Solar Gas-Phase CO2 Hydrogenation by Multifunctional UiO-66 Photocatalysts

Sola Gas-Phase CO2Hyd ogena ion by Mul i unc ional UiO-66
Pho oca alys s
Celia M. Rueda-Na a o, Zah aa Abou Khalil, A ianna Melillo, Belén Fe e , Raul Mon e o,
Asie Longa e, Ma co Da u i, Ignacio Vayá, Mohamad El-Roz, Vi ginia Ma ínez-Ma ínez,
He me G. Baldo í,*and Se gio Na alón*
Ci e This: ACS Ca al. 2024, 14, 6470−6487
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sı Suppo ing In o ma ion
ABSTRACT: Sola -assis ed CO2con e sion in o uels and chemical p oduc s
in ol es a ange o echnologies aimed a d i ing indus ial deca boniza ion me hods.
In his wo k, we epo on he de elopmen o a se ies o mul i unc ional me al−
o ganic amewo ks (MOFs) based on ni o- o amino- unc ionalized UiO-66(M) (M:
Z o Z /Ti) suppo ed RuOxNPs as pho oca alys s, ha ing di e en ene gy band
le el diag ams, o CO2hyd ogena ion unde simula ed concen a ed sunligh
i adia ion. RuOx(1 w %; 2.2 ±0.9 nm)@UiO-66(Z /Ti)-NO2was ound o be a
eusable pho oca alys , o be selec i e o CO2me hana ion (5.03 mmol g−1a e 22
h;, appa en quan um yield a 350, 400, and 600 nm o 1.67, 0.25, and 0.01%,
espec i ely), and o show abou 3−6 imes ac i i y compa ed wi h p e ious
in es iga ions. The pho oca alys s we e cha ac e ized by ad anced spec oscopic
echniques like em o- and nanosecond ansien abso p ion, spin elec on esonance,
and pho oluminescence spec oscopies oge he wi h (pho o)elec ochemical measu emen s. The pho oca aly ic CO2me hana ion
mechanism was assessed by ope ando FTIR spec oscopy. The esul s indica e ha he mos ac i e pho oca alys ope a es unde a
dual pho ochemical and pho o he mal mechanism. This in es iga ion shows he po en ial o mul i unc ional MOFs as pho oca alys s
o sola -d i en CO2 ecycling.
KEYWORDS: he e ogeneous pho oca alysis, mul i unc ional me al−o ganic amewo ks: UiO-66 opology, CO2me hana ion, sola ligh
1. INTRODUCTION
The p esen le el o bu ning ossil uels o mee he wo ld’s
ene gy equi emen s is s eadily aising he CO2emissions
eleased in o he a mosphe e and is esponsible o global
wa ming and clima e change.
1,2
The e is hus an u gen need
o shi om hese uels o enewable ene gy ob ained om
na u al esou ces like he sun, wind, wa e , o biomass.
3,4
The
de elopmen o echnologies based on ca bon- ee ene gy
ca ie s like g een hyd ogen is conside ed i al o help
deca bonize he wo ld’s economies,
5,6
whe eas ca bon cap u e,
s o age, and u iliza ion (CCSU) a e some p ocesses ha can
minimize he nega i e e ec s o CO2emissions.
7,8
E en hough
ce ain CCS p ocesses ha e achie ed ela i e success, mos o
he echnologies used o con e CO2in o aluable p oduc s o
uels a e s ill unde de elopmen ,
7−13
including sola -assis ed
pho oca alysis, which is conside ed o be a p omising cos -
e icien and sus ainable p ocess o ecycling CO2.
14−19
In
1978, a pionee ing s udy epo ed on he possibili y o
educing CO2using GaP as he pho oelec oca alys .
20
Since
hen, many o he ino ganic semiconduc o s
18,21−24
and, mo e
ecen ly, pe o ski es,
23,25
ca bon-based ma e ials simila o
g aphenes,
23,26,27
o ca bon ni ides,
23,28
among o he s,
23,29
ha e been used o his pu pose. H2as he educing agen
seems o be mo e sui able o achie ing be e pe o mance
han H2O.
30
Because i is expec ed ha g een hyd ogen will be
economically easible in he medium and long e m, his
inno a ion will boos he la ge-scale p oduc ion o compounds
and uels om CO2hyd ogena ion.
31
O hese, he pho o-
ca aly ic sola -d i en educ ion o CO2by H2 o CH4, a
p ocess also e med as he pho oca aly ic Saba ie eac ion, is
a ac ing inc easing in e es o he ansi ion o ze o ne
emissions.
32−34
This p ocess conside ably imp o es he
e iciency o he he moca aly ic eac ion e en when wo king
unde mild eac ion condi ions.
32
Fo example, pho oca aly ic
CO2me hana ion can be ca ied ou a much lowe eac ion
empe a u es (∼200 °C)
25
han he he moca aly ic e sion
(300−350 °C) while achie ing simila esul s.
25,32
The
syn he ic me hane hus ob ained can hen be di ec ed o he
exis ing na u al gas in as uc u es o minimize i s implemen-
a ion cos s.
33
To a lesse ex en , o he ela ed s udies ha e also
Recei ed: Janua y 12, 2024
Re ised: Ma ch 28, 2024
Accep ed: Ap il 2, 2024
Published: Ap il 12, 2024
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shown he possibili y o pe o ming he pho oca aly ic CO2
30
o CO
35
hyd ogena ion in o C2+ and e en C5+ alue-added
chemicals and uels.
A ela i ely new eme ging esea ch ield o sola -d i en
pho oca aly ic Saba ie eac ion using me al−o ganic ame-
wo ks (MOFs).
36
is unde de elopmen . MOFs a e po ous
c ys alline ma e ials buil om mul i opic o ganic ligands
coo dina ed o me al ions, me al clus e s, o me al-oxo
chains.
37−39
Fo abou 20 yea s, MOFs ha e been conside ed
as highly unable pho oca alys s o many o ganic and
ino ganic eac ions.
31,40−42
In he ield o CO2pho o educ ion,
mos o he knowledge achie ed so a has come om he
liquid-phase eac ion using o ganic sol en s in he p esence o
sac i icial elec on dono s unde UV− is o isible ligh
i adia ion.
40
Ace oni ile is equen ly used as a sol en o
a o CO2dissolu ion, whe eas ie hanolamine is employed as
he elec on dono o eco e pho ogene a ed holes, minimize
elec on−hole ecombina ion, and hus inc ease he e iciency
o he educ ion p ocess.
