Hyb id biopolyme /me al–o ganic amewo k 3D-sponges owa ds he
cap u e o he ‘big i e’ hea y me als
Ma ía Calles Ga cía
a
, Hugo Salaza
a
, Syl ia B i o
b
, Oleksand Tomchuk
b
,
Ped o M. Ma ins
c,d
, A una a P adhan
c,d
, Fe nanda C´
assio
c,d
,
Senen xu Lance os Mendez
a,e
, Ko o de la Caba
a,
, Ped o Gue e o
a, ,g,*
,
Vik o Pe enko
a,e,*
, Robe o Fe n´
andez de Luis
a,*
a
BCMa e ials, Basque Cen e o Ma e ials, Applica ions and Nanos uc u es, UPV/EHU Science Pa k, 48940, Leioa, Spain
b
ISIS Neu on and Muon Sou ce, Science and Technology Facili ies Council, Ru he o d Apple on Labo a o y, Didco , OX11 0QX, Uni ed Kingdom
c
Cen e o Molecula and En i onmen al Biology, Uni e si y o Minho, 4710-057, B aga, Po ugal
d
IB-S – Ins i u e o Resea ch and Inno a ion on Bio-Sus ainabili y, Uni e si y o Minho, 4710-057, B aga, Po ugal
e
IKERBASQUE, Basque Founda ion o Science, 48009, Bilbao, Spain
BIOMAT Resea ch G oup, Uni e si y o he Basque Coun y (UPV/EHU), Escuela de Ingenie ía de Gipuzkoa, Plaza de Eu opa 1, 20018 Donos ia-San Sebas i´
an, Spain
g
P o einma Ma e ials SL, A enida de Tolosa 72, 20018, Donos ia-San Sebas i´
an, Spain
ARTICLE INFO
Keywo ds:
Adso p ion
Biopolyme s
Fil e s
Hea y me als
Me al-o ganic amewo ks
ABSTRACT
Access o clean wa e in isola ed egions emains a majo challenge, pa icula ly due o con amina ion by he i e
mos p e alen hea y me als: Hg(II), Pb(II), Cd(II), As(III/V), and C (VI). T adi ional so ben s a e limi ed in hei
abili y o cap u e all he “big i e” hea y me als, since hey occu as ca ionic, neu al, o anionic species unde
s anda d condi ions. To add ess his challenge, we ha e in eg a ed a hiol ich Z (IV)- Me al-O ganic F amewo k
(MOF), namely BCM-1, in o a soy p o ein (SPI) and chi in (CHI) sponge in o de o enginee a 3D-hyb id wa e
il e . The componen s and he composi e sys ems we e ho oughly cha ac e ised by con en ional means.
Addi ionally, neu on imaging was used o e eal he 3D-in e connec ed mic o- o mac opo ous s uc u e o he
il e s, while Small-Angle X- ay Sca e ing (SAXS) con i med he p esence o BCM-1 as monodispe se nano-
pa icles. The 3D-sponge combines mechanical s abili y, high pe meabili y, and b oad chemical a ini y, allowing
he e icien emo al o all i e hea y me als h ough simple adjus men s o i s ac i a ion condi ions. Adso p ion
expe imen s demons a ed o e 90 % emo al o mos a ge me als depending i he hyb id-sponge is employed
as syn hesised, o a e ac i a ing a pH =1. When es ed wi h 1 ppm solu ions, hey exhibi adso p ion e i-
ciencies o Hg(II), Pb(II), Cd(II), As(V), and C (VI) o 60.8/100 %, 94.4/74.8 %, 15.7/69.1 %, 100/38.2 %, 5.7/
100 %, and 13.5/97.4 %, be o e and a e he ac i a ion o he 3D-sponge, espec i ely. The me ics a e
consis en ly main ained o e h ee adso p ion/deso p ion cycles in su ace wa e samples. On he whole, his
wo k p o ides a scalable and sus ainable app oach o combine biopolyme s and MOFs o eal-wo ld wa e
emedia ion applica ions and highligh s he key ole o hei p o ona ion s a e on hei abso p i e p ope ies.
1. In oduc ion
Hea y me al pollu ion emains a eal h ea o he local en i onmen
and popula ions on hese isola ed a eas ha lack wa e ea men plan s.
He e, he de elopmen o po able adso p ion sys ems eme ges as one o
he mos p omising echnologies o access po able/d inking wa e . The
a ional design o an adso ben is in insically go e ned by he physi-
cochemical p ope ies o he a ge me al species o be emo ed om he
en i onmen . In en i onmen al science, he e m “hea y me al” is
commonly associa ed wi h he acu e oxici y o hese ions. In ligh o
* Co esponding au ho s a : BCMa e ials, Basque Cen e o Ma e ials, Applica ions and Nanos uc u es, UPV/EHU Science Pa k, 48940, Leioa, Spain
E-mail add esses: [email p o ec ed] (M. Calles Ga cía), [email p o ec ed] (H. Salaza ), [email p o ec ed] (S. B i o), oleksand .
[email p o ec ed] (O. Tomchuk), [email p o ec ed] (P.M. Ma ins), [email p o ec ed] (A. P adhan), [email p o ec ed] (F. C´
assio),
[email p o ec ed] (S. Lance os Mendez), [email p o ec ed] (K. de la Caba), [email p o ec ed] (P. Gue e o), ik o .
[email p o ec ed] (V. Pe enko), [email p o ec ed] (R. Fe n´
andez de Luis).
Con en s lis s a ailable a ScienceDi ec
Chemical Enginee ing Jou nal
jou nal homepage: www.else ie .com/loca e/cej
h ps://doi.o g/10.1016/j.cej.2025.169442
Recei ed 3 July 2025; Recei ed in e ised o m 25 Sep embe 2025; Accep ed 8 Oc obe 2025
Chemical Enginee ing Jou nal 524 (2025) 169442
A ailable online 13 Oc obe 2025
1385-8947/© 2025 The Au ho s. Published by Else ie B.V. This is an open access a icle unde he CC BY-NC license (
h p://c ea i ecommons.o g/licenses/by-
nc/4.0/ ).
his, he ‘big i e’ membe s o his amily—ch omium, a senic, cad-
mium, me cu y, and lead—a e eadily iden i iable due o hei impac in
human heal h and en i onmen al ha m. In ac , he e a e se e al sce-
na ios whe e some o he “big i e” hea y me als a e concu en ly
p esen in pollu ed wa e s, as in he case wi h indus ial e luen s, acid
mine d ainages o ex ile and anne y was ewa e . F om a echnological
s andpoin , designing an adso p ion sys em able o concu en ly cap u e
he ‘big i e’ hea y me als is a challenge owing o he di e se specia ion
ha he “big i e” membe s show in wa e media. [1]. In he usual pH/
eH condi ions ound in pollu ed wa e s (i.e. pH 4–9 and eH –200 o
+600 mV) [2], Pb(II) and Cd(II) a e usually s abilized as isola ed ca -
ions, Hg(II) and As(III) end o o m non-cha ged HgCl
2
and As(OH)
3
species, and As(V) and C (VI) a e complexed as H
2
AsO
4
−
/HAsO
4
2−
and
HC O
4
−
/C
2
O
7
−2
oxyanions, espec i ely. All in all, he concu en cap-
u e o he “big i e” equi es he de elopmen o a mul i ace ed so ben
able o ap ca ionic, neu al, and anionic species h ough a combina ion
o adso p ion mechanisms.
