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 Read Online ACCESS Me ics & Mo e A icle Recommenda ions * 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 Resea ch A iclepubs.acs.o g/acsca alysis © 2024 The Au ho s. Published by Ame ican Chemical Socie y 6470 h ps://doi.o g/10.1021/acsca al.4c00266 ACS Ca al. 2024, 14, 6470−6487 This a icle is licensed unde CC-BY 4.0 Downloaded ia UNIV DEL PAIS VASCO on Augus 8, 2024 a 11:54:12 (UTC). See h ps://pubs.acs.o g/sha ingguidelines o op ions on how o legi ima ely sha e published a icles. 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. ACS Ca alysis pubs.acs.o g/acsca alysis Resea ch A icle h ps://doi.o g/10.1021/acsca al.4c00266 ACS Ca al. 2024, 14, 6470−6487 6471 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). ACS Ca alysis pubs.acs.o g/acsca alysis Resea ch A icle h ps://doi.o g/10.1021/acsca al.4c00266 ACS Ca al. 2024, 14, 6470−6487 6472 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. ACS Ca alysis pubs.acs.o g/acsca alysis Resea ch A icle h ps://doi.o g/10.1021/acsca al.4c00266 ACS Ca al. 2024, 14, 6470−6487 6473 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. ACS Ca alysis pubs.acs.o g/acsca alysis Resea ch A icle h ps://doi.o g/10.1021/acsca al.4c00266 ACS Ca al. 2024, 14, 6470−6487 6474 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. ACS Ca alysis pubs.acs.o g/acsca alysis Resea ch A icle h ps://doi.o g/10.1021/acsca al.4c00266 ACS Ca al. 2024, 14, 6470−6487 6475 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. ACS Ca alysis pubs.acs.o g/acsca alysis Resea ch A icle h ps://doi.o g/10.1021/acsca al.4c00266 ACS Ca al. 2024, 14, 6470−6487 6476 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. ACS Ca alysis pubs.acs.o g/acsca alysis Resea ch A icle h ps://doi.o g/10.1021/acsca al.4c00266 ACS Ca al. 2024, 14, 6470−6487 6477 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. ACS Ca alysis pubs.acs.o g/acsca alysis Resea ch A icle h ps://doi.o g/10.1021/acsca al.4c00266 ACS Ca al. 2024, 14, 6470−6487 6478 ■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”. 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