40
These s udies on MOFs ep esen
an in e es ing a ea o esea ch in unde s anding he heo e ical
and p ac ical aspec s o CO2con e sion.
A se ies o ecen s udies ha e epo ed on using MOFs as
pho oca alys s o gas-phase CO2 educ ion by H2unde
in e es ing eac ion condi ions o la ge-scale p ocesses. The
possibili y o using MOF-based ma e ials o he pho oca aly ic
gas-phase Saba ie eac ion unde UV− is a 215 °C
36
was
epo ed o he i s ime in 2019. Since hen, o he s udies
ha e desc ibed a p ocess wi h MOF-based pho oca alys s
modi ied wi h RuOxNPs o sola -assis ed CO2me hana ion a
200 °C. RuOxNPs a e he benchma k coca alys in achie ing
high e iciency du ing CO2(pho o)me hana ion.
32
Some o
hese pho oca alys s include Ti-MOFs, such as MIP-208(Ti)
43
o MIL-125(Ti)-NH2
44
unc ionalized wi h NH2g oups. The
p esence o amino g oups de e mines he MOF ene gy band
le el, i.e., a band gap educ ion and a nega i e shi o he
lowes unoccupied c ys al o bi al (LUCO) wi h espec o he
non unc ionalized pa en MOF, and a o s he he mody-
namics o he educ ion p ocesses.
45,46
O he s udies ha e
epo ed ha amino g oups in MOFs a o he s abiliza ion o
pho ogene a ed holes and, in u n, he pho oinduced cha ge
sepa a ion e iciency.
47,48
Amino-MOFs like UiO-66(Z )-NH2
ha e a highe CO2adso p ion capaci y han he analogous
UiO-66(Z )-NO2due o he bonding capaci y o he amino
g oups.
49
Despi e he esea ch on he possibili y o uning he
ene gy band diag am o MOFs wi h unc ional g oups o he
han amino g oups, such as ni o, b omo, o me hyl g oups,
and hei esul ing pho oca aly ic ac i i y, ew s udies ha e o
da e add essed i s in luence on pho oca aly ic CO2hyd o-
gena ion.
45,50,51
O he ela ed s udies ha e shown ha mixed-
me al MOFs in ol e highe pho oca aly ic ac i i y in CO2
educ ion.
45,52
Fo example, he be e pe o mance o he
UiO-66(Z /Ti)-based pho oca alys han UiO-66(Z ) is
associa ed wi h he ole o Ti(IV) as he elec on media o
ha a o s pho oinduced ligand- o-me al cha ge ans e
(LMCT) p ocesses om he o ganic ligand o he me al
node.
52,53
Despi e hese impo an indings, as a as we know,
no s udies ha e ye explo ed he possibili y o de eloping
mul i unc ional MOF-based ma e ials wi h a unique ene gy
band diag am de e mined by he p esence o speci ic unc ional
g oups, e.g., he amino o ni o g oups, simul aneously
con aining mixed-me al nodes o mo e e ec i e pho oinduced
Figu e 1. XRD o simula ed UiO-66 (a0, b0) o PXRD o UiO-66(Z )-NH2(a) o UiO-66(Z )-NO2(b) ma e ials. Legend panel a: UiO-66(Z )-
NH2(a1), RuOx@UiO-66(Z )-NH2(a2), UiO-66(Z /Ti)-NH2(a3), and RuOx@UiO-66(Z /Ti)-NH2(a4). Legend panel b: UiO-66(Z )-NO2
(b1), RuOx@UiO-66(Z )-NO2(b2), UiO-66(Z /Ti)-NO2(b3), and RuOx@UiO-66(Z /Ti)-NO2(b4). (c) HRTEM image and RuOxpa icle
size dis ibu ion o RuOx@UiO-66(Z /Ti)-NO2; RuOxa e age pa icle size and s anda d de ia ion o 2.08 ±0.82 nm. (d) d-spacing is de e mined
(0.32 nm) om he HRTEM image o RuOx@UiO-66(Z /Ti)-NO2.
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cha ge sepa a ion and coca alys s o boos he sola -assis ed
pho oca aly ic Saba ie eac ion.
In his con ex , we epo he e he de elopmen o
mul i unc ional ni o- o amino unc ionalized Z (IV)- o
Z (IV)/Ti(IV)-based-MOFs wi h a UiO-66 opology-sup-
po ed RuOxNPs o he sola -d i en solid−gas phase Saba ie
eac ion. The ma e ials we e cha ac e ized by powde X- ay
di ac ion (PXRD), analy ical, spec oscopic, and elec on
mic oscopy echniques, and hei pho oca aly ic ac i i ies we e
es ed unde simula ed concen a ed sunligh i adia ion.
Fem o- and nanosecond ansien abso p ion (TAS), pho o-
luminescence (PL), elec on spin esonance (ESR), and
elec ochemical impedance (EIS) spec oscopies oge he
wi h ansien pho ocu en measu emen s and addi ional
speci ic pho oca aly ic expe imen s we e used o de e mine he
ole o MOF coun e pa s du ing CO2pho ome hana ion ia a
likely dual pho ochemical and pho ochemical mechanism. The
pho oca aly ic CO2hyd ogena ion pa hway was s udied by
ope ando FTIR spec oscopy.
2. EXPERIMENTAL SECTION
De ails o he ma e ials, p epa a ion, cha ac e iza ion, and
pho oca aly ic p ocedu es used in he s udy can be ound in
he Suppo ing In o ma ion (Sec ions S1−S3).
2.1. Ma e ials, P epa a ion Me hods, and Cha ac e -
iza ion. All he ma e ials employed in his s udy we e o
analy ical o HPLC g ade and supplied by Me ck. UiO-66(Z )-
NH2and UiO-66(Z )-NO2we e p epa ed acco ding o
p e ious p ocedu es
54−56
and we e pos syn he ically modi ied
by a i anium(IV) chlo ide e ahyd o u an complex
[TiCl4(THF)2] complex o ob ain UiO-66(Z /Ti)-NH2and
UiO-66(Z /Ti)-NO2as epo ed.
57,58
RuOxNPs we e
suppo ed on hese ou UiO-66 solids using he pho o-
deposi ion me hod.
44
The solids we e cha ac e ized by PXRD, UV− is di use
e lec ance (UV− is DRS), X- ay pho oelec on (XPS),
elec on spin esonance (ESR), s eady-s a e PL, EIS, em o-
and nanosecond TAS spec oscopies, and elec on mic oscopy,
including ansmission elec on mic oscopy (TEM) o
scanning ansmission elec on mic oscopy (SEM) coupled
wi h an ene gy-dispe si e X- ay elec on (EDX) de ec o .