In his con ex , MOFs ha e eme ged as highly p omising mic opo-
ous so ben s, exhibi ing excep ional capaci ies and kine ics o he
seques a ion o hea y me als [3]. Z -MOFs s and ou among he MOF
- amily because o hei hyd oly ic and chemical s abili y, a he same
ime ha show an ou s anding amewo k unabili y. These ea u es
oge he enable he selec i e cap u e o anionic species a de ec si es
wi hin he s uc u e, while ca ionic o neu al species may be e ec i ely
abso bed h ough chemiso p ion o elec os a ic in e ac ions a he
unc ional g oups ins alled a he linke si es [4]. Howe e , despi e hei
chemical e sa ili y, no single Z -MOF has ye demons a ed he ca-
paci y o cap u e o all he ‘big i e’ membe s. Mo eo e , he inhe en
powde ed na u e o MOFs con inues o pose a signi ican ba ie o hei
applica ion in p ac ical wa e ea men [5]. When MOF powde s a e
employed in a bed-con igu a ion, hey usually need o be pelle ized o
shaped o p e en a backp essu e inc ease du ing he wa e pe mea ion.
A he same ime, shaping MOFs is usually linked o a pa ial dec ease o
hei su ace a ea, which is in u n associa ed o c ys allini y-loss o
su ace inac i a ion a ising om he p ocessing condi ions (i.e. p es-
su iza ion, empe a u e, sol en s…). [6]
The inclusion o MOFs in o classic polyme ma ices (i.e. PVDF o i s
chemical esis ance [7], Polyu e hanes o lexibili y [8], polysul one
(PSU) and polye he sul one (PES) o he mal s abili y [9], and poly-
amide (PA) o selec i e pe meabili y [10]) is one o he po en ial
s a egies explo ed o o e come his limi a ion. Mos usually, syn he ic
polyme s p o ide mechanical suppo o MOF pa icles adding negli-
gible o seconda y abso p ion unc ions o he composi e sys em. By
using con en ional polyme p ocessing echniques—such as molding,
cas ing, o elec ospinning, a wide ange o composi es has been
assembled and applied o wa e emedia ion, including hea y me als
adso p ion. Howe e , he design o MOF/polyme composi es s ill aces
limi a ions ha es ic hei p ac ical applica ion, including s uc u al
he e ogenei ies om non-uni o m MOF dis ibu ion wi hin he poly-
me —such as pa ial encapsula ion [11]—and limi ed pe meabili y o
hei applica ion in con inuous- low sys ems.
This is p ecisely whe e he in eg a ion o MOFs in o biopolyme ic
composi es comes in o play. Biopolyme s usually a e easie and g eene
o p ocess han syn he ic polyme s. In addi ion, depending on hei
su ace chemis y, hey show an ac i e ole o chela e me al ions. Thei
easy p ocessing has pa ed he way o he design o h ee-dimensional
composi es ea u ing in e connec ed mic o- o mac opo ous s uc u es
as ae ogels, monoli hs, and 3D-p in ed s uc u es. In addi ion o exhibi
mechanical obus ness, MOF/biopolyme composi es posses a he same
ime syne gic abso p ion unc ions a ising om he combina ion o
biopolyme and MOF componen s (Scheme 1). [7,12] While p e ious
s udies ha e epo ed he in eg a ion o MOFs wi h na u al biopolyme s
o hea y me al adso p ion, such as chi osan–Z -MOF c yogels o dual-
unc ionalised polyme /MOF sponges o a ge ed ion emo al, [8,9]
hese o en ocus on a limi ed numbe o me al species and lack s udied
on hei simul aneous cap u e. No able examples o success ul com-
posi es include chi osan and i on me al-o ganic amewo k sponges,
which demons a ed excep ional adso p ion capaci ies o 2857–2326
mg/g o o ganic pollu an s, o 3D p in ed po ous chi osan/UIO-66 il-
e s based on ca boxyl acids unc ionalized algina e and chi osan, which
ha e shown ou s anding hea y me al emo al capabili ies. [13] Ano he
p omising sys em in ol es Fe/MOF-5@chi osan composi e ilms syn-
hesised by doping 5 w % o Fe/MOF-5 in o chi osan ilms, which
combine he mechanical p ope ies o he biopolyme ma ix wi h he
high su ace a ea and selec i i y o he MOF componen . [14] In con as
o syn he ic polyme s, he chemical e sa ili y and g een p ocessabili y
o MOF/biopolyme composi es a e coun e balanced by a pa ial limi-
a ion in hei chemical s abili y window, which es ic s he ange o
condi ions unde which hese composi es can be applied. Ne e heless,
hey emain highly sui able o he ypical en i onmen s o su ace and
g oundwa e sou ces con amina ed wi h hea y me als.
In his s udy, we ha e le e aged he ich chemical unc ionali y o
soy p o ein isola e (SPI) and chi in (CHI) biopolyme s o cons uc a
me al-chela o MOF- unc ionalised polyme ic 3D-sponge capable o
simul aneously cap u ing all he ‘big i e’ hea y me als [15]. This pe -
o mance is a ibu ed o he p esence o amino, hyd oxyl, and ca bonyl
unc ional g oups inhe en o he SPI and CHI ma ices, in conjunc ion
wi h he de ec i e and hiol- ich a chi ec u e o he zi conium me cap-
osuccina e MOF—he ea e e e ed o as BCM-1 [16]. The hiol and
amino ich s uc u es o he BCM-1 and SPICHI componen s assu es he
e icien cap u e o so o in e media e ca ionic and neu al hea y me al
species; whils he linke -de ec i e posi ions in BCM-1 endows he il e
wi h he capaci y o cap u e oxyanions a e i s ac i a ion unde acidic
condi ions. Mul iple cha ac e isa ion echniques ha e been employed o
ully unde s and he a omic o mac o-me ic scale s uc u e o ou sys-
em, including X- ay di ac ion (XRD), small-angle X- ay sca e ing and
Scheme 1. S a egy employed in his esea ch.
M. Calles Ga cía e al.
Chemical Enginee ing Jou nal 524 (2025) 169442
2
neu on imaging. Thus, ou esea ch has unco e ed he bene icial and
de imen al adso p ion e ec s a ising om he combina ion o hese
h ee componen s in a highly pe meable sponge echnology, iden i ying
he po en ial ou es o ully unblock i s po en ial o i s applica ion as
hea y me al so ben s in eal scena ios.
