i Technol 2009, 69 (1), 78–86. h ps://doi.o g/10.1016/j.seppu .2009.06.026.
(198) Salaza , H.; Nunes-Pe ei a, J.; Co eia, D. M.; Ca doso, V. F.; Gonçal es, R.; Ma ins, P. M.;
Fe do , S.; Ma ins, M. D.; Bo elho, G.; Lance os-Méndez, S. Poly(Vinylidene Fluo ide-
Hexa luo op opylene)/Baye i e Composi e Memb anes o E icien A senic Remo al om
Wa e . Ma e Chem Phys 2016, 183, 430–438.
h ps://doi.o g/10.1016/j.ma chemphys.2016.08.049.
(199) Yuennan, J.; Sukwisu e, P.; Muensi , N. E ec o Hyd a ed Sal s on he Mic os uc u e and Phase
T ans o ma ion o Poly(Vinylidene luo ide-Hexa luo op opylene) Composi es. Ma e Res
Exp ess 2018, 5 (5), 055702. h ps://doi.o g/10.1088/2053-1591/aab 4d.
(200) Das, A.; Ghosh, P.; Ganguly, S.; Bane jee, D.; Ka gup a, K. Sal ‐leaching Technique o he
Syn hesis o Po ous Poly(2,5‐benzimidazole) (ABPBI) Memb anes o Fuel Cell Applica ion. J
Appl Polym Sci 2018, 135 (5). h ps://doi.o g/10.1002/app.45773.
(201) Be a, R.; Pa ia, S.; Ka an, S. K.; Das, A. K.; Mai a, A.; Kha ua, B. B. NaCl Leached Sus ainable
Po ous Flexible Fe3O4 Deco a ed RGO-Polyaniline/PVDF Composi e o Du able Applica ion
agains Elec omagne ic Pollu ion. Exp ess Polym Le 2017, 11 (5), 419–433.
h ps://doi.o g/10.3144/exp esspolymle .2017.40.
(202) Iannace, S.; Di Maio, E.; Nicolais, L. P epa a ion and Cha ac e iza ion o Polyu e hane Po ous
Memb anes by Pa icula e-Leaching Me hod. Cellula Polyme s 2001, 20 (5), 321–338.
h ps://doi.o g/10.1177/026248930102000502.
(203) Tha ana han, R. N.; Ki u , F. S. Chi in — The Undispu ed Biomolecule o G ea Po en ial. C i
Re Food Sci Nu 2003, 43 (1), 61–87. h ps://doi.o g/10.1080/10408690390826455.
Chap e 1
54
(204) Pieka ska, K.; Siko a, M.; Owcza ek, M.; Jóźwik-P uska, J.; Wiśniewska-W ona, M. Chi in and
Chi osan as Polyme s o he Fu u e—Ob aining, Modi ica ion, Li e Cycle Assessmen and Main
Di ec ions o Applica ion. Polyme s (Basel) 2023, 15 (4), 793.
h ps://doi.o g/10.3390/polym15040793.
(205) De inge , V. L.; Engle , U.; D onskowski, R. Na u e, S eng h, and Coope a i i y o he
Hyd ogen-Bonding Ne wo k in α-Chi in. Biomac omolecules 2016, 17 (3), 996–1003.
h ps://doi.o g/10.1021/acs.biomac.5b01653.
(206) Sala a i, M. Mechanical P ope ies o α-Chi in and Chi osan Biocomposi e: A Molecula Dynamic
S udy. Oc obe 13, 2023. h ps://doi.o g/10.20944/p ep in s202310.0895. 1.
(207) Ogawa, Y.; Lee, C. M.; Nishiyama, Y.; Kim, S. H. Absence o Sum F equency Gene a ion in
Suppo o O ho hombic Symme y o α-Chi in. Mac omolecules 2016, 49 (18), 7025–7031.
h ps://doi.o g/10.1021/acs.mac omol.6b01583.
(208) Hou, J.; Aydemi , B. E.; Dumanli, A. G. Unde s anding he S uc u al Di e si y o Chi ins as a
Ve sa ile Bioma e ial. Philosophical T ansac ions o he Royal Socie y A: Ma hema ical, Physical
and Enginee ing Sciences 2021, 379 (2206). h ps://doi.o g/10.1098/ s a.2020.0331.
(209) Chen, S.; Shi, S. Q.; Zhou, W.; Li, J. De elopmen s in Bio‐Based Soy P o ein Adhesi es: A
Re iew. Mac omol Ma e Eng 2022, 307 (10). h ps://doi.o g/10.1002/mame.202200277.
(210) He ia achchy, N. S.; Kalapa hy, U. Func ional P ope ies o Soy P o eins; 1998; pp 80–95.
h ps://doi.o g/10.1021/bk-1998-0708.ch006.
(211) Wang, S.; Sue, H.-J.; Jane, J. E ec s o Polyhyd ic Alcohols on he Mechanical P ope ies o
Soy P o ein Plas ics. Jou nal o Mac omolecula Science, Pa A 1996, 33 (5), 557–569.
h ps://doi.o g/10.1080/10601329608010878.
(212) Tian, H.; Guo, G.; Fu, X.; Yao, Y.; Yuan, L.; Xiang, A. Fab ica ion, P ope ies and Applica ions o
Soy-P o ein-Based Ma e ials: A Re iew. In J Biol Mac omol 2018, 120, 475–490.
h ps://doi.o g/10.1016/j.ijbiomac.2018.08.110.
(213) KM, D.; VK, S. Soy P o ein Based G een Composi e: A Re iew. Resea ch & Re iews: Jou nal
o Ma e ial Sciences 2017, 05 (02). h ps://doi.o g/10.4172/2321-6212.1000171.
(214) Reddy, N. A Re iew on Comple ely Biodeg adable Composi es De eloped Using Soy-Based
Ma ices. Jou nal o Rein o ced Plas ics and Composi es 2015, 34 (18), 1457–1475.
h ps://doi.o g/10.1177/0731684415573815.
(215) Zhu, Q.-L.; Xu, Q. Me al–O ganic F amewo k Composi es. Chem. Soc. Re . 2014, 43 (16),
5468–5512. h ps://doi.o g/10.1039/C3CS60472A.
(216) Yang, C.; Xue, Z.; Wen, J. Recen Ad ances in MOF-Based Ma e ials o Remedia ion o Hea y
Me als and O ganic Pollu an s: Insigh s in o Pe o mance, Mechanisms, and Fu u e
Oppo uni ies. Sus ainabili y 2023, 15 (8), 6686. h ps://doi.o g/10.3390/su15086686.
(217) He, Y.; Wang, Y.; Shi, J.; Lu, X.; Liu, Q.; Liu, Y.; Zhu, T.; Wang, D.; Yang, Q. Inco po a ing Me al–
O ganic F amewo ks in o Subs a es o En i onmen al Applica ions. Chemical Enginee ing
Jou nal 2022, 446, 136866. h ps://doi.o g/10.1016/j.cej.2022.136866.
(218) Zhang, Q.; Yang, H.; Zhou, T.; Chen, X.; Li, W.; Pang, H. Me al–O ganic F amewo ks and Thei
Composi es o En i onmen al Applica ions. Ad anced Science 2022, 9 (32).
h ps://doi.o g/10.1002/ad s.202204141.
(219) Li, S.; Huo, F. Me al–O ganic F amewo k Composi es: F om Fundamen als o Applica ions.
Nanoscale 2015, 7 (17), 7482–7501. h ps://doi.o g/10.1039/C5NR00518C.
(220) Val e de, A.; de Fe nandez‐de Luis, R.; Salaza , H.; Gonçal es, B. F.; King, S.; Almásy, L.;
K iechbaum, M.; Laza, J. M.; Vilas‐Vilela, J. L.; Ma ins, P. M.; Lance os‐Mendez, S.; Po o, J.
M.; Pe enko, V. I. On The Mul iscale S uc u e and Mo phology o PVDF‐HFP@MOF
Memb anes in The Scope o Wa e Remedia ion Applica ions. Ad Ma e In e aces 2023, 10
(31). h ps://doi.o g/10.1002/admi.202300424.
Ma e ials and Cha ac e isa ion
61
Chap e 2
Ma e ials and Cha ac e isa ion
This chap e p esen s an o e iew o he ma e ials, eagen s, and gene al p ocedu es
used h oughou he expe imen al wo k, a oiding unnecessa y epe i ion in la e
sec ions. I also summa ises he main chemicals in ol ed, as well as he undamen al
p inciples, wo king condi ions, and equipmen ela ed o he key expe imen al and
cha ac e isa ion echniques applied du ing his esea ch.
2.1. Chemicals
All chemicals used in his hesis we e o eagen g ade and employed as ecei ed om
comme cial supplie s, wi hou u he pu i ica ion. Tables 2.1 o 2.4 compile he
ele an in o ma ion o each compound, including he chemical o mula, molecula
weigh (MW), comme cial supplie (CS), assay (AS), and he co esponding Chemical
Abs ac s Se ice (CAS) numbe .
Table 2.1. Reagen s and sol en s o MOF syn hesis.
Name
Fo mula
Cs
As
MW
(g/mol)
CAS
Zi conium (IV) chlo ide
Z Cl4
Al a Aesa
99%
233.3
10026–
11–6
Thiomalic acid
C4H6O4S
Al a Aesa
98%
150.2
70–49–5
T ans-aconi ic acid
C6H6O6
Al a Aesa
98%
174.1
4023-65-8
L-Aspa ic acid
C4H7NO4
Al a Aesa
99%
133.1
56-84-8
(2R, 3S)-2,3-
Dime cap osuccinic acid
C4H6O4S2
Fluo ochem
95%
188.2
304-55-2
Fo mic acid
HCOOH
Labbox
99%
46.0
64-18-6
Sodium hyd oxide
NaOH
Fluo ochem
98%
40.0
1310-73-2
Me hanol
CH3OH
Al a Aesa
99%
32.0
67-56-1

Chap e 2
62
Table 2.2. Reagen s and sol en s o polyme composi e syn hesis.
Name
Fo mula
Cs
As
MW
(g/mol)
CAS
Poly( inylidene
luo ide-
hexa luo op opylene)
(C2H2F2)x(C3F6)
Sol ay
8% PVDF
12% HFP
600.0
9011-17-0
Sodium chlo ide
NaCl
Fishe
100%
58.4
7647-14-5
N, N –
dime hyl o mamide
HCON(CH3)2
Sigma-
Ald ich
99%
73.1
68-12-2
Soy p o ein isola e,
PROFAM 974
C13H10N2
ADM
90%
-
9010-10-0
β-chi in
(C8H13NO5)x
Squid
pens
100%
-
-
Glyce ol
C₃H₈O₃
Pan eac
99%
92,1
56-81-5
Table 2.3. Me al sal s a e used o ob ain me al solu ions o adso p ion expe imen s.
Name
Fo mula
Cs
As
MW
(g/mol)
CAS
Me cu y (II)
chlo ide
HgCl2
Sigma
99%
271.5
7487-94-7
Lead (II) ni a e
Pb(NO3)2
Labkem
99%
331.2
10099-74-8
Cadmium (II)
ni a e e ahyd a e
Cd(NO3)2·4H2O
Sigma
98%
308.5
10022-68-1
Coppe (II) chlo ide
dihyd a e
CuCl2·2H2O
Ac os
O ganics
99%
170.5
10125-13-0
Nickel (II) chlo ide
NiCl2
Sigma
98%
129.6
7718-54-9
Cobal (II) chlo ide
hexahyd a e
CoCl2·6H2O
Sigma
98%
237.9
7791-13-1
Lan hanum (III)
ni a e hexahyd a e
La(NO3)3·6H2O
Sigma
100%
433.0
10277-43-7
Y ium (III)
chlo ide
YCl3
Sigma
99%
195.3
10361-92-9
Eu opium (III)
ni a e
Eu(NO3)3·6H2O
Al a
Aesa
99%
446.1
10031-53-5
Sodium
(me a)a seni e
NaAsO2
Sigma
90%
129.9
7784–46–5
Sodium a sena e
dibasic
hep ahyd a e
Na2HAsO4·7H2O
Sigma
98
312.0
10048-95-0
Po assium
dich oma e
K2C 2O7
Ac os
O ganics
99%
294.2
7778-50-9
Ma e ials and Cha ac e isa ion
63
Table 2.3. Reagen s o we oxida ion ca alysis assays.
Name
Fo mula
Cs
As
MW (g/mol)
CAS
Dopamine
C8H11NO2
Sigma
98%
153.2
51-61-6
4-Aminoan ipy ine
C11H13N3O
Al a aesa
97%
203.2
83-07-8
Hyd ogen pe oxide
H2O2
Sigma
30% w/w
in wa e
34.0
7722-84-1
2.2. Cha ac e isa ion echniques
X- ay Sca e ing Techniques
X- ay sca e ing in ol es he in e ac ion be ween X- ay adia ion and ma e o analyse
he s uc u al p ope ies o ma e ials a he a omic and molecula le els. The echnique
is based on he elas ic sca e ing o X- ays by elec ons in he sample ma e ial, whe e
in e e ence occu s acco ding o B agg's law1 (Eq. 2.1), enabling he de e mina ion o
c ys al la ice pa ame e s and s uc u al a angemen s om X- ay di ac ion da a.
𝑛𝜆 = 2𝑑𝑠𝑖𝑛 𝜃
Equa ion 2.1. B agg’s law.
When X- ays, whose wa eleng h (λ) is on he same o de o magni ude as he
in e a omic dis ances in c ys alline solids, s ike a sample, hey a e sca e ed by he
alence elec ons o he a oms in he la ice. The esul ing sca e ed wa es in e e e
wi h one ano he , and his in e e ence can be ei he cons uc i e o des uc i e
depending on he angle o incidence (θ) and he in e plana spacing (d).
Figu e 2.1. Schema ic ep esen a ion o he X- ay di ac ion.
θ
Inciden
beam
Di ac ed
beam
d
θ
2θ
Chap e 2
64
This non-des uc i e echnique p o ides quan i a i e in o ma ion abou c ys alline
s uc u e, pa icle size, shape, and o ien a ion by analysing he angula dis ibu ion o
sca e ed X- ays.2
2.2.1.1. Powde X- ay Di ac ion
Powde X- ay di ac ion (PXRD) is an analy ical echnique used o iden i ying
c ys alline phases and cha ac e ising he s uc u e o ma e ials. The me hod is based
on di ec ing monoch oma ic X- ay adia ion on o a inely g ound sample and eco ding
he in ensi y o di ac ed beams as a unc ion o sca e ing angle.
In powde di ac ion, he sample consis s o nume ous andomly o ien ed c ys alli es.
This andom o ien a ion ensu es ha o any se o la ice planes, enough c ys alli es
will be o ien ed a he app op ia e angle o sa is y he B agg di ac ion condi ion. The
di ac ed X- ays o m cha ac e is ic pa e ns ha a e de ec ed and eco ded as
in ensi y peaks plo ed agains he di ac ion angle (2θ). Each c ys alline phase
exhibi s a dis inc i e di ac ion pa e n ha se es as a unique s uc u al signa u e
whe e i s s uc u al model can be de e mined by compa ing he expe imen al pa e n
wi h e e ence pa e ns ob ained, o example, om he Camb idge S uc u al
Da abase (CSD).3,4
Peak posi ions a e di ec ly ela ed o he uni cell pa ame e s h ough B agg's law,
while peak in ensi ies depend on he a omic sca e ing ac o s and he dis ibu ion o
a oms wi hin he uni cell. Peak p o ile analysis p o ides addi ional s uc u al
in o ma ion ha allows o o de e mina ion o a e age c ys alli e size and he p esence
o s uc u al de ec s wi hin he ma e ial. The sha pness and na owness o di ac ion
peaks, e lec ed in a low ull wid h a hal maximum (FWHM), a e gene ally associa ed
wi h he p esence o la ge, well-o de ed c ys alli es. In con as , peak b oadening,
e idenced by an inc eased FWHM, is ypically co ela ed wi h educed c ys alli e size
and he p esence o s uc u al diso de wi hin he c ys al la ice. Consequen ly, e e y
ma e ial exhibi s a dis inc i e di ac ion inge p in , which can be heo e ically de i ed
om i s s uc u al model and he expe imen al condi ions unde which he
measu emen is pe o med.
Con empo a y di ac ome e s u ilise a ious de ec o echnologies o enhance da a
collec ion e iciency. In his hesis, all samples we e measu ed a oom empe a u e
Ma e ials and Cha ac e isa ion
65
using a Panaly ical X´pe CuKα di ac ome e in he ollowing condi ions: 2θ ange =
5–70°, s ep size = 0.05°, exposu e ime = 10 s pe s ep. Panaly ical X´pe is a
polyc ys alline sample di ac ome e wi h he a- he a geome y, a p og ammable sli ,
seconda y g aphi e monoch oma o adjus ed o a coppe adia ion and a as solid
s a e PixCel de ec o adjus ed o a 3.347º ac i e leng h in 2θ(°). This di ac ome e
belongs o he Gene al Resea ch Se ices (SGIke ) o he UPV/EHU.
