Compu a ional Mechanism o Me hyl Le ulina e Con e sion o
γ‑Vale olac one on UiO-66 Me al O ganic F amewo ks
Manuel A. O uno,*Ma cos Rellán-Pinei o, and Ra ael Luque
Ci e This: ACS Sus ainable Chem. Eng. 2022, 10, 3567−3573
Read Online
ACCESS Me ics & Mo e A icle Recommenda ions *
sıSuppo ing In o ma ion
ABSTRACT: Me al−o ganic amewo ks (MOFs) a e gaining
impo ance in he field o biomass con e sion and alo iza ion
due o hei po osi y, well-defined ac i e si es, and b oad unabili y.
Bu o a p ope ca alys design, we fi s need de ailed insigh o he
sys em a he a omic le el. He ein, we p esen he eac ion
mechanism o me hyl le ulina e o γ- ale olac one on Z -based
UiO-66 by means o pe iodic densi y unc ional heo y (DFT). We
demons a e he ole o Z -based nodes in he ca aly ic ans e
hyd ogena ion (CTH) and cycliza ion s eps. F om he e, we
pe o m a compu a ional sc eening o e eal key ca alys
modifica ions o imp o e he p ocess, such as node doping and
linke exchange.
KEYWORDS: Densi y unc ional heo y (DFT), Me al o ganic amewo k (MOF), Ca alys design, Biomass alo iza ion,
Ca aly ic ans e hyd ogena ion (CTH)
■INTRODUCTION
The cu en scena io domina ed by c ude oil and na u al gas is
no longe easible, and ou socie y needs o de ise new
sus ainable ways o ulfill he eeds ock demand o an
inc easing wo ld popula ion. We mus abandon he limi ed
supply o ossil uels and u n o enewable esou ces such as
biomass. Indeed, he upg ading o eadily a ailable lignin and
(hemi)cellulose o high- alue p oduc s is al eady leading he
way owa d a sus ainable economy.
1
In ha ega d, se e al
biobased molecules ha e been iden ified as p omising building
blocks.
2
Among hem, we he e a ge he ans o ma ion o
me hyl le ulina e (ML), eadily a ailable om lignocellulose,
in o γ- ale olac one (GVL), a pla o m molecule used as
sol en , uel, and eeds ock o high- alue chemicals.
3
This eac ion is ypically ca alyzed in he he e ogeneous
phase and en ails a di ec hyd ogena ion ia p ecious me als.
4
Al e na i ely, ampho e ic ca alys s, such as hose based on Z ,
can p omo e a ca aly ic ans e hyd ogena ion (CTH) using
alcohols as a hyd ogen sou ce (Scheme 1),
5,6
hus a oiding he
need o hyd ogen gas and expensi e me als. Z -based oxides
can indeed p omo e his p ocess,
7,8
bu he a ie y o ac i e
si es on he ca alys su ace may become de imen al due o
undesi ed side eac ions.
To be e con ol he design o ca aly ic si es, we u n o
me al−o ganic amewo ks (MOFs), a amily o po ous
ma e ials ha comp ises ino ganic nodes connec ed h ough
o ganic linke s.
9
Thei high su ace a ea, a iable po osi y, and
well-defined coo dina ion modes make hem e y aluable o
gene al ca aly ic applica ions.
10
This scope has been expanded
o biomass con e sion in ecen yea s.
11,12
Due o he he mal
s abili y and ca aly ic p ope ies o MOFs con aining Z 6O8
nodes (Figu e 1),
13
hey we e es ed in he alo iza ion o alkyl
le ulina es o GVL ia CTH. UiO-66 exhibi ed high ac i i y
and selec i i y owa d GVL in bo h ba ch
14
and flow
15
se ups.
In e es ingly, while NH2- and COOH- unc ionalized linke s
did no imp o e he ca aly ic pe o mance,
14
he p esence o
SO3H g oups had a posi i e impac , p esumably due o a
coope a i e effec be ween Lewis base nodes and B øns ed acid
linke s.
16
O he MOFs wi h simila Z 6O8nodes (MOF-808,
14
DUT-52,
17
and Z F
18
) can also ca alyze his eac ion wi h high
con e sion and mode a e- o-good selec i i y, as well as some
H -based analogues.
19
The imp o ed ca aly ic ac i i y ob ained
Recei ed: No embe 26, 2021
Re ised: Feb ua y 24, 2022
Published: Ma ch 4, 2022
Scheme 1. Con e sion o Me hyl Le ulina e (ML) in o γ-
Vale olac one (GVL) ia Ca aly ic T ans e Hyd ogena ion
Resea ch A icle
pubs.acs.o g/jou nal/ascecg
© 2022 The Au ho s. Published by
Ame ican Chemical Socie y 3567
h ps://doi.o g/10.1021/acssuschemeng.1c08021
ACS Sus ainable Chem. Eng. 2022, 10, 3567−3573
Downloaded ia UNIV DE SANTIAGO DE COMPOSTELA on Sep embe 6, 2022 a 12:40:55 (UTC).
See h ps://pubs.acs.o g/sha ingguidelines o op ions on how o legi ima ely sha e published a icles.
by MOF uning is gene al and can be ex apola ed o o he
p ocesses, as ecen ly demons a ed in UiO-66-ca alyzed
ca bohyd a e con e sion.
20
These p omising esul s encou age u he mechanis ic
unde s anding o ca alys op imiza ion. He e is whe e
compu a ional chemis y comes in o play o p o ide quan um
mechanical insigh a he a omic le el o de ail.