2. Ma e ials and me hods
2.1. BCM-1 syn hesis
BCM-1 was p epa ed by scaling up en old he hyd o he mal syn-
hesis epo ed in he p e ious s udy o ou esea ch eam [17]. To his
end, zi conium chlo ide (2.33 g, 10 mmol) was dissol ed in 10 mL o
dis illed wa e unde magne ic s i ing in a 50 mL Py ex ® eac o . A -
e wa ds, 570
μ
L o o mic acid (FA) was added unde con inuous s i -
ing a oom empe a u e. Las ly, hiomalic acid was added o he me al
solu ion while s i ing igo ously un il a clea solu ion was ob ained.
The eac o was sealed and placed in a p ehea ed o en a 120 ◦C o 24 h.
A e he c ys allisa ion o BCM-1 was comple ed, he eac o was
allowed o cool down o oom empe a u e and he MOF powde was
eco e ed by cen i uga ion (He ich EBA21, 6500 pm, 20 min) and
washed wi h wa e (50 mL, h ee imes) o e nigh . Finally, he sample
was d ied a 80 ◦C o 12 h. Ano he h ee samples, wo o BCM-1 cubic
a ian , and one o he BCM-2 hexagonal a ian , we e syn hesised by
a ying he addi ion o FA in o he eac ion media o modula e he
pa icle size and he inal s uc u e o he zi conium me cap osuccina e
MOFs. [18,19] The wo BCM-1 samples we e exclusi ely employed o
assess hei eco oxici y in case o leaching du ing adso p ion. BCM-2
sample was employed o elucida e whe he he c ys al s uc u e o he
MOF a ec s i s eco- oxici y.
2.2. P epa a ion o SPICHI@BCM-1 composi e 3D-sponges
I is impo an o no e ha he con en o BCM-1 in he memb anes
was a ied by con olling i s addi ion in he composi e il e s’ o mu-
la ion. Fo he p epa a ion o SPICHI@BCM-1 il e wi h a 6 w % o
BCM-1 (he ea e deno ed as SPICHI@BCM-1(6 %)), i s ly, 5 g o SPI,
0.5 g o BCM-1 (6 w %) and 1.5 g o CHI (30 w % based on he SPI
d y basis) we e mixed in 125 mL o dis illed wa e and s i ed o 30 min.
Then 30 w % glyce ol (based on he SPI d y basis) was added o he
solu ion. The pH was adjus ed o a alue o 7 wi h a NaOH (1 M) solu ion
o la e hea i a 80 ◦C o 30 min unde magne ic s i ing. Finally, he
blend was pou ed in o moulds, kep in a eeze a −22 ◦C o 48 h, and
eeze-d ied o 72 h o ob ain he composi e il e s. The same p o ocol
was ollowed o he p epa a ion o SPICHI@BCM-1(20 %), bu 2 g BCM-
1 we e added du ing he o mula ion o he blend.
2.3. S uc u al, ex u al and unc ional cha ac e isa ion
The expe imen al de ails o he physic-chemical cha ac e isa ion
p o ocols (i.e. XRD, Scanning Elec on Mic oscopy (SEM), Fou ie
T ans o m In a ed Spec oscopy (FTIR), The mog a ime ic Analysis
(TGA), Di e en ial Scanning Calo ime y (DSC)) employed o he
cha ac e isa ion o BCM-1, SPICHI, and SPICHI@BCM-1 a e de ailed in
he Suppo ing In o ma ion. Below, we desc ibe he expe imen al con-
di ions o SAXS, neu on imaging and eco oxici y expe imen s. Finally,
we ou line he p o ocols o e alua ing he me al adso p ion o he
mic opo ous BCM-1, he SPICHI biopolyme , and he SPICHI@BCM-1
composi e il e s.
2.3.1. Small-angle X- ay sca e ing
SAXS measu emen s we e conduc ed on I22 beamline a Diamond
Ligh Sou ce (Didco , U.K.) [20]. 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 =4
π
/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 [21,22]. All
sca e ing cu es we e i ed acco ding o unc ions p o ided by SasView
6.0.1, including Indi ec Fou ie T ans o ma ion analysis ou ine.
2.3.2. Neu on imaging
Neu on omog aphy measu emen s 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 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
o
, 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 105 mm lens and an 80
μ
m hick ZnS/6LiF
scin illa o p o iding a pixel size o 48
μ
m. An exposu e ime o 60 s 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 Imaging [18] so wa e
package. [23] Po osi y analysis was pe o med using Po espy. [24] Fo
he po osi y p o ile analysis, a 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 calcula ion o pe cen age po osi y.
2.3.3. Assessmen o hea y me als adso p ion kine ics and capaci y
The pH alues o he s ock hea y me als solu ions, ha ing a con-
cen a ion o 100 ppm, we e measu ed and ound o be wi hin he ange
o 5.5 o 6.6 (As(III) =6.6, As(V) =5.9, C (VI) =4.8, Hg(II) =6.4, Cd
(II) =6.1, Pb(II) =5.5). The pH was app oxima ely main ained wi hin
he same alue ange when he solu ions we e dilu ed o pe o m he
adso p ion expe imen s desc ibed in he ollowing. The me al specia ion
dependence on he pH, eV and me al concen a ion was calcula ed wi h
Hyd a-Medusa so wa e.
2.3.3.1. P elimina y adso p ion. Expe imen s we e conduc ed a oom
empe a u e wi h an adso ben dosage o 1 mg mL
−1
. Fo a con en ional
ba ch expe imen , a ound 10 mg o he MOF, SPICHI o SPICHI@MOF
we e imme sed in 10 mL o me al solu ion. A e a gi en ime (4 h), he
suspension was cen i uged, he supe na an was collec ed and hen
il e ed using a hyd ophilic 0.22
μ
m il e . The me al concen a ion in
he p e- and pos -adso p ion condi ions was analysed by Induc i ely
Coupled Plasma A omic Emission Spec oscopy (ICP −AES).
2.3.3.2. Adso p ion iso he ms. 10 mg o BCM-1, SPICHI, o
SPICHI@BCM-1(6 and 20 %) we e imme sed in 10 mL o hea y me al
solu ions (i.e. NaAsO
2
, H
3
AsO
4
, K
2
C
2
O
7
, HgCl
2
, Cd(NO
3
)
2
⋅4H
2
O and Pb
(NO
3
)
2
) wi h concen a ions anging om 0.5 o 2000 ppm. The iso-
he ms we e i ed o Langmui and F eundlich models.
