2D Covalent Organic Frameworks as Intrinsic Photocatalysts for Visible Light-Driven CO2 Reduction

Article abstract of DOI:10.1021/jacs.8b09705

Covalent organic framework (COF) represents an emerging class of porous materials that have exhibited great potential in various applications, particularly in catalysis. In this work, we report a newly designed 2D COF with incorporated Re complex, which exhibits intrinsic light absorption and charge separation (CS) properties. We show that this hybrid catalyst can efficiently reduce CO₂ to form CO under visible light illumination with high electivity (98%) and better activity than its homogeneous Re counterpart. More importantly, using advanced transient optical and X-ray absorption spectroscopy and in situ diffuse reflectance spectroscopy, we unraveled three key intermediates that are responsible for CS, the induction period, and rate limiting step in catalysis. This work not only demonstrates the potential of COFs as next generation photocatalysts for solar fuel conversion but also provide unprecedented insight into the mechanistic origins for light-driven CO₂ reduction.

Full text of DOI:10.1021/jacs.8b09705

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Communication
2D Covalent Organic Frameworks as Intrinsic
Photocatalysts for Visible Light-Driven CO2 Reduction
Sizhuo Yang, Wenhui Hu, Xin Zhang, Peilei He, Brian Pattengale, Cunming
Liu, Melissa Cendejas, Ive Hermans, Xiaoyi Zhang, Jian Zhang, and Jier Huang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b09705 • Publication Date (Web): 24 Oct 2018
Downloaded from http://pubs.acs.org on October 24, 2018
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DꢀCovalentꢀOrganicꢀFrameworksꢀasꢀIntrinsicꢀPhotocatalystsꢀforꢀVis-
ibleꢀLight-DrivenꢀCO ꢀReductionꢀ
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a
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ꢀa
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c
SizhuoꢀYang, ꢀWenhuiꢀHu, ꢀXinꢀZhang, ꢀPeileiꢀHe ,ꢀBrianꢀPattengale, ꢀCunmingꢀLiu, ꢀMelissaꢀ
Cendejas, ꢀIveꢀHermans, ꢀXiaoyiꢀZhang, ꢀJianꢀZhang, *ꢀandꢀJierꢀHuang *ꢀ
d
d,e
c
b,f
ꢀa
aDepartmentꢀofꢀChemistry,ꢀMarquetteꢀUniversity,ꢀMilwaukee,ꢀWisconsin,ꢀ53201ꢀ
bDepartmentꢀofꢀChemistry,ꢀUniversityꢀofꢀNebraska-Lincoln,ꢀLincoln,ꢀNebraska,ꢀ68588ꢀ
cX-rayꢀScienceꢀDivision,ꢀArgonneꢀNationalꢀLaboratory,ꢀArgonne,ꢀIllinois,ꢀ60349ꢀ
dDepartmentꢀofꢀChemistry,ꢀUniversityꢀofꢀWisconsin,ꢀMadison,ꢀWisconsin,ꢀ53706ꢀ
eDepartmentꢀofꢀChemicalꢀandꢀBiologicalꢀEngineering,ꢀUniversityꢀofꢀWisconsin,ꢀMadison,ꢀWisconsin,ꢀ53706ꢀ
fMolecularꢀFoundry,ꢀLawrenceꢀBerkeleyꢀNationalꢀLaboratory,ꢀBerkeley,ꢀCaliforniaꢀ94720ꢀ
ꢀ
ABSTRACT:ꢀCovalentꢀorganicꢀframeworkꢀ(COF)ꢀrepresentsꢀanꢀemergingꢀclassꢀofꢀporousꢀmaterialsꢀthatꢀhaveꢀexhibitedꢀgreatꢀ
potentialꢀinꢀvariousꢀapplications,ꢀparticularlyꢀinꢀcatalysis.ꢀInꢀthisꢀwork,ꢀweꢀreportꢀaꢀnewlyꢀdesignedꢀ2DꢀCOFꢀwithꢀincorpo-
ratedꢀReꢀcomplex,ꢀwhichꢀexhibitsꢀintrinsicꢀlightꢀabsorptionꢀandꢀchargeꢀseparationꢀ(CS)ꢀproperties.ꢀWeꢀshowꢀthatꢀthisꢀhybridꢀ
catalystꢀcanꢀefficientlyꢀreduceꢀCO ꢀtoꢀformꢀCOꢀunderꢀvisibleꢀlightꢀilluminationꢀwithꢀhighꢀelectivityꢀ(98%)ꢀandꢀbetterꢀactivityꢀ
2
thanꢀitsꢀhomogeneousꢀReꢀcounterpart.ꢀMoreꢀimportantly,ꢀusingꢀadvancedꢀtransientꢀopticalꢀandꢀX-rayꢀabsorptionꢀspectros-
copyꢀandꢀinꢀsituꢀdiffuseꢀreflectanceꢀspectroscopy,ꢀweꢀunraveledꢀthreeꢀkeyꢀintermediatesꢀthatꢀareꢀresponsibleꢀforꢀCS,ꢀtheꢀin-
ductionꢀperiod,ꢀandꢀrateꢀlimitingꢀstepꢀinꢀcatalysis.ꢀThisꢀworkꢀnotꢀonlyꢀdemonstratesꢀtheꢀpotentialꢀofꢀCOFsꢀasꢀnextꢀgenerationꢀ
photocatalystsꢀforꢀsolarꢀfuelꢀconversionꢀbutꢀalsoꢀprovideꢀunprecedentedꢀinsightꢀintoꢀtheꢀmechanisticꢀoriginsꢀforꢀlight-drivenꢀ
CO ꢀreduction.ꢀ
2
EfficientlyꢀcapturingꢀCO
itꢀtoꢀchemicalꢀfuelsꢀdrivenꢀbyꢀsolarꢀenergyꢀisꢀaꢀpromisingꢀ
approachꢀ toꢀ addressꢀ energyꢀ crisisꢀ andꢀ climateꢀ issues.1-3
2
ꢀandꢀsimultaneouslyꢀconvertingꢀ
Schemeꢀ 1.ꢀ a)ꢀ Theꢀ synthesisꢀ ofꢀ COFꢀ andꢀ Re-COF.ꢀ (b)ꢀ
Sideꢀ viewꢀ andꢀ (c)ꢀ unitꢀ cellꢀ ofꢀ AAꢀ stackingꢀ COF.ꢀ (d)ꢀ
ꢀ
Theꢀessentialꢀchallengeꢀinꢀreachingꢀthisꢀelusiveꢀgoalꢀisꢀtoꢀ
formulateꢀaꢀrationallyꢀdesignedꢀphotocatalyticꢀsystemꢀthatꢀ
canꢀeffectivelyꢀcoupleꢀaꢀgivenꢀphotosensitizerꢀ(PS)ꢀwithꢀanꢀ
appropriateꢀ molecularꢀ catalystꢀ (MC),ꢀ therebyꢀ enablingꢀ
efficientꢀ photosensitizationꢀ ofꢀ multi-electronꢀ reductionꢀ
catalysis.4-6ꢀ Whileꢀ manyꢀ molecular-ꢀ orꢀ semiconductor-
basedꢀphotocatalyticꢀsystemsꢀhaveꢀbeenꢀdesigned,ꢀtheyꢀallꢀ
sufferꢀdifficulties,ꢀsuchꢀasꢀpoorꢀCO2ꢀadsorption,ꢀinappropri-
ateꢀarchitectureꢀofꢀactiveꢀsites,ꢀrapidꢀchargeꢀrecombinationꢀ
ProposedꢀcatalyticꢀmechanismꢀforꢀCO ꢀreduction.ꢀ
2
a)
b)
c)
+
5
Re(CO) Cl
d)
-
CR)ꢀorꢀlowꢀselectivityꢀetc.1,ꢀ7-9
(
ꢀ
Asꢀanꢀemergingꢀclassꢀofꢀcrystallineꢀporousꢀmaterials,ꢀco-
valentꢀ organicꢀ frameworksꢀ (COFs)ꢀ representꢀ aꢀ versatileꢀ
platformꢀ offeringꢀ newꢀ promiseꢀ forꢀ photocatalyticꢀ CO ꢀ re-
hυ
-
2
duction.10-20ꢀCOFsꢀareꢀbuiltꢀfromꢀperiodicꢀorganicꢀbuildingꢀ
blocksꢀviaꢀcovalentꢀbondꢀformation,ꢀprovidingꢀanꢀinnova-
tiveꢀapproachꢀforꢀtheꢀconstructionꢀofꢀrobustꢀphotocatalyticꢀ
materialsꢀwithꢀbuilt-inꢀPSꢀ(i.e.ꢀextendedꢀπ-conjugation)ꢀandꢀ
MCꢀ (e.g.ꢀ incorporatedꢀ viaꢀ postsyntheticꢀ modification),ꢀ
therebyꢀ facilitatingꢀ efficientꢀ chargeꢀ separationꢀ (CS)ꢀ andꢀ
preciseꢀdeterminationꢀofꢀtheꢀnatureꢀofꢀtheꢀincorporatedꢀMC.ꢀ
Moreover,ꢀtheseꢀstructurallyꢀdiverseꢀmaterials,ꢀwithꢀlargeꢀ
surfaceꢀareasꢀandꢀreadilyꢀtunableꢀporeꢀsizesꢀareꢀexpectedꢀ
+
-
-
TEOA
CO
Cl-
I
III
TEOA+
-
-
II
-
Cl-
CO2
toꢀprovideꢀanꢀidealꢀscaffoldꢀforꢀCO ꢀadsorption,ꢀdiffusion,ꢀ
andꢀactivation.ꢀHowever,ꢀthisꢀundeniableꢀpotentialꢀhasꢀyetꢀ
toꢀbeꢀrealized,ꢀwithꢀsomeꢀrecentlyꢀstudiedꢀinitialꢀsystemsꢀ
2
TEOA -(Re-COF)-
+
CO
2
Adduct
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Journal of the American Chemical Society
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a)
c)
TTA
N-H
differenceꢀ betweenꢀ theꢀ simulatedꢀ andꢀ experimentalꢀ dataꢀ
middleꢀpanelꢀofꢀFigureꢀ1c),ꢀsuggestingꢀtheꢀvalidityꢀofꢀcom-
putationalꢀmodel.ꢀꢀ
bipyridine-ligand
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C=O
Re-COF
(
COF
C=N
C-H
Re-COF
ReꢀmoietyꢀwasꢀthenꢀincorporatedꢀintoꢀCOFꢀviaꢀreactionꢀ
5
Re(bpy)(CO) Cl
C
≡O
betweenꢀbipyridineꢀligandꢀandꢀRe(CO)
5
ClꢀtoꢀformꢀRe-COFꢀ
3000
2000
Wavenumber(cm
1500
COF
36
-1
(Schemeꢀ1aꢀandꢀSI). ꢀThisꢀisꢀconfirmedꢀbyꢀtheꢀadditionalꢀ
)
ꢀ
-1ꢀ
peaksꢀ atꢀ 1887,ꢀ 1916 andꢀ 2022ꢀ cm inꢀ FT-IRꢀ spectrumꢀ ofꢀ
Re-COF,ꢀ correspondingꢀ toꢀ -COꢀ vibrationalꢀ stretchingꢀ ofꢀ
b)
Re(bpy)(CO)
ꢀ(Figureꢀ1a).36-38ꢀTheꢀXRDꢀpatternsꢀ(Figureꢀ1c)ꢀ
3
ofꢀRe-COFꢀmatchꢀwellꢀwithꢀtheꢀsimulatedꢀdataꢀofꢀCOF,ꢀindi-
catingꢀ theꢀ preservationꢀ ofꢀ itsꢀ crystalꢀ parametersꢀ afterꢀ Reꢀ
incorporation.ꢀ Thisꢀ isꢀ furtherꢀ supportedꢀ byꢀ theꢀ 13Cꢀ NMRꢀ
spectrumꢀ(FigureꢀS1)ꢀandꢀSEMꢀimagesꢀ(InsetꢀofꢀFigureꢀ1c)ꢀ
ofꢀ Re-COFꢀ andꢀ COF.ꢀ Inꢀ addition,ꢀ theꢀ localꢀ coordinationꢀ
structureꢀ ofꢀ Reꢀ inꢀ Re-COFꢀ measuredꢀ usingꢀ X-rayꢀ absorp-
Re-COF
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AA stacking
COF
Re(bpy)(CO) Cl
3
00
400
500
600
700
5
10
15
20
25
30
Wavelength(nm)
2
θ (degree)
tionꢀ spectroscopyꢀ retainsꢀ thatꢀ ofꢀ Re(bpy)(CO)
S2ꢀ andꢀ Tableꢀ S1),ꢀ suggestingꢀ thatꢀ Re(bpy)(CO)
3
Clꢀ (Figureꢀ
Clꢀ isꢀ wellꢀ
Figureꢀ 1.ꢀ FT-IRꢀ (a)ꢀ andꢀ diffuseꢀ reflectanceꢀ UV-visibleꢀ
spectraꢀ(b)ꢀofꢀCOF,ꢀRe-COFꢀandꢀtheirꢀstartingꢀmaterials.ꢀ
c)ꢀPowderꢀXRDꢀpatternsꢀofꢀRe-COFꢀandꢀCOFꢀobtainedꢀ
experimentallyꢀ (green),ꢀ throughꢀ Pawleyꢀ refinementꢀ
(red),ꢀ andꢀ viaꢀ simulationꢀ usingꢀ AAꢀ stackingꢀ modeꢀ
(blue).ꢀTheꢀpurpleꢀplotꢀinꢀtheꢀmiddleꢀpanelꢀisꢀtheꢀdiffer-
enceꢀpatternꢀbetweenꢀexperimentalꢀandꢀsimulatedꢀdata.ꢀ
TheꢀinsetsꢀareꢀtheꢀpicturesꢀandꢀSEMꢀimagesꢀofꢀRe-COFꢀ
andꢀCOF.ꢀ
3
(
preservedꢀ inꢀ Re-COF.ꢀ However,ꢀ itꢀ isꢀ notableꢀ thatꢀ theꢀ UV-
visibleꢀspectrumꢀofꢀRe-COFꢀareꢀextendedꢀtoꢀbroaderꢀregionꢀ
(Figureꢀ 1b).ꢀ Thisꢀ canꢀ beꢀ attributedꢀ toꢀ eitherꢀ theꢀ vibronicꢀ
39
broadeningꢀofꢀCOFs, ꢀorꢀtheꢀincreasedꢀdelocalizationꢀdueꢀ
toꢀtheꢀchelationꢀofꢀRe(bpy)(CO) Cl.ꢀTheꢀpermanentꢀporosi-
3
tyꢀofꢀCOFꢀandꢀRe-COFꢀwasꢀconfirmedꢀbyꢀN
urementsꢀatꢀ77ꢀKꢀ(FigureꢀS3).ꢀ
2
ꢀsorptionꢀmeas-
exhibitingꢀ moderateꢀ efficiencies.21-24ꢀ Givenꢀ theꢀ inherentꢀ
advantagesꢀ ofꢀ COFsꢀ asꢀ photocatalystsꢀ andꢀ theirꢀ potentialꢀ
impactꢀonꢀtheꢀglobalꢀenergyꢀcrisis,25-29ꢀnoꢀtimeꢀshouldꢀbeꢀ
wastedꢀinꢀundertakingꢀaꢀwell-designedꢀplanꢀtoꢀfurtherꢀde-
velopꢀusefulꢀdevices.ꢀꢀ
AsꢀlightꢀabsorptionꢀandꢀCSꢀareꢀtheꢀkeyꢀinitialꢀstepꢀtoꢀde-
termineꢀwhetherꢀRe-COFꢀcanꢀbeꢀusedꢀasꢀphotocatalystꢀforꢀ
CO ꢀ reduction,ꢀ weꢀ firstꢀ examinedꢀ theꢀ CSꢀ dynamicsꢀ inꢀ Re-
2
COFꢀusingꢀtransientꢀabsorptionꢀ(TA)ꢀspectroscopyꢀfollow-
ingꢀ 530ꢀ nmꢀ excitationꢀ (whereꢀ theꢀ TAꢀ spectraꢀ ofꢀ
Re(bpy)(CO) Clꢀshowꢀnegligibleꢀsignal).ꢀTheꢀTAꢀspectraꢀofꢀ
3
Addressingꢀthisꢀpressingꢀneed,ꢀherein,ꢀweꢀreportꢀaꢀnewlyꢀ
designedꢀCOFꢀphotocatalystꢀwithꢀaꢀphotoactiveꢀ2Dꢀtriazineꢀ
COFꢀ asꢀ PSꢀ andꢀ incorporatedꢀ tricarbonylchloro(bipyridyl)ꢀ
Reꢀcomplexꢀ(Re(bpy)(CO)
edꢀ Re-COF).ꢀ Weꢀ showꢀ thatꢀ Re-COFꢀ canꢀ effectivelyꢀ reduceꢀ
CO ꢀtoꢀCOꢀwithꢀhighꢀselectivityꢀ(98%)ꢀandꢀdurabilityꢀuponꢀ
visibleꢀlightꢀillumination.ꢀMoreꢀimportantly,ꢀtheꢀcombina-
tionꢀofꢀinꢀsituꢀandꢀtime-resolvedꢀabsorptionꢀspectroscopyꢀ
uncoveredꢀtheꢀkeyꢀintermediateꢀspeciesꢀthatꢀareꢀresponsi-
COFꢀ(Figureꢀ2a)ꢀshowꢀaꢀpositiveꢀfeatureꢀatꢀ600ꢀnm,ꢀwhichꢀ
canꢀbeꢀassignedꢀtoꢀtheꢀabsorptionꢀofꢀexcitedꢀICT,41-42ꢀandꢀaꢀ
negativeꢀbandꢀcenteredꢀatꢀ500ꢀnm,ꢀwhichꢀisꢀlikelyꢀdueꢀtoꢀ
stimulatedꢀemissionꢀ(SE)40-41ꢀ(FigureꢀS4)ꢀalthoughꢀtheꢀcon-
3
Cl)ꢀasꢀCO
2
ꢀreductionꢀMCꢀ(denot-
tributionꢀ fromꢀ groundꢀ stateꢀ (GS)ꢀ bleachꢀ cannotꢀ beꢀ com-
2
a)
COF
b)
0
Re-COF@ICT
COF@ICT
1
bleꢀforꢀCO
Theꢀ triazineꢀ COFꢀ wasꢀ synthesizedꢀ fromꢀ 2,2-bipyridyl-
,5-dialdehydeꢀ (BPDA)ꢀ andꢀ 4,4’,4’’-(1,3,5-triazine-2,4,6-
triyl)ꢀtrianilineꢀ(TTA)ꢀbyꢀsolvothermalꢀreactionsꢀ (Schemeꢀ
aꢀandꢀSI).ꢀTheꢀformationꢀofꢀimineꢀlinkagesꢀbetweenꢀalde-
hydeꢀ andꢀ TTAꢀ inꢀ COFꢀ wasꢀ confirmedꢀ byꢀ FT-IRꢀ spectrumꢀ
Figureꢀ 1a),ꢀ whereꢀ weꢀ observedꢀ theꢀ formationꢀ ofꢀ C=Nꢀ
2
ꢀreduction. ꢀ
1
2
1
ps
0ps
00ps
5ps
50ps
200ps
2ns
ꢀ
5
1ns
ns
-3
4
0
1
1
500
600
700
0
10
1000
Wavelength(nm)
Time Delay (ps)
c)
Re-COF
d)
Re-COF
(
-1
stretchingꢀ modesꢀ atꢀ 1626ꢀ cm ꢀ thatꢀ isꢀ characteristicꢀ ofꢀ
imineꢀinꢀCOFꢀandꢀtheꢀvanishingꢀofꢀaminoꢀbandꢀ(3213-3435ꢀ
2p3/2 5d
0
-1
-1
cm )ꢀandꢀaldehydeꢀbandꢀ(1673-1692ꢀcm )ꢀthatꢀwereꢀpre-
sentꢀinꢀTTAꢀandꢀBPDA.15-16,ꢀ30-32ꢀTheꢀformationꢀofꢀtheꢀCOFꢀ
macrostructureꢀ wasꢀ furtherꢀ supportedꢀ byꢀ theꢀ additionalꢀ
absorptionꢀbandꢀ(~ꢀ440ꢀnm)ꢀobservedꢀinꢀitsꢀdiffuseꢀreflec-
tanceꢀUV-visibleꢀspectrumꢀ(Figureꢀ1b),ꢀwhichꢀarisesꢀfromꢀ
theꢀdelocalizedꢀintramolecularꢀchargeꢀtransferꢀ(ICT)ꢀbandꢀ
dueꢀ toꢀ π-conjugationꢀ ofꢀ TTAꢀ andꢀ BPDA.33-35ꢀ Powderꢀ XRDꢀ
patternsꢀofꢀCOFꢀshowꢀprominentꢀdiffractionꢀpeaksꢀ(Figureꢀ
Laser-off spectrum
1ps
5ps
20ps
50ps
200ps
2ns
100ps
-2
1ns
0
4ns
Difference spectrum(x30)
500
600
700
10.53 10.56 10.59 10.62
E (keV)
Wavelength (nm)
Figureꢀ2.ꢀTransientꢀopticalꢀspectraꢀofꢀCOFꢀ(a)ꢀandꢀRe-COFꢀ
c)ꢀ followingꢀ 530ꢀ nmꢀ excitation.ꢀ (b)ꢀ Theꢀ comparisonꢀ ofꢀ
kineticsꢀforꢀICTꢀofꢀCOFꢀandꢀRe-COF.ꢀ(d)ꢀTheꢀXANESꢀspec-
trumꢀ ofꢀ Re-COFꢀ atꢀ Reꢀ L -edge.ꢀ Theꢀ bottomꢀ panelꢀ isꢀ theꢀ
(
1
c),ꢀindicatingꢀitsꢀcrystallineꢀnature.ꢀTheꢀlatticeꢀmodelꢀwasꢀ
30
simulatedꢀusingꢀMaterialꢀStudioꢀ8.0, ꢀfromꢀwhichꢀweꢀob-
tainedꢀtheꢀmostꢀprobableꢀstructureꢀofꢀCOFꢀwithꢀAAꢀstack-
ingꢀ modeꢀ (Schemeꢀ 1bꢀ andꢀ 1c).ꢀ Pawleyꢀ refinementꢀ ofꢀ theꢀ
simulatedꢀ structureꢀ yieldsꢀ XRDꢀ patternsꢀ thatꢀ agreeꢀ wellꢀ
withꢀtheꢀexperimentalꢀdata,ꢀasꢀindicatedꢀbyꢀtheꢀnegligibleꢀ
3
differenceꢀspectrumꢀafterꢀsubtractingꢀtheꢀlaser-offꢀspec-
trumꢀ fromꢀ laser-onꢀ spectrumꢀ collectedꢀ atꢀ 150ꢀ psꢀ delayꢀ
time.ꢀ
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Journal of the American Chemical Society
pletelyꢀexcluded.ꢀTheꢀformationꢀ(risingꢀcomponent)ꢀofꢀtheꢀ
nentꢀwhiteꢀlineꢀtransitionꢀcorrespondingꢀtoꢀdipoleꢀallowedꢀ
2p3/2-5dꢀtransition.43-44ꢀAlsoꢀshownꢀinꢀFigureꢀ2dꢀisꢀtheꢀdif-
ferenceꢀspectrumꢀobtainedꢀbyꢀsubtractingꢀtheꢀGSꢀspectrumꢀ
fromꢀtheꢀspectrumꢀcollectedꢀatꢀ150ꢀps.ꢀTheꢀpositiveꢀsignalꢀ
observedꢀ atꢀ 10.531ꢀ keVꢀ directlyꢀ supportsꢀ thatꢀ Reꢀ edgeꢀ
shiftsꢀ toꢀ lowerꢀ energy,ꢀ suggestingꢀ thatꢀ photoexcitationꢀ ofꢀ
Re-COFꢀleadsꢀtoꢀtheꢀreductionꢀofꢀReꢀcenterꢀinꢀRe-COF.ꢀThisꢀ
isꢀ furtherꢀ supportedꢀ byꢀ theꢀ negativeꢀ featureꢀ observedꢀ atꢀ
10.538ꢀkeV:ꢀtheꢀreductionꢀofꢀReꢀdecreasedꢀtheꢀnumberꢀofꢀ
emptyꢀdꢀorbitals,ꢀprohibitingꢀ2p3/2ꢀ-5dꢀtransitionꢀandꢀthusꢀ
decreasingꢀitsꢀabsorptionꢀintensity.ꢀTheseꢀresults,ꢀtogetherꢀ
withꢀelongatedꢀICTꢀlifetimeꢀobservedꢀinꢀTAꢀstudies,ꢀsuggestꢀ
thatꢀ theꢀ electronsꢀ inꢀ theꢀ excitedꢀ ICTꢀ stateꢀ ofꢀ Re-COFꢀ areꢀ
1
2
3
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excitedꢀICTꢀ(COF@ICT,ꢀFigureꢀ2b)ꢀisꢀultrafastꢀwithꢀ~200ꢀfsꢀ
timeꢀconstantꢀandꢀtheꢀCRꢀtimeꢀisꢀ19.4ꢀpsꢀ(TableꢀS2).ꢀCom-
paredꢀtoꢀthatꢀofꢀCOF,ꢀtheꢀTAꢀspectraꢀofꢀRe-COFꢀshowꢀaꢀsimi-
larꢀSEꢀbandꢀandꢀtheꢀformationꢀofꢀtheꢀexcitedꢀICTꢀstateꢀ(Fig-
ureꢀ 2c).ꢀ However,ꢀ itsꢀ excitedꢀ ICTꢀ bandꢀ isꢀ muchꢀ broaderꢀ
thanꢀthatꢀinꢀCOF,ꢀwhichꢀcanꢀbeꢀattributedꢀtoꢀitsꢀbroaderꢀGSꢀ
spectrum.ꢀMoreꢀinterestingly,ꢀthisꢀexcitedꢀICTꢀstateꢀofꢀRe-
COFꢀ (Re-COF@ICT,ꢀ Figureꢀ 2b)ꢀ exhibitsꢀ muchꢀ longerꢀ life-
timeꢀ(τ =ꢀ171ꢀps)ꢀthanꢀthatꢀofꢀCOF,ꢀsuggestingꢀthatꢀtheꢀin-
corporationꢀofꢀRe(bpy)(CO)
3
ClꢀinhibitsꢀCRꢀinꢀRe-COF.ꢀ
1
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Toꢀ gainꢀ insightꢀ onꢀ theꢀ roleꢀ ofꢀ Re(bpy)(CO)
3
Clꢀ playꢀ inꢀ
elongatingꢀ theꢀ excitedꢀ ICTꢀ lifetime,ꢀ weꢀ directlyꢀ examinedꢀ
theꢀelectronꢀdensityꢀatꢀtheꢀReꢀcenterꢀinꢀRe-COFꢀusingꢀX-rayꢀ
transientꢀabsorptionꢀ(XTA)ꢀspectroscopy.ꢀFigureꢀ2dꢀshowsꢀ
theꢀX-rayꢀabsorptionꢀnearꢀedgeꢀstructureꢀspectrumꢀofꢀRe-
partiallyꢀ locatedꢀ inꢀ Re(bpy)(CO)
3
Cl,ꢀ i.e.,ꢀ electronꢀ transferꢀ
Cl,ꢀ whichꢀ
(
ET)ꢀ indeedꢀ occursꢀ fromꢀ COFꢀ toꢀ Re(bpy)(CO)
3
explainsꢀtheꢀretardedꢀCRꢀinꢀRe-COF.ꢀ
COFꢀcollectedꢀatꢀReꢀL
3
-edge,ꢀwhichꢀisꢀfeaturedꢀbyꢀaꢀpromi-
a)
b)
c)
Step III
6
3
Step II
5h
7h
II
Step I
9h
4
2
I
10
Wavelength(nm)
400 500 600 700 800
2
1
0
0
1
2
0min
1min
5min
15min
30min
45min
1h
2h
3h
III
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Time(h)
0
5
10
Time(h)
15
20
400
500
600
700
800
400
500
600
700
800
Wavelength(nm)
Wavelength(nm)
ꢀ
Figureꢀ3.ꢀ(a)ꢀAmountꢀofꢀCOꢀproducedꢀasꢀaꢀfunctionꢀofꢀtime.ꢀTheꢀtopꢀleftꢀinsetꢀshowsꢀtheꢀzoomedꢀinꢀprofileꢀinꢀtheꢀfirstꢀ2ꢀhours’ꢀreac-
tion,ꢀandꢀtheꢀlowerꢀrightꢀinsetꢀshowsꢀtheꢀrecyclabilityꢀofꢀtheꢀsystemꢀafterꢀthreeꢀ3-hourꢀexperiments.ꢀTheꢀinꢀsituꢀdiffuseꢀreflectanceꢀ
UV-visibleꢀspectraꢀofꢀRe-COFꢀunderꢀstandardꢀphotocatalyticꢀconditionsꢀwithinꢀ15ꢀminꢀ(b)ꢀandꢀ3ꢀhꢀ(c).ꢀTheꢀinsetꢀofꢀcꢀshowsꢀtheꢀinꢀ
situꢀspectraꢀcollectedꢀfromꢀ5ꢀhꢀtoꢀ9ꢀh.ꢀ
ꢀ
TheꢀdemonstrationꢀofꢀETꢀfromꢀCOFsꢀtoꢀRe(bpy)(CO)
3
Clꢀ
ICTꢀ bandꢀ increasesꢀ inꢀ theꢀ firstꢀ 15ꢀ mins,ꢀ accompaniedꢀ byꢀ