Iso he mal N2adso p ion, he mog a ime ic, and pho o-
elec ochemical measu emen s we e also used.
2.3. Pho oca aly ic Ac i i y. Pho oca aly ic eac ions
we e ca ied ou unde ba ch eac ion condi ions (Sec ion
S3), and he da a gi en he e a e he a e age o a leas h ee
sepa a e expe imen s.
3. RESULTS AND DISCUSSION
3.1. Pho oca alys Cha ac e iza ion. The MOF-based
ma e ials p epa ed, i.e., UiO-66(M)-X (M: Z and/o Ti; X:
NH2o NO2), bo h loaded o unloaded wi h RuOxNPs, we e
cha ac e ized by di e en echniques. PXRD analyses e ealed
ha hese solids had he expec ed UiO-66 opology (Figu e
1).
56
The ICP-OES analyses o acid-diges ed MOFs we e used
o quan i y he zi conium and/o i anium elemen s, ei he
loaded o no loaded wi h RuOxNPs a 1 w % o u henium.
UiO-66(Z /Ti)-NH2and UiO-66(Z /Ti)-NO2ha e a i a-
nium con en o 0.9 and 1.3 w %, espec i ely. In his ega d,
p e ious s udies epo ed ha pos syn he ic modi ica ion
(PSM) o UiO-66(Z ) based ma e ials wi h TiCl4(THF)2
complex esul s in he inco po a ion o Ti(IV) in he solid
by me al exchange and/o g a ing on o he me al node a he
linke acancy.
59
Pa ial eplacemen o Z (IV) by Ti(IV) ions
wi h smalle ionic adii con ac s he uni cell e lec ed in
PXRD by a small nega i e shi o he posi ion o he
di ac ion peaks. In he p esen wo k, UiO-66(Z /Ti)-X (X:
NH2o NO2) solids showed simila PXRD peak posi ions o
hose in zi conium, indica ing ha Ti(IV) ions a e mos ly
g a ed on o he MOF me al nodes.
57,59
The PXRD o UiO-66
solids loaded wi h RuOxNPs ha e simila ea u es o hose o
he pa en MOFs. The absence o RuOxdi ac ion peaks was
a ibu ed o he low u henium loading (1 w %) in he MOF
and/o good dispe sion o small NPs.
44
The HR-SEM analyses showed ha UiO-66 c ys als a e
cha ac e ized by he agglome a ion o small cubes wi h a e age
pa icle sizes and s anda d de ia ions o 118 ±57 nm (Figu e
S1). HR-SEM in combina ion wi h EDX analyses (Figu es S2−
S10) showed a good dis ibu ion o MOF elemen s wi hin he
pa icles. The ela i ely low in ensi y o u henium due o i s
low loading (1 w % Ru) was wi hin he ins umen ’s de ec ion
limi . DF-STEM coupled wi h EDX and HR-TEM measu e-
men s cha ac e ized RuOxNPs (2.14 ±0.86 nm) suppo ed
on UiO-66 pa icles. HRTEM measu emen s (Figu es S11−
S14) indica ed he p esence o 0.32 nm la ice spacings
(Figu es S15−S17), cha ac e is ic o he (110) ace o
RuO2.
60
The UiO-66 samples we e also cha ac e ized by XPS (Figu e
2and Figu es S18−S21) o de e mine he oxida ion s a e o
he elemen s wi hin he solids. The XPS spec a o he C 1s
Figu e 2. XPS su ey (a), C 1s (b), O 1s (c), N 1s (d), Z 3d (e), and
Ti 3p ( ) o UiO-66(Z )-NH2(1), UiO-66(Z /Ti)-NH2(2), UiO-
66(Z )-NO2(3), and UiO-66(Z /Ti)-NO2(4).
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egion a e associa ed wi h he p esence o he 2-amino o 2-
ni o e eph hala es ligands o he MOFs: C−C sp2bonds
(284.4 eV), COO−g oups (288 eV), and C−N bonds o
amino o ni o (∼285 eV) g oups. The N 1s XPS o amino-
unc ionalized UiO-66 solids shows he expec ed C−N signal
a abou 399 eV. In he case o ni o- unc ionalized UiO-66
ma e ials, N 1s XPS spec a a e domina ed by a main band a
405 eV due o he ni o g oup, whe eas a signal associa ed wi h
he p esence o an amino g oup can also be de ec ed. This
si ua ion, i.e., he p esence o a small band assigned o he
amino g oup when p epa ing ni o- unc ionalized UiO-66
solids, has p e iously been epo ed.
51
Fo he se ies o RuOx
NPs suppo ed UiO-66 solids, he XPS Ru 3d spec a showed a
weak band cen e ed a abou 282 eV (Figu es S22 and S25),
pa ially o e lapping wi h C−C sp2bond signals (284.4 eV),
which can be assigned o he p esence o RuO2NPs.
44
Suppo ed RuO2NPs we e u he cha ac e ized by Ru 3p
XPS, whe e he expec ed wo bands could be seen a abou
462.5 and 485 eV cha ac e is ic o Ru 3p3/2 and Ru 3 p1/2,
espec i ely. The O 1s XPS signal was assigned o he p esence
o COO−g oups (532 eV) and M−O bonds (M: Z , Ti o Ru)
(530 eV). Z 3d and Ti 2p XPS spec a showed he expec ed
signals o Z (IV) and Ti(IV) ions in he UiO-66 s uc u e. Z
3d XPS spec a had wo bands cen e ed a abou 182 and 185
eV due o Z 3d5/2 and Z 3d3/2, espec i ely. The XPS spec a
o he Ti 2p egion o mixed-me al UiO-66(Z /Ti)-X (X:
NH2o NO2) con i med he p esence o Ti(IV) indica ed by
wo bands a 459 and 464 eV due o Ti 2p3/2 and Ti 2p1/2,
espec i ely.
The UiO-66 solids we e analyzed by FTIR spec oscopy
(Figu e S26). In all cases, COO−g oups we e cha ac e ized by
s e ching ib a ions a abou 1574 and 1423 cm−1,
espec i ely. Amino- unc ionalized UiO-66 solids showed wo
bands a 3488 and 3374 cm−1due o he asymme ic and
symme ic ib a ions o −NH2, espec i ely, oge he wi h
ano he band a 1255 cm−1due o C−N s e ching ib a ion.