21
Despi e he
many compu a ional con ibu ions on MOF ca alysis,
22,23
he
mechanis ic ea u es o how hese ma e ials pa icipa e in
biomass alo iza ion a e s ill sca ce. Mos o hese s udies
employ fini e-size clus e s,
24
which igno e he pe iodici y o he
ma e ial and canno accoun o confinemen effec s wi hin he
po es. To add ess his gap in knowledge, he e we employ
pe iodic densi y unc ional heo y (DFT) o c ea e a mo e
ealis ic en i onmen . We compu e he eac ion mechanism o
ML o GVL a UiO-66 using isop opanol as a hyd ogen sou ce.
We iden i y he key s eps o he ca aly ic cycle and e alua e he
impac o diffe en ca alys modifica ions. Such mechanis ic
insigh would guide he a ional design o ca alys s o de elop
mo e efficien and selec i e expe imen al sys ems.
■COMPUTATIONAL SECTION
Calcula ions we e pe o med a he pe iodic Densi y Func-
ional Theo y (DFT) le el using he Vienna Ab-Ini io
Simula ion Package (VASP).
25,26
The PBE densi y unc ional
27
was employed, and dispe sion in e ac ions we e conside ed
wi h G imme’s D2 scheme.
28
Co e elec ons we e desc ibed by
p ojec o augmen ed wa e (PAW) pseudopo en ials,
29
and
alence elec ons we e ep esen ed by plane wa es wi h a
kine ic ene gy cu offo 450 eV. A Hubba d co ec ion
30
o 4.5
eV was applied o Ce(4 ) elec ons as sugges ed in he
li e a u e.
31,32
The simula ion cell o UiO-66 (14.737 ×20.840
×14.737 Å3,Figu e S1) was aken om p e ious DFT
calcula ions.
33
The B illouin zone was sampled a he Γ-poin
ia he Monkho s −Pack me hod.
34
T ansi ion s a e s uc u es
we e loca ed wi h he climbing image nudged elas ic band
35
and imp o ed dime
36
algo i hms. Minima and ansi ion s a es
we e cha ac e ized by diagonalizing he nume ical Hessian
ma ix (±0.015 Å displacemen s). Vib a ional pa i ion
unc ions we e compu ed using nume ical equencies a 513
K as in expe imen s,
15
whe e only selec ed a oms we e allowed
o mo e.
37
Open access
38
o all inpu s and ou pu s epo ed he ein,
including aw ene gies and geome ies, is p o ided by he
ioChem-BD pla o m
39
in he ollowing da abase.
40
■RESULTS AND DISCUSSION
The UiO-66 MOF is o med by Z 6O4(OH)4nodes connec ed
o 12 1,4-benzenedica boxyla e linke s.
41
The p is ine ma e ial
does no ha e any open me al si es, bu he p esence o de ec s,
i.e., missing linke s, is known o be esponsible o ca aly ic
ac i i y.
42,43
Thus, we fi s need o p opose a easible ac i e si e
whe e he ML- o-GVL con e sion may ake place.
The uni cell o UiO-66 con ains ou ino ganic nodes.
41
To
sa e compu a ional esou ces, we use a smalle cell con aining
wo ino ganic nodes.
33
The emo al o one dica boxyla e linke
c ea es wo node de ec s wi h ou me al acancies o e all,
which we hen balance wi h OH/H2O g oups.
44
Unde
eac ion condi ions, we expec a displacemen o H2O and
exchange o [OH]−by [iP O]−, yielding he po en ial ac i e
species 1(Figu e 2). We will use his s uc u e as a s a ing
poin o compu ing he eac ion mechanism.
Reac ion Mechanism a De ec i e UiO-66. We s a he
mechanis ic s udy om he p e iously discussed s uc u e 1
which con ains one iP O g oup and one Z acan si e. We
es ablish his s age as he ze o o ene gies. The ollowing alues
co espond o Gibbs ene gies compu ed a 513 K in eV. All
species a e deno ed wi h numbe s in bold, whe e ansi ion
s a es include he p efixTS.
The p oposed eac ion mechanism is depic ed in Figu e 3
and en ails ca aly ic ans e hyd ogena ion o ML ollowed by
cycliza ion o GVL. Fi s , species 1binds ML h ough i s
ca bonyl g oup o ming 2(0.14 eV). The hyd ogen ans e
om iP O o he ac i a ed ML occu s ia TS2−3(0.61 eV)
in ol ing wo Z cen e s
45
and yields in e media e 3(0.39 eV).
F om he e, ace one is eleased ia 4(−0.09 eV) and he
alkoxide ea anges o o m he biden a e species 5(−0.51
eV), whe e he es e ca bonyl g oup is also bound o Z . An
in amolecula nucleophilic a ack ia TS5−6(0.13 eV)
gene a es he in e media e 6(−0.14 eV). The subsequen
elimina ion o MeOH is assis ed by he μ3-OH g oup o he
node.
46−48
I akes place ia TS6−7(0.15 eV) and esul s in
he o ma ion o bounded GVL in 7(−0.35 eV). The
nonassis ed elimina ion ia TS6−8(0.46 eV), which yields he
Z −OMe in e media e 8, is less a o ed (Figu e S2). Finally,
an incoming iP OH eac an molecule eleases he GVL
p oduc and egene a es ca alys 1. The compu ed mechanism
is in line wi h he expe imen al p oposal, which in ol es wo Z
a oms om he same node
14
( a he han wo Z a oms om
adjacen nodes
16
).
The Gibbs ene gy p ofile o he eac ion mechanism
ca alyzed by de ec i e UiO-66 is displayed in Figu e 4 ( he
elec onic ene gy p ofile can be ound in Figu e S3). The
coo dina ion o ML o he ca alys 1is sligh ly uphill by 0.14
Figu e 1. Rep esen a ion o Z -based nodes. Z = da k g een, O = ed,
H = whi e.
Figu e 2. Compu ed s uc u e 1a de ec i e UiO-66 MOF. The
pe iodic s uc u e was c opped o be e isualiza ion. The black
squa e indica es a Z acan si e. Z = da k g een, O = ed, H = whi e.