The ob ained esul s we e analysed using FullP o 5,6 o con i m he o ma ion o he
a ge phase a e syn hesis, exclude he p esence o seconda y co-c ys allised
compounds, and assess he c ys allini y and s abili y o he ma e ials unde he applied
expe imen al condi ions. Full peak p o ile i ing was sys ema ically pe o med o all
samples o e i y he absence o impu i ies and o cha ac e ise hei s uc u al
ea u es. The c ys al s uc u es o he MOFs desc ibed in Chap e s 3 and 4 we e
al eady epo ed; hus, hei s uc u al models we e e ie ed om da abases o
compa ison. In Chap e 5, he c ys alline s uc u e o BCM-5 was examined by
Rie eld e inemen , a me hod ha enables he de e mina ion o de ailed s uc u al
pa ame e s, including p ecise a omic posi ions, h ough a leas -squa es adjus men o
he en i e di ac ion pa e n o a p o ile calcula ed om a s uc u al model.
2.2.1.2. Small-Angle X- ay Sca e ing (SAXS)
Small-Angle Neu on Sca e ing (SANS) and (SAXS a e well-known echniques o
p obe s uc u al ea u es on leng h scales anging om app oxima ely 1 o 100
nanome e s7 This in es iga es la ge -scale s uc u al inhomogenei ies, nanopa icle
size dis ibu ions, mac omolecula dimensions, po e sizes a he nanoscale, and
cha ac e is ic dis ances in pa ially o de ed ma e ials (Fig. 2.2).
Chap e 2
66
Figu e 2.2. Small-angle sca e ing scheme.
Fo sca e ing objec s exceeding se e al nanome e s o hund eds o nanome es,
SAXS p o ides in o ma ion on in e nal in e aces by analysing he elas ic sca e ing o
X- ays (λ = 0.06–0.3 nm, which co esponds o a pho on ene gy ange o
app oxima ely 4 o 25 keV) a small angles (0.1–10°). The echnique is pa icula ly
powe ul o cha ac e ising po ous ma e ials, as i can p o ide in o ma ion abou po e
size dis ibu ions, speci ic su ace a eas, and po e connec i i y.
SAXS measu emen s we e conduc ed on he I22 beamline a Diamond Ligh Sou ce
(Didco , U.K.).8 Da a we e collec ed wi h a Pila us P3-2 M de ec o . SAXS da a we e
educed and azimu hally a e aged o ob ain he iso opic sca e ing in ensi y as a
unc ion o sca e ing ec o modulus q = 4π/λ sin(θ/2), whe e θ is he sca e ing angle
and λ = 1 Å is he X- ay wa eleng h, using he DAWN so wa e package.9,10 All
sca e ing cu es we e i ed acco ding o unc ions p o ided by SasView 6.0.1,
including he Indi ec Fou ie T ans o ma ion analysis ou ine.
qy
qx
Ø
~ π/R

Ma e ials and Cha ac e isa ion
67
Neu on Sca e ing Techniques
Neu on sca e ing echniques a e based on he in e ac ion o neu ons wi h a omic
nuclei h ough he s ong nuclea o ce, a he han elec omagne ic in e ac ions wi h
elec ons as in X- ay me hods. This nuclea in e ac ion mechanism p o ides unique
analy ical capabili ies: deep pene a ion in o dense ma e ials, excep ional sensi i i y
o ligh elemen s (especially hyd ogen), and he abili y o dis inguish iso opes o he
same elemen .11
Neu ons exhibi wa e-pa icle duali y desc ibed by he de B oglie ela ion (Eq. 2.2), λ
is he wa eleng h, m he mass o he neu on, ʋ he eloci y o he neu on and ħ he
educed Planck cons an . This equa ion e eals ha he mal neu ons possess
wa eleng hs compa able o hose o X- ays (λ ≈ 0.1 nm) bu wi h signi ican ly lowe
ene gies in he ange o 1 o 100 meV, which is pa icula ly ad an ageous o s udying
dynamic p ocesses, as i allows he de ec ion o small ene gy changes.
𝜆 = ℎ
𝑚𝑣
Equa ion 2.2. B oglie equa ion.
Neu on p oduc ion acili ies a e classi ied as ei he eac o -based sou ces, which
p o ide con inuous neu on beams h ough nuclea ission, o spalla ion sou ces,
which gene a e pulsed neu on beams by bomba ding hea y me al a ge s wi h high-
ene gy p o ons. Reac o sou ces ypically employ monoch oma o s o wa eleng h
selec ion, while spalla ion sou ces u ilise ime-o - ligh echniques o de e mine
neu on ene gies and pe o m expe imen s simul aneously wi h di e en wa eleng hs
o neu ons.
Sca e ing e en s a e ca ego ised as elas ic, whe e no ene gy exchange occu s
be ween he neu on and sample, o inelas ic, in ol ing ene gy ans e ha p o ides
in o ma ion abou molecula dynamics and phonon spec a.
Neu on Imaging
Neu on imaging is a non-des uc i e cha ac e isa ion echnique ha p oduces isual
ep esen a ions o he in e nal s uc u e o ma e ials by measu ing how neu ons a e
abso bed o ansmi ed as hey pass h ough a sample.12 The echnique c ea es
Chap e 2
68
con as based on he di e en neu on abso p ion p ope ies o a ious elemen s and
compounds wi hin he ma e ial (Fig. 2.3).
The measu emen p ocess in ol es di ec ing a beam o neu ons h ough he sample
and de ec ing he in ensi y o neu ons ha success ully ansmi h ough he o he
side o he sample. Ma e ials ha s ongly abso b neu ons will appea da k in he
esul ing image, while ma e ials ha allow neu ons o pass h ough easily will appea
b igh . This c ea es a isual map showing he dis ibu ion o di e en componen s
wi hin he sample.
Neu on imaging p o ides unique ad an ages due o he speci ic way neu ons in e ac
wi h ma e . The echnique shows excep ional sensi i i y o hyd ogen-con aining
ma e ials such as wa e , making hese subs ances clea ly isible e en when
embedded wi hin o he ma e ials.13 This echnique can be pe o med in di e en
con igu a ions depending on he in o ma ion equi ed. Two-dimensional adiog aphy
p oduces c oss-sec ional images, while omog aphic app oaches econs uc
comple e h ee-dimensional ep esen a ions o he sample in e io .
Figu e 2.3. Schema ic iew o a basic neu on imaging expe imen al se -up.
In Chap e 4 o his hesis, he composi e ma e ials ha e been s udied by neu on
omog aphy measu emen s ha we e ca ied ou a IMAT, he neu on imaging
ins umen a he ISIS Neu on and Muon Sou ce (Didco , U.K.). Samples we e
w apped in aluminium oil and placed inside an aluminium ube, which was moun ed
Ma e ials and Cha ac e isa ion
69
on a o a ion s age. Tomog aphic p ojec ions we e acqui ed by o a ing he sample
o e 360 deg ees, wi h angula s eps chosen o sa is y he Nyquis c i e ion. The
ins umen geome y was con igu ed o a collima ion a io (L/D) o 260, whe e L is he
dis ance om he pinhole o he de ec o and D is he pinhole ape u e. Images we e
aken wi h he Ando Ikon-L 936 CCD came a coupled wi h a 105mm lens and an
80µm hick ZnS/6LiF scin illa o p o iding a pixel size o 48µm. An exposu e ime o
60s was used o each p ojec ion. Fla - ield images ( eco ded wi hou he sample in
he beam) and da k- ield images ( eco ded wi h he beam o ) we e acqui ed o image
no malisa ion. Tomog aphic econs uc ions o he p ojec ion da a we e ca ied ou
using he Man id Imaging14 so wa e package. Po osi y analysis was pe o med using
Po espy.15 Fo he po osi y p o ile analysis, an ROI ha alls wi hin he sample a ea
was i s selec ed o he analysis. Image segmen a ion was hen done using O su
h esholding be o e he calcula ion o pe cen age po osi y.
2.3. The mog a ime ic analysis (TGA)
TGA is a he mal analy ical echnique ha measu es he mass changes o a sample
as a unc ion o empe a u e o ime unde con olled a mosphe ic condi ions.16 The
echnique ope a es by subjec ing he sample o a p og ammed empe a u e p o ile
while con inuously moni o ing mass a ia ions using a p ecision mic obalance. The
esul ing da a is p esen ed as a he mog am, which p o ides aluable in o ma ion
abou he mal s abili y, decomposi ion p ocesses, and ma e ial composi ion.
The undamen al p inciple o TGA elies on de ec ing mass changes associa ed wi h
he mal e en s such as dehyd a ion, decomposi ion, oxida ion, sublima ion, o
deso p ion p ocesses. The measu emen a mosphe e can be p ecisely con olled,
u ilising ine gases (ni ogen, a gon), oxidising en i onmen s (ai , oxygen), o educing
condi ions ( o ming gas mix u es), depending on he analy ical equi emen s. The
con olled hea ing a e and a mosphe e selec ion enable he di e en ia ion o a ious
he mal p ocesses and p o ide insigh s in o ma e ial beha iou unde speci ic
condi ions.
Mode n TGA ins umen s a e o en coupled wi h di e en ial scanning calo ime y
(DSC) capabili ies, c ea ing simul aneous he mal analysis sys ems.17 DSC measu es
he hea low di e ences be ween a sample and an ine e e ence ma e ial as bo h
Chap e 2
70
a e subjec ed o iden ical empe a u e p og ams. This echnique de ec s he mal
ansi ions ha may o may no in ol e mass changes, such as phase ansi ions,
c ys allisa ion, mel ing, o glass ansi ions. The DSC signal is ob ained by moni o ing
he empe a u e di e ence be ween he sample and e e ence c ucibles, whe e
endo he mic p ocesses equi e addi ional hea inpu o main ain empe a u e
equilib ium, while exo he mic p ocesses elease hea .
The combina ion o TGA and DSC p o ides comp ehensi e he mal cha ac e isa ion
by simul aneously moni o ing mass changes and he mal e en s. This dual app oach
enables he co ela ion o mass loss p ocesses wi h hei co esponding en halpy
changes, acili a ing he iden i ica ion and unde s anding o complex he mal
deg ada ion mechanisms. The echnique is pa icula ly aluable o analysing mul i-
componen sys ems whe e o e lapping he mal e en s may occu , as he
complemen a y in o ma ion om bo h measu emen s aids in p ocess iden i ica ion and
quan i ica ion.
TGA-DSC analysis in his hesis was ca ied ou unde syn he ic ai (80% N2 and 20%
O2) wi h a 25 mL/min lux in a NETZSCH STA 449F3 DSC–TGA ins umen , wi h a
p ecise sample p epa a ion, whe e 25 mg o ma e ial was placed in an alumina
c ucible, ha was hea ed a 5 °C min–1 in he empe a u e ange 30–700 °C.
This echnique was pe o med o e alua e he mal deg ada ion p ocesses and quan i y
he deg ee o linke de ec s pe o mula uni in he MOFs. The a e age numbe o
linke -de ec posi ions pe o mula uni was de e mined om he weigh loss
co esponding o he calcina ion o he o ganic linke . This app oach was applied in
Chap e 3 o in es iga e he de ec s uc u e o C4MOFs and in Chap e 5 o es ablish
he chemical o mula o BCM-5, whe e he de ec deg ee o each sample was u he
con i med h ough complemen a y 1H-NMR analysis. The de ec deg ee o each
sample was de e mined om he weigh loss co esponding o he calcina ion o he
o ganic linke a empe a u es abo e ~300 °C.18 The TGA p o ile o hese ma e ials
e eals h ee dis inc weigh -loss egions. The i s , occu ing be ween 30 and 100 °C,
co esponds o he emo al o sol en molecules con ined wi hin he po ous
amewo k. The second s ep, in he 100–300 °C ange, is a ibu ed o he dehyd a ion
and dehyd oxyla ion o he Z -hexanuclea clus e s. The inal weigh -loss e en ,
Ma e ials and Cha ac e isa ion
77
2.8. Scanning Elec on Mic oscopy (SEM)
SEM is an elec on mic oscopy echnique wi h a de ailed isual image o a pa icle
wi h high-quali y and spa ial esolu ion wi hin he ange o 5µm o 1mm. SEM is a
mul ipu pose s a e-o - he-a ins umen which is la gely employed o obse e he
su ace phenomena o he ma e ials.31 This echnique employs a ocused beam o
high-ene gy elec ons gene a ed by an elec on gun, which is di ec ed h ough a se ies
o elec omagne ic lenses unde high- acuum condi ions. Upon in e ac ing wi h he
sample su ace, hese elec ons p o ide de ailed in o ma ion abou i s mo phological
and s uc u al ea u es.
Mode n SEM ins umen s a e equipped wi h mul iple de ec o s o cap u e di e en
ypes o signals simul aneously. Mo eo e , ene gy-dispe si e X- ay (EDX) de ec o s
a e commonly in eg a ed in o SEM sys ems, allowing o elemen al analysis and
composi ional mapping o he sample su ace wi h 1-2 µm esolu ion.32 Bo h
echniques p o ide in o ma ion abou pa icle size and shape, su ace ex u e, c ys al
s uc u e, and elemen al dis ibu ion, making hem an indispensable ool o ma e ials
cha ac e isa ion.
In his hesis, wo di e en scanning elec on mic oscopes ha e been used. Fo he
s udy o pa icle mo phology o C4MOF in Chap e 3 and BCM-5 in Chap e 5, a
HITACHI S-4800 wi h Field Emission Gun (FEG) cold ca hode (0.5-30 kV) om SGIke
was used. The samples we e dispe sed in me hanol unde ul asonica ion, and
a e wa ds a d op was deposi ed in he coppe sample holde and me allised wi h a
gold conduc i e laye o p e en cha ge o ma ion on non-conduc i e samples unde
he elec on beam, which can impac he quali y o he image and also des oy he
sample. Fo he SEM images, including EDX mapping o C4MOF in Chap e 3 o s udy
he empi ical o mula, a Ca l-Zeiss EVO-40 Elec onic Scanning Mic oscopy
equipmen om SGIke was used, whe eby bo h images in high acuum mode (wi h
me alliza ion o he samples) and in ex ended p essu e o low acuum and we sample
mode (wi hou he need o me allise he samples) can be employed. The equipmen
ea u es a seconda y elec on de ec o (SED) and a e o-sca e ed elec on de ec o ,
oge he wi h an EDX elemen a y analyse , which allows pe o ming bo h punc ual and
mapping analyses o he samples.

Chap e 2
78
2.9. In a ed Spec oscopy (IR)
IR ep esen s a undamen al analy ical echnique ex ensi ely employed o he
iden i ica ion and cha ac e isa ion o molecula s uc u es h ough he de ec ion o
speci ic ib a ional modes.33 This me hod elies on he in e ac ion be ween in a ed
elec omagne ic adia ion and ma e , speci ically a ge ing he ib a ional ene gy
le els o chemical bonds wi hin molecules. The in a ed egion o he elec omagne ic
spec um, ypically anging om 4000 o 400 cm-1, p o ides su icien ene gy o exci e
molecula ib a ions wi hou causing elec onic ansi ions o bond dissocia ion.
The undamen al p inciple unde lying in a ed spec oscopy is based on he selec i e
abso p ion o in a ed adia ion by molecules ha possess a pe manen o induced
dipole momen . When in a ed adia ion in e ac s wi h a molecule, ene gy ans e
occu s only when he equency o he inciden adia ion co esponds o he na u al
ib a ional equency o speci ic bonds o unc ional g oups wi hin he molecule. This
esonance condi ion esul s in he exci a ion o ib a ional modes, leading o
measu able abso p ion o in a ed ene gy a cha ac e is ic equencies.
Molecula ib a ions can be ca ego ised in o wo undamen al ypes: s e ching and
bending modes (Fig. 2.5). S e ching ib a ions in ol e pe iodic a ia ions in bond
leng hs along he in e nuclea axis, whe eas bending ib a ions encompass changes
in bond angles be ween adjacen a omic bonds.34 These ib a ional modes gene a e
cha ac e is ic abso p ion pa e ns ha se e as diagnos ic inge p in s o speci ic
unc ional g oups and molecula s uc u es. The in ensi y o abso p ion bands in
in a ed spec a depends on he magni ude o he change in dipole momen du ing he
ib a ional mo ion. Symme ic ib a ions ha do no esul in dipole momen changes
a e in a ed-inac i e and he e o e unde ec able by his echnique. Con e sely,
asymme ic ib a ions ha p oduce signi ican dipole momen a ia ions yield in ense
abso p ion peaks.
Ma e ials and Cha ac e isa ion
79
Figu e 2.5. Schema ic ep esen a ion o molecula ib a ions.
FTIR spec ome e s o e supe io pe o mance compa ed o con en ional dispe si e
ins umen s. FTIR sys ems simul aneously measu e all in a ed equencies, esul ing
in enhanced signal- o-noise a ios, imp o ed spec al esolu ion, and educed
measu emen imes. The ma hema ical ans o ma ion o he in e e og am h ough
Fou ie analysis yields he inal abso p ion spec um. Con e sely, A enua ed To al
Re lec ion (ATR) sampling is a echnique ha elimina es he complexi y associa ed
wi h adi ional sample p epa a ion p ocedu es while main aining high spec al quali y
and ep oducibili y. In ATR-FTIR measu emen s, he in a ed beam unde goes o al
in e nal e lec ion wi hin a high e ac i e index c ys al, gene a ing an e anescen wa e
ha pene a es he sample in con ac wi h he c ys al su ace. The dep h o
pene a ion, ypically anging om 0.5 o 2 mic ome es, allows o su ace-sensi i e
analysis o a ious sample ypes, including solids, liquids, and pas es.