2.3.3.3. Kine ic expe imen s. 50 mg o BCM-1, SPICHI, o SPICHI@MOF
we e added o 50 mL o he hea y me al solu ions a a concen a ion o
10 ppm. The solu ions we e s i ed o 4 h o ensu e ha he adso p ion
equilib ium was eached. Aliquo s o he samples we e aken a di e en
imes o he expe imen s o ollow up on he hea y me al concen a ion
decay du ing adso p ion. The kine ic cu es we e i ed acco ding o
pseudo- i s , pseudo-second o de , and in apa icle di usion non-linea
o ms desc ibed in Eqs. (1), (2), and (3), espec i ely [25]:
Q =Qe(1−e(− K1 ))(1)
Q =Q2
cK2
1+QcK2 (2)
Q =kid
1
/
2
+C(3)
M. Calles Ga cía e al.
Chemical Enginee ing Jou nal 524 (2025) 169442
3
whe e Q
e
and Q
(mg/g) a e he adso p ion capaci ies o hea y me als a
equilib ium and a a speci ic ime, espec i ely. K
1
(min
−1
) is he
pseudo- i s o de adso p ion a e cons an , K
2
(g/mg min)) is he
pseudo-second o de adso p ion a e cons an , K
id
is he in apa icle
di usion a e cons an (mg/g min
-1/2
), is he ime (min), and C is a
pa ame e ela ed o he bounda y laye e ec .
The adso p ion capaci y (q
e
) o BCM-1, SPICHI, and SPICHI@BCM-1
was de e mined based on he Eq. (4):
qe=(Co−Ceq)×VT
(m)TOTAL
≡mg
g(4)
whe e V
T
deno es he olume o he solu ion exp essed in millili es
(mL), m indica es he mass o he adso ben in g ams (g), and C
0
and C
e
ep esen he ini ial and equilib ium concen a ions o he me als wi hin
he solu ion, espec i ely.
2.3.3.4. Reusabili y. The adso p ion and deso p ion e iciency o SPI-
CHI@BCM-1(20 %) was s udied o e 3 cycles. A solu ion o all he i e
hea y me als – ha ing a concen a ion o 1 ppm o each o he indi idual
ions - was p epa ed (pH =6.0). Fo he deso p ion and egene a ion,
SPICHI@BCM-1(20 %) was imme sed in o a 0.1 M HCl solu ion and
s i ed o 2 h. A e wa ds, an aliquo was wi hd awn o quan i y he
concen a ion o he hea y me als in he elu ion solu ion; and in u n, o
calcula e he e iciency o he deso p ion. SPICHI@BCM-1(20 %) was
hen imme sed in o ul apu e wa e and s i ed o ano he 2 h. A e
his washing s ep, employed o neu alize he pH o he memb ane, he
il e was employed in a new abso p ion cycle.
Fig. 1. Illus a ion o he c ys al s uc u es o (a) BCM-1, (b) chi in and (c) soy p o ein; (d) XRD pa e ns o BCM-1 (1), SPICHI (2), SPICHI@BCM-1(6 %) (3) and
SPICHI@BCM-1(20 %) (4); (e) p o ile i ing o SPICHI@BCM-1(6 %); ( ) TGA o BCM-1 (1), SPICHI (2), SPICHI@BCM-1(6 %) (3) and SPICHI@BCM-1(20 %) (4); and
(g-h) Acu e le hal e ec s (mo ali y in % o unexposed con ol) o h ee MOFs o di e en size and/o s uc u e, designa ed as BCM-2 (hexagonal), BCM-1 m (cubic
mic ome ic) and BCM-1n (cubic nanome ic) on (g) eshwa e ju enile o i e B achionus calyci lo us (24 h exposu e), (h) eshwa e mac oin e eb a e sh edde s
Allogamus sp. (96 h exposu e) and (i) Limnephilus sp. (96 h exposu e). Mean ±SEM, n =3.
M. Calles Ga cía e al.
Chemical Enginee ing Jou nal 524 (2025) 169442
4
3. Resul s and discussion
3.1. Cha ac e isa ion o MOF and SPI/CHI@MOF composi e 3D-sponges
3.1.1. Mul iscale cha ac e isa ion o composi e 3D-sponges
BCM-1, SPICHI, and SPICHI@BCM-1 we e i s cha ac e ised by XRD
a e hei syn hesis, washing and ac i a ion a 80 ◦C a a mosphe ic
p essu e. No ably, he syn hesis condi ions o BCM-1 we e scaled up
en old compa ed o ou p e ious s udy, yielding nea ly 1 g o ma e ial
pe ba ch using jus 10 mL o wa e as a sol en .
The XRD pa e n o BCM-1 ma ched he simula ed da a calcula ed
om he cubic s uc u al model wi h a F23 symme y. [18] The ull-
p o ile ma ching analysis con i ms ha he c ys allog aphic cell and
space g oup symme y o he scaled-up BCM-1 closely align wi h hose
epo ed in ou p e ious s udy wi h only a mino di e ence (Fig. S1). As
illus a ed in Fig. 1a, he c ys al s uc u e o BCM-1 consis s o he
a che ypal hexame ic [Z
6
(
μ
3
O)
4
(
μ
3
OH)
4
]
12+
clus e s connec ed by
me cap osuccinic linke s. The 12-connec ed amewo k adop s a ypical
cubic “ cu” opology, whe e he diso de o he linke s esul s in a po e
space deco a ed wi h -SH unc ions (Fig. 1a). In con as o he non-
scaled homologue, he di ac ion pa e n o he scaled-up
BCM-1 shows a low-in ensi y p e-di ac ion maximum a app oxi-
ma ely 6◦. This ea u e is linked o he p esence o long- ange co ela ed
nanodomains o clus e de ec s wi hin i s c ys al s uc u e. [26]. These
de ec i e nano egions induce a educ ion o he local symme y o a P23
space g oup, as illus a ed by he ull p o ile ma ching analysis shown in
Fig. S1.
As expec ed, he XRD pa e n o SPICHI exhibi s low c ys allini y,
wi h b oad di ac ion maxima ha a ise om he diso de ed packing o
CHI and SPI s uc u es. As shown in Fig. 1b, he c ys al s uc u e o CHI
consis s o ca bohyd a e chains o ien ed along he c-axis and packed
along he [100] and [010] di ec ions. SPI adop s a globula -like s uc-
u e due o he olding o amino acid chains sequence [27] (Fig. 1c),
which u he s acks in o a h ee-dimensional amewo k s abilized by
weak in e ac ions. When CHI and SPI a e combined, he XRD pa e n
e ealed h ee key ea u es: a low-in ensi y maximum nea 9◦, and h ee
b oad signals a app oxima ely 18◦, 29◦, and 42◦. Al hough he low
c ys allini y o SPICHI limi s he ex ac ion o p ecise s uc u al in o -
ma ion, i is e iden ha he packing o CHI and SPI uni s leads o a
dis inc a angemen in compa ison o p e iously s udied chi osan o
chi osan/pec in composi es [28], whose di ac ion pa e ns exhibi
sligh ly di e en ea u es.
No signi ican changes a e obse ed in he di ac ion da a when
BCM-1 is in eg a ed in o SPICHI. The pa e ns o SPICHI@MOF sponges
show he h ee b oad signals a 2θ =19.3, 27.5 and 40.2◦a ibu ed o
he SPICHI sca old. In addi ion, hey exhibi he wo cha ac e is ic
di ac ion maxima o BCM-1 a low 2θ alues o 8.5◦and 9.8◦. The
in ensi y o he maxima inc eases as he MOF concen a ion in he
composi e aises (Fig. 1d). Las bu no leas , a p o ile i ing o he XRD-
da a was pe o med o semi quan i y he p esence o BCM-1 in he 3D-
sponge (Fig. 1e). As expec ed, he in ensi y a io be ween he mos
in ense di ac ion ea u es o MOF and SPICHI componen s inc eases as
he MOF con en does.