ACS Sus ainable Chemis y & Enginee ing pubs.acs.o g/jou nal/ascecg Resea ch A icle
h ps://doi.o g/10.1021/acssuschemeng.1c08021
ACS Sus ainable Chem. Eng. 2022, 10, 3567−3573
3568
eV, bu his s ep is empe a u e-sensi i e, and compu ed Gibbs
ene gies ypically o e s abilize sepa a ed eac an s due o
en opic con ibu ions. The hyd ogen ans e TS2−3has a
ba ie o 0.61 eV abo e 1and a ela i e ba ie o 0.47 eV
abo e 2. Simila alues we e ecen ly ound in he CTH o
u u al o u u yl alcohol using fini e-size clus e models o
UiO-66
49
and MOF-808.
50
The elease o ace one ollowed by
he biden a e coo dina ion o he subs a e is qui e a o ed,
wi h 5a 0.51 eV below 1. Nex , he cycliza ion akes place ia
nucleophilic a ack and elimina ion o MeOH, whe e bo h
TS5−6and TS6−7p esen simila ba ie s o 0.64 and 0.66
eV abo e 5, espec i ely. The elease o GVL and he addi ion
o iP OH eco e he ca alys 1wi h global exoe gic
he modynamics o 0.49 eV.
The s uc u es o selec ed ansi ion s a es confined wi hin
he MOF po e a e displayed in Figu e 5.TS2−3shows he
hyd ogen ans e ; also, he es e g oup o ML o ms a H bond
wi h he μ3-OH g oup. TS5−6desc ibes he in amolecula
a ack o he alkoxy o he ca bonyl g oup. Finally, TS6−7
ep esen s he depa u e o he me hoxy g oup and he
concomi an abs ac ion o a p o on om he μ3-OH g oup o
he node. Fu he simula ions a he PBE le el wi h and
wi hou D2 dispe sion co ec ions demons a e he impo ance
o such confinemen effec s (Figu e S4), wi h TS2−3
(hyd ogen ans e ) mo e affec ed han TS5−6and TS6−7
(cycliza ion).
These simula ions p edic o e all Gibbs ene gy ba ie s o
ca. 0.65 eV o he UiO-66 ca alys . I demons a es ha he
p oposed mechanism is easible unde he epo ed expe -
imen al condi ions, ei he in ba ch
14,16
o flow eac o s.
15
They
also p edic ha he cycliza ion p ocess is likely a e-
de e mining, which is in line wi h he de ec ion o sligh
amoun s o me hyl 4-hyd oxypen anoa e.
15,16
Due o he
impo ance o he node in he mechanism, we nex e alua e
se e al MOF modifica ions ha di ec ly impac he Z 6O8
co e: changing he na u e o he me als ( uning he node) and
changing he ligands bound o hem ( uning he linke ).
To acili a e u u e eading and compa ison, om now on we
will label all species o he o iginal unmodified UiO-66 wi h he
Figu e 3. Reac ion mechanism o ML o GVL a de ec i e UiO-66 wi h ela i e Gibbs ene gies (in eV). R = (CH2)2CO2Me.
Figu e 4. Gibbs ene gy eac ion p ofile (in eV) a de ec i e UiO-66
wi h ela i e ba ie s o each s ep.
Figu e 5. DFT-op imized TS s uc u es. Rele an a oms a e display in
ball-and-s ick o ma , he es o hem in ube o ma . Selec ed
dis ances a e shown in Å.
ACS Sus ainable Chemis y & Enginee ing pubs.acs.o g/jou nal/ascecg Resea ch A icle
h ps://doi.o g/10.1021/acssuschemeng.1c08021
ACS Sus ainable Chem. Eng. 2022, 10, 3567−3573
3569
p efixA(e.g., A-1). We will use le e s in bold o diffe en
modifica ions oge he wi h numbe s in bold o in e media es
and ansi ion s a es. The co espondence be ween le e s and
modifica ions will be indica ed in he ollowing sec ions. The
nume ic no a ion does no change, and he co espondence
be ween numbe s and s uc u es can be consul ed in Figu e 3.
Tuning he Node. The p e ious eac ion mechanism
shows ha Z a oms efficien ly ac as Lewis acids o ca bonyl
g oups. We hen conside whe he o he M(IV) a oms (H , Ti,
and Ce) can acili a e he eac ion. Al hough such doping is
no i ial om an expe imen al poin o iew, mixed-me al
nodes
51,52
andCe-basednodes
53
ha e been p e iously
epo ed in he li e a u e.
Conside ing he wo Z a oms in ol ed in he p ocess (A),
we exchange hem by H , Ti, and Ce (B−J) as shown in Figu e
6a. We hen compu e ene gy ba ie s o each s ep: hyd ogen
ans e ( om 1 o TS2−3), nucleophilic a ack ( om 5 o
TS5−6), and elimina ion ( om 5 o TS6−7). Fo he H
de i a i es B−D, he diffe ences in elec onic ene gy wi h
espec o Aa e less han 0.05 eV (Figu e S5), and we expec
simila Gibbs ene gy p ofiles o bo h Z - and H -based nodes.
Howe e , mo e changes a e no ed o Ti and Ce de i a i es,
and ep esen a i e sys ems a e shown in Figu e 6b. Fo Fwi h
one Ti, he hyd ogen ans e is significan ly mo e demanding
(F-TS2−3a 1.14 eV) due o a weak adso p ion o ML (F-2 a
0.50 eV), while he nucleophilic a ack emains oughly he
same and he elimina ion becomes easie (F-TS6−7a 0.38
eV, 0.54 eV abo e F-5). Fo Iwi h one Ce, he hyd ogen
ans e and elimina ion s eps a e only ma ginally be e , and
he nucleophilic a ack does no change. In e es ingly, o J,
which includes wo Ce a oms, all ba ie s a e educed. The
adso p ion o ML is sligh ly s onge (J-2 a −0.10 eV), and
he hyd ogen ans e ba ie is lowe (J-TS2−3a 0.41 eV,
0.51 eV abo e J-2). Likewise, he alkoxy in e media e is mo e
s able and he cycliza ion p ocess is o e all as e .