The esul ing in a ed spec um p o ides a comp ehensi e molecula inge p in ha
enables he iden i ica ion o unc ional g oups, he de e mina ion o molecula
s uc u e, and he moni o ing o chemical ans o ma ions. Each abso p ion band
co esponds o speci ic ib a ional modes, allowing o de ailed s uc u al analysis and
quan i a i e measu emen s when app op ia e calib a ion s anda ds a e employed.
In his hesis, he in a ed spec a ha e been ob ained in a spec opho ome e wi h a
Fou ie - ans o m Jasco FT/IR-6100 spec ome e in A enua ed To al Re lec ance
S e ching ib a ions
Bending ib a ions
Asymm icalSymm ical
Twis ing Wagging Rocking Scisso ing
Chap e 2
80
mode (FTIR-ATR). Each spec um was eco ded om 600 o 4000 cm-1 wa enumbe s
wi h a 1 cm-1 esolu ion. 64 scans we e measu ed and a e aged o ob ain he inal
spec a.
FTIR spec oscopy was employed o cha ac e ise he ma e ials syn hesised in his
wo k, allowing he iden i ica ion o unc ional g oups inco po a ed in o he MOFs du ing
syn hesis (Chap e 3). In Chap e s 4 and 5, he echnique was u he applied o
in es iga e possible chemical in e ac ions be ween he MOFs and he polyme ic ma ix
du ing memb ane ab ica ion, and o analyse he MOFs a e me al adso p ion o
e alua e s uc u al modi ica ions induced by me al exposu e and o elucida e he
binding mechanisms.
2.10. X- ay Pho oelec on Spec oscopy (XPS)
XPS is a su ace-sensi i e analy ical echnique based on he pho oelec ic e ec ,
whe e high-ene gy X- ay pho ons in e ac wi h co e-le el elec ons in a oms, causing
he emission o pho oelec ons wi h cha ac e is ic kine ic ene gies.35 In his p ocess,
he su ace o a sample is i adia ed wi h X- ay pho ons ha in e ac wi h co e
elec ons, whe e pho oelec ons a e emi ed i he pho on ene gy exceeds he binding
ene gy o he elec ons.
XPS p o ides su ace-sensi i e analysis o ma e ials, e ealing chemical s a es,
oxida ion s a es, and bonding en i onmen s h ough cha ac e is ic co e-elec on
binding ene gies. Di e en chemical s a es o he same elemen p oduce dis inc
peaks in he XPS spec um, enabling he iden i ica ion and quan i ica ion o a ious
chemical species p esen on he su ace.
In his hesis, he ma e ials desc ibed in Chap e s 4 and 5 we e s udied a e me al
adso p ion. Each sample was imme sed in independen 100 ppm solu ions o he
a ge me als o 4 hou s. Subsequen ly, he ma e ials we e eco e ed, ex ensi ely
insed wi h dis illed wa e , d ied a 80 °C o 2 hou s, and inally s udied by XPS
analysis.
To his pu pose, a Ve sap obe III AD sys em (Physical Elec onics, ULVAC) equipped
wi h a monoch oma ic Al Kα adia ion sou ce (1486.7 eV) om SGIke was used. An
ini ial su ey scan was pe o med o iden i y he elemen s p esen (wide scan: s ep
Ma e ials and Cha ac e isa ion
81
ene gy 0.2 eV, pass ene gy 224 eV), ollowed by high- esolu ion scans o he de ec ed
elemen s (de ail scan: s ep ene gy 0.05 eV, pass ene gy 27 eV, ime pe s ep 20 ms)
using an elec on ake-o angle o 45°. The spec ome e was p e iously calib a ed
using sil e (Ag 3d5/2, 368.26 eV). The spec a we e i ed using CasaXPS so wa e
e sion 2.3.26, which models he signal con ibu ions a e backg ound sub ac ion
using he Shi ley me hod.
2.11. High Pe o mance Liquid Ch oma og aphy
(HPLC) coupled wi h UV- isible de ec ion
HPLC is a sepa a ion echnique ha enables he esolu ion o complex mix u es in o
indi idual componen s based on hei di e en ial in e ac ions wi h s a iona y and
mobile phases. The sepa a ion mechanism elies on he dis inc a ini ies o analy es
o he s a iona y phase packed wi hin he ch oma og aphic column and he mobile
phase ha lows h ough i . Componen s wi h di e en pola i ies, molecula sizes, o
chemical p ope ies mig a e h ough he column a di e en a es, achie ing empo al
sepa a ion as hey elu e om he column.
The ch oma og aphic sepa a ion occu s as he mobile phase ca ies sample
componen s h ough a column packed wi h s a iona y phase pa icles. The coupling
o HPLC wi h UV- isible de ec ion (HPLC-UV-Vis) moni o s he abso p ion o ligh by
elu ing compounds as hey pass h ough a low cell, enabling immedia e de ec ion and
quan i ica ion o sepa a ed componen s. Each compound exhibi s cha ac e is ic
abso p ion a speci ic wa eleng hs, allowing quali a i e iden i ica ion and quan i a i e
de e mina ion based on Bee -Lambe law p inciples.
HPLC-UV-Vis is use ul o o ganic compounds wi h ch omopho e g oups, o e ing
excellen selec i i y h ough ch oma og aphic sepa a ion and sensi i e de ec ion
h ough UV-Vis abso p ion. Quan i a i e analysis is achie ed by compa ing peak a eas
wi h calib a ion s anda ds o known concen a ions.
The ch oma og aphic analyses o Chap e 3 o his hesis we e pe o med using
an Agilen In ini y 1260 ch oma og aphic sys em, equipped wi h a Diode A ay
De ec o (DAD) se o moni o a a wa eleng h o 277 nm o phenol and ca echol, 292
nm o hyd oquinone, 280 nm o dopamine and 264 nm o pa ace amol. The sys em
Chap e 2
82
was equipped wi h an In ini yLab Po oshell 120 EC-C18 column (3.0 × 100 mm, 2.7
µm pa icle size) coupled wi h a gua d column o he same ma e ial. Mobile phase A
was 0.1% ( / ) o mic acid in wa e , and mobile phase B was ace oni ile con aining
0.1% ( / ) o mic acid. The ch oma og aphic g adien began wi h 0% o mobile phase
B a 0.00 minu es. F om 0.00 o 7.00 minu es, he pe cen age o mobile phase B
inc eased linea ly o 60%. A 7.01 minu es, a apid s ep inc ease b ough mobile phase
B o 100%, which was main ained isoc a ically om 7.01 o 8.00 minu es. Finally, he
g adien e u ned o 0% mobile phase B a 8.00 minu es and was held a his
composi ion un il 15.00 minu es o e-equilib a e he column. The mobile phase low
a e was main ained a 0.5 mL/min, and he column empe a u e was se o 40°C o
ensu e consis en e en ion imes and peak esolu ion. Sample injec ion olumes
we e 5 µL. Calib a ion cu es o all he molecules we e ob ained wi h solu ions o 0.1,
1, 2.5, 5, 7.5, 10, 100 and 1000 ppm p epa ed om a pa en solu ion a a concen a ion
o 1000 ppm. The measu emen s we e done in iplica e o each o he solu ions
2.12. Induc i ely Coupled Plasma A omic
Emission Spec oscopy (ICP-AES)
ICP-AES is an analy ical echnique ha employs high- empe a u e plasma o a omise
and exci e elemen s in a sample, causing hem o emi cha ac e is ic elec omagne ic
adia ion. The echnique is based on he p inciple ha a oms and ions, when exci ed
o highe ene gy s a es, e u n o hei g ound s a es by emi ing pho ons a
wa eleng hs speci ic o each elemen . Liquid samples a e in oduced h ough
nebuliza ion, con e ing hem in o ine ae osols ha a e anspo ed in o he plasma
by a gon ca ie gas. The ex eme plasma empe a u es ensu e comple e a omiza ion
and exci a ion o analy e elemen s, esul ing in cha ac e is ic emission spec a.36
The emi ed adia ion is collec ed and dispe sed by an op ical sys em, enabling
simul aneous o sequen ial de ec ion o mul iple wa eleng hs co esponding o
di e en elemen s. The in ensi y o emission lines is di ec ly p opo ional o elemen al
concen a ions, allowing quan i a i e analysis h ough calib a ion wi h s anda d
solu ions. ICP-AES o e s a wide linea dynamic ange, mul i-elemen capabili y, and
low de ec ion limi s. The high plasma empe a u e minimises chemical in e e ences
and ma ix e ec s, enabling accu a e analysis o complex samples.37

Ma e ials and Cha ac e isa ion
83
Th oughou Chap e s 3, 4, and 5 o his hesis, he concen a ion o he me al solu ions
was quan i ied using a Ho iba Yobin Y on Ac i a a omic emission spec ome e wi h
induc i ely coupled plasma (ICP-AES) om SGIke . The sys em is equipped wi h a
glass and Te lon nebulise , allowing he analysis o samples ob ained om acidic
diges ion using ni ic acid. The ins umen is con olled by he Ac i a Analys 5.4
so wa e, which enables sequen ial mul i-elemen analysis and suppo s he accu a e
de e mina ion o bo h majo and ace elemen s. Fo he adso p ion assays, samples
we e dilu ed o he de ec ion limi s o he equipmen , pe o ming iplica e
measu emen s o each solu ion.
2.13. Adso p ion Expe imen s and Models
In gene al, all adso p ion expe imen s we e conduc ed using 1 mg o so ben pe 1 mL
o solu ion. The o al olume a ied depending on he equi emen s o each
expe imen . Di e en concen a ions we e es ed, bu all expe imen s we e un o 4 h,
since p e ious s udies in his g oup ha e shown MOF deg ada ion beyond ha ime.
The pH was main ained wi hin he ange in which he MOF emains s able.
I is impo an o no e ha he hea y-me al cap u e mechanism o he composi e elies
on a combina ion o abso p ion wi hin he MOF’s po e s uc u e and adso p ion a bo h
he biopolyme sca old su ace and he MOF/polyme in e ace. Fo simplici y, he
e m “adso p ion” will be used h oughou his hesis. Howe e , depending on whe he
he MOF, he composi e, o he composi e@MOF componen s a e employed,
abso p ion, adso p ion, o a combina ion o bo h p ocesses may be esponsible o
me al immobilisa ion.
In he ollowing sec ion, he iso he m and kine ic models applied o i he expe imen al
me al-adso p ion da a ob ained in his hesis a e desc ibed.
Kine ic models
Adso p ion kine ic models desc ibe how as adso ba es a e emo ed om solu ion
and bind on o he adso ben su ace o e ime. These models help unde s and
adso p ion mechanisms and he s eps ha con ol he a e, which may include physical
adso p ion, chemical in e ac ions, and di usion p ocesses.38 In his hesis, he
Chap e 2
84
expe imen al kine ic da a ob ained om me al-ion adso p ion expe imen s ha e been
analysed using he pseudo- i s -o de (PFO) and pseudo-second-o de (PSO) models.
The PFO model assumes ha he adso p ion a e depends on he numbe o
unoccupied si es,39 And i is o en sui able o p ocesses domina ed by physical
adso p ion o di usion-con olled s eps. I s linea ised o m is (Eq. 2.5):
𝑙𝑛(𝑞𝑒− 𝑞𝑡)=𝑙𝑛𝑞𝑒− 𝑘1𝑡
Equa ion 2.4. Pseudo- i s o de equa ion.
Whe e k1 is he pseudo- i s o de cons an a e, q is he amoun o adso ba e
adso bed a ime , and qe is he equilib ium adso p ion capaci y.
The PSO model assumes he adso p ion a e ela es o he squa e o he numbe o
unoccupied si es, o en in e p e ed as ep esen ing chemiso p ion p ocesses.40 The
linea ised o m o he pseudo-second-o de equa ion is gi en as (Eq. 2.6):
𝑡
𝑞𝑡=1
𝑘2𝑞𝑒
2+𝑡
𝑞𝑒
Equa ion 2.5. Pseudo- i s o de equa ion.
Whe e k2 is he pseudo-second o de cons an a e, q is he amoun o adso ba e
adso bed a ime and qe is he equilib ium adso p ion capaci y.
While he PSO model o en p o ides a be e i o expe imen al da a, i is impo an o
emembe ha hese models a e empi ical. Good i ing alone canno de ini i ely p o e
whe he he adso p ion is physical o chemical. The models’ applicabili y depends on
expe imen al condi ions such as ini ial adso ba e concen a ion and adso ben
p ope ies, and hei pa ame e s should be in e p e ed cau iously and complemen ed
wi h addi ional mechanis ic e idence.
To illus a e he applica ion o bo h models, Figu e 2.6 shows he adso p ion kine ics.
The expe imen al da a a e p esen ed as poin s, and he solid line co esponds o he
model i . In he pseudo- i s o de model, om he linea ised plo o ln(qe−q ) e sus ,
he adso p ion pa ame e s qe and k1 can be ob ained, and in he pseudo-second o de
model, om he linea ised plo o /q e sus , he adso p ion pa ame e s qe and k2
can be de e mined. Compa ing goodness-o - i (R2) p o ides insigh in o a e-
con olling s eps bu is insu icien o conclusi ely de e mine mechanisms wi hou
u he cha ac e isa ion.
Ma e ials and Cha ac e isa ion
85
Figu e 2.6. Adso p ion kine ics o a) pseudo- i s o de model and b) pseudo-second o de model.
Compa ing goodness-o - i (be e R2) p o ides insigh in o a e-con olling s eps bu
is insu icien o conclusi ely de e mine mechanisms wi hou u he cha ac e isa ion.
Iso he m models
Adso p ion iso he m models ma hema ically desc ibe he equilib ium ela ionship
be ween he amoun o adso ba e bound o he adso ben su ace and i s
concen a ion in solu ion a a cons an empe a u e.41 In his hesis, me al-ion
adso p ion iso he ms we e i ed using he Langmui and he F eundlich models, which
o e insigh s in o adso p ion mechanisms and su ace cha ac e is ics.
The Langmui model assumes monolaye adso p ion on a homogeneous su ace wi h
a ini e numbe o iden ical si es. I pos ula es equal adso p ion ene gies o all
adso bed molecules and no in e ac ion be ween hem. The Langmui equa ion is
exp essed as (Eq. 2.7):
𝑞𝑒= 𝑄𝑚𝑎𝑥𝐾𝐿𝐶𝑒
1 + 𝐾𝐿𝐶𝑒
Equa ion 2.6. Langmui equa ion.
Whe e qe is he equilib ium adso p ion capaci y, Qmax is he maximum monolaye
adso p ion capaci y, Ce is he equilib ium concen a ion, and KL is he Langmui
equilib ium cons an . This model sui s adso p ion sys ems whe e monolaye co e age
is p edominan and p o ides pa ame e s ela ed o adso p ion capaci y and a ini y.42
qe= 0.03
k1 = 11.8
R2 = 0.9998
qe= 0.001
k2 = 17.2
R2 = 0.9993
a) b)
Chap e 2
86
The F eundlich model desc ibes adso p ion on he e ogeneous su aces wi h non-
uni o m si es and a iable adso p ion ene gies. This empi ical model accoun s o
mul ilaye adso p ion and is exp essed as (Eq. 2.8):
𝑞𝑒= 𝐾𝐹𝐶𝑒1/𝑛
Equa ion 2.7. F eundlich equa ion.
Whe e qe is he adso p ion capaci y a equilib ium condi ions, Ce is he equilib ium
concen a ion, and KF is he F eundlich cons an ela ed o adso p ion capaci y ( he
highe KF, he mo e adso p ion capaci y we ha e), and n is he he e ogenei y ac o
ha indica es he deg ee o non-linea i y and adso p ion in ensi y. Values o n be ween
1 and 10 gene ally indica e a ou able adso p ion condi ions, wi h highe alues
sugges ing mo e a ou able adso p ion p ocesses.43
To illus a e he applica ion o bo h models, Figu e 2.7 shows he adso p ion iso he ms.
The expe imen al da a a e p esen ed as poin s, while he solid lines co espond o he
Langmui and he F eundlich model i s. In he Langmui model, om he linea ised
plo o Ce/qe e sus Ce, he adso p ion pa ame e s qmax and KL can be de e mined. In
he F eundlich model, om he linea ised plo o lnqe e sus lnCe, he cons an s KF and
1/n a e ob ained.
Figu e 2.7. Adso p ion iso he ms o a) he Langmui model and b) he F eundlich model.
While hese wo models emain he mos commonly applied due o hei simplici y and
in e p e abili y, no single iso he m pe ec ly cap u es all adso p ion beha iou s. The
Langmui model assumes uni o m si es and monolaye co e age, whe eas he
F eundlich model be e desc ibes he e ogeneous su aces and mul ilaye adso p ion.