In he case o ni o- unc ionalized UiO-66 solids, wo bands
could be seen a abou 1543 and 1496 cm−1due o he
cha ac e is ic asymme ic and symme ic ib a ion bands o
his g oup, espec i ely. These spec a also showed small bands
a ibu able o he p esence o amino g oups, in good
ag eemen wi h he XPS analyses. These XPS and FTIR
esul s indica e a need o he de elopmen o new syn he ic
me hodologies o p epa e UiO-66 solids wi h only 2-
ni o e eph hal e ligands in hei s uc u e.
Iso he mal N2adso p ion measu emen s we e used o
es ima e he BET su ace a eas (Figu e S27) and po e olumes
o p is ine mono- and bime allic UiO-66 solids wi h alues
anging om 600 o 700 m2/g and 0.23 o 0.26 cm3/g,
espec i ely, in ag eemen wi h p e ious s udies.
57
TGA
analyses unde oxidan (ai ) o ine (ni ogen) a mosphe es
u he con i med ha hese UiO-66 samples a e he mally
s able a empe a u es o abou 300 °C, and hese obse a ions
a e in ag eemen wi h p e ious epo s (Figu e S28).
57,61,62
I
should be commen ed ha he s abili y obse ed below 300 °C
unde hese a mosphe es migh di e somehow he s abili y
unde he eac ion condi ions o pho oca aly ic CO2hyd o-
gena ion (H2/CO2mola a io 4:1 a 200 °C). Addi ionally, a
con ol expe imen e ealed ha he TGA o UiO-66(Z /Ti)-
NO2solid p e iously submi ed o hese eac ion condi ions
exhibi ed a e y simila TGA p o ile unde ai han he esh
sample, hus con i ming i s ela i e s abili y unde s udied
eac ion condi ions.
The op ical p ope ies o he UiO-66 ma e ials we e s udied
by UV− is DRS measu emen s. Figu e 3 shows ha he
p esence o NO2and especially NH2g oups in he MOF
o ganic ligand a o s isible ligh abso p ion wi h abso p ion
onse s a abou 400 and 450 nm, espec i ely. In he case o
amino- unc ionalized UiO-66 solids, he band cen e ed a
abou 365 nm is due o he in e ac ion o he lone pai o
elec ons o amino g oup wi h he π*-o bi al o a oma ic ing,
and his si ua ion esul s in a new highe HOCO le el ha
a o s isible ligh abso p ion.
63
Tauc plo analyses using he
UV− is DRS da a (Figu e S29) con i med ha he op ical
band gaps o amino- unc ionalized UiO-66 solids we e lowe
han hose o he ni o- unc ionalized UiO-66 solids.
64
Besides,
mixed-me al UiO-66 solids exhibi somehow lowe op ical
band gaps associa ed wi h he ole o Ti(IV) ions as elec on
media o s in ag eemen wi h p e ious expe imen al
48,58
and
heo e ical s udies.
65
XPS alence band measu emen s (Figu e
S30) we e used o es ima e he UiO-66 ene gy band diag ams
oge he wi h he op ical band gaps. In gene al, all he solids
possessed he he modynamic equi emen s o pho oca aly ic
CO2hyd ogena ion unde sunligh i adia ion, whe eas he
UV− is DRS o RuOxNPs on UiO-66 solids showed an ex a
weak abso p ion band in he isible egion associa ed wi h he
esonance plasmon band o hese NPs (Figu e S31).
3.2. Pho oca aly ic CO2Hyd ogena ion. UiO-66-based
solids we e i s es ed as pho oca alys s o CO2hyd o-
gena ion a 200 °C unde simula ed concen a ed sunligh
i adia ion (200 mW/cm2). Fo his pu pose, he qua z
Figu e 3. (a) UV− is DRS and (b) ene gy band le el diag am o UiO-66 solids as indica ed.
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eac o is hea ed wi h a man le, and hen he sys em was
i adia ed (see de ails in Sec ion 2). I should be emembe ed
ha 1 sun is de ined as 100 mW/cm2o i adiance. F om he
poin o iew o p ac ical applica ions, sola concen a o s
could be used o each he simula ed concen a ed sunligh
i adia ions used in his s udy. P is ine UiO-66 solids showed
li le ac i i y, and me hane was he only p oduc de ec ed (<30
μmol g−1). Speci ically, o illus a e he impo ance o
suppo ed RuOxNPs in enhancing he pho oca aly ic ac i i y,
he pe o mance o UiO-66(Z )-NH2, UiO-66(Z /Ti)-NH2,
UiO-66(Z )-NO2, and UiO-66(Z /Ti)-NO2was e alua ed and
obse ing only 2, 13, 3, and 4 μmol·g−1a e 22 h, espec i ely.
Howe e , RuOxNPs suppo ed UiO-66 ma e ials boos ed
ac i i ies owa d me hane gene a ion by a ious deg ees, in
ag eemen wi h he ole o RuOxNPs as benchma k coca alys s
o selec i e CO2(pho o)ca aly ic me hana ion.
32
RuOxNPs
ha e he abili y o a o chemiso p ion CO2and i s eac ion
in e media es like CO o H2CO wi h su icien s eng h o be
comple ely hyd ogena ed o me hane.
34
E en hough ou
analyses allow iden i ica ion and quan i ica ion o se e al
ca bon p oduc s such as CO o sho -chain hyd oca bons (see
Suppo ing In o ma ion Sec ion S3), me hane was he main
p oduc oge he wi h small amoun s o e hane de ec ed o all
es ed pho oca alys s. In o he wo ds, all (pho o)ca aly ic es s
ca ied ou in his s udy esul ed in me hane selec i i ies highe
han 99%. Con ol expe imen s in which CO2was eplaced by
A did no indica e he o ma ion o me hane o any o he
p oduc . Because o he simila pa icle size dis ibu ion o
RuOxNPs suppo ed on UiO-66 solids, i.e., a mean a e age
pa icle size and s anda d de ia ions o 2.14 ±0.04 nm, we
conside ha he composi ion o he UiO-66 pho oca alys s
de e mines he esul ing ac i i ies. Fu he mo e, i was ound
ha p oduc selec i i y is no in luenced by he use o UiO-66
composi ion loaded o no wi h RuOxNPs. As an example, he
p oduc selec i i y dis ibu ion o he mos ac i e RuOx@UiO-
66(Z /Ti)-NO2indica es a CH4selec i i y highe han 99%
accompanied by e hane. Figu e 4 shows ha ni o- unc ion-
alized UiO-66 pho oca alys s a e mo e ac i e han amino-
unc ionalized UiO-66 pho oca alys s. This is an impo an
inding because, as commen ed in he in oduc ion, amino-
unc ionalized MOFs like UiO-66 a e among he p e e ed
solids o pho oca aly ic applica ions, including CO2 educ ion.