To sum up, he p esence o Ti can speed up he cycliza ion
p ocess a he expense o slowing down he hyd ogen ans e .
Ce-con aining nodes p o ide a gene al dec ease o ba ie s o
all s eps, in line wi h simula ions on chemical wa a e
decomposi ion.
54
Wi h hese esul s, we hypo hesize ha
a e-ea h-based MOFs
55
could also exhibi simila o
imp o ed ca aly ic ac i i y o biomass- ela ed p ocesses.
Tuning he Linke . No only nodes bu also linke s can be
fine- uned in MOF ca alys s. The e o e, we now conside
changing he g oups a ound he me als h ough linke
modifica ions. P e ious heo e ical s udies ha e poin ed ou
ha unc ionalizing he a oma ic linke s has li le effec on
compu ed ene gy ba ie s
46,56
and equencies.
57
We hus ake
adiffe en app oach and change he ype o connec i i y
be ween he linke and he node.
As men ioned be o e, he unmodified MOF is labeled wi h
he p efixA, whe e L is he o iginal benzenedica boyla e (bdc).
Conside ing he linke s bound o he pa icipa ing Z a oms,
we exchange hem by Laand Lbas shown in Figu e 7a. In La,
one biden a e ca boxyla e g oup is emo ed, and one
monoden a e hyd oxo is bound o Z (Kand L), hus o mally
in oducing a new acan si e a he node. In Lb, one
ca boxyla e g oup is subs i u e by one sul ona e g oup
58
(M
and N). The ela i e Gibbs ene gy ba ie s a e summa ized in
Figu e 7b. Fo K, he adso p ion o ML does no change much
Figu e 6. (a) H -, Ti-, and Ce-doped nodes and (b) ela i e Gibbs
ene gy ba ie s (in eV) o selec ed models. Ba ie s a e compu ed
om he ansi ion s a e o he p e ious mos s able in e media e.
Figu e 7. (a) Linke -modified nodes and (b) ela i e Gibbs ene gy
ba ie s (in eV) o selec ed models. Ba ie s a e compu ed om he
ansi ion s a e o he p e ious mos s able in e media e.
ACS Sus ainable Chemis y & Enginee ing pubs.acs.o g/jou nal/ascecg Resea ch A icle
h ps://doi.o g/10.1021/acssuschemeng.1c08021
ACS Sus ainable Chem. Eng. 2022, 10, 3567−3573
3570
(K-2 a 0.25 eV) bu he hyd ogen ans e becomes mo e
difficul (K-TS2−3a 1.03 eV). This is due o a s onge
in e ac ion be ween he iP O and he unsa u a ed Z , which
dec eases he nucleophilici y o he o me . On he o he hand,
o L, he adso p ion o ML is enhanced a he unsa u a ed Z
(L-2 a −0.39 eV), and he hyd ogen ans e becomes as e
(L-TS2−3a 0.41 eV abo e L-2). Al hough an elec on
deficien Z is beneficial in he fi s s ep, i la e binds o he
alkoxy in e media e s ongly (L-5 a −1.57 eV), c ea ing a
he modynamic sink ha hinde s he cycliza ion p ocess. Fo
Mand N, bo h sys ems beha e he same, and only Nis
discussed o simplici y. The sul ona e g oup in Ndoes no
in oduce la ge changes, c . he ca boxyla e g oup in A, and
simila ba ie s a e ob ained in bo h cases.
O e all, hese esul s indica e ha he excess o acancies a
Z a oms is coun e p oduc i e o ac i i y, which may ela e o
he wo se ca aly ic pe o mance a e losing o ganic linke s.
15
They also sugges ha he eac ion is easible wi h MOFs
con aining SO3-modified linke s. Al hough he e is no s ong
imp o emen in e ms o compu ed eac ion ba ie s, hese
ma e ials may p esen o he ad an ages om a p ac ical poin
o iew, such as highe numbe o de ec s along he amewo k
(i.e., mo e ca aly ic si es) while inc easing he s abili y o he
ma e ial, as epo ed ecen ly.
58
■CONCLUSIONS
In his wo k, we s udy he ole o UiO-66 in he con e sion o
me hyl le ulina e o γ- ale olac one using isop opanol as a
hyd ogen sou ce. By means o pe iodic DFT simula ions, we
p opose a easible eac ion mechanism in ag eemen wi h
expe imen s, which consis s o ans e hyd ogena ion and
cycliza ion (nucleophilic a ack ollowed by elimina ion). We
find simila Gibbs ene gy ba ie s o all s eps, hus no unique
a e-de e mining s ep can be asc ibed. No ably, he μ3-OH
g oup a he node ac i ely pa icipa es in he eac ion by
o ming H-bonds wi h eac an s and assis ing in he
elimina ion p ocess.
As o design, we explo e se e al ca alys s by sys ema ically
a ying he me al a oms in he node as well as he connec ing
g oup be ween he linke and he node. Ou compu a ional
app oach p o ides a p ecise con ol o MOF changes ha
allows us o inspec he impac o each modifica ion on each
s ep o he mechanism. In his way, we demons a e ha Ti (a
ha d Lewis acid) imp o es he hyd ogen ans e bu is
de imen al o he cycliza ion, while highly unsa u a ed Z
ope a es he o he way a ound. We also find ha Ce-based
nodes dec ease all h ee eac ion ba ie s and explo ing ela ed
MOFs con aining a e-ea h elemen s would be in e es ing.