3.1.2. Physicochemical cha ac e isa ion
FTIR analysis was ca ied ou o elucida e whe he any chemical
in e ac ions be ween SPICHI and BCM-1 occu when in eg a ing bo h
componen s in he 3D-sponge. The FTIR spec a o SPICHI@BCM-1
mainly show he cha ac e is ic inge p in s o SPICHI wi h sub le
con ibu ion om BCM-1 (Fig. S15). SPICHI exhibi ed h ee cha ac e -
is ic bands common o all p o eins [15]: amide I (1630 cm
−1
), a ibu ed
o C
–
–
O s e ching; amide II (1540 cm
−1
), associa ed wi h N
–
H
bending; and amide III (1235 cm
−1
), co esponding o C
–
N s e ching
and N
–
H bending, indica i e o β-shee s uc u es [29]. By analysing
hyd ogen bonding wi hin he polyme ’s FTIR spec um, he amide A
egion (3310–3270 cm
−1
) is also e alua ed o ollow up a ia ions o he
N
–
H s e ching ib a ion. This egion is pa o he Fe mi esonance
double , and i s second componen , amide B, which exhibi s weak ab-
so p ion in he 3100–3030 cm
−1
ange [30]. Addi ionally, s e ching
ib a ions o C
–
H bonds can be obse ed be ween 2960 and 2865 cm
−1
.
Fu he , he dis inc i e abso p ion bands o C
–
O bonds om CHI
componen a e p esen in he 1180–953 cm
−1
ange [16].
BCM-1 shows a b oad abso p ion signal anging om 2600 o 3680
cm
−1
co esponding o
O–H s e ching ib a ions om wa e adso bed om oom condi-
ions. Two abso p ion maxima loca ed a app oxima ely 1587 and 1415
cm
−1
[31] domina e he con ibu ion in he MOF spec um and a e
assigned o ʋ
asym
and ʋ
sym
o (COO
−
) g oups belonging o he o ganic
linke s. In addi ion, a weak band a 2560 cm
−1
is assigned o he
s e ching ib a ion o S
–
H [32]. I is in e es ing o no e ha he wo
weak signals obse ed a app oxima ely 1720 cm
−1
and 1322 cm
−1
a e
a ibu ed o he C
–
–
O and C
–
O s e ching ib a ions, and in u n,
con i m he p esence o uncoo dina ed linke s-s uc u al de ec s in
BCM-1. Finally, a p ominen band appea s nea 650 cm
−1
, which is
ela ed o Z
–
O s e ching ib a ions [33].
The signals om SPICHI la gely domina ed he FTIR spec a o SPI-
CHI@MOF composi es. Howe e , sub ac ing he SPICHI con ibu ion
om he SPICHI@BCM-1 da a allows iden i ying he abso p ion band
associa ed wi h ʋ
asym
(COO
−
) o me cap osuccina e linke s. Simila ly,
he signal a 650 cm
−1
is a ibu ed o Z
–
O ib a ional modes, which
u he con i ms he p esence o BCM-1 in he composi e. As expec ed,
he in ensi y o hese bands inc eases wi h he BCM-1 con en in he
il e s. Since none o he epo ed bands exhibi a signi ican shi in
posi ion when compa ed o he ones o SPICHI and BCM-1, s ong
chemical in e ac ions a e no expec ed be ween he su ace unc ional
g oups o bo h ma e ials in eg a ed in he 3D-sponges.
This endency is also obse ed in he he mal p ope ies, whe e he
p o ile o
SPICHI@BCM-1 is he weigh ed a e age o he TGA-cu es o SPI-
CHI and BCM-1. The he mog a ime y o BCM-1 shows h ee he mal
p ocesses (Fig. 1 ). Ini ially, BCM-1 exhibi s a weigh loss a ibu ed o
he e apo a ion o adso bed mois u e (25–130 ◦C). This is ollowed by
he elease o he o mic acid modula o , coo dina ed wa e and hy-
d oxyl molecules (150–250 ◦C). The las deg ada ion s age, occu ing
be ween 250 and 650 ◦C, co esponds o he calcina ion o he o ganic
linke . The weigh loss associa ed o he las wo he mal p ocesses was
employed o quan i y he a e age linke de ec s pe o mula in BCM-1.
As de ailed in he Table S1, 1.5 linke de ec s pe o mula uni we e
es ima ed based on he weigh loss o he he mog a ime ic cu e be-
ween 220 and 550 ◦C. The he mal deg ada ion o SPICHI s a s abo e
150 ◦C, con inue wi h se e al mul is ep weigh losses, and ends a e he
o e all calcina ion o he polyme . A mino ino ganic esidue was
obse ed as a known impu i y o SPICHI. The he mal deg ada ion o
composi e 3D-sponges esembles ha o SPICHI wi h a sub le di e ence.
The emaining weigh loss in he s udied composi es inc eases wi h he
con en o BCM-1, linked wi h he gene a ion o Z O
2
as esidue. By
analysing he weigh pe cen age o he inal esidue o he TGA p o iles,
he inal MOF w % in he SPICHI@BCM-1 sponges was es ima ed. As
de ailed in he Table S2, BCM-1 con en is sligh ly lowe han he ex-
pec ed bu s ill shows a quali a i e di ec co ela ion wi h he ini ial
weigh used o he sponges´assembly.
3.1.3. Eco oxicological assessmen
Eco oxici y assays we e employed o es ima e whe he he elease o
BCM-1 pa icles om he biopolyme ic composi es pose a isk o he
en i onmen . The eshwa e o i e species B achionus calyci lo us is a
small me azoan in e eb a e, ecologically ele an in len ic ecosys ems
and is gene ally sensi i e o a wide ange o con aminan s, including
me al nanopa icles [34]. On he o he hand, Allogamus sp. and Limne-
philus sp. a e mac oin e eb a es widely dis ibu ed in Ibe ian s eams,
ecologically ele an in lo ic ecosys ems, and, hey a e also sensi i e o
wa e quali y [35–37], [38].
M. Calles Ga cía e al.
Chemical Enginee ing Jou nal 524 (2025) 169442
5
Two BCM-1 ma e ials wi h di e en pa icle sizes we e s udied o
he eco oxicological assays: BCM-1 m (mic on-sized MOF pa icles) and
BCM-1n (nanome ic MOF pa icles). In addi ion, he zi conium me -
cap osuccina e hexagonal a ian , namely BCM-2, was syn hesised o
sake o compa ison. The 24 h acu e exposu e o he eshwa e o i e s
B. calyci lo us o BCM-1 and BCM-2 samples did no show signi ican
mo ali y up o 10 mg L
−1
MOF concen a ion (Fig. 1g). Two-way
ANOVA e ealed ha only he concen a ion o he MOFs had a signi -
ican e ec (P <0.05), whe eas he e ec s o pa icle size and MOF
s uc u e ype we e s a is ically insigni ican (P >0.05; Fig. 1g–i).