Rega dless o UiO-66(Z )-NO2’s highe op ical band gap han
UiO-66(Z )-NH2(3.16 s 2.79 eV), i s be e educ ion and
oxida ion capaci y han hose o he amino g oup seems o
de e mine i s pho oca aly ic ac i i y (see Figu e 3). Figu e 4
also shows ha he pho oca aly ic ac i i ies o RuOxNPs
suppo ed UiO-66(Z )-X (X: NH2o NO2) a e u he
inc eased by he p epa a ion o analogous mixed-me al Z /Ti
ma e ials. P e ious s udies ha e demons a ed he ole o
Ti(IV) ions in he me al node o UiO-66(Z /Ti)-NH2as
pho oinduced elec on ans e media o s.
48,58
As will be
shown below, he be e pe o mance o mixed-me al UiO-66
pho oca alys s suppo ed by RuOxNPs han hose analogous
monome allic ones can be a ibu ed o he inc eased
pho oinduced cha ge sepa a ion e iciency, as shown by he
spec oscopic and elec ochemical cha ac e iza ion.
To u he e i y he ole o ni o o amino g oups in UiO-
66(Z )-X (X: NO2o NH2) on he esul ing pho oca aly ic
ac i i y, an analogous pho oca alys e med as UiO-66(Z ) was
Figu e 4. (a) Pho oca aly ic CO2me hana ion using RuOx@UiO-66 solids unde simula ed concen a ed sunligh i adia ion. Legend: (a1) UiO-
66(Z )-NH2, (a2) UiO-66(Z /Ti)-NH2, (a3) UiO-66(Z )-NO2, and (a4) UiO-66(Z /Ti)-NO2. In luence o eac ion empe a u e on me hane
gene a ion du ing pho oca aly ic CO2 educ ion unde ligh (b) o da k (c) condi ions. (d) The A henius plo ob ained om ini ial eac ion a es
o me hane gene a ion as a unc ion o he eac ion empe a u e unde da k o ligh condi ions as indica ed. Reac ion condi ions: pho oca alys (15
mg), CO2/H2(1:4), 200 °C, simula ed concen a ed sunligh (200 mW/cm2) i adia ion.
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p epa ed using e eph halic acid as o ganic ligand and u he
modi ied wi h RuOxNPs by he pho odeposi ion me hod. The
samples we e cha ac e ized by PXRD, spec oscopic (UV− is,
XPS), analy ical (TGA), ex u al (iso he mal N2adso p ion),
and elec on mic oscopic echniques (Figu es S32−S37).
PXRD con i med ha RuOx@UiO-66(Z ) and UiO-66(Z )
samples a e isos uc u al c ys alline ma e ials wi h UiO-66
opology (Figu e S32). XPS analyses e ealed he gene al
expec ed ea u es o XPS C 1s, O 1s, Z Ru 3d, and 3p (Figu e
S33). These solids a e cons i u ed by pa icles o 98 ±63 nm
as e ealed by SEM analyses (Figu e S34). TEM measu e-
men s e ealed he p esence o suppo ed RuOxNPs wi h sizes
o 2.4 ±0.8 nm (Figu e S35). The sample exhibi ed good
po osi y (1008 m2/g and 0.38 cm3/g) and he mal s abili y
unde ai a mosphe e (>400 °C) (Figu e S36). The ene gy
band le el diag am o UiO-66(Z ) is cha ac e ized by a wide
op ical band gap (3.7 eV) wi h HOCO and LUCO posi ions o
+1.81 and −2.15 V, espec i ely (Figu e S37). The use o
RuOx@UiO-66(Z ) and p is ine UiO-66(Z ) as pho oca alys s
unde condi ions desc ibed in Figu e 4 showed a selec i e
me hane p oduc ion o 500 and 2 μmol g−1, espec i ely, a e
22 h. The ac i i y o his RuOx@UiO-66(Z ) pho oca alys is
sligh ly lowe han ha o RuOx@UiO-66(Z )-NH2and abou
h ee imes lowe han ha achie ed using he RuOx@UiO-
66(Z )-NO2pho oca alys . Rega dless o he lowe CO2
adso p ion capaci y and highe op ical band gap o UiO-
66(Z ) compa ed o UiO-66(Z )-NH2, hei pho oca aly ic
ac i i ies a e simila o each o he . In con as , as p e iously
commen ed, RuOx@UiO-66(Z )-NO2exhibi s highe ac i i y
associa ed wi h i s unique s uc u e due o he p esence o
ni o unc ional g oups. The pe o mance o he mos ac i e
RuOx@UiO-66(Z /Ti)-NO2sample (∼13% CO2con e sion;
5.03 mmolCH4·g−1a e 22 h) du ing pho oca aly ic CO2
hyd ogena ion o CH4was u he s udied. A pho oca aly ic
expe imen using labeled 13CO2and gas-phase aliquo analysis
by GC coupled o mass spec ome e using an elec on
ioniza ion me hod con i med he o ma ion o 13CH4(m/z17)
a e 22 h o eac ion a 200 °C (Figu e S38). I should be
no ed, howe e , ha he cha ac e is ic ioniza ion p o ile o
me hane di e s o some ex en o he one ob ained and
associa ed wi h he con ibu ion o o he molecules like H2O
and ai om ambien du ing he injec ion ha a e no
ch oma og aphically sepa a ed in ou sys em. As will be shown
la e in Sec ion 3.3.2, he ans o ma ion o CO2in o CH4has
been u he con i med by using ope ando FTIR analyses. A
con ol expe imen unde da k eac ion condi ions a 200 °C
also e ealed lowe CH4p oduc ion (1.9 mmol g−1a e 22 h)
han ha achie ed unde simula ed concen a ed sunligh
i adia ion. The obse a ion o some ac i i y unde da k
eac ion condi ions was no unexpec ed because p e ious
s udies ha e epo ed ha RuOxNPs a e an ac i e and
selec i e coca alys du ing he mal ca aly ic p ocesses.