The e o e, compa ing i ing esul s can p o ide insigh s in o whe he adso p ion
occu s mainly as monolaye adso p ion on homogeneous si es o in ol es mul ilaye
a) b)
qmax = 30.8
kL= 0.08
R2 = 0.987
KF = 5.43
1/n = 0.39
R2 = 0.917
Syn hesis o C4 dica boxylic acids MOFs
93
Chap e 3
Syn hesis o C4 dica boxylic
acids MOFs
This chap e p esen s he syn hesis and cha ac e isa ion o ou zi conium-based
me al-o ganic amewo ks cons uc ed using C4 dica boxylic acids as o ganic linke s:
aspa ic acid (MIP-202), ans-aconi ic acid (MIP-205), hiomalic acid (BCM-1), and
meso-2,3-dime cap osuccinic acid (BCM-5). A sys ema ic explo a ion o wa e -based
c ys allisa ion condi ions enabled he con olled ansi ion o opology be ween he
cubic " cu", hexagonal "hcp" and mixed " cu- eo" phases by modula ing he
concen a ions o he p ecu so and o mic acid. Mul i a ia e combina ions o hiol (-
SH), amino (-NH2), and ca boxyl (-COOH) unc ionalised linke s we e syn hesised in
o de o in es iga e he syne gis ic e ec s on he adso p ion capaci y o hea y me als.
Comp ehensi e sc eening e ealed excep ional selec i i y owa ds Hg(II), Pb(II),
Cu(II) and Cd(II). The esul s es ablish clea s uc u e-composi ion ela ionships and
demons a e he unabili y o C4 MOF-based ma e ials o a ge ed hea y me al
emo al applica ions.
3.1. In oduc ion
This chap e epo s he syn hesis o ou di e en zi conium-based po ous
amewo ks cons uc ed using dica boxylic acids based on ou ca bons (C4) as
o ganic linke s. To in oduce speci ic unc ional p ope ies, ou di e en dica boxylic
acids we e employed: aspa ic acid, ans-aconi ic acid, hiomalic acid, and meso-2,3-
dime cap osuccinic acid. These ligands led o he o ma ion o he me al–o ganic
amewo ks (MOFs) MIP-202, MIP-205, BCM-1, and BCM-5, espec i ely. The main
s a egy o e alua ing he pe o mance o hese MOFs is o c ea e a mul i a ia e

Chap e 3
94
sys em by combining MIP-202, MIP-205 and BCM-1 in di e en p opo ions, in o de
o in es iga e hei me al adso p ion capaci ies.
Fo he syn hesis o he zi conium-based MOFs BCM-1, MIP-202, and MIP-205, an
ex ensi e sc eening o wa e -based c ys allisa ion condi ions was conduc ed.
Con olling he addi ion o he o mic acid modula o and he me al concen a ion has
enabled modula ing he pa icle size om he mic ome ic down o he nanome ic
ange, esul ing in ma e ials wi h dis inc opologies, e e ed o he ein as C4MOF-SH,
C4MOF-NH2 and C4MOF-COOH. Thei mul i a ia e combina ions ha e been
designa ed as C4MOF-SH/NH2, C4MOF-SH/COOH, and C4MOF-SH/COOH. The
speci ic mola a ios o he linke s ha e been epo ed only o hese mul i a ia e
sys ems, pa icula ly when de ia ing om equimola composi ions.
Each syn hesised compound has been ully cha ac e ised be o e es ing i s adso p ion
capaci y o Hg(II), Pb(II), Cd(II), La(III), Y(III), Eu(III), Cu(II), Ni(II) and Co(II).
The s uc u al e sa ili y o highly o de ed Me al-O ganic F amewo ks (MOFs) has
opened he doo o he design o a my iad o ma e ials wi h di e en opologies and
po osi y me ics. Mo e speci ically, Z IV, H IV o CeIV based MOFs a e one o he mos
p omising g oups o e icula ma e ials due o hei chemical and hyd oly ic obus ness
a ising om he high connec i i y o hei ino ganic building uni s. Today, mos o he
membe s wi hin MIV-MOFs a e cons uc ed om he hexame ic [MIV6µ3-O4(µ3-OH)4]12+
clus e s, which a e assembled h ough o ganic linke s in o h ee dimensional
amewo ks exhibi ing pe manen po osi y. Depending on he connec i i y o he
ino ganic and o ganic blocks, he opology, and hence he po osi y me ics o he inal
amewo k can be con olled. Today, mo e han hal o he possible opologies ha e
al eady been syn hesised o MIV-MOFs ha ing [MIV6µ3-O4(µ3-OH)4]12+ clus e s. He e,
he design o new o ganic linke s has a p ominen ole o une no only he opology o
he inal s uc u e, bu also he p ope ies and unc ionali y o he inal MIV-MOF.
Un o una ely, in mos cases, he sophis ica ion o he o ganic componen s in MOFs is
linked o en i onmen ally un iendly syn hesis pa hs, and ene gy, ime and esou ce-
consuming p ocesses. All o his hinde s he applicabili y o MOF ma e ials beyond he
lab-scale.
He e is whe e he design o MIV ma e ials based on C4 o ganic linke s gains
impo ance in e ms o hei po en ial applicabili y due o hei low oxici y, limi ed p ice,
Syn hesis o C4 dica boxylic acids MOFs
95
and chi al na u e o he o ganic componen . In addi ion, due o he high solubili y o
C4-linke s in wa e , MIV-MOFs can be ob ained h ough high-yield g een syn hesis
p o ocols a low o mode a e empe a u es, in ol ing wa e as sol en , and o mic acid
as a modula o . None heless, despi e he chemical e sa ili y o C4-linke s, o da e only
ou a ian s o MIV-MOF ma e ials ha e been syn hesised based on uma a e (MOF-
801), aspa a e (MIP-202), succina e and mala e (MIP-203-S, MIP-203-M) and ans-
aconi a e (MIP-205) o ganic linke s. In compa ison o he UiO-66 amily, whe e
coun less a ian s and mul i a ia e ma e ials based on di e en composi ions o he
[MIVO4(OH)4]12+ uni s (i.e. Z IV, H IV, CeIV, REEIII, Z IV-TiIV…) and o ganic linke s ha ing
di e en unc ions (i.e. -amino, -hyd oxy, - ni o, -me hyl, - alkyl, - hiol, -b omine…)
ha e been syn hesised, MIV-MOFs based on C4 linke s a e s ill unde explo ed.
In addi ion, as he esea ch communi y wo king on MOFs gains con ol o e he
syn hesis pa ame e s con olling hei c ys allisa ion, he con ol o he c ys allisa ion
o a ian s a ising om a local o long- ange co ela ed diso de has been ob ained in
he same sys em. I is well known ha missing linke (ML) local de ec i i y expands
e en mo e he ichness o hei chemical and physical p ope ies o MIV-MOFs. E en
mo e, when missing linke (ML) and clus e (MC) de ec s a e co ela ed in a local o
long- ange o de , he de ec i i y wi hin he amewo ks can gi e access o he design
o ma e ials beyond he a che ypal “ cu” cubic a ian usually ob ained o MIV-MOFs.
This is he case o Z IV and H IV UiO-66 and UiO-67 sys ems, whe e he linke and
clus e de ec i i y guide he c ys allisa ion o UiO-66 and UiO-67 ma e ials owa ds i e
di e en opologies: 12-c “ cu”, 8-c “hex”, 8-c “ eo”, 9-c “hcp” and 6-c “hxl”. Mo e
in e es ingly, he symme y and opology wi hin he s uc u e o all hese a ian s can
be quali a i ely in e linked by applying local o long- ange co ela ed de ec i i y wi hin
he highly symme ic pa en ma e ial. Thus, by sys ema ically explo ing he syn hesis
pa ame e space, i is possible o mo e om (I) “ cu” MIV-MOFs ma e ials wi h di e en
deg ees o unco ela ed ML, o (II) “ cu + eo” and “ eo” a ian s wi h co ela ed MC
domains o inally, a collapse o he cubic symme y o a hexagonal amewo k a ising
om he co ela ed ML de ec s in o he same c ys allog aphic plane.
In his esea ch we ha e duly in es iga ed he syn he ic pa ame e s ha con ol he
local and long- ange de ec i i y in C4- and mul i a ia e C4-MVI-MOFs based on
hiomalic (THIO), aspa ic (ASP), ans-aconi ic (TRANS) and dime cap osuccinic acid
(DMSA), o guide he sys em om he ideal “ cu” cubic opology owa ds a local “ eo”
Chap e 3
96
de ec i e amewo k, and inally o he “hcp” hexagonal a ian s whe e he o de ed
local ML de ec i i y gene a es he collapse o he ABCBC packing shown he “ cu- eo”
amewo k in o a ABABAB packing ela ed wi h an hexagonal “hcp” a ian showing
Z 12 clus e s as he nodes o he s uc u e. We ha e explo ed how he dilu ion o he
concen a ion o he ini ial eagen s, and he addi ion o o mic acid modula o o he
media con ol de ec i eness and guide he c ys allisa ion owa ds he “hcp” a ian s,
as well as how he mul i a ia e combina ion o he linke s aids o supp esses he
ansi ion om a “ cu” o a “ cu- eo” and “hcp” sys em. Las bu no leas , once
con igu ed, he di e en a ian s o he ma e ials, ma e ials ha e been employed o
s udy hei adso p ion capaci y in a mul ime al wa e en i onmen .
3.2. Syn hesis and Cha ac e isa ion
The design o me al-o ganic amewo ks (MOFs) has e ol ed om basic syn hesis
me hods o mo e complex app oaches o a ge unc ional modi ica ions and une hei
p ope ies.1,2. Thei syn hesis in ol es a complex in e play be ween a ious
pa ame e s ha signi ican ly a ec c ys allisa ion kine ics and inal mo phology.
Modula o s, sol en s, pH, empe a u e, and o he ac o s play c ucial oles in
con olling MOF o ma ion.
The use o chemical addi i es o adjus he p ope ies o ma e ials has become
inc easingly common in new app oaches. Among hese addi i es, modula o s ha e
eme ged as powe ul ools ha allow con ol o he c ys allisa ion p ocess, o e ing a
pa hway o o e come he inhe en challenges o con olling nuclea ion and g ow h in
hese complex ma e ials.
These molecula addi i es wo k h ough coo dina ion modula ion, whe e he
modula o molecules compe e wi h he linke molecules o me al coo dina ion si es.3.
This mechanism enables modula o s o ac as molecula swi ches o speci ic
c ys allisa ion pa hways and he eby in luence key ma e ial p ope ies, including
c ys allini y, pa icle size, mo phology, and de ec i i y.4. The acidi y and concen a ion
o modula o s a e impo an o achie ing phase-pu e c ys alline amewo ks.5 and
hus equi e op imisa ion when wo king wi h obus amewo ks such as Z -based
MOFs, whe e s ong me al-ligand in e ac ions can o he wise lead o poo ly con olled
c ys allisa ion esul s.
Syn hesis o C4 dica boxylic acids MOFs
97
In e es ingly, while modula o s ypically decele a e MOF o ma ion, unexpec ed
accele a ing e ec s can occu unde ce ain condi ions. Fo ins ance, he p esence o
wa e has been obse ed o accele a e Z - uma a e MOF syn hesis, highligh ing he
complex in e play be ween modula o s, sol en s, and o he syn hesis pa ame e s.6
Linke design also plays a c ucial ole in uning MOF s uc u e and unc ion, wi h
adjus men s o geome y, leng h, a io, and unc ional g oups allowing o ailo ed
p ope ies such as su ace a ea, po e ape u e, and molecula ecogni ion.7. The
in e play be ween modula o s, sol en s, and o he syn hesis pa ame e s is complex
and can signi ican ly a ec he kine ics o c ys allisa ion. Unde s anding hese
mechanisms is c ucial o designing MOFs wi h speci ic mo phologies and p ope ies.8
As a con ibu ion o C4-based Z -MOFs, in his wo k, we in es iga ed he wa e -based
syn hesis and c ys allisa ion o ou di e en MOFs o zi conium, hiomalic (SH),
aspa ic (NH2) and ans-aconi ic (COOH) mic opo ous amewo ks.
To p o ide con ex o he syn hesis condi ions explo ed, a ep esen a i e p ocedu e
is i s ou lined and illus a ed in Figu e 3.1. As a common p ocedu e, Z Cl4 (2.33 g,
10 mmol) was dissol ed in 10 mL o wa e unde magne ic s i ing in a 50 mL Py ex®
au ocla e, hen dica boxylic acid linke (20 mmol) was added. Finally, 570 μL o o mic
acid (FA) was in oduced as a modula o o he mix u e. The Py ex® eac o was
closed and placed in a p ehea ed o en a 120 °C o 24 h. The ob ained solid was
eco e ed by cen i uga ion (6000 pm, 30 min) and a e wa ds washed h ee imes o
h ee consecu i e days wi h wa e . Finally, he samples we e d ied a 80 °C o 24 h.
Figu e 3.1. Rep esen a ion o he C4-based Z -MOFs syn hesis p ocess.
F om hese es ablished condi ions, we ocused on wo key pa ame e s: he
concen a ions o he p ecu so (Z Cl4) and he modula o (FA). Va ying hese wo
pa ame e s led o he o ma ion o dis inc c ys alline phases. Once he op imal
Chap e 3
98
condi ions o p og essi ely in oducing de ec s in o he amewo k and ansi ioning
be ween c ys allog aphic a ian s we e iden i ied, he syn hesis p o ocol was applied
o all C4-o ganic linke s s udied in his wo k: aspa ic acid (ASP), hiomalic acid (THIO)
and ans-aconi ic acid (TRANS) (Table 3.1).
Table 3.1. Concen a ions o C4-dica boxylic acids and Z Cl4 o he c ys allog aphic a ian s s udy.
Name
[Z Cl4]
[FA]
Geome y
AspA1
0.1
1.5
hcp- -c- cu
AspA2
0.1
5
hcp
AspA3
0.1
10
hcp
AspB1
0.5
1.5
c- cu-monoclinic o e agonal?
AspB2
0.5
5
c- cu-hcp
AspB3
0.5
10
Hcp-monoclinic o e agonal?
AspC1
0.75
1.5
Monoclinic o e agonal?
AspC2
0.75
5
Monoclinic o e agonal
AspC3
0.75
10
monoclinic o e agonal
AspD1
1
1.5
c- cu
AspD2
1
5
c- cu-monoclinic o e agonal?
AspD3
1
10
c- cu-monoclinic o e agonal?
ThioA1
0.1
1.5
c- cu
ThioA2
0.1
5
c- cu-hcp
ThioA3
0.1
10
c- cu-hcp
ThioB1
0.5
1.5
c- cu
ThioB2
0.5
5
c- cu
ThioB3
0.5
10
- cu
ThioC1
0.75
1.5
c- cu
ThioC2
0.75
5
c- cu
ThioC3
0.75
10
c- cu
ThioD1
1
1.5
c- cu
ThioD2
1
5
c- cu
ThioD3
1
10
c- cu
T ansA1
0.1
1.5
c- cu
T ansA2
0.1
10
c- cu
T ansA3
0.1
20
c- cu
T ansB1
0.5
1.5
c- cu - eo
T ansB2
0.5
10
c- cu- eo
T ansB3
0.5
20
c- cu
T ansC1
0.75
1.5
c- cu - eo
T ansC2
0.75
10
c- cu - eo
T ansC3
0.75
20
c- cu
T ansD1
1
1.5
c- cu - eo
T ansD2
1
10
c- cu - eo
T ansD3
1
20
c- cu

Syn hesis o C4 dica boxylic acids MOFs
99
Analysis o he di ac ion pa e ns o he ob ained ASP- ype compounds e eals
no iceable changes as he [Z Cl4] and [FA] concen a ion change. The di ac ion
pa e n o AspD1, ob ained using he ypical p ocedu e p e iously epo ed, shows
s ong simila i ies o ha o MOF-801, which ypically exhibi s i s mos in ense peaks
a a ound 8° and 10° in 2θ. Addi ionally, he ull p o ile ma ching analysis o he
di ac ion pa e ns con i ms he o ma ion o a cubic phase wi h he same s uc u e as
MOF-801 (Fig. 3.2).
Figu e 3.2. Pa e n ma ching p o ile analysis o he aspa ic acid (ASP) sample. Red poin s:
expe imen al. Red line: calcula ed. Blue line: di e ence. G een e ical ba s: B agg planes.
This symme y e eals ha , in gene al, inc easing [FA] and dec easing [Z Cl4] p oduce
no iceable changes in he di ac ion peaks, leading o he o ma ion o dis inc
s uc u al geome ies. As he concen a ions o bo h [Z Cl4] and [FA] dec ease om
high o low, he di ac ion pa e ns change signi ican ly, wi h he mos in ense peaks
shi ing owa d lowe 2θ alues. Compa ison wi h known e eph hala e-based Z -
MOFs sugges s ha his pa e n co esponds o a hexagonal s uc u al a ian .