Tukey’s mul iple compa isons es s showed ha exposu e only o 50 mg
L
−1
o BCM-1n induced signi ican mo ali y (P <0.05) on o i e s,
al hough i was only abou he 13 % (Fig. 1g). BCM-1 m and BCM-2 did
no show any signi ican mo ali y e ec s (P >0.05) (Fig. 1h-i) on his
eshwa e mic o-in e eb a e.
The 96 h acu e exposu e o he wo di e en s eam mac o-
in e eb a e species, Allogamus sp. and Limnephilus sp., showed sligh ly
a ied esul s a he highes exposu e concen a ion (Fig. 1h-i). None o
he species exhibi ed mo ali y in unexposed con ols a e 96 h. Two-
way ANOVAs con i med he negligible e ec s o ype and concen a-
ion o MOFs on Limnephilus sp. (P >0.05). Howe e , exposu e o
Allogamus sp. showed simila esponse pa e ns upon exposu e o h ee
MOFs as obse ed o o i e s. Exposu e only o 50 mg L
−1
o BCM-1n
induced signi ican mo ali y (P <0.05) o o i e s, howe e , he mo -
ali y was abou 7 % (Fig. 1h). In con as , no mo ali y was obse ed o
Limnephilus sp. e en a e exposu e o 50 mg L
−1
o each MOF (Fig. 1i).
Acu e exposu e es s clea ly indica e ha a en i onmen ally ele-
an exposu e concen a ions, none o he h ee MOFs exhibi ed le hal
oxici y o he mic o- o mac oin e eb a es. A low mo ali y (<15 %)
o B. calyci lo us and Allogamus sp. was obse ed only a he highes
exposu e concen a ion o BCM-1n, p obably due o i s smalle size
compa ed o BCM-1 m and BCM-2. The ou comes o ou acu e exposu e
es s also emphasised he impo ance o he eco oxicological s udies o
MOFs conside ing hei applica ion o en i onmen al emedia ion.
3.1.4. Nano o mic ome ic scale cha ac e isa ion o hyb id 3D-sponges
In he ollowing, he combined in o ma ion ob ained om SEM,
SAXS and Neu on Imaging we e employed o econs uc he nano o
mic ome ic scale cha ac e is ics o SPICHI and SPICHI@BCM-1 3D-
sponges. Mic oscopy pic u es and neu on imaging expe imen s we e
conduc ed o acqui e a deepe in o ma ion o he in e nal po osi y o a
ep esen a i e econs uc ed neu on omog aphy slice o he composi e
sponge (Fig. 2a-b). The omog aphic slice exhibi s egions wi h a ying
g ey-scale in ensi ies (a bi a y uni s), which e lec he no malised
neu on a enua ion (Fig. 2b). Highe g ey alues co espond o egions
o g ea e neu on a enua ion (lowe ansmission), whe eas lowe g ey
alues indica e educed a enua ion (highe ansmission). Quan i a i e
analysis o he mac opo osi y dis ibu ion along he il e dep h, pe -
o med h ough po e segmen a ion, e ealed a minimum po e diame e
exceeding 200
μ
m (equi alen o mo e han ou pixels) (Fig. 2c), and an
in e connec ed po ous sys em whe e he pe cen age o po osi y a ia es
wi h he dep h o he sponge. This in o ma ion is showing a pic u e o
he mac oscopic s uc u a ion o he mic ome ic in e connec ed po e
s uc u e in he 3D-sponge, obse ed bo h by con en ional mic oscopy
and neu on imaging.
SEM p esen s challenges in di ec ly isualising he BCM-1 nano-
pa icles s abilized wi hin he polyme ic ma ix. E en so, i enables he
ex ac ion o in o ma ion abou hei impac on he nano o mic ome ic
s uc u e o he po ous composi e. Fi s , as de i ed om he SEM images
analysis by ImageJ so wa e, he MOF shows a ela i ely homogeneous/
monodispe se pa icle size dis ibu ion wi h an a e age pa icle diam-
e e o 42.5 nm (Fig. 2d). Second, a sligh di e ence can be obse ed
be ween he su ace mo phology o SPICHI (Fig. 2e) and SPICHI@BCM-
1 (Fig. 2 ). Fo bo h samples, a loppy po ous s uc u e is e ealed,
which in u n is o med by he in e connec ion o hin SPICHI lamella
walls. When he MOF nanopa icles a e in eg a ed in o he polyme
ma ix, he a e age size o he in e connec ed ca i ies wi hin he
memb ane is educed (Fig. 2 ). This expe imen al e idence sugges s ha
BCM-1 can modula e he po e s uc u e o he polyme ic sca old, mos
p obably al e ing he in e ac ion be ween he composi e and he sol en
du ing he lyophilisa ion s age. This phenomenon has been epo ed o
chi osan/MOF-808 beads. [39]
SAXS expe imen s we e conduc ed o gain u he insigh s in o he
nanos uc u e o he sponges. Acco ding o he SAXS spec a (Fig. 2g)
SPICHI p esen s a smoo h cu e wi h a powe law beha iou , cha ac-
e is ic o la ge and ex ended polydispe se s uc u es displaying ac al-
like o ganisa ion [40]. The sum o wo powe laws (I(q) =scale
1
⋅q
-p1
+
scale
2
⋅q
-p2
we e used o i expe imen al da a. The powe law exponen s,
p
1
=4.1(1) and p
2
=2.6(1), we e ob ained om he i ing and a e
en a i ely a ibu ed o po es o mic ome e size o la ge in he sample.
Upon in eg a ion o BCM-1 o SPICHI, in addi ion o he powe -law
sca e ing obse ed in bo h he low- and high q- egions, an addi ional
SAXS signal eme ges in he in e media e q- ange. This signal is cha -
ac e ised by wo oscilla ions, indica i e o ai ly monodispe se nano-
pa icles in he sys em. I is impo an o no e ha he powe -law
exponen s a e nea ly iden ical ac oss all samples, indica ing a simila
mac o po e-s uc u e in bo h he polyme ic sponge and he MOF-hyb id
homologues.