32
Quan i a i e in o ma ion on he pe o mance o RuOx@UiO-
66(Z /Ti)-NO2as a pho oca alys a 200 °C was ob ained by
es ima ing he appa en quan um yield (AQY) a speci ic
wa eleng hs. A e deduc ing he ac i i y obse ed unde da k
eac ion condi ions, he AQYs achie ed by i adia ion a 350,
400, and 600 nm we e 1.67, 0.25, and 0.01%, espec i ely. The
in luence o he eac ion empe a u e on he pho oca aly ic
ac i i y o RuOx@UiO-66(Z /Ti)-NO2was hen s udied (see
esul s in Figu e 4b). As can be seen, pho oca aly ic me hane
gene a ion as a unc ion o he eac ion empe a u e ollows
he A henius law and allowed us o es ima e an appa en
ac i a ion ene gy (Ea) o 58.7 kJ/mol. In a se ies o analogous
expe imen s ca ied ou in he absence o i adia ion ( he mal
ca alysis), he es ima ed Ea esul ed o be 84.3 kJ/mol. Based
on analogous s udies
66−68
and as will be u he s udied in
Sec ion 3.3, his signi ican dec ease in Ea can be a ibu ed o
he ope a ion o a pho o he mal eac ion pa hway.
Figu e 5. (a) Reusabili y o RuOx@UiO-66(Z /Ti)-NO2du ing pho oca aly ic CO2me hana ion. (b) PXRD o RuOx@UiO-66(Z /Ti)-NO2 esh
(1) and used (2). (c) TEM image and pa icle size dis ibu ion o used pho oca alys . (d) HRTEM o in e plana dis ance.
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The pho oca aly ic ac i i y o RuOx@UiO-66(Z /Ti)-NO2
was compa ed wi h hose MOF-based pho oca alys s epo ed
in p e ious s udies, and he esul s a e summa ized in Table
S1. The use o he same eac ion condi ions han mos o he
s udies in Table S1, i.e., PH2 = 1.05 ba and PCO2 = 0.25 ba
ins ead he p e ious PH2 = 1.2 ba and PCO2 = 0.3 ba , esul ed
in a me hane p oduc ion dec ease o abou 5% in ag eemen
wi h Cha elie ’s p inciple. RuOxNPs suppo ed ime allic
UiO-66(Z /Ce/Ti) was ecen ly epo ed as one o he mos
ac i e MOF-based pho oca alys s o CO2me hana ion unde
simula ed concen a ed sunligh i adia ion (1.8 mmol g−1CH4
a e 22 h a 200 °C) (Table S1, en y 2), showing ha he
ac i i y o RuOx@UiO-66(Z /Ti)-NO2is abou 3 imes highe
han his pho oca alys unde simila eac ion condi ions.
Fu he mo e, RuOx@UiO-66(Z /Ti)-NO2exhibi s an ac i i y
3−6 imes highe han ha achie ed using analogous solids
based on RuOxNPs suppo ed on Ti-based MOFs, such as
MIL-125(Ti)-NH2(Table S1, en ies 3 and 4) o MIP-
208(Ti) (Table S1, en y 5). I is ema kable ha he ac i i y
o RuOx@UiO-66(Z /Ti)-NO2(Table S1, en y 1) is mo e
han wo imes compa ed wi h RuOx@MIL-125(Ti)-NH2
(Table S1, en y 4) ha ing double he amoun o u henium
(2 w %). I should be no ed ha all hese pho oca alys s ha e
a simila RuOxNP loading (1 w % o u henium) and an
a e age pa icle size (∼2 nm). The highe ac i i y o RuOx@
UiO-66(Z /Ti)-NO2 hus appea s o be ela ed o he ene gy
band diag am le el o he pho oca alys de e mined by he
combina ion o 2-ni o e eph hala es ligands and mixed-me al
Z (IV)/Ti(IV) me al nodes, which boos s he e iciency o he
eac ion. Rega dless o hese commen s, i is pe inen o
men ion ha he s a e-o - he-a in cu en pho oca aly ic
gaseous me hana ion has epo ed ac i i ies, in some cases,
g ea e han 100 mmol g−1h−1. In one o hese examples,
ul a hin Mg−Al laye ed double hyd oxide nanoshee
suppo ed Ru NPs we e ound o achie e e icien pho o-
he mal CO2me hana ion (277 mmol h−1g−1; 300 W Xe
lamp) unde con inuous low ope a ion.
69
The ac i i y and s abili y o RuOx@UiO-66(Z /Ti)-NO2
we e s udied by pe o ming consecu i e euse expe imen s.
Figu e 5 shows ha he pho oca alys can be eused wi hou
signi ican loss o ac i i y o ou consecu i e imes wi h an
accumula ed eac ion ime o 90 h. Acco ding o PXRD
analysis, he c ys allini y o he ou - imes used pho oca alys is
p ese ed. TEM analyses o he eused pho oca alys
con i med ha RuOxa e age pa icle size and s anda d
de ia ion (2.32 ±0.90 nm) a e simila compa ed o he
esh sample (2.08 ±0.82 nm). Besides, HR-TEM cha ac e -
iza ion o he used pho oca alys e ealed he p esence o
la ice inges wi h spacings o abou 0.203 and 0.32 nm, which
we e asc ibed o he c ys al planes (101) and (110) o Ru(0)
and RuO2, espec i ely (Figu es 5d and S39).
C 1s, O 1s, Z 3d, and Ti 2p XPS analyses o he ou - imes
used pho oca alys (Figu e S40) showed simila ea u es o
hose o he esh ma e ial, whe eas N 1s and Ru 3d XPS
showed small bu app eciable di e ences wi h espec o he
esh sample (Figu e 6 and Figu e S41). N 1s XPS o he used
pho oca alys e ealed sligh hyd ogena ion o he ni o g oup
o he amino g oup (Figu e 5). Speci ically, he esh and used
RuOx@UiO-66(Z /Ti)-NO2pho oca alys s ha e a p opo ion
in weigh pe cen o NO2 e sus NH2o 55.2/44.8 and 46.8/
53.2, espec i ely. Al hough pa ial educ ion o NO2 o NH2is
obse ed in he used RuOx@UiO-66(Z /Ti)-NO2pho o-
ca alys by XPS, he s uc u al in eg i y o he used
pho oca alys s ill con ains enough NO2g oups (46.8 a %)
o p omo e he pho oca alys ac i i y wi hou much signi ican
di e ence (Figu e 6). Fu he mo e, UV− is DRS o he used
sample showed an ex a abso p ion band wi h onse abso p ion
a abou 430 nm, which ag ees wi h he pa ial ni o
hyd ogena ion o he amino g oup (Figu e 5). In he case o
Ru 3d XPS, a small shi o he Ru 3 d5/2 was seen owa d
lowe binding ene gies wi h espec o he esh sample (281.9
s 280.8 eV). These esul s ag ee wi h p e ious s udies ha
also showed he suppo ed RuOxNPs employed as coca alys s
du ing (pho o)ca aly ic hyd ogena ions a empe a u es o
abou 200 °C can be con e ed o some ex en o he me allic
phase.