Finally, Z nodes wi h SO3-modified linke s a e compe i i e, c .
he pa en ma e ial, and can imp o e he o e all pe o mance
o he ca aly ic sys em.
■ASSOCIATED CONTENT
*
sıSuppo ing In o ma ion
The Suppo ing In o ma ion is a ailable ee o cha ge a
h ps://pubs.acs.o g/doi/10.1021/acssuschemeng.1c08021.
Al e na i e mechanism, elec onic ene gy p ofile, addi-
ional ene gy ba ie s (PDF)
■AUTHOR INFORMATION
Co esponding Au ho
Manuel A. O uno−Cen o Singula de In es igaciónen
Química Biolóxica e Ma e iais Molecula es (CIQUS),
Uni e sidade de San iago de Compos ela, 15782 San iago de
Compos ela, Spain; Ins i u e o Chemical Resea ch o
Ca alonia, ICIQ, and he Ba celona Ins i u e o Science and
Technology, BIST, 43007 Ta agona, Spain;
Email: [email p o ec ed]
Au ho s
Ma cos Rellán-Pinei o −Cen o Singula de In es igaciónen
Química Biolóxica e Ma e iais Molecula es (CIQUS),
Uni e sidade de San iago de Compos ela, 15782 San iago de
Compos ela, Spain
Ra ael Luque −Depa amen o de Química O gánica,
Uni e sidad de Có doba, E-14014 Có doba, Spain; Peoples
F iendship Uni e si y o Russia (RUDN Uni e si y), 117198
Moscow, Russian Fede a ion; o cid.o g/0000-0003-4190-
1916
Comple e con ac in o ma ion is a ailable a :
h ps://pubs.acs.o g/10.1021/acssuschemeng.1c08021
No es
The au ho s decla e no compe ing financial in e es .
■ACKNOWLEDGMENTS
This wo k has ecei ed financial suppo om he Bea iu de
Pinós pos doc o al p og am o he Go e nmen o Ca alonia’s
Sec e a ia o Uni e si ies and Resea ch (2017-BP-00039),
MINECO (unde p ojec PID2020-119116RA-I00), Xun a
Dis inguished Resea che p og am (ED431H 2020/21), he
Xun a de Galicia (Cen o singula de in es igación de Galicia
acc edi a ion 2019-2022, ED431G 2019/03), and he Eu o-
pean Union (Eu opean Regional De elopmen Fund - ERDF).
R.L. g a e ully acknowledges unding om MINECO unde
p ojec PID2019-109953GB-I00. The au ho s acknowledge
CESGA (“Cen o de Supe compu ación de Galicia”) and RES-
HPC (QS-2020-3-0019 and QS-2020-3-0022) o p o iding
gene ous compu a ional esou ces. This publica ion has been
suppo ed by RUDN Uni e si y S a egic Academic Leade -
ship P og am (R.L.).
■REFERENCES
(1) Tuck, C. O.; Pé ez, E.; Ho á h, I. T.; Sheldon, R. A.; Poliako ,
M. Valo iza ion o Biomass: De i ing mo e Value om Was e. Science
2012,337, 695−699.
(2) Bozell, J. J.; Pe e sen, G. R. Technology De elopmen o he
P oduc ion o Biobased P oduc s om Bio e ine y Ca bohyd a es
The US Depa men o Ene gy’s“Top 10”Re isi ed. G een Chem.
2010,12, 539−554.
(3) Alonso, D. M.; We s ein, S. G.; Dumesic, J. A. Gamma-
Vale olac one, a Sus ainable Pla o m Molecule De i ed om
Lignocellulosic Biomass. G een Chem. 2013,15, 584−595.
(4) W igh , W. R. H.; Palko i s, R. De elopmen o He e ogeneous
Ca alys s o he Con e sion o Le ulinic acid o γ-Vale olac one.
ChemSusChem 2012,5, 1657−1667.
(5) Gilkey, M. J.; Xu, B. He e ogeneous Ca aly ic T ans e
Hyd ogena ion as an E ec i e Pa hway in Biomass Upg ading. ACS
Ca al. 2016,6, 1420−1436.
(6) Shi ha e, A.; Kuma , A.; S i as a a, R. An Accoun o he
Ca aly ic T ans e Hyd ogena ion and Hyd ogenolysis o Ca bohy-
d a e-De i ed Renewable Pla o m Chemicals o e Non-P ecious
He e ogeneous Me al Ca alys s. ChemCa Chem. 2021,13,59−80.
ACS Sus ainable Chemis y & Enginee ing pubs.acs.o g/jou nal/ascecg Resea ch A icle
h ps://doi.o g/10.1021/acssuschemeng.1c08021
ACS Sus ainable Chem. Eng. 2022, 10, 3567−3573
3571
(7) Chia, M.; Dumesic, J. A. Liquid-Phase Ca aly ic T ans e
Hyd ogena ion and Cycliza ion o Le ulinic Acid and I s Es e s o γ-
Vale olac one o e Me al Oxide Ca alys s. Chem. Commun. 2011,47,
12233−12235.
(8) Tabanelli, T.; Paone, E.; Vásquez, P. B.; Pie opaolo, R.; Ca ani,
F.; Mau iello, F. T ans e Hyd ogena ion o Me hyl and E hyl
Le ulina e P omo ed by a Z O2Ca alys : Compa ison o Ba ch s
Con inuous Gas-Flow Condi ions. ACS Sus ainable Chem. Eng. 2019,
7, 9937−9947.
(9) 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
2013,341, 1230444.
(10) Ba ykina, A.; Kolobo , N.; Khan, I. S.; Bau, J. A.; Rami ez, A.;
Gascon, J. Me al-O ganic F amewo ks in He e ogeneous Ca alysis:
Recen P og ess, New T ends, and Fu u e Pe spec i es. Chem. Re .