The Indi ec Fou ie T ans o m (IFT) [41] o he SAXS da a o
SPICHI@BCM-1 was done a in e media e q- alues [42]. IFT enables
ep esen ing he sca e ing da a in e ms o he pai dis ance dis ibu ion
unc ion (PDD), p( ) (Fig. 2h). Despi e he SAXS cu es ep esen ed as
PDD a e qui e simila , a sligh di e ence associa ed o he size o he
BCM-1 componen , was obse ed. Namely R
g
=24.2 nm and Rg =19.6
nm alues we e ob ained om he i ing o he SAXS spec a o SPI-
CHI@BCM-1(6 %) and (20 %), co espondingly (Fig. 2h). Taking in o
accoun he sphe ical shape o BCM-1 nanopa icles, we can es ima e he
size o he sphe es om he well-known ela ion be ween adius o gy-
a ion, Rg and adius o he sphe e, R, Rg
2
=3
5R2 [43].Thus, i is
concluded ha SPICHI@BCM-1(20 %) co esponds well o he size o
ini ial MOF pa icles, whils some deg ee o agglome a ion can be
obse ed in SPICHI@BCM-1(6 %). The bell-like o m o he PDD unc-
ions indica es he symme ical na u e o he pa icle size dis ibu ion,
which signi ican ly ma ches he one obse ed by he pa icle size dis-
ibu ion ob ained by SEM (Fig. 2i). This is con i med by he analysis o
he polydispe si y indices based on he in a ian s o he sca e ing
cu es, which indica es ha he size dis ibu ion is closes o gaussian
[44].
3.2. Func ional cha ac e isa ion
3.2.1. Hea y me als adso p ion sc eening
Be o e p esen ing he expe imen al esul s in his sec ion, i is
impo an o no e ha he hea y-me al cap u e mechanism o he
SPICHI@BCM-1 composi e elies on a combina ion o abso p ion wi hin
he MOF po e s uc u e and adso p ion a bo h he su ace o he
biopolyme sca old and he MOF/biopolyme in e ace. In he ollowing
discussion, and o he sake o simplici y, he e m adso p ion will be
used. Howe e , i should be no ed ha , depending on whe he he MOF,
SPICHI, o SPICHI@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
he immobiliza ion o he me al species.
The s abili y o he memb anes was i s e alua ed in 100 ppm so-
lu ions o he i e s udies hea y me als and in aqueous solu ions o
di e en pH alues (Table S5). No signi ican pH changes we e obse ed
a e imme sing 10 mg o SPICHI@BCM-1 (20 %) sponge in 10 mL o he
a o emen ioned solu ions, excep o he solu ion wi h an ini ial pH o
8.7, which dec eased o 7.2 upon con ac wi h he memb ane. UV–Vis
spec a o acidic solu ions (pH ≤5) ollowing con ac wi h he sponge
exhibi ed an inc ease o he abso bance wi hin 200 and 250 nm,
consis en wi h he elease o mino componen s om SPICHI@BCM-1
M. Calles Ga cía e al.
Chemical Enginee ing Jou nal 524 (2025) 169442
6
Fig. 2. (a) Op ical mic oscope image o he SPICHI@BCM-1; (b) Neu on omog aphy; (c) Mac opo osi y dis ibu ion ob ained om he p ocessing o neu on
omog aphy da a (d- ) SEM images o (d) BCM-1, (e) SPICHI and ( ) SPICHI@BCM-1; (g) SAXS da a o SPICHI and SPICHI@BCM-1 il e s. Expe imen al da a: do s.
Fi ing: solid lines; (h) The ob ained p( ) unc ions o SPICHI and SPICHI@BCM-1, oge he wi h Rg and Ø a e p esen ed in he inse ; (i) Pa icle size dis ibu ion
ob ained om he analysis o he SEM images.
M. Calles Ga cía e al.
Chemical Enginee ing Jou nal 524 (2025) 169442
7
(Fig. S41). This elease appea s negligible, as simila abso bance alues
a e obse ed when only e y low concen a ions o hiomalic acid o
chi osan a e dissol ed in wa e . Acco dingly, o subsequen expe i-
men s, he pH o he me al solu ions was main ained a sligh ly acidic
condi ions o minimize he hyb id 3D-sponges´des abiliza ion.
P elimina y adso p ion expe imen s we e conduc ed o BCM-1,
SPICHI, SPICHI@BCM-1(6 %) and SPICHI@BCM-1 (20 %) in 5 ppm
solu ions o he “big i e” hea y me als—Hg(II), Pb(II), Cd(II), C (VI), As
(III), and As(V) (Fig. 3). The esul s poin ha SPICHI has i sel
adso p ion e iciencies o e he 90 % o Hg(II), Pb(II), and Cd(II). In
con as , i showed negligible capaci y o adso b C (VI), As(V), and As
(III), which emain s abilized in solu ion as anionic and neu al species,
espec i ely. In con as , BCM-1 shows excellen e iciency o he cap-
u e o C (VI), As(V), and As(III). When SPICHI and BCM-1 a e combined
in o a 3D sponge-like con igu a ion, hei adso p ion pe o mance is
modula ed depending on he me al ion. The adso p ion capaci ies o
SPICHI/BCM-1 composi es o Hg(II), Pb(II), and As(III) closely ma ch
he weigh ed a e age pe o mance o he indi idual SPICHI and BCM-1
componen s. In e es ingly, a syne gis ic e ec was obse ed o Cd(II)
adso p ion, wi h SPICHI@BCM-1 composi es ou pe o ming bo h indi-
idual ma e ials. In con as , he SPICHI@BCM-1 hyb ids signi ican ly
unde pe o med he weigh -a e aged igu es ob ained om BCM-1 and
SPICHI o As(III), o C (VI) and As(V). Since BCM-1 is he ac i e
componen o he cap u e o he la e species, i s immobiliza ion
wi hin he composi e appea s o pa ially block he access o anionic
me alloid species o he MOF pa icles. This ac can be easily explained
conside ing he isoelec ic poin o SPI, CHI and BCM-1. A he in e -
media e pH alues whe e he adso p ion expe imen s ha e been ca ied
ou (Table S5), SPI [45] and CHI [46] exhibi a sligh ly nega i ely
cha ged su ace, which may epulse a sena e and ch oma e anions o
access he s uc u e o he il e , and hence, he BCM-1 pa icles.
Al hough BCM-1 exhibi s an isoelec ic poin o app oxima ely 3.9
(Fig. S32), i s chemiso p ion a ini y o e oxyanions enables b eaking
he elec os a ic epulsion o ces a su ace scale. Thus, inc easing he
BCM-1 con en enhances he composi e’s adso p ion capaci y o hea y
me als ha a e s abilized as oxyanions. Howe e , he expe imen ally
ob ained capaci y is signi ican ly lowe han ha p edic ed om he
weigh ed-a e age calcula ed capaci y (Fig. 3b), con i ming ha he
blocking e ec o he biopolyme sca old on anions ou weighs he
chemiso p ion a ini y o BCM-1.
3.2.2. Adso p ion kine ics and iso he ms
I is impo an o no e ha he equilib ium capaci ies ob ained om
he kine ic expe imen s a e signi ican ly highe han hose epo ed in
he ini ial sc eening (Fig. 3), because 10 ppm ini ial me al concen a ion
was employed ins ead o he 5ppms o he p e ious assays. E en hough
he adso p ion ends ob ained in p elimina y expe imen s a e mi o ed
in he kine ics s udy.