44,69−72
In he p esen s udy, addi ional in si u XPS expe imen s in
which he esh RuOx@UiO-66(Z /Ti)-NO2sample is
submi ed o a H2 he mal ea men a 200 °C also e ealed
ha suppo ed RuOxNPs a e suscep ible o be pa ially
educed o me allic NPs unde he s udied eac ion condi ions
(Figu e S42). I should be no ed ha me allic u henium
species ha e been p oposed as esponsible species o ac i a e
molecula H2and ini ia e CO2hyd ogena ion.
69,70,72,73
Be-
sides, as will be shown la e , RuOxand Ru species also a o
CO2and CO chemiso p ion as e idenced by FTIR spec os-
copy. O e all, hese esul s demons a e ha RuOxNPs
suppo ed on UiO-66(Z /Ti)-NO2a e pa ially educed
du ing he pho oca aly ic CO2hyd ogena ion p ocess, leading
o he coexis ence o suppo ed RuOx and Ru(0) species
wi hin he pho oca alys .
In he a ea o pho oca alysis using MOFs, some s udies ha e
epo ed UV− is i adia ion o ca boxyla e-based MOFs a 200
°C ha esul ed in pa ial deca boxyla ion.
74
To add ess his
issue, a pho oca aly ic con ol expe imen in which CO2was
eplaced by A e ealed he p esence o CO2, a ibu ed o he
pa ial deca boxyla ion o he e eph hala e MOF ligand du ing
he eac ion (1.8 w % wi h espec o he amoun o he ini ial
ca boxyla e). These esul s indica e a need o de elop ac i e
MOF-based pho oca alys s ha can ope a e unde milde
eac ion condi ions wi h ope a ional s abili ies.
Figu e 6. (a) C 1s + Ru 3d, (b) Ti 2p + Ru 3p, (c) N 1s XPS o esh
(1) and used (2) pho oca alys , and (d) UV− is o esh and used
RuOx@UiO-66(Z /Ti)-NO2.
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3.3. Pho oca aly ic Reac ion Pa hways. 3.3.1. Explo a-
ion o Pho ochemical and Pho o he mal Reac ion Mech-
anisms. Based on p e ious epo s, pho oca aly ic CO2
educ ion using me al/me al oxide NPs suppo ed on MOFs
o o he ma e ials can occu ia pho ochemical
24,34
and/o
pho o he mal eac ion mechanisms.
24,34,75−77
Du ing he
pho ochemical pa hway, he i adia ion o he pho oca alys s
esul s in he o ma ion o educing and oxidizing elec on and
hole pai s, espec i ely. This is a common eac ion mechanism
ound when using MOFs as pho oca alys s when hei
i adia ion by app op ia e wa eleng hs p oduces pho oinduced
elec on ans e om he o ganic ligand o he me al node.
43
The p esence o MNPs like RuOxas coca alys s can also a o
pho ochemical pa hway e iciency by opening new channels o
cha ge ca ie sepa a ion and enhancing pho oca aly ic
ac i i y.
44
RuOxNPs ha e also been epo ed o p omo e he
pho o he mal eac ion pa hway in which ligh ene gy is
ans o med in o hea , which a o s CO2me hana ion.
75
Se e al cha ac e iza ion echniques we e used o u he
s udy hese possible eac ion pa hways using RuOxNPs
suppo ed UiO-66(Z and/o Ti)-X (X: NH2o NO2). I
should be no ed ha , as shown in Figu e 6, he RuOx@UiO-
66(Z /Ti)-NO2pho oca alys used exhibi s a pa ial educ ion
o suppo ed RuOxNPs wi h espec o he esh sample. To
conside he possible in luence o he RuOxoxida ion s a e on
he subsequen cha ac e iza ion da a, some compa a i e
measu emen s we e ca ied ou using bo h esh and used
pho oca alys s.
To e alua e he pho oinduced p ocesses a ising om he
exci a ion o he di e en UiO-66(Z /Ti)-X (X: NH2o NO2)
pho oca alys s a 267 nm,
30,75
hese we e i s s udied by
em osecond TAS ( s-TAS). This echnique has been shown o
be sensi i e and p ecise o in es iga ing p ocesses occu ing a
a e y ea ly s age a e exci a ion, including ul a as elec on
ans e o cha ge sepa a ion.
78
The eco ded ansien
abso p ion spec a (Figu e S43) and kine ics (Figu e S44) o
UiO-66(Z )-NH2showed good ag eemen wi h p e iously
epo ed obse a ions,
79
whe eas no able di e ences we e
ound in he ansien abso p ion spec a when using NO2
(Figu e S45). The ansien abso bance o he la e samples
co e s he en i e isible spec um and does no exhibi any
ema kable band/ ea u e (Figu e S45). A se o he kine ic
aces anging om 550 o 750 nm we e analyzed by means o
a global i , including wo- ime cons an s, o desc ibe he
dynamics du ing he i s nanoseconds a e pho oexci a ion.
Table S2 includes he esul ing ime cons an s o all he
species s udied. The as es componen s (o he o de o a ew
ens o picoseconds) we e associa ed wi h elec on ans e
p ocesses om HOCO o LUCO o MOFs,
79
whe esa he
longe -li ed componen s, which emained up o he nano-
second ime scale, we e assigned o a deep ap s a e.
80
Figu es
7a shows o ni o- unc ionalized UiO-66 solids a compa ison
o he ansien s oge he wi h he a e age li e imes calcula ed
o each p obe wa eleng h on he basis o he ime cons an s
de i ed om he global i . The da a e eal ha he as es
elaxa ion dynamics is ha o RuOx@UiO-66(Z /Ti)-NO2
ollowed by an analogous mixed-me al UiO-66(Z /Ti)-NO2
pa en sample, whe eas monome allic UiO-66(Z )-NO2
exhibi ed longe -li ed componen s. Simila conclusions can
be d awn o amino- unc ionalized UiO-66 ma e ials (Figu e
S44). In his ega d, kine ic aces ha e been used as indica o s
o e alua e elec on−hole sepa a ion e iciency o he pho o-
ca alys s. I is he e o e p oposed, by means o compa isons
wi h p e ious ul a as esul s om ela ed MOFs,
79
ha he
as e he elaxa ion dynamics is, he highe is he cha ge-
sepa a ion e iciency. In ac , he o de o pho oca aly ic
ac i i y in ou case ag ees, o some ex en , wi h he elaxa ion
ace kine ics using ul a as TAS measu emen s.