XRD analysis enabled he de e mina ion o he cubic and hexagonal phases in he
di e en syn he ic condi ions explo ed, hus allowing he cons uc ion o c ys allisa ion
s abili y maps o each opology (Fig. 3.3a, 3.5a and 3.7a).
Chap e 3
100
Figu e 3.3. (a) C ys allisa ion phase diag am o he Z -ASP sys em and (b) di ac ion pa e ns o he
sc eening syn hesis.
The ini ial sc eening was conduc ed using Z Cl4 and ASP a concen a ions o 1.0 M
and 1.5 M, espec i ely. Wi hin his p elimina y syn hesis ma ix, o mic acid (FA) was
added in olumes o 1.9 mL and 3.8 mL, co esponding o inal FA concen a ions o 5
M and 10 M. Unde hese condi ions, a se ies o eac ions was pe o med wi h a ying
Z Cl4 concen a ions (0.75 M, 0.5 M, and 0.1 M), as summa ised in he c ys allisa ion
s abili y map (Fig. 3.3a).
By co ela ing he c ys allisa ion phase diag am wi h he co esponding di ac ion
pa e ns, i becomes e iden ha highe concen a ions o Z Cl4 a ou he o ma ion
o he c- cu phase, al hough wi h educed c ys allini y. As he Z Cl4 concen a ion
dec eases, a p og essi e mo phological ansi ion is obse ed: a 0.75 M, he p oduc
exhibi s a monoclinic o e agonal phase; a 0.5 M, a mix u e o hexagonal and
e agonal (o monoclinic) phases eme ges; and a 0.1 M, he ma e ial adop s a
p edominan ly hexagonal s uc u e. In hese la e h ee cases, lowe concen a ions
o o mic acid a e associa ed wi h a u he dec ease in c ys allini y.
The same sc eening s a egy was applied o he THIO sys em. In his case, a ia ion
o he Z Cl4 and o mic acid concen a ions esul ed in minimal changes in he
di ac ion pa e ns o he esul ing THIO-based ma e ials. No ably, he di ac ion
pa e n o ThioD1 closely ma ches ha o MOF-801. Full-p o ile pa e n-ma ching
analysis u he con i ms he o ma ion o a cubic phase consis en wi h he s uc u e
o MOF-801 (Fig. 3.4).
Syn hesis o C4 dica boxylic acids MOFs
101
Figu e 3.4. Pa e n ma ching p o ile analysis o he hiomalic acid sample. Red poin s: expe imen al.
Black line: calcula ed. Blue line: di e ence. G een e ical ba s: B agg planes.
A de ailed co ela ion be ween he c ys allisa ion phase diag am and he
co esponding di ac ion pa e ns shows ha high concen a ions o Z Cl4 a ou he
o ma ion o a cubic phase bu wi h a signi ican dec ease in c ys allini y (Fig. 3.5b).
Reducing he Z Cl4 concen a ion o 0.1 M esul s in a p og essi e phase
ans o ma ion owa ds a hexagonal opology. The concen a ion o o mic acid u he
modula es his s uc u al ansi ion: a 0.5 M, a biphasic sys em consis ing o cubic and
e agonal domains eme ges, whe eas a 0.1 M, he c ys allisa ion pa hway a ou s
he o ma ion o a p edominan ly hexagonal phase.
Figu e 3.5. (a) C ys allisa ion phase diag am o he Z -THIO sys em and (b) di ac ion pa e ns o he
sc eening syn hesis.
A simila sc eening app oach was applied o he TRANS sys em. In his case, analysis
o he di ac ion pa e ns o he esul ing TRANS- ype ma e ials showed no signi ican
changes as he concen a ions o Z Cl4 and o mic acid we e a ied. The di ac ion
pa e n o T ansD1 was also compa ed wi h ha o MOF-801. Full-p o ile ma ching
Chap e 3
102
analysis con i med he o ma ion o a cubic phase, displaying cha ac e is ic eo- ype
e lec ions consis en wi h he cubic s uc u e o MOF-801 (Fig. 3.6).
Figu e 3.6. Pa e n ma ching p o ile analysis o he ans-aconi ic acid (TRANS) sample. Red poin s:
expe imen al. Red line: calcula ed. Blue line: di e ence. G een e ical ba s: B agg planes.
An ini ial sc eening was also ca ied ou using Z Cl4 and TRANS a concen a ions o
1.0 M and 1.5 M, espec i ely. In his syn hesis ma ix, o mic acid (FA) was added in
olumes o 3.8 mL and 7.6 mL, co esponding o inal FA concen a ions o 10 M and
20 M. A se ies o eac ions was hen conduc ed unde hese condi ions, a ying he
Z Cl4 concen a ion o 0.75 M, 0.5 M, and 0.1 M. The ou comes o hese expe imen s
a e summa ised in he c ys allisa ion s abili y map shown in Figu e 3.7a.
Figu e 3.7. (a) C ys allisa ion phase diag am o he Z -TRANS sys em and (b) di ac ion pa e ns o
he sc eening syn hesis.
Co ela ion o he c ys allisa ion phase diag am wi h he co esponding di ac ion
pa e ns e eals ha highe concen a ions o Z Cl4 combined wi h lowe
concen a ions o o mic acid (FA) p omo e he o ma ion o he eo-c- cu phase. When
Syn hesis o C4 dica boxylic acids MOFs
109
equimola p opo ions, he ma e ial becomes p edominan ly amo phous (Fig. 3.14c).
These indings clea ly demons a e ha he in oduc ion o he aspa ic acid linke in o
he mul i a ia e sys em p omo es amo phisa ion o he amewo k. The PXRD pa e n
o C4MOF-NH₂ does no exhibi he supe s uc u al e lec ions ypically associa ed wi h
eo- ype nanodomains. As a esul , he pa e n canno be accu a ely i ed using he
highe -symme y F23 model. Ins ead, lowe ing he symme y o he Pn3 space g oup
is equi ed o ob ain a be e i . This model success ully accoun s o he
supe s uc u al e lec ion a 6.5° bu s ill ails o ep oduce he e lec ion consis en ly
obse ed a 5.0°, indica ing limi a ions in i s abili y o ully desc ibe he s uc u al
ea u es o he ma e ial.
Figu e 3.14. Rep esen a i e XRD-pa e ns o C₄MOFs based on -NH₂, -COOH and -SH g oups and
o hei equimola on (a) -SH/-NH2, (b) -SH/-COOH, (c) -COOH/-NH2 and -COOH/-SH mul i a ia e
combina ions and pa e n ma ching p o ile analysis o he 1:1 mul i a ia e composi ions: (d) C4MOF-
SH/-NH2, (e) C4MOF-SH/-COOH and ( ) C4MOF-COOH/-NH2. Red poin s: expe imen al. Red line:
calcula ed. Blue line: di e ence. G een e ical ba s: B agg planes.

Chap e 3
110
Fo he mul i a ia e combina ions be ween C4MOF-NH2 (Pn-3) and -COOH o -SH
(F23/P23) a ian s, he ansi ion be ween hese endmembe s o he sequence is
dis up ed wi hin an in e media e composi ional egion. The in eg a ion o a seconda y
THIO o TRANS linke in o he Pn-3 s uc u e o he ASP a ian ini ially induces he
appea ance o he supe s uc u al e lec ions associa ed wi h clus e -de ec i e eo
nanodomains. This is ollowed by a sudden b oadening o he di ac ion maxima wi hin
a e y na ow composi ional window. Fu he in eg a ion o seconda y linke s in o he
s uc u e gi es ise o he eco e y o he c ys allini y o he ma e ial, s ill he PRXD
da a show he p esence o he supe s uc u al e lec ions associa ed wi h - eo
nanodomains.
Fou ie - ans o m in a ed (FTIR) spec oscopy was employed o con i m he
inco po a ion o he unc ional g oups associa ed wi h he C4-MOFs (ASP, THIO, and
TRANS) in bo h single-linke and mul i a ia e Z -based MOFs (Fig. 3.15–3.18). The
spec a display he cha ac e is ic inge p in egions associa ed wi h Z -based C4-
MOFs, as well as he ib a ional signa u es o each unc ional linke . No ably, no
signi ican shi s in ib a ional equencies a e obse ed when compa ing single-linke
amewo ks wi h hei mul i a ia e analogues, indica ing ha he inco po a ion o
mul iple ligands does no subs an ially al e he coo dina ion en i onmen a he
molecula le el (Fig. 3.15).
Figu e 3.15. FTIR spec a o compounds (a) C4MOF-(SH), (b) C4MOF-(NH2) and (c) C4MOF-
(SH)/(NH2)/(COOH) and (c) C4MOF-(COOH).
The mos dis inc i e ea u e o he THIO ligand is he p esence o i s hiol g oup, which
is clea ly e idenced by a sha p S-H s e ching band a ound 2550 cm-1 and a weake
Syn hesis o C4 dica boxylic acids MOFs
111
C-S ib a ion a app oxima ely 635 cm-1. Al hough his la e signal pa ially o e laps
wi h he Z -O ib a ions, i can s ill be seen in he spec a.
Figu e 3.16. FTIR spec a o compounds (a) C4MOF-(SH), (b) C4MOF-(SH)/(NH2) and (c) C4MOF-
(SH).
The spec a o all samples exhibi he ypical b idging coo dina ion o ca boxyla e
g oups, con i med by he sepa a ion be ween he asymme ic (∼1575 cm-1) and
symme ic (∼1420 cm-1) s e ching bands o he ca boxyla e g oup.
Figu e 3.17. FTIR spec a o compounds (a) C4MOF-(SH), (b) C4MOF-(SH)/(COOH) and (c) C4MOF-
(COOH).
An addi ional abso p ion band a app oxima ely 1210 cm⁻¹, associa ed wi h C–O
s e ching ib a ions, is also de ec ed and shows inc eased in ensi y in ma e ials
inco po a ing he TRANS ligand (Fig. 3.16 and 3.17).
Fu he mo e, a weak abso p ion band cen ed a ound 1715 cm-1 is obse ed in mos
o he ma e ials, which is a ibu ed o he asymme ic s e ching o non-coo dina ed
Chap e 3
112
C=O bonds. This ea u e e lec s he p esence o ee ca boxylic acid g oups in he
amewo k.
Figu e 3.18. FTIR spec a o compounds (a) C4MOF-(NH2), (b) C4MOF-(COOH)/(NH2) and (c)
C4MOF-(COOH).
The mog a ime ic analysis (TGA) and 1H nuclea magne ic esonance (¹H NMR)
spec oscopy p o ide complemen a y ools o e alua ing he a e age o ou ma e ials
(Fig. 3.19-3.24). As p e iously es ablished, he weigh loss obse ed in TGA,
pa icula ly ha associa ed wi h clus e dehyd a ion and o ganic linke decomposi ion,
can be used o es ima e he numbe o missing linke s pe o mula uni in M(IV)-based
MOFs.
To exempli y his app oach, he he mog a ime ic and di e en ial scanning
calo ime y (DSC) cu es o he pu e-linke amewo ks we e employed, as hey
ep esen he ex eme beha iou s wi hin he se ies. The MTV ma e ials exhibi he mal
p o iles ha lie be ween hose o hei single-linke coun e pa s. In gene al, he TGA
and DSC da a e eal wo main he mal e en s. The i s weigh loss, occu ing be ween
oom empe a u e and ~125 °C, co esponds o he elease o physically adso bed o
apped sol en molecules wi hin he po e sys em. The second weigh loss p ocess,
ini ia ed a ound 300 °C, is associa ed wi h he mul is ep decomposi ion o he o ganic
linke s. Comple e ans o ma ion in o he co esponding M(IV) oxides occu s be ween
600 and 650 °C, depending on he chemical na u e o he C4 linke employed in each
ma e ial.
To semi-quan i a i ely es ima e he a e age linke de ec i i y in each MOF, he TGA
weigh loss eco ded a ound 300 °C, jus be o e he onse o in ense exo he mic
Syn hesis o C4 dica boxylic acids MOFs
113
decomposi ion obse ed in he DSC ace, was aken as a e e ence. This alue was
no malised o 100% and used o ecalcula e he ela i e esidue mass. The esul ing
expe imen al alues we e hen co ela ed wi h he heo e ical he mal decomposi ion
desc ibed in Equa ion 3.1:
Z 6O6+x(C4-L)6-x → (Z O2)6 + CO2 + H2O
Equa ion 3.1. The mal decoposi ion o Z compounds.
Whe e x deno es he numbe o linke acancies pe o mula uni . Theo e ical weigh
loss alues we e calcula ed o di e en de ec deg ees (x) and plo ed o gene a e a
linea co ela ion, which was used o ex ac he expe imen al de ec i i y om he TGA
da a.
I is impo an o highligh ha he heo e ical model behind Equa ion 3.1 assumes
comple e emo al o o ma e modula o molecules, in addi ion o dehyd a ion o he
zi conium oxo-clus e s, by 300 °C. In he cu en sys em, he onse o linke
deg ada ion may hinde ull dehyd a ion o he clus e s. None heless, a 300 °C,
subs an ial o ma e emo al and a signi ican deg ee o clus e dehyd a ion a e
expec ed.
Complemen a ily, 1H NMR was employed o quan i y he amoun o o ma e e ained
wi hin he s uc u e. The spec a we e eco ded a e diges ing he samples in 2 M
NaOH solu ion in D2O, allowing accu a e de e mina ion o he chemical o mula o
each ma e ial unde ambien condi ions. This analysis e ealed ha no all missing
linke si es a e compensa ed by o ma e anions; a signi ican ac ion o he de ec s
wi hin he Z 6 clus e s a e ins ead occupied by e minal wa e molecules and hyd oxyl
g oups. These indings suppo he hypo hesis ha de ec compensa ion in hese
ma e ials ollows a mixed mechanism in ol ing bo h modula o coo dina ion and
hyd oly ic e mina ion.
To u he cla i y he composi ion o he MTV MOFs—pa icula ly ega ding he
p o ona ion s a e o he inco po a ed linke s—ene gy-dispe si e X- ay spec oscopy
(EDX) analysis was pe o med o suppo he de e mina ion o he empi ical o mula
o he ma e ials (Table 3.3). Based on he elemen al da a, i was concluded ha he
ASP linke is p esen in i s p o ona ed o m as NH3Cl, while he emaining linke s
(THIO and TRANS) a e inco po a ed in hei neu al o ms.
Chap e 3
114
Table 3.3. Quan i ica ion o a oms o MTV sys em componen s by EDX.
Code
C
N
O
S
Cl
Z
C4MOF-NH2
35.4±3.61
2.98±0.16
19.4±1.91
-
6.86±0.46
20.6±1.43
C4MOF-SH/NH2
43.4±7.43
1.31±0.30
18.5±3.24
1.70±0.31
2.21±0.43
13.7±2.48
C4MOF-COOH/NH2
35.1±14.9
1.15±0.57
15.7±7.02
-
0.98±0.18
17.7±5.64
Conside ing hese assump ions, he eac ion condi ions employed o he g am-scale
syn hesis o he MTV M(IV)-C4-MOFs yield a e age linke de ec i i ies in he ange o
0.2 o 2.3 acancies pe o mula uni (Table 3.4).
Figu e 3.19. (a) 1H NMR and (b) TGA and DSC o C4MOF-SH.
Figu e 3.20. (a) 1H NMR and (b) TGA and DSC o C4MOF-(SH)0.52/(NH2)0.48.

Syn hesis o C4 dica boxylic acids MOFs
115
Figu e 3.21. (a) 1H NMR and (b) TGA and DSC o C4MOF-NH2.
Figu e 3.22. (a) 1H NMR and (b) TGA and DSC o C4MOF-(NH2)0.59/(COOH)0.41.
Figu e 3.23. (a) 1H NMR and (b) TGA and DSC o C4MOF-COOH.
Chap e 3
116
Figu e 3.24. (a) 1H NMR and (b) TGA and DSC o C4MOF-(COOH)0.41/(NH2)0.59.
Table 3.4. Fo mula and de ec s o he MTV sys em calcula ed by NMR and TGA.
Code
Fo mula
De ec s
C4MOF-SH
Z 6O4(OH)4(C4SH4O4)4.9((H2O)(OH))2.2
1.1
C4MOF-SH/NH2
Z 6O4(OH)4(C4H3NH3ClO4)1.8(C4SH4O4)2.1(HCOO)0.07((H2O)(OH))4.1
2.1
C4MOF-NH2
Z 6O4(OH)4(C4H3NH3ClO4)5.6(HCOO)0.3((H2O)(OH))0,5
0.4
C4MOF-COOH/NH2
Z 6O4(OH)4(C4H3NH3ClO4)2.1(C6H3O6)1,6(HCOO)0.1((H2O)(OH))4.6
2.3
C4MOF-COOH
Z 6O4(OH)4(C6H3O6)4,80((H2O)(OH))2.4
1.20
C4MOF-COOH/SH
Z 6O4(OH)4(C6H3O6)2.4(C4SH4O4)3.4(HCOO)0.3((H2O)(OH))0,1
0.2
The po osi y o he samples was e alua ed h ough high-p essu e CO2 adso p ion
iso he ms (Fig. 3.25). All samples exhibi a ype I iso he m p o ile, cha ac e is ic o
mic opo ous ma e ials. In hese cu es, he majo i y o CO2 up ake occu s a low
ela i e p essu es, ollowed by a g adual inc ease a highe p essu es due o
in apa icle condensa ion.
Figu e 3.25. CO2 adso p ion iso he ms o he MTV sys em.
Syn hesis o C4 dica boxylic acids MOFs
117
Su ace a ea alues we e de e mined using he linea po ion o he iso he ms a low
ela i e p essu e, whe e adso p ion beha iou ollows he B unaue –Emme –Telle
(BET) model. Fo bo h cu and cu/ eo phase ma e ials, ega dless o he unc ional
g oup p esen on he C4 linke , he calcula ed su ace a eas ange om 215 o
390 m2/g (Table 3.5). These alues a e signi ican ly lowe han hose p edic ed based
on he c ys allog aphic models (app oxima ely 750-800 m2/g)9. This disc epancy is
mainly a ibu ed o he mild ac i a ion condi ions employed, which a e cons ained by
he he mal sensi i i y o he ma e ials and limi he comple e emo al o gues species.
Table 3.5. Mic opo e su ace a eas o MTV ma e ials by adso p ion iso he ms.
Code
Speci ic su ace (m2/g)
C4MOF-SH
259.44
C4MOF-SH/NH2
387.05
C4MOF-NH2
215.30
C4MOF-COOH/NH2
317.04
C4MOF-COOH
387.55
C4MOF-COOH/SH
307.53
Scanning elec on mic oscopy (SEM) analysis (Fig. 3.26) o e s aluable insigh in o
he mic os uc u e o he syn hesised ma e ials. Al hough he MOFs exhibi a ying
mo phologies depending on hei speci ic s uc u al composi ion, all samples show a
ela i ely uni o m and monodispe se pa icle size dis ibu ion.
Figu e 3.26. SEM images o MTV samples.
Ze a po en ial analysis p o ides insigh in o he su ace elec ical po en ial o pa icles
by measu ing he ol age di e ence be ween he pa icle su ace and he su ounding
Chap e 3
118
i mly a ached coun e -ions. This pa ame e is essen ial o unde s anding and
con olling he elec os a ic dispe sion and colloidal s abili y o he pa icles.10
In his s udy, he ze a po en ial o he C4-MOFs was measu ed o e alua e hei su ace
cha ge p ope ies. As shown in Figu e 3.27, measu emen s we e conduc ed o e a pH
ange o 3 o 9. Ac oss his ange, all ma e ials exhibi ed a nea ly consis en ly nega i e
su ace cha ge. Mo eo e , inc easing he pH led o a p og essi e enhancemen o he
nega i e ze a po en ial, eaching alues o app oxima ely 40 mV a pH 9.
These esul s indica e ha he su ace o he C4-MOF pa icles emains nega i ely
cha ged unde mos condi ions, which a ou s elec os a ic in e ac ions wi h posi i ely
cha ged species, such as hea y me al ca ions.
Figu e 3.27. Ze a po en ial measu emen s o MTV ma e ials.
3.3. Applica ion o C4MOFs
3.3.1. Abso p ion o phenolic compounds
To e alua e he po en ial applica ions o he syn hesised MOFs as adso ben
ma e ials, a sys ema ic adso p ion s udy was conduc ed using i e ep esen a i e
a oma ic compounds: phenol, ca echol, hyd oquinone, dopamine, and pa ace amol
(Fig. 3.28). These molecules exhibi di e en unc ional g oups and subs i u ion
pa e ns ha allow o he analysis o selec i i y and adso p ion mechanisms o he
syn hesised ma e ials.
Syn hesis o C4 dica boxylic acids MOFs
125
Figu e 3.31. Abso p ion capaci y (mg/g) o MTV sys em ma e ials o e Co(II), Ni(III), La(III), Eu(III)
and Y(III). Expe imen s we e pe o med wi h an ini ial me al ion concen a ion o 10 ppm, using a 1 mg
adso ben /mL dosage.
To acili a e a clea e in e p e a ion o hese ends, he esul s will be discussed
sepa a ely o each g oup o me al ions (Fig. 3.32).
As shown in Figu e 3.32b, he ASP-based ma e ial exhibi ed negligible adso p ion
capaci y o all me als excep Hg(II), o which a mode a e up ake was obse ed. In
con as , he THIO-based ma e ial demons a ed signi ican a ini y o Hg(II), Pb(II),
Cd(II), and Cu(II) (Fig. 3.32c), while he TRANS-based ma e ial s ood ou o i s abili y
o adso b a e-ea h elemen s (RREEs), as shown in Figu e 3.32a.
When e alua ing he mul i a ia e ma e ials, he TRANS/ASP combina ion (Fig. 3.32d)
did no show any imp o emen in adso p ion pe o mance compa ed o he indi idual
componen s. In he case o he THIO/ASP ma e ial (Fig. 3.32 ), al hough no syne gis ic
enhancemen was e iden , he indi idual adso p ion capaci ies we e la gely e ained.
No ably, he THIO/TRANS ma e ial (Fig. 3.32e) exhibi ed a clea imp o emen ,
combining high adso p ion capaci ies o Hg(II), Pb(II), and Cu(II) wi h mode a e
up ake o he emaining me al ions. Finally, he e na y TRANS/THIO/ASP ma e ial
(Fig. 3.32g) displayed a sligh enhancemen in Hg(II) adso p ion, while main aining
simila pe o mance le els o he o he me als compa ed o he bina y sys ems.

Chap e 3
126
Figu e 3.32. Abso p ion capaci y (mg/g) o each MTV sys em ma e ial o e Hg(II), Pb(II), Cd(II),
Cu(II), Co(II), Ni(III), La(III), Eu(III) and Y(III).
Based on he ini ial esul s, wo addi ional adso p ion iso he ms we e pe o med using
he THIO and THIO/TRANS ma e ials, which had shown he mos p omising
pe o mance. These expe imen s aimed o u he e alua e hei adso p ion capaci ies
unde a ying me al concen a ions.
As in p e ious es s, all expe imen s we e ca ied ou in iplica e o ensu e
ep oducibili y and assess he eliabili y o he p ocedu e. The MOF suspensions we e
s i ed magne ically o 4 hou s o allow equilib ium o be eached. A e wa ds, he
suspensions we e il e ed using hyd ophilic 0.22 μm memb anes. Adso p ion capaci y
o each poin o he iso he m cu e was de e mined based on Equa ion 3.2.
The expe imen al da a ob ained om he adso p ion iso he ms we e i ed o he
Langmui and he F eundlich models o cha ac e ise he in e ac ion be ween he MOF
su ace and he a ge me al ions. These models a e widely applied in adso p ion
Syn hesis o C4 dica boxylic acids MOFs
127
s udies in ol ing po ous ma e ials, as hey p o ide insigh in o he adso p ion capaci y,
a ini y, and su ace he e ogenei y o he ma e ials. The Langmui model assumes
monolaye adso p ion on o a homogeneous su ace wi h a ini e numbe o iden ical
si es and is pa icula ly use ul o es ima ing he maximum adso p ion capaci y (Qmax)
and he Langmui cons an (KL), which e lec s he a ini y be ween he adso ben and
he adso ba e.
In con as , he F eundlich model is empi ical and assumes adso p ion on a
he e ogeneous su ace, allowing mul ilaye adso p ion and a iable adso p ion
ene gies. This model yields wo key pa ame e s: he F eundlich cons an (KF), which
is ela ed o adso p ion capaci y, and he he e ogenei y ac o (n), which p o ides
insigh in o he in ensi y o he adso p ion p ocess.
Bo h he Langmui and he F eundlich models we e applied o he expe imen al da a
o e alua e he adso p ion pe o mance o he THIO and THIO/TRANS ma e ials
owa d he selec ed me al ions (Figs. 3.33 and 3.37). The quali y o he i ing, along
wi h he ex ac ed pa ame e s, p o ides aluable insigh in o he adso p ion
mechanisms and su ace cha ac e is ics o he ma e ials. A summa y o he i ed
pa ame e s is p esen ed in Tables 3.7 o 3.10 and illus a ed in Figs. 3.34, 3.35, 3.36,
and 3.38.
A lowe me al concen a ions (10 ppm), he THIO/TRANS ma e ial demons a ed
sligh ly highe adso p ion e iciencies o Hg(II), Pb(II), and Cd(II) compa ed o he
single-linke THIO analogue. Howe e , as he me al concen a ion inc eased, he
iso he m p o iles e ealed ha he THIO ma e ial exhibi ed supe io adso p ion
capaci ies ac oss he concen a ion ange (Fig. 3.33).
Figu e 3.33. Abso p ion iso he ms o THIO and THIO/TRANS o e (a) Hg(II), (b) Pb(II) and (c) Cd(II).
Chap e 3
128
This end sugges s ha while he mul i a ia e THIO/TRANS amewo k may p esen
mo e accessible o highe -a ini y binding si es a low me al concen a ions—possibly
due o syne gis ic e ec s be ween he ligands o imp o ed su ace dispe sion— hese
ad an ages may become less signi ican a highe concen a ions. Unde such
condi ions, he THIO ma e ial likely bene i s om a highe densi y o e ec i e
coo dina ion si es o a mo e homogeneous su ace chemis y, enabling g ea e up ake
be o e eaching sa u a ion.
Addi ionally, he inco po a ion o wo di e en linke s in he THIO/TRANS sys em migh
in oduce a deg ee o s uc u al he e ogenei y o pa ial s e ic hind ance, educing he
numbe o a ailable adso p ion si es unde high loading. This highligh s he impo ance
o op imising linke combina ions no only o ini ial binding a ini y bu also o
main aining pe o mance a ele a ed con aminan le els, which is c i ical o eal-wo ld
applica ions in wa e emedia ion.
Figu e 3.34. Hg(II) iso he m cu es o (a) THIO and (b) THIO/TRANS ma e ials.
Table 3.7. Hg(II) iso he ms adjus men s.
Model
Pa ame e
THIO
THIO/TRANS
Langmui
Qmax (mg/g)
52.8±11.5
30.7±5.47
KL (L/mg)
15.0±6.50
0.25±0.11
R2
0.94
0.92
F eundlich
KF (mg1-1/n·L1/n/g)
155±37.7
7.03±0.95
1/n
0.68±0.09
0.49±0.06
R2
0.93
0.95
Syn hesis o C4 dica boxylic acids MOFs
129
Figu e 3.35. Pb(II) iso he m cu es o (a) THIO and (b) THIO/TRANS ma e ials.
Table 3.8. Pb(II) iso he ms adjus men s.
Model
Pa ame e
THIO
THIO/TRANS
Langmui
Qmax (mg/g)
151±17.10
40.24±5.28
KL (L/mg)
0.05±0.01
0.15±0.05
R2
1
0.96
F eundlich
KF (mg1-1/n·L1/n/g)
7.92±0.73
6.28±0.42
1/n
0.77±0.04
0.54±0.03
R2
1
0.99
Figu e 3.36. Pb(II) iso he m cu es o (a) THIO and (b) THIO/TRANS ma e ials.
Chap e 3
130
Table 3.9. Cd(II) iso he ms adjus men s.
Model
Pa ame e
THIO
THIO/TRANS
Langmui
Qmax (mg/g)
102±9.96
25.26±1.53
KL (L/mg)
0.01±0
0.03±3·10-3
R2
1
1
F eundlich
KF (mg1-1/n·L1/n/g)
1.44±0.05
1.16±0.05
1/n
0.80±0.01
0.64±0.01
R2
1
1
O e all, he Langmui model p o ided a supe io i o he expe imen al da a o he
THIO ma e ial, sugges ing ha he adso p ion p ocess p edominan ly ollows a
monolaye mechanism on a ela i ely homogeneous su ace wi h ene ge ically
equi alen binding si es. This beha iou is consis en wi h a well-o ganised and
uni o m dis ibu ion o unc ional g oups capable o coo dina ing he me al ions.
In con as , he THIO/TRANS ma e ial exhibi ed sligh ly be e o compa able
co ela ion wi h he F eundlich model, which accoun s o adso p ion on
he e ogeneous su aces and allows o he possibili y o mul ilaye o ma ion. This
implies ha he in oduc ion o he second linke (TRANS) may lead o a mo e complex
su ace en i onmen , possibly in oducing a ia ions in he a ini y and accessibili y o
adso p ion si es.
These esul s highligh he s uc u al and chemical impac o mul i a ia e linke
combina ions on adso p ion beha iou , indica ing ha he balance be ween su ace
uni o mi y and unc ional di e si y plays a key ole in de ining he dominan adso p ion
mechanism.
Gi en ha he THIO/TRANS ma e ial exhibi ed he mos p omising p elimina y
adso p ion pe o mance o he a e ea h elemen s La(III), Y(III), and Eu(III), ull
iso he m s udies we e conduc ed o e alua e i s capaci y in g ea e de ail. Among he
h ee, Y(III) showed he highes up ake, ollowed by La(III) and hen Eu(III), as
illus a ed in Figu e 3.37.

Syn hesis o C4 dica boxylic acids MOFs
131
Figu e 3.37. Abso p ion iso he ms o THIO/TRANS o e (a) La(III), (b) Y(III) and (c) Eu(III).
This end may be a ibu ed o di e ences in ionic adii, hyd a ion ene gies, o
coo dina ion p e e ences among he a e ea h elemen s, which can in luence hei
in e ac ion wi h he unc ional g oups p esen in he MOF s uc u e. The hiol and
ca boxyla e unc ionali ies om THIO and TRANS linke s likely play a syne gis ic ole
in acili a ing he binding o i alen me al ca ions, pa icula ly Y(III), which appea s o
exhibi highe a ini y o he a ailable adso p ion si es.
Figu e 3.38. THIO/TRANS iso he m cu es o (a) La(III), (b) Y(III) and (c) Eu(III).
Table 3.10. La(III), Y(III) and Eu(III) iso he ms adjus men s.
Model
Pa ame e
THIO/TRANS
La(III)
THIO/TRANS
Y(III)
THIO/TRANS
Eu(III)
Langmui
Qmax (mg/g)
7.71±0.77
18.8±3.67
7.00±0.55
KL (L/mg)
0.11±0.03
0.02±0.01
0.22±0.06
R2
0.94
0.95
0.95
F eundlich
KF (mg1-1/n·L1/n/g)
1.69±0.14
0.79±0.16
2.15±0.28
1/n
0.35±0.02
0.60±0.05
0.29±0.04
R2
0.98
0.97
0.93
The adso p ion iso he m da a o La(III), Y(III), and Eu(III) we e be e desc ibed by he
F eundlich model, sugges ing a he e ogeneous dis ibu ion o binding si es on he
su ace o he THIO/TRANS ma e ial. This beha iou implies ha he adso p ion o
Chap e 3
132
hese i alen ca ions does no occu h ough a uni o m monolaye , bu a he h ough
a mul ilaye p ocess in luenced by a ia ions in si e a ini y and accessibili y.
The imp o ed i o he F eundlich model may s em om he complex coo dina ion
beha iou o a e ea h elemen s, which a e known o in e ac wi h mul iple unc ional
g oups and can adop a ious coo dina ion geome ies. In he mul i a ia e
THIO/TRANS amewo k, he coexis ence o hiol and ca boxyl g oups likely c ea es a
di e se a ay o adso p ion si es wi h di e en binding ene gies, a ou ing he s epwise
adso p ion cha ac e is ic o he F eundlich iso he m.
Taken oge he , hese esul s sugges ha he adso p ion mechanisms a e s ongly
in luenced by he in e play be ween su ace unc ionali y and s uc u al o ganisa ion.
While he THIO ma e ial ends o a ou monolaye adso p ion on mo e homogeneous
su aces—as e idenced by he be e Langmui i — he in oduc ion o TRANS linke s
in o he amewo k enhances su ace he e ogenei y, leading o mul ilaye o si e-
ene gy-dis ibu ed adso p ion, be e desc ibed by he F eundlich model.
Ul ima ely, his compa a i e analysis unde sco es he e sa ili y and unabili y o
mul i a ia e MOFs o a ge ing di e en classes o me al ions. I also highligh s he
impo ance o a ional linke selec ion in op imising adso p ion e iciency, selec i i y,
and mechanism, depending on he na u e o he a ge con aminan .
3.4. Conclusions
This chap e p o ides a ho ough in es iga ion in o he syn hesis, cha ac e isa ion and
applica ion o C4 dica boxylic acid-based zi conium me al-o ganic amewo ks
(MOFs), es ablishing a solid basis o he design o ma e ials speci ically de eloped
o hea y me al adso p ion applica ions.
A sys ema ic explo a ion o wa e -based c ys allisa ion condi ions success ully
enabled he con olled syn hesis o ou di e en zi conium-based amewo ks: MIP-
202, MIP-205, BCM-1 and he no el BCM-5. By sys ema ically a ying he
concen a ions o he Z Cl4 p ecu so and he FA modula o , i was possible o achie e
p ecise con ol o e he opology o he amewo ks, enabling ansi ions be ween he
cubic " cu", hexagonal "hcp" and mixed " cu- eo" phases. The de eloped
c ys allisa ion s abili y maps p o ide a aluable oadmap o a ge ing speci ic
Syn hesis o C4 dica boxylic acids MOFs
133
s uc u al a ian s and show ha lowe zi conium concen a ions and highe o mic
acid concen a ions a ou he o ma ion o hexagonal phases wi h be e c ys allini y.
In oducing mul i a ia e sys ems ha combine hiomalic (THIO), aspa ic (ASP), and
ans-aconi ic (TRANS) linke s e ealed complex c ys allisa ion beha iou ha
depends on he composi ion o he linke s. No ably, he inco po a ion o ASP
consis en ly p omo es amewo k amo phisa ion, while THIO-TRANS combina ions
acili a e he o ma ion o eo- ype nanodomains. These indings es ablish clea
s uc u e-composi ion ela ionships ha a e essen ial o he design o MOFs in a
a ge ed way.
Comp ehensi e cha ac e isa ion con i med he success ul inco po a ion o he linke ,
while e ealing signi ican de ec densi ies anging om 0.2 o 2.3 acancies pe
o mula uni . The ma e ials exhibi ed mic opo ous cha ac e is ics, wi h BET su ace
a eas be ween 215 and 390 m²/g; howe e , alues emained below heo e ical
p edic ions due o sligh ac i a ion limi a ions imposed by he mal s abili y. Ze a
po en ial measu emen s e ealed consis en ly nega i e su ace cha ges ac oss pH 3–
9, wi h enhanced nega i i y a highe pH alues. This indica es a ou able elec os a ic
en i onmen s o ca ionic me al coo dina ion.
Ini ial sc eening using phenolic compounds demons a ed ma e ial selec i i y, wi h
ca echol and dopamine exhibi ing signi ican up ake, whe eas phenol, hyd oquinone
and pa ace amol showed negligible adso p ion. Al hough TRANS had he highes BET
su ace a ea, THIO showed be e ca echol emo al, sugges ing ha adso p ion
pe o mance is mo e in luenced by speci ic chemical in e ac ions be ween unc ional
g oups han by po e size.
Wa e apou adso p ion s udies e ealed s ong co ela ions be ween unc ional
g oup chemis y and hyd ophilic beha iou . The THIO-ASP mul i a ia e sys em
demons a ed excep ional wa e up ake, ou pe o ming i s indi idual componen s,
con i ming he p esence o syne gis ic e ec s be ween amino and hiol unc ionali ies.
These esul s demons a e ha he ma e ials can in e ac e ec i ely wi h aqueous-
phase species.
Compe i i e mul i-me al sc eening expe imen s e ealed a clea pa e n o selec i i y,
wi h all ma e ials exhibi ing an excep ional a ini y o Hg(II), ollowed by Pb(II), Cu(II)
and Cd(II). Acco ding o Langmui modelling, he THIO-based amewo k pe o med
Chap e 3
134
be e o so me al ions, while he THIO-TRANS mul i a ia e sys em had a s ong
abili y o emo e a e ea h elemen s.
Iso he m analysis e ealed di e en adso p ion mechanisms. THIO and THIO/TRANS
ma e ials exhibi ed Langmui beha iou , which is indica i e o monolaye adso p ion
on homogeneous su aces. In con as , mul i a ia e sys ems exhibi ed F eundlich
cha ac e is ics, which sugges he e ogeneous, mul ilaye p ocesses. This di e si y o
mechanisms highligh s he unabili y ha can be achie ed h ough he s a egic
combina ion o linke s.
Building upon he p omising adso p ion esul s ob ained wi h he THIO ma e ial, he
nex s age o his hesis in ol es in eg a ing he ma e ial in o a biopolyme ic
memb ane. The aim is o de elop a s able, p ocessable pla o m ha can inco po a e
MOFs o p ac ical applica ions in hea y me al emo al. This app oach no only
add esses he limi a ions associa ed wi h powde ed MOFs, such as eco e y and
euse, bu also opens he doo o p oducing scalable, mul i unc ional ma e ials sui able
o eal-wo ld wa e emedia ion. A he same ime, he po en ial o he DMSA ma e ial
is also being explo ed. This is a s uc u ally simila linke ha con ains an addi ional
hiol g oup. Due o i s enhanced unc ionalisa ion, i is expec ed ha DMSA will exhibi
imp o ed adso p ion a ini y owa ds so hea y me al ions. Consequen ly, a PVDF-
HFP-based composi e memb ane inco po a ing he MOF has been de eloped and
e alua ed o i s me al up ake pe o mance.
In summa y, he esul s p esen ed in his chap e es ablish he basis o he design o
MOF-based ma e ials ailo ed o hea y me al adso p ion, se ing he s age o hei
in eg a ion in o unc ional memb ane sys ems explo ed in he ollowing chap e s.
PVDF-HFP@MOF Memb ane o Hea y Me al Cap u e
237
Figu e 5.33. High esolu ion XPS-spec a o a) Hg(II), b) Pb(II) and c) Cd(II) a e hei immobilisa ion
wi hin BCM-5.
The adso p ion esul s sugges ha he di usion o me al ions in o he in e nal egions
o BCM-5 is es ic ed by mass ans e limi a ions due o i s na ow po e dimensions.
Inco po a ing he MOF in o he memb ane imp o es bo h pa icle dispe sibili y and he
o e all adso p ion capaci y, compa ed o he p is ine MOF. Ne e heless, he
memb ane a chi ec u e can in oduce addi ional di usion ba ie s ha limi he
accessibili y o ce ain me al ions o immobilised BCM-5 pa icles. While hese kine ic
limi a ions may slow he adso p ion p ocess, he imp o ed dispe sibili y o BCM-5
wi hin he PVDF ma ix inc eases he equilib ium adso p ion capaci y.
5.4. Conclusions
This s udy p esen s he de elopmen and comp ehensi e s uc u al cha ac e isa ion
o a no el hiol- unc ionalized Z (IV)-based me al-o ganic amewo k, deno ed as
CdSCdO
c)
PbSPbO
α-HgSβ-HgS
α-HgO
a) b)

Chap e 5
238
BCM-5. The amewo k o his ma e ial has been buil employing comme cially
a ailable succime me al chela o as he o ganic linke . The unique combina ion o
po e a chi ec u e consis ing o hiol- ich and wa e /hyd oxyl-abundan egions c ea es
a main ca i y s uc u e con aining h ee dis inc hyd ophilic, hyd ophobic, and
amphiphilic adso p ion en i onmen s. These s uc u al ea u es can be linked wi h he
selec i i y ends o adso p ion obse ed o Hg(II), Cd(II), and Pb(II) hea y me al
species.
Inco po a ing BCM-5 in o po ous PVDF-HFP memb anes using a sal -leaching
me hodology signi ican ly imp o es he dispe sibili y o he MOF pa icles, esul ing in
an imp o emen in adso p ion capaci y pe o mance compa ed o p is ine MOF
ma e ial. Kine ic and equilib ium s udies e eal he he e ogeneous na u e o he
adso p ion p ocess, emphasising he impo ance o MOF loading concen a ion and
pa icle dis ibu ion o op imal unc ionali y. While he po ous s uc u e o he PVDF-
HFP memb ane p o ides s uc u al bene i s, i s inhe en hyd ophobic p ope ies limi
i s abili y o abso b hea y me als. These limi a ions a ise om he PVDF-HFP ma ix's
undamen al p ope ies and a e also in luenced by mo phological changes ha occu
du ing sol en -induced phase sepa a ion in he p esence o MOF pa icles.
Spec oscopic and c ys allog aphic analyses pe o med a e adso p ion e eal ha
he up ake o hea y me als is d i en by he o ma ion o s able me al–sulphu and
me al–oxygen coo dina ion bonds, in ol ing bo h hiol and hyd oxyl/wa e g oups.
These esul s show ha he p ocess is go e ned by a chemiso p ion mechanism.
O e all, hese indings demons a e ha in eg a ing hiol- unc ionalised MOFs in o
polyme ic memb anes ia sal -leaching yields a obus , scalable and e sa ile high-
pe o mance pla o m o selec i ely emo ing hea y me als om aqueous
en i onmen s. As well as ad ancing he undamen al unde s anding o MOF–polyme
composi es, his wo k p o ides a solid basis o de eloping nex -gene a ion adso ben
ma e ials ha exploi comme cially a ailable me al-chela ing agen s o use in
en i onmen al emedia ion. On he o he hand, he di usion ba ie imposed by he
PVDF-HFP ma ix in he memb anes would need o be mi iga ed o imp o e he
adso p ion kine ics in u u e sys ems.
PVDF-HFP@MOF Memb ane o Hea y Me al Cap u e
239
5.5. Re e ences
(1) Sha ma, R.; Ag awal, P. R.; Kuma , R.; Gup a, G.; I ish ee. Cu en Scena io o Hea y Me al
Con amina ion in Wa e . In Con amina ion o Wa e ; Else ie , 2021; pp 49–64.
h ps://doi.o g/10.1016/B978-0-12-824058-8.00010-4.
(2) Ag awal, P. R.; Singhal, S.; Sha ma, R. Hea y Me al Con amina ion in G oundwa e Sou ces. In
G oundwa e Geochemis y; Wiley, 2021; pp 57–78.
h ps://doi.o g/10.1002/9781119709732.ch4.
(3) Tchounwou, P. B.; Yedjou, C. G.; Pa lolla, A. K.; Su on, D. J. Hea y Me al Toxici y and he
En i onmen ; 2012; pp 133–164. h ps://doi.o g/10.1007/978-3-7643-8340-4_6.
(4) Khulbe, K. C.; Ma suu a, T. Remo al o Hea y Me als and Pollu an s by Memb ane Adso p ion
Techniques. Appl Wa e Sci 2018, 8 (1), 19. h ps://doi.o g/10.1007/s13201-018-0661-6.
(5) El-Sewi y, I. M.; Ma, S. Recen De elopmen o Me al–O ganic F amewo ks o Wa e
Pu i ica ion. Langmui 2024, 40 (10), 5060–5076. h ps://doi.o g/10.1021/acs.langmui .3c03818.
(6) Adminis a o , O. J. S. T. METAL-ORGANIC FRAMEWORKS APPLIED FOR WATER
PURIFICATION. Resou ce-E icien Technologies 2018, No. 1, 1–16.
h ps://doi.o g/10.18799/24056537/2018/1/177.
(7) J ad, A.; Damace , P.; Yaghi, Z.; Ahmad, M.; Hmadeh, M. Z -Based Me al–O ganic F amewo k
Nanoc ys als o Wa e Remedia ion. ACS Appl Nano Ma e 2022, 5 (8), 10795–10808.
h ps://doi.o g/10.1021/acsanm.2c02128.
(8) Diaman is, S. A.; Pou na a, A. D.; Kou sou oubi, E. D.; Moula as, C.; Deligiannakis, Y.; A ma as,
G. S.; Ha zidimi iou, A. G.; Manos, M. J.; Laza ides, T. De ec ion and So p ion o Hea y Me al
Ions in Aqueous Media by a Fluo escen Z (IV) Me al–O ganic F amewo k Func ionalized wi h
2-Picolylamine Recep o G oups. Ino g Chem 2022, 61 (20), 7847–7858.
h ps://doi.o g/10.1021/acs.ino gchem.2c00434.
(9) Zhou, Y.; Xiong, J.; Wang, L.; Li, F.; Bai, H.; Wang, S.; Yang, X. Mul i-Ligand S a egy o
Enhanced Remo al o Hea y Me al Ions by Thiol-Func ionalized De ec i e Z -MOFs. J Haza d
Ma e 2024, 479, 135723. h ps://doi.o g/10.1016/j.jhazma .2024.135723.
(10) Bjø klund, G.; C isponi, G.; Nu chi, V. M.; Cappai, R.; Buha Djo dje ic, A.; Aase h, J. A Re iew
on Coo dina ion P ope ies o Thiol-Con aining Chela ing Agen s Towa ds Me cu y, Cadmium,
and Lead. Molecules 2019, 24 (18), 3247. h ps://doi.o g/10.3390/molecules24183247.
(11) Wong, Y.-L.; Diao, Y.; He, J.; Zelle , M.; Xu, Z. A Thiol-Func ionalized UiO-67-Type Po ous Single
C ys al: Filling in he Syn he ic Gap. Ino g Chem 2019, 58 (2), 1462–1468.
h ps://doi.o g/10.1021/acs.ino gchem.8b03000.
(12) Fu ukawa, H.; Co do a, K. E.; O’Kee e, M.; Yaghi, O. M. The Chemis y and Applica ions o
Me al-O ganic F amewo ks. Science (1979) 2013, 341 (6149).
h ps://doi.o g/10.1126/science.1230444.
(13) Ding, L.; Luo, X.; Shao, P.; Yang, J.; Sun, D. Thiol-Func ionalized Z -Based Me al–O ganic
F amewo k o Cap u e o Hg(II) h ough a P o on Exchange Reac ion. ACS Sus ain Chem Eng
2018, 6 (7), 8494–8502. h ps://doi.o g/10.1021/acssuschemeng.8b00768.
(14) Wang, S.; Wahiduzzaman, M.; Da is, L.; Tisso , A.; Shepa d, W.; Ma o , J.; Ma ineau-Co cos,
C.; Hamdane, D.; Mau in, G.; De au ou -Vino , S.; Se e, C. A Robus Zi conium Amino Acid
Me al-O ganic F amewo k o P o on Conduc ion. Na Commun 2018, 9 (1), 4937.
h ps://doi.o g/10.1038/s41467-018-07414-4.
(15) Wang, S.; Wahiduzzaman, M.; Ma ineau‐Co cos, C.; Mau in, G.; Se e, C. A Mic opo ous
Zi conium Me al‐O ganic F amewo k Based on T ans ‐Aconi ic Acid o Selec i e Ca bon
Dioxide Adso p ion. Eu J Ino g Chem 2019, 2019 (22), 2674–2679.
h ps://doi.o g/10.1002/ejic.201801284.
Chap e 5
240
(16) Wang, X.; Xiao, C.; Liu, H.; Huang, Q.; Fu, H. Fab ica ion and P ope ies o PVDF and PVDF‐
HFP Mic o il a ion Memb anes. J Appl Polym Sci 2018, 135 (40).
h ps://doi.o g/10.1002/app.46711.
(17) Kang, G.; Cao, Y. Applica ion and Modi ica ion o Poly(Vinylidene Fluo ide) (PVDF) Memb anes
– A Re iew. J Memb Sci 2014, 463, 145–165. h ps://doi.o g/10.1016/j.memsci.2014.03.055.
(18) Ribei o, C.; Cos a, C. M.; Co eia, D. M.; Nunes-Pe ei a, J.; Oli ei a, J.; Ma ins, P.; Gonçal es,
R.; Ca doso, V. F.; Lance os-Méndez, S. Elec oac i e Poly(Vinylidene Fluo ide)-Based
S uc u es o Ad anced Applica ions. Na P o oc 2018, 13 (4), 681–704.
h ps://doi.o g/10.1038/np o .2017.157.
(19) Wang, Y.; Huang, K.; Zhang, P.; Li, H.; Mi, H. PVDF-HFP-Based Polyme Elec oly es wi h High
Li+ T ans e ence Numbe Enhancing he Cycling Pe o mance and Ra e Capabili y o Li hium
Me al Ba e ies. Appl Su Sci 2022, 574, 151593. h ps://doi.o g/10.1016/j.apsusc.2021.151593.
(20) Quei ós, J. M.; Salaza , H.; Val e de, A.; Bo elho, G.; Fe nández de Luis, R.; Teixei a, J.; Ma ins,
P. M.; Lance os-Mendez, S. Reusable Composi e Memb anes o Highly E icien Ch omium
Remo al om Real Wa e Ma ices. Chemosphe e 2022, 307, 135922.
h ps://doi.o g/10.1016/j.chemosphe e.2022.135922.
(21) Vidal-Ma in, E.; Calles Ga cía, M.; A ias, P. L.; Oya zabal, I.; Rogale , A.; Yu onkie, N. J.;
Agi ezabal-Telle ía, I.; Sáiz, J.; Pe enko, V.; Gil-Cal o, M.; Fe nández De Luis, R. Tuning he
Oxida i e Ac i i y o Coppe -Si es in Z (IV)-C4 Me al-O ganic F amewo ks. Ca al Today 2025,
460, 115484. h ps://doi.o g/10.1016/j.ca od.2025.115484.
(22) Millwa d, A. R.; Yaghi, O. M. Me al−O ganic F amewo ks wi h Excep ionally High Capaci y o
S o age o Ca bon Dioxide a Room Tempe a u e. J Am Chem Soc 2005, 127 (51), 17998–
17999. h ps://doi.o g/10.1021/ja0570032.
(23) Je ozal, R. T.; Kim, J.; Ma, C.; Pi , T. A.; Lee, J.-H.; Milne , P. J. Enhancing Selec i e
Hyd o luo oca bon G eenhouse Gas Cap u e ia Halogena ion o Me al–O ganic F amewo ks.
J Am Chem Soc 2025, 147 (8), 7127–7136. h ps://doi.o g/10.1021/jacs.5c00393.
(24) Wang, S.; Wahiduzzaman, M.; Ma ineau‐Co cos, C.; Mau in, G.; Se e, C. A Mic opo ous
Zi conium Me al‐O ganic F amewo k Based on T ans ‐Aconi ic Acid o Selec i e Ca bon
Dioxide Adso p ion. Eu J Ino g Chem 2019, 2019 (22), 2674–2679.
h ps://doi.o g/10.1002/ejic.201801284.
(25) L , D.; Chen, J.; Yang, K.; Wu, H.; Chen, Y.; Duan, C.; Wu, Y.; Xiao, J.; Xi, H.; Li, Z.; Xia, Q.
Ul ahigh CO2/CH4 and CO2/N2 Adso p ion Selec i i ies on a Cos -E ec i ely L-Aspa ic Acid
Based Me al-O ganic F amewo k. Chemical Enginee ing Jou nal 2019, 375, 122074.
h ps://doi.o g/10.1016/j.cej.2019.122074.
(26) Wang, S.; Xha e aj, N.; Wahiduzzaman, M.; Oyekan, K.; Li, X.; Wei, K.; Zheng, B.; Tisso , A.;
Ma o , J.; Shepa d, W.; Ma ineau-Co cos, C.; Filinchuk, Y.; Tan, K.; Mau in, G.; Se e, C.
Enginee ing S uc u al Dynamics o Zi conium Me al–O ganic F amewo ks Based on Na u al C4
Linke s. J Am Chem Soc 2019, 141 (43), 17207–17216. h ps://doi.o g/10.1021/jacs.9b07816.
(27) Xiang, Y.; Xue, L.; Shen, J.; Lin, H.; Liu, F. E ec o Sol en s on Mo phology and Polymo phism
o Poly inylidene Fluo ide Memb ane ia Supe c i ical CO 2 Induced Phase Sepa a ion. J Appl
Polym Sci 2014, 131 (22). h ps://doi.o g/10.1002/app.41065.
(28) Val e de, A.; de Fe nandez‐de Luis, R.; Salaza , H.; Gonçal es, B. F.; King, S.; Almásy, L.;
K iechbaum, M.; Laza, J. M.; Vilas‐Vilela, J. L.; Ma ins, P. M.; Lance os‐Mendez, S.; Po o, J.
M.; Pe enko, V. I. On The Mul iscale S uc u e and Mo phology o PVDF‐HFP@MOF
Memb anes in The Scope o Wa e Remedia ion Applica ions. Ad Ma e In e aces 2023, 10
(31). h ps://doi.o g/10.1002/admi.202300424.
(29) Kulak, H.; Thü , R.; Vankelecom, I. F. J. MOF/Polyme Mixed-Ma ix Memb anes P epa a ion:
E ec o Main Syn hesis Pa ame e s on CO2/CH4 Sepa a ion Pe o mance. Memb anes (Basel)
2022, 12 (4), 425. h ps://doi.o g/10.3390/memb anes12040425.
PVDF-HFP@MOF Memb ane o Hea y Me al Cap u e
241
(30) Hess, S. C.; G ass, R. N.; S a k, W. J. MOF Channels wi hin Po ous Polyme Film: Flexible,
Sel -Suppo ing ZIF-8 Poly(E he Sul one) Composi e Memb ane. Chemis y o Ma e ials 2016,
28 (21), 7638–7644. h ps://doi.o g/10.1021/acs.chemma e .6b02499.
(31) Val e de, A.; To a , G. I.; Rio-López, N. A.; To es, D.; Rosales, M.; Wu ke, S.; Fidalgo-Ma ijuan,
A.; Po o, J. M.; Jiménez-Ruiz, M.; Ga cía Sakai, V.; Ga cía, A.; Laza, J. M.; Vilas-Vilela, J. L.;
Lezama, L.; A io ua, M. I.; Copello, G. J.; Fe nández de Luis, R. Designing Me al-Chela o -like
T aps by Encoding Amino Acids in Zi conium-Based Me al–O ganic F amewo ks. Chemis y o
Ma e ials 2022, 34 (21), 9666–9684. h ps://doi.o g/10.1021/acs.chemma e .2c02431.
(32) P adhana, E. A.; Elma, M.; O hman, M. H. D.; Huda, N.; Ul-haq, M. D.; Rampun, E. L. A.; Rahma,
A. The Func ionaliza ion S udy o PVDF/TiO2 Hollow Fib e Memb anes Unde Vacuum
Calcina ion Exposu e. J Phys Con Se 2021, 1912 (1), 012035. h ps://doi.o g/10.1088/1742-
6596/1912/1/012035.
(33) G ego io, R. De e mina ion o he α, β, and γ C ys alline Phases o Poly(Vinylidene Fluo ide)
Films P epa ed a Di e en Condi ions. J Appl Polym Sci 2006, 100 (4), 3272–3279.
h ps://doi.o g/10.1002/app.23137.
(34) Ma ins, P.; Lopes, A. C.; Lance os-Mendez, S. Elec oac i e Phases o Poly(Vinylidene
Fluo ide): De e mina ion, P ocessing and Applica ions. P og Polym Sci 2014, 39 (4), 683–706.
h ps://doi.o g/10.1016/j.p ogpolymsci.2013.07.006.
(35) Ma ins, P.; Lopes, A. C.; Lance os-Mendez, S. Elec oac i e Phases o Poly(Vinylidene
Fluo ide): De e mina ion, P ocessing and Applica ions. P og Polym Sci 2014, 39 (4), 683–706.
h ps://doi.o g/10.1016/j.p ogpolymsci.2013.07.006.
(36) Ba bosa, J. C.; Gonçal es, R.; Val e de, A.; Ma ins, P. M.; Pe enko, V. I.; Má on, M.; Fidalgo-
Ma ijuan, A.; Fe nández de Luis, R.; Cos a, C. M.; Lance os-Méndez, S. Me al O ganic
F amewo k Modi ied Poly(Vinylidene Fluo ide-Co-Hexa luo op opylene) Sepa a o Memb anes
o Imp o e Li hium-Ion Ba e y Capaci y Fading. Chemical Enginee ing Jou nal 2022, 443,
136329. h ps://doi.o g/10.1016/j.cej.2022.136329.
(37) Val e de, A.; de Fe nandez‐de Luis, R.; Salaza , H.; Gonçal es, B. F.; King, S.; Almásy, L.;
K iechbaum, M.; Laza, J. M.; Vilas‐Vilela, J. L.; Ma ins, P. M.; Lance os‐Mendez, S.; Po o, J.
M.; Pe enko, V. I. On The Mul iscale S uc u e and Mo phology o PVDF‐HFP@MOF
Memb anes in The Scope o Wa e Remedia ion Applica ions. Ad Ma e In e aces 2023, 10
(31). h ps://doi.o g/10.1002/admi.202300424.
(38) Alhoshan, M.; Shukla, A. K.; Alam, J. P epa a ion o Zn–Me al O ganic F amewo k–Based
Poly(Vinylidene Fluo ide-Co-Hexa luo o-P opylene) Ul a il a ion Memb ane wi h Imp o ed
An i ouling P ope ies. Wa e Ai Soil Pollu 2023, 234 (7), 448. h ps://doi.o g/10.1007/s11270-
023-06455-w.
(39) Zeng, B.; Lin, G.; Li, J.; Wang, W.; Zhang, L. Thiodiace ic Acid-Func ionalized Z -MOFs as a
Robus Adso ben o E icien Remo al o Hg(II) and Pb(II) om Aqueous Solu ion. Mic opo ous
and Mesopo ous Ma e ials 2022, 345, 112251.
h ps://doi.o g/10.1016/j.mic omeso.2022.112251.
(40) Wang, J.; Guo, X. Adso p ion Kine ic Models: Physical Meanings, Applica ions, and Sol ing
Me hods. J Haza d Ma e 2020, 390, 122156. h ps://doi.o g/10.1016/j.jhazma .2020.122156.
(41) Yee, K.-K.; Reime , N.; Liu, J.; Cheng, S.-Y.; Yiu, S.-M.; Webe , J.; S ock, N.; Xu, Z. E ec i e
Me cu y So p ion by Thiol-Laced Me al–O ganic F amewo ks: In S ong Acid and he Vapou
Phase. J Am Chem Soc 2013, 135 (21), 7795–7798. h ps://doi.o g/10.1021/ja400212k.
(42) Li, M.-Q.; Wong, Y.-L.; Lum, T.-S.; Sze-Yin Leung, K.; Lam, P. K. S.; Xu, Z. Dense Thiol A ays
o Me al–O ganic F amewo ks: Boiling Wa e S abili y, Hg Remo al beyond 2 Ppb and Facile
C osslinking. J Ma e Chem A Ma e 2018, 6 (30), 14566–14570.
h ps://doi.o g/10.1039/C8TA04020F.
(43) Powell, K. J.; B own, P. L.; By ne, R. H.; Gajda, T.; He e , G.; Sjöbe g, S.; Wanne , H. Chemical
Specia ion o Hg(II) wi h En i onmen al Ino ganic Ligands. Aus J Chem 2004, 57 (10), 993.
h ps://doi.o g/10.1071/CH04063.
Chap e 5
242
(44) Li, J.; Li, X.; Alsaedi, A.; Haya , T.; Chen, C. Syn hesis o Highly Po ous Ino ganic Adso ben s
De i ed om Me al-O ganic F amewo ks and Thei Applica ion in E icien Elimina ion o
Me cu y(II). J Colloid In e ace Sci 2018, 517, 61–71. h ps://doi.o g/10.1016/j.jcis.2018.01.112.
(45) Rosales, M.; O i e, J.; Espinoza-González, R.; Fe nández de Luis, R.; Gau in, R.; B odusch,
N.; Rod íguez, B.; G acia, F.; Ga cía, A. E alua ing he Bi-Func ional Capaci y o A senic Pho o-
Oxida ion and Adso p ion on Ana ase TiO2 Nanos uc u es wi h Tunable Mo phology. Chemical
Enginee ing Jou nal 2021, 415, 128906. h ps://doi.o g/10.1016/j.cej.2021.128906.
(46) G‐Saiz, P.; Gonzalez Na a e e, B.; Du a, S.; Vidal Ma ín, E.; Reizabal, A.; Oya zabal,
I.; Wu ke, S.; Lance os‐Méndez, S.; Rosales, M.; Ga cía, A.; Fe nández de Luis, R.
Me al‐O ganic F amewo ks o Dual Pho o‐Oxida ion and Cap u e o A senic om Wa e .
ChemSusChem 2024, 17 (24). h ps://doi.o g/10.1002/cssc.202400592.

In oduc ion
243
Chap e 6
Conclusions and Fu u e T ends
245
Chap e 6
Conclusions and Fu u e T ends
2.1. Conclusions
This doc o al hesis has explo ed he use o zi conium-based me al–o ganic
amewo ks and hei inco po a ion in o memb ane sys ems o he adso p ion o
hea y me als o wa e emedia ion. Th ough a well-s uc u ed app oach inco po a ing
con olled MOF syn hesis and in eg a ing hese amewo ks in o memb anes, he
s udy demons a es he high e iciency and p ac ical applicabili y o he ma e ials. In
ligh o he esea ch indings, he ollowing key conclusions can be d awn:
Fi s ly, a obus p o ocol o he con olled syn hesis o Z -based MOFs unde aqueous
c ys allisa ion condi ions has been es ablished. The de elopmen o c ys allisa ion
s abili y maps ep esen s a signi ican me hodological con ibu ion, p o iding a p ecise
oadmap o ob aining speci ic opologies (“ cu”, “hcp”, and “ cu– eo”) h ough he
sys ema ic con ol o Z Cl4 and o mic acid modula o concen a ions. This app oach
allowed he success ul syn hesis o ou di e en amewo ks: MIP-202, MIP-205,
BCM-1, and he no el BCM-5. The analysis o mul i a ia e sys ems has e ealed
complex bu p edic able s uc u e-composi ion ela ionships. In pa icula , i was
demons a ed ha he inco po a ion o ASP linke s p omo es amewo k
amo phisa ion, whe eas THIO–TRANS combina ions acili a e he o ma ion o eo-
ype s uc u es. These indings es ablish clea guidelines o he a ge ed enginee ing
o MOFs wi h ailo ed p ope ies.
Ex ensi e cha ac e isa ion o he syn hesised ma e ials con i med he success ul
inco po a ion o unc ionalised linke s, e ealing signi ican de ec densi ies ha , i was
ound, inc eased adso p ion pe o mance. The BET su ace a eas ob ained, al hough
lowe han heo e ical p edic ions due o he mal ac i a ion limi a ions, we e su icien
o e ec i e adso p ion applica ions. A key conclusion d awn om his wo k is ha
246
adso p ion pe o mance is p edominan ly in luenced by he na u e o speci ic chemical
in e ac ions be ween unc ional g oups, a he han by he accessible su ace a ea.
This is exempli ied by he THIO-based ma e ials, which, despi e hei lowe BET
su ace a eas, exhibi supe io adso p ion capaci ies compa ed o hei TRANS
coun e pa s. Ze a po en ial measu emen s e ealed consis en ly nega i e su ace
cha ges (pH 3–9), c ea ing a ou able elec os a ic en i onmen s o he coo dina ion
o ca ionic me als.
Mul i-me al sc eening expe imen s es ablished a clea selec i i y pa e n: Hg(II) >
Pb(II) > Cu(II) > Cd(II), wi h THIO-based amewo ks exhibi ing excep ional a ini y
owa ds so me al ions. Iso he m analyses e ealed he coexis ence o di e en
adso p ion mechanisms: Langmui - ype (monolaye adso p ion) beha iou o pu e
THIO amewo ks, and F eundlich- ype (he e ogeneous, mul ilaye p ocesses) o
mul i a ia e sys ems. The demons a ed abili y o he THIO–TRANS sys em o emo e
a e ea h elemen s ex ends he applicabili y o hese ma e ials beyond adi ional
hea y me al emedia ion, highligh ing hei po en ial o c i ical me al eco e y.
The de elopmen o wo di e en memb ane pla o ms (SPICHI@BCM-1 and PVDF-
HFP@BCM-5) demons a ed he possibili y o inco po a ing MOFs in o polyme ic
ma ices while e aining hei adso p ion unc ionali y. The SPICHI@BCM-1 sys em
exhibi ed no ewo hy adso p ion capaci ies o Hg(II), Pb(II) and Cd(II), a ising om
in e acial in e ac ions be ween he MOF and SPICHI componen s ( hiol, amide, and
ca boxyl g oups). These in e ac ions enable he e icien simul aneous emo al o
mul iple hea y me als om eal su ace and g oundwa e samples, along wi h he
ad an ages o egene a ion and unable selec i i y. The sal -leaching app oach
applied o PVDF-HFP@BCM-5 memb anes esul ed in be e adso p ion pe o mance
compa ed o he p is ine MOF, he eby highligh ing he c i ical ole o con olled MOF
pa icle dispe sion wi hin he polyme ma ix. In addi ion, pos -adso p ion
spec oscopic and c ys allog aphic analyses con i med ha hea y me al up ake akes
place ia chemiso p ion, in ol ing he o ma ion o s able me al–sulphu and me al–
oxygen coo dina ion bonds.
Taken oge he , he esea ch o his hesis demons a es ha Z -based chela ing MOFs
ep esen a po en ial solu ion o add essing he c i ical challenge o hea y me al
con amina ion in wa e esou ces. The combina ion o con olled syn hesis,
Cu iculum Vi ae and Con ibu ions
253
elemen s” M. Calles, L. Celaya. R. Fe nández de Luis. Eu opean Open Day,
May-2023, B ussels, Belgium.
•3 d In e na ion School on Po ous Ma e ials. Como, I aly – Online (19 h - 23 d o
June, 2023). 30 hou s
•Dissemina ion Webina : Raw Ma e ials o sus ainable de elopmen and he
ci cula economy. Huel a, Spain - Online (12 h o July, 2023).
•Wo kshop: Ma e ials o En i onmen and Beyond (INDESMOF-RISE-MSCA
p ojec ). B aga, Po ugal – Online (19 h Decembe , 2023).
•ISIS Neu on and Muon Sou ce wo kshop: Oppo uni ies o build collabo a ions
and impac ul science. Leioa, Spain (7 h – 8 h o Feb ua y, 2024) – Pos e
con ibu ion.
•Ca ac e ización Químico-Física de la Supe icie de Adso ben es y
Ca alizado es II. Ja andilla de la Ve a, Spain (11 h – 14 h o June, 2024). 15
hou s.
•Fo nigh ly Semina : De elopmen o New Me al-Chela o MOFs o me als-
immobiliza ion. Leioa, Spain (10 h o July, 2024) – O al p esen a ion.
A.5. Resea ch s ays
•Resea ch s ay a Ins i u o de Química y Me abolismo del Fá maco (IQUIMEFA-
CONICET), Facul ad de Fa macia y Bioquímica, Uni e sidad de Buenos Ai es,
A gen ina (1s o Sep embe – 1s o Decembe , 2023).
•Resea ch s ay a Wise4Au oma ion company (W4A), B aga, Po ugal (22nd o
Feb ua y – 27 h o May, 2024).

Annex
254