The kine ic cu es allow gaining signi ican insigh s in o he ime
dependence o adso p ion. To his end, he concen a ion o he “big
i e” hea y me als was moni o ed o e an adso p ion pe iod o up o
240 min using BCM-1, SPICHI, and SPICHI@BCM-1 (20 %) as so ben s
(Fig. 4). Pseudo- i s and pseudo-second o de models we e employed o
i he kine ic da a and o ex ac he pa ame e s desc ibing he so ba-
e–so ben a ini y and equilib ium adso p ion capaci y (Con inuous line
in Fig. 4). The i ings we e employed o calcula e he kine ic p o ile o
SPICHI@BCM-1(20 %) based on he weigh -a e aged con ibu ions
om he BCM-1 and SPICHI kine ic cu es (dashed line in Fig. 4). Fo
de ailed in o ma ion abou he calcula ions, he eade may consul he
expe imen al sec ion.
As shown in he Fig. 4, BCM-1 exhibi s a as up ake wi h equilib ium
imes below 30 min o C (VI), As(V), As(III) and Hg(II). These me als
a e usually s abilized as (C
2
O
7
)
2−
/(HC O
4
)
−
, (H
2
AsO
4
)
−
oxyanions;
neu al a seni e (H
3
AsO
4
) and HgCl
2
species in wa e (Fig. S33-S36),
espec i ely. Consis en wi h p e ious s udies [47–51], he cap u e o
hese species by Z -MOFs wi h hiol- ich linke s is based on chemi-
so p ion a he de ec i e posi ions o BCM-1 s uc u e, and/o h ough
he gene a ion o me al/sulphide (i.e. S
–
As and S
–
Hg) b idges.
In con as , e en i SPICHI shows negligible adso p ion o C (VI)
and As(V), he hiol- ich s uc u e o SPI welcomes he cap u e o Hg(II)
and As(III), likely h ough he o ma ion o S
–
As and S
–
Hg co alen
linkages as well. In compa ison, he kine ics o hei cap u e a e usually
slowe han hose shown by BCM-1. The mic opo ous o de ed na u e o
BCM-1 plays a bene icial ole in accele a ing he up ake o hese hea y
me als, compa ed o a SPICHI composi e, which shows an o e all lowe
su ace a ea. I is wo h no ing ha , al hough he adso p ion kine ics o
SPICHI@BCM-1 ollows in gene al he weigh ed a e age cu e de i ed
om he indi idual kine ic p o iles o SPICHI and BCM-1, no able pos-
i i e and nega i e de ia ions a e obse ed in e ms o adso p ion a e,
equilib ium, and capaci y.
In de ail, Hg(II) up ake by SPICHI@BCM-1 ollows a simila and
apid adso p ion kine ics o ha calcula ed o he ini ial s age o he
expe imen ; howe e , he maximum up ake is lowe han expec ed.
Simila ly, he kine ics and capaci y o As(III) up ake in he composi e
sponge a e abo e he calcula ed alue. This conclusion sugges s a
bene icial syne gis ic adso p ion, likely om he in e phase be ween he
BCM-1 and SPICHI componen s combined in he il e . In con as ,
SPICHI@BCM-1 exhibi s a s ong inhibi ion o adso p ion kine ics o
a sena e and ch oma e anions, indica ing ha SPICHI plays a dominan
epealing ole o oxyanions.
The adso p ion kine ics o Cd(II) and Pb(II) ions- usually s abilized
as ca ionic species in wa e (Fig. S37-S38)- a e slowe han hose
Fig. 3. (a) Adso p ion capaci y (mg/g) o BCM-1, SPICHI and SPICHI@BCM-1 o e Hg(II), Pb(II), Cd(II), C (VI), As(III) and As(V). Expe imen s we e pe o med wi h
an ini ial me al ion concen a ion o 5 ppm, using 1 mg adso ben /mL dosage in 10 mL o solu ion. Measu emen s we e done a e 4 h. (b) Adso p ion di e ence
ob ained om he di e ence be ween he expe imen al alue and he one calcula ed om he weigh ed a e age o he con ibu ions a ising om he MOF and
polyme componen s o he composi e il e s.
M. Calles Ga cía e al.
Chemical Enginee ing Jou nal 524 (2025) 169442
8
obse ed o anionic o neu al hea y me als. The equilib ium ime
expands abo e 60 min o Pb(II) and abo e 90 min o Cd(II). The ime
dependence o he me al up ake a ies signi ican ly om BCM-1 o
SPICHI. Su p isingly, he esponse o SPICHI@BCM-1 ai ly escapes
om he expec ed calcula ed in e media e endency. Pb(II) cap u e by
SPICHI@BCM-1 shows a S- ype p o ile ha sugges a double-si e-based
cap u e. Once he i s si e is occupied by he me al ions, he adso p ion
is as ened un il sa u a ion o he second si e. Fo Cd(II), he composi e
sponge su passes he pe o mance o he indi idual componen s in e ms
o adso p ion capaci y and a e.
Once he indi idual and composi e sys ems’ gene al adso p ion
ends and kine ics we e iden i ied, adso p ion iso he ms o he “big
i e” membe s we e in es iga ed. Iso he ms p o ide wo key pa ame-
e s: (a) he sa u a ion capaci y, which e lec s he densi y o a ailable
adso p ion si es, and (b) he adso p ion a ini y, which indica es he
ma e ial’s e iciency in cap u ing speci ic hea y me al ions a low con-
cen a ions. These wo pa ame e s we e quan i ied by i ing he
expe imen al da a o he F eundlich iso he m model, as indica ed by he
con inuous lines in Fig. 5. Al hough al e na i e models—such as Lang-
mui and Temkin—we e also conside ed, hey yielded signi ican ly
poo e i s. The F eundlich- i ing o he iso he ms indica es ha he
adso p ion in BCM-1, SPICHI, and especially SPICHI@BCM-1 a e he -
e ogeneous, sugges ing he p esence o mul iple adso p ion si es wi h
sligh ly di e en na u es. [52] A simila end is obse ed o BCM-1.
Al hough i s c ys al s uc u e sugges s he p esence o homogeneous
dis ibu ion and na u e o he adso p ion si es, he expe imen al da a
indica e a ce ain deg ee o he e ogenei y. This de ia ion may be
a ibu ed o su ace adso p ion, which can lead o a beha iou ha
di e ges om he ideal single-si e adso p ion occu ing a he in e nal
po e space o BCM-1. Such su ace e ec s likely con ibu e o he non-
ideal iso he ms obse ed in ou s udy. [18]
The iso he ms o BCM-1, SPICHI, and SPICHI@BCM-1 (20 %) show
wo dis inc ends linked o he adso p ion o : (I) me als s abilized in
ca ionic o ms and (II) oxyanions o neu al species. The i s g oup o
Fig. 4. Adso p ion kine ics o BCM-1, SPICHI and SPICHI@BCM-1 o e Hg(II), Pb(II), Cd(II), C (VI), As(III) and As(V). T iplica e expe imen s we e pe o med wi h
an ini ial me al ion concen a ion o 10 ppm, using 1 mg adso ben /mL dosage in a 50 mL o me al solu ion.
M. Calles Ga cía e al.
Chemical Enginee ing Jou nal 524 (2025) 169442
9
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