Long-li ed ap s a es o UiO-66 pho oca alys s we e
u he in es iga ed on longe ime scales by he lase lash
pho olysis (LFP) echnique a λexc = 266 nm. The spec a
ob ained o he di e en ni o- (Figu e 7b and Figu e S46)
and amino- (Figu e S47) unc ionalized UiO-66 pho oca alys s
in an A a mosphe e on he nanosecond ime scale we e
cha ac e ized by a con inuous abso p ion band om 300 o
750 nm. P e ious TAS s udies by some o us using UiO-
66(Z )-X (X: NH2o NO2) assigned hese ansien
abso p ion bands o pho ogene a ed elec on and holes
based on selec i e quenching expe imen s.
51,54
Simila
conclusions ha e been ob ained in he p esen case using
me hanol as hole quenche o he se ies o amino- unc ion-
alized UiO-66 solids. Figu e S48 shows ha me hanol
quenches he egion om 300 o 400 nm, esul ing in a
pa allel inc ease o he ansien signals a ound 600 nm, which
indica es ha hole deac i a ion enhances he yield o
pho ogene a ed elec ons, an e ec p e iously ound in o he
ela ed MOF-based pho oca alys s.
81,82
These esul s ag ee
wi h hose ob ained om ul a as TAS and demons a e he
pho ogene a ion o cha ge sepa a ion species as elec ons and
holes. In line wi h he ul a as esul s, LFP decay aces a 400
and 680 nm show ha he as e he decay componen s a e
(see Table S2), he highe is he pho oca aly ic ac i i y o all
he s udied RuOxNPs suppo ed UiO-66(Z /Ti)-X (X: NH2
o NO2) in hei se ies. In sho , in e ms o pho oca alys
decay elaxa ion dynamics, bo h s- and ns-TAS se e as
Figu e 7. (a) Fem osecond ansien abso p ion eco ded a 586 nm and (b) LFP decay aces eco ded a 520 nm o UiO-66(Z )-NO2(black),
UiO-66(Z /Ti)-NO2( ed), and RuOxUiO-66(Z /Ti)-NO2(blue). s-TAS measu emen s we e pe o med a λexc = 267 nm in ae a ed MeCN,
whe eas hose o LFP we e done a λexc = 266 nm in MeCN unde an A a mosphe e.
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indica o s o cha ge sepa a ion e iciency and ag ee wi h he
o de obse ed in hei pho oca aly ic ac i i y.
To u he e alua e he pho oinduced cha ge sepa a ion
e iciency o UiO-66 solids and hei ela ionship wi h hei
pho oca aly ic ac i i ies, pho oca alys s we e cha ac e ized by
PL spec oscopy and ansien pho ocu en and EIS measu e-
men s. PL spec oscopy is commonly used in he e ogeneous
pho oca alysis, including MOFs, o e alua e he pho oexci ed
cha ge ans e and ecombina ion p ocesses.
83,84
Amino
unc ionalized UiO-66 solids ha e a di e en deg ee o
luo escence, whe eas negligible emission was ound when
using he ni o- unc ionalized solids. These esul s ag ee wi h
some o ou p e ious esul s showing ha ace oni ile solu ions
o 2-amino e eph hala e emi much mo e on exci a ion a 266
nm han he analogous 2-ni o e eph hala e ace oni ile
solu ions.
54
Figu e 8a shows ha he UiO-66(Z /Ti)-NH2
suspension has lowe emissions han UiO-66(Z )-NH2, which
ag ees wi h simila s udies ha highligh ed he highe e iciency
o pho oinduced cha ge sepa a ion o mixed-me al UiO-
66(Z /Ti)-NH2solids, in which Ti(IV) a oms ac as he
elec on media o du ing he p ocess.
48
Simila measu emen s
using esh o used RuOxNPs suppo ed UiO-66(Z )-NH2,
and specially UiO-66(Z /Ti)-NH2solids, p oduced consid-
e ably less luo escence emission in ensi y. Rega dless o he
much lowe luo escence emission in ensi y obse ed when
using ni o- unc ionalized UiO-66-based solids compa ed o
amino ones, analogous conclusions abou he luo escence
quenching in mixed-me al solids wi h o wi hou esh and
used RuOx wi h espec o he pa en sample can be d awn
(Figu e 8b). These esul s indica e ha he p esence o RuOx
NPs in he UiO-66 solids educes he ecombina ion a e o
pho ogene a ed elec on−hole pai s and hus inc eases he
e iciency o pho oinduced cha ge sepa a ion.
The ansien pho ocu en esul s using UiO-66 solids
unde se e al on/o illumina ion cycles a e shown in Figu e 8.
Fo hese measu emen s, UiO-based pho oca alys s we e
Figu e 8. (a) PL measu emen s pe o med in ace oni ile MOF suspension ha ing he same op ical abso p ion (ca. 35 au) a 266 nm co esponding
wi h he monoch oma ic exci a ion wa eleng h o he MOF o ganic. (b) Cu en in ensi y esponse o amino- (c) o ni o-based (d) UiO-66 solids.
Nyquis plo s o amino- (e) o ni o-based ( ) UiO-66 solids unde da k o simula ed concen a ed sunligh i adia ion as indica ed. Legend: (c1)
UiO-66(Z )-NH2, (c2) UiO-66(Z /Ti)-NH2, (d1) UiO-66(Z )-NO2, (d2) UiO-66(Z /Ti)-NO2, (d3) RuOx@UiO-66(Z /Ti)-NO2 esh, and
(d4) RuOx@UiO-66(Z /Ti)-NO2used.
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■ACKNOWLEDGMENTS
C.M.R.N. hanks he suppo o PRE2019-089877 unded by
MICIU/AEI/10.13039/501100011033. I.V. hanks he sup-
po o g an PID2020-115010RB-I00 unded by MICIU/AEI/
10.13039/501100011033. A.L. hanks he suppo om he
MICIU h ough g an PID2021-127918NB-I00. V.M.M.
hanks inancial suppo o g an s PID2020-114347RB-C32
unded by MICIU/AEI/10.13039/501100011033 as well as
Vasco-Eusko Jau la i za (p ojec IT1639-22) and by ERDF “A
way o making Eu ope”. The METHASOL p ojec ecei es
unding om he Eu opean Union Ho izon 2020 esea ch and
inno a ion p og amme unde G an Ag eemen N°10102264.
Funding o open access cha ge: CRUE-Uni e si a Poli ecnica
de Valencia. S.N. hanks he suppo o g an PID2021-
123856OBI00 unded by MICIU/AEI/10.13039/
501100011033 and by ERDF “A way o making Eu ope”.
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