2020,120, 8468−8535.
(11) He bs , A.; Janiak, C. MOF Ca alys s in Biomass Upg ading
Towa ds Value-Added Fine Chemicals. C ys EngComm 2017,19,
4092−4117.
(12) Fang, R.; Dhakshinamoo hy, A.; Li, Y.; Ga cia, H. Me al
O ganic F amewo ks o Biomass Con e sion. Chem. Soc. Re . 2020,
49, 3638−3687.
(13) Rimoldi, M.; Howa h, A. J.; DeS e ano, M. R.; Lin, L.;
Goswami, S.; Li, P.; Hupp, J. T.; Fa ha, O. K. Ca aly ic Zi conium/
Ha nium-Based Me al-O ganic F amewo ks. ACS Ca al. 2017,7,
997−1014.
(14) Valeka , A. H.; Cho, K.-H.; Chi ale, S. K.; Hong, D.-Y.; Cha,
G.-Y.; Lee, U.-H.; Hwang, D. W.; Se e, C.; Chang, J.-S.; Hwang, Y. K.
Ca aly ic T ans e Hyd ogena ion o E hyl Le ulina e o γ-
Vale olac one o e Zi conium-Based Me al-O ganic F amewo ks.
G een Chem. 2016,18, 4542−4552.
(15) Ouyang, W.; Zhao, D.; Wang, Y.; Balu, A. M.; Len, C.; Luque,
R. Con inuous Flow Con e sion o Biomass-De i ed Me hyl
Le ulina e in o γ-Vale olac one Using Func ional Me al O ganic
F amewo ks. ACS Sus ainable Chem. Eng. 2018,6, 6746−6752.
(16) Kuwaha a, Y.; Kango, H.; Yamashi a, H. Ca aly ic T ans e
Hyd ogena ion o Biomass-De i ed Le ulinic Acid and I s Es e s o γ-
Vale olac one o e Sul onic Acid-Func ionalized UiO-66. ACS
Sus ainable Chem. Eng. 2017,5, 1141−1152.
(17) Ku isingal, J. F.; Rachu i, Y.; Palakkal, A. S.; Pillai, R. S.; Gu, Y.;
Choe, Y.; Pa k, D.-W. Wa e -Tole an DUT-Se ies Me al-O ganic
F amewo ks: A Theo e ical-Expe imen al S udy o he Chemical
Fixa ion o CO2and Ca aly ic T ans e Hyd ogena ion o E hyl
Le ulina e o γ-Vale olac one. ACS Appl. Ma e . In e aces 2019,11,
41458−41471.
(18) Yun, W.-C.; Yang, M.-T.; Lin, K.-Y. A. Wa e -Bo n Zi conium-
Based Me al O ganic F amewo ks as G een and E ec i e Ca alys s o
Ca aly ic T ans e Hyd ogena ion o Le ulinic Acid o γ-Vale olac-
one: C i ical Roles o Modula o s. J. Colloid In e ace Sci. 2019,543,
52−63.
(19) Rojas-Buzo, S.; Ga cía-Ga cía, P.; Co ma, A. Ca aly ic T ans e
Hyd ogena ion o Biomass-De i ed Ca bonyls o e Ha nium-Based
Me al-O ganic F amewo ks. ChemSusChem 2018,11, 432−438.
(20) Ronaghi, N.; Shade, D.; Moon, H. J.; Najmi, S.; Cle eland, J.
W.; Wal on, K. S.; F ance, S.; Jones, C. W. Modula ion and Tuning o
UiO-66 o Lewis Acid Ca alyzed Ca bohyd a e Con e sion:
Con e sion o Unp o ec ed Aldose Suga s o Polyhyd oxyalkyl and
C-Glycosyl Fu ans. ACS Sus ainable Chem. Eng. 2021,9, 11581−
11595.
(21) Odoh, S. O.; C ame , C. J.; T uhla , D. G.; Gaglia di, L.
Quan um-Chemical Cha ac e iza ion o he P ope ies and Reac-
i i ies o Me al-O ganic F amewo ks. Chem. Re . 2015,115, 6051−
6111.
(22) Rogge, S. M. J.; Ba ykina, A.; Hajek, J.; Ga cía, H.; Oli os-
Sua ez, A. I.; Sepul eda-Esc ibano, A.; Vimon , A.; Cle , G.; Bazin, P.;
Kap eijn, F.; Da u i, M.; Ramos-Fe nandez, E. V.; Llab és i Xamena,
F. X.; Van Speyb oeck, V.; Gascon, J. Me al-O ganic and Co alen
O ganic F amewo ks as Single-Si e Ca alys s. Chem. Soc. Re . 2017,
46, 3134−3184.
(23) McCa e , G. A.; Rajeshkuma , T.; Vogia zis, K. D. Compu a-
ional Ca alysis o Me al-O ganic F amewo ks: An O e iew. Coo d.
Chem. Re . 2021,436, 213777.
(24) Yeh, J.-Y.; Li, S.-C.; Chen, C. H.; Wu, K. C.-W.; Li, Y.-P.
Quan um Mechanical Calcula ions o Biomass Valo iza ion o e
Me al-O ganic F amewo ks (MOFs). Chem.Asian J. 2021,16,
1049−1056.
(25) K esse, G.; Fu hmulle , J. E icien I e a i e Schemes o Ab
Ini io To al-Ene gy Calcula ions Using a Plane-Wa e Basis Se . Phys.
Re . B: Condens. Ma e Ma e . Phys. 1996,54, 11169−11186.
(26) K esse, G.; Fu hmulle , J. E iciency o Ab-Ini io To al Ene gy
Calcula ions o Me als and Semiconduc o s Using a Plane-Wa e
Basis Se . Compu . Ma e . Sci. 1996,6,15−50.
(27) Pe dew, J. P.; Bu ke, K.; E nze ho , M. Gene alized G adien
App oxima ion Made Simple. Phys. Re . Le . 1996,77, 3865−3868.
(28) G imme, S. Semiempi ical GGA- ype Densi y Func ional
Cons uc ed wi h a Long-Range Dispe sion Co ec ion. J. Compu .
Chem. 2006,27, 1787−1799.
(29) K esse, G.; Joube , D. F om Ul aso Pseudopo en ials o he
P ojec o Augmen ed-Wa e Me hod. Phys. Re . B: Condens. Ma e
Ma e . Phys. 1999,59, 1758−1775.
(30) Duda e , S. L.; Bo on, G. A.; Sa aso , S. Y.; Humph eys, C. J.;
Su on, A. P. Elec on-Ene gy-Loss Spec a and he S uc u al S abili y
o Nickel Oxide: An LSDA+U s udy. Phys. Re . B: Condens. Ma e
Ma e . Phys. 1998,57, 1505−1509.
(31) Fab is, S.; de Gi oncoli, S.; Ba oni, S.; Vica io, G.; Balducci, G.
Taming Mul iple Valency wi h Densi y Func ionals: A Case S udy o
De ec i e Ce ia. Phys. Re . B: Condens. Ma e Ma e . Phys. 2005,71,
041102.
(32) Capde ila-Co ada, M.; Łodziana, Z.; López, N. Pe o mance o
DFT+U App oaches in he S udy o Ca aly ic Ma e ials. ACS Ca al.
2016,6, 8370−8379.
(33) Vandichel, M.; Hajek, J.; Ghysels, A.; De Vos, A.; Wa oquie ,
M.; Van Speyb oeck, V. Wa e Coo dina ion and Dehyd a ion
P ocesses in De ec i e UiO-66 Type Me al O ganic F amewo ks.
C ys EngComm 2016,18, 7056−7069.
(34) Monkho s , H. J.; Pack, J. D. Special Poin s o B illouin-zone
In eg a ions. Phys. Re . B 1976,13, 5188−5192.
(35) Henkelman, G.; Jónsson, H. Imp o ed Tangen Es ima e in he
Nudged Elas ic Band Me hod o Finding Minimum Ene gy Pa hs
and Saddle Poin s. J. Chem. Phys. 2000,113, 9978−9985.
(36) Heyden, A.; Bell, A. T.; Keil, F. J. E icien Me hods o Finding
T ansi ion S a es in Chemical Reac ions: Compa ison o Imp o ed
Dime Me hod and Pa i ioned Ra ional Func ion Op imiza ion
Me hod. J. Chem. Phys. 2005,123, 224101.
(37) F equencies below 200 cm−1we e eplaced by 200 cm−1 o
species o a oid spu ious e o s when compu ing Gibbs ene gies.
(38) Bo, C.; Mase as, F.; López, N. The Role o Compu a ional
Resul s Da abases in Accele a ing he Disco e y o Ca alys s. Na .
Ca al. 2018,1, 809−810.
(39) Al a ez-Mo eno, M.; De G aa , C.; López, N.; Mase as, F.;
Poble , J. M.; Bo, C. Managing he Compu a ional Chemis y Big
Da a P oblem: he ioChem-BD Pla o m. J. Chem. In . Model. 2015,
55,95−103.
(40) ioChem-BD Da abase. h ps://iochem-bd.bsc.es/b owse/
handle/100/200147.DOI: 10.19061/iochem-bd-6-116.
(41) 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, 13850−13851.
(42) Vandichel, M.; Hajek, J.; Ve moo ele, F.; Wa oquie , M.; De
Vos, D.; Van Speyb oeck, V. Ac i e Si e Enginee ing in UiO-66 Type
Me al-O ganic F amewo ks by In en ional C ea ion o De ec s: A
Theo e ical Ra ionaliza ion. C ys EngComm 2015,17, 395−406.
(43) Cani e , J.; Vandichel, M.; Fa usseng, D. O igin o Highly
Ac i e Me al-O ganic F amewo k Ca alys s: De ec s? De ec s! Dal on
T ans. 2016,45, 4090−4099.
(44) Ling, S.; Sla e , B. Dynamic Acidi y in De ec i e UiO-66. Chem.
Sci. 2016,7, 4706−4712.
ACS Sus ainable Chemis y & Enginee ing pubs.acs.o g/jou nal/ascecg Resea ch A icle
h ps://doi.o g/10.1021/acssuschemeng.1c08021
ACS Sus ainable Chem. Eng. 2022, 10, 3567−3573
3572
(45) Gonell, F.; Bo ona , M.; Co ma, A. S uc u e-Reac i i y
Rela ionship in Isola ed Z Si es P esen in Z -Zeoli e and Z O2 o
he Mee wein-Ponndo -Ve ley Reac ion. Ca al. Sci. Technol. 2017,7,
2865−2873.
(46) Hajek, J.; Vandichel, M.; Van de Voo de, B.; Bueken, B.; De
Vos, D.; Wa oquie , M.; Van Speyb oeck, V. Mechanis ic S udies o
Aldol Condensa ions in UiO-66 and UiO-66-NH2Me al O ganic
F amewo ks. J. Ca al. 2015,331,1−12.
(47) Ca a elli, C.; Hajek, J.; Ci ujano, F. G.; Wa oquie , M.; Llab és
i Xamena, F. X.; Van Speyb oeck, V. Na u e o Ac i e Si es on UiO-66
and Bene icial In luence o Wa e in he Ca alysis o Fische
Es e i ica ion. J. Ca al. 2017,352, 401−414.
(48) O uno, M. A.; Be nales, V.; Gaglia di, L.; C ame , C. J.
Compu a ional S udy o Fi s -Row T ansi ion Me als Suppo ed on
MOF NU-1000 o Ca aly ic Accep o less Alcohol Dehyd ogena ion.
J. Phys. Chem. C 2016,120, 24697−24705.
(49) Si iwong, J.; Boonma k, S.; Nun haki goson, W.; Maihom, T.;
Wa anaki , C.; Lim akul, J. Densi y Func ional In es iga ion o he
Con e sion o Fu u al o Fu u yl Alcohol by Reac ion wi h i-
P opanol o e UiO-66 Me al-O ganic F amewo k. Ino g. Chem. 2021,
60, 4860−4868.
(50) Valeka , A. H.; Lee, M.; Yoon, J. W.; Kwak, J.; Hong, D.-Y.; Oh,
K.-R.; Cha, G.-Y.; Kwon, Y.-U.; Jung, J.; Chang, J.-S.; Hwang, Y. K.
Ca aly ic T ans e Hyd ogena ion o Fu u al o Fu u yl Alcohol
unde Mild Condi ions o e Z -MOFs: Explo ing he Role o Me al
Node Coo dina ion and Modi ica ion. ACS Ca al. 2020,10, 3720−
3732.
(51) Kim, M.; Cahill, J. F.; Fei, H.; P a he , K. A.; Cohen, S. M.
Pos syn he ic Ligand and Ca ion Exchange in Robus Me al-O ganic
F amewo ks. J. Am. Chem. Soc. 2012,134, 18082−18088.
(52) Lee, Y.; Kim, S.; Kang, J. K.; Cohen, S. M. Pho oca aly ic CO2
Reduc ion by a Mixed Me al (Z /Ti), Mixed Ligand Me al-O ganic
F amewo k Unde Visible Ligh I adia ion. Chem. Commun. 2015,
51, 5735−5738.
(53) Lamme , M.; Wha mby, M. T.; Smolde s, S.; Bueken, B.; Lieb,
A.; Lomachenko, K. A.; De Vos, D.; S ock, N. Ce ium-Based Me al
O ganic F amewo ks wi h UiO-66 A chi ec u e: Syn hesis, P ope ies
and Redox Ca aly ic Ac i i y. Chem. Commun. 2015,51, 12578−
12581.
(54) Momeni, M. R.; C ame , C. J. Compu a ional Sc eening o
Roles o De ec s and Me al Subs i u ion on Reac i i y o Di e en
Single- s Double-Node Me al-O ganic F amewo ks o Sa in
Decomposi ion. J. Phys. Chem. C 2019,123, 15157−15165.
(55) Sa aci, F.; Quezada-No oa, V.; Donna umma, R.; Howa h, A.
J. Ra e-Ea h Me al-O ganic F amewo ks: F om S uc u e o
Applica ions. Chem. Soc. Re . 2020,49, 7949−7977.
(56) Vi illo, J. G.; Lu, C. C.; C ame , C. J.; Bhan, A.; Gaglia di, L.
In luence o Fi s and Second Coo dina ion En i onmen on
S uc u al Fe(II) Si es in MIL-101 o C-H Bond Ac i a ion in
Me hane. ACS Ca al. 2021,11, 579−589.
(57) Wei, R.; Gaggioli, C. A.; Li, G.; Islamoglu, T.; Zhang, Z.; Yu, P.;
Fa ha, O. K.; C ame , C. J.; Gaglia di, L.; Yang, D.; Ga es, B. C.
Tuning he P ope ies o Z 6O8Nodes in he Me al O ganic
F amewo k UiO-66 by Selec ion o Node-Bound Ligands and
Linke s. Chem. Ma e . 2019,31, 1655−1663.
(58) Feng, X.; Hajek, J.; Jena, H. S.; Wang, G.; Vee apandian, S. K.
P.; Mo en , R.; De Gey e , N.; Leyssens, K.; Ho man, A. E. J.;
Meynen, V.; Ma quez, C.; De Vos, D. E.; Van Speyb oeck, V.; Leus,
K.; Van De Voo , P. Enginee ing a Highly De ec i e S able UiO-66
wi h Tunable Lewis-B øns ed Acidi y: The Role o he Hemilabile
Linke . J. Am. Chem. Soc. 2020,142, 3174−3183.
ACS Sus ainable Chemis y & Enginee ing pubs.acs.o g/jou nal/ascecg Resea ch A icle
h ps://doi.o g/10.1021/acssuschemeng.1c08021
ACS Sus ainable Chem. Eng. 2022, 10, 3567−3573
3573
Recommended by ACS
Re isi ing Vib a ional Spec oscopy o Tackle he
Chemis y o Z 6O8 Me al-O ganic F amewo k Nodes
Ignacio Rome o-Muñiz, Ana E. Pla e o-P a s,
e al.
MAY 31, 2022
ACS APPLIED MATERIALS & INTERFACES READ
Tuning Ca aly ic Si es on Z 6O8 Me al–O ganic
F amewo k Nodes ia Ligand and De ec Chemis y
P obed wi h
e
-Bu yl Alcohol Dehyd a ion o Isobu...
Dong Yang, B uce C. Ga es,
e al.
APRIL 05, 2020
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY READ
Tuning Z 12O22 Node De ec s as Ca aly ic Si es in he
Me al–O ganic F amewo k hcp UiO-66
Xi Chen, Dong Yang,
e al.
JANUARY 31, 2020
ACS CATALYSIS READ
Modula ing Chemical En i onmen s o Me al–O ganic
F amewo k-Suppo ed Molybdenum(VI) Ca alys s o
Insigh s in o he S uc u e–Ac i i y Rela ionship in...
Yongwei Chen, Oma K. Fa ha,
e al.
FEBRUARY 18, 2022
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY READ
Ge Mo e Sugges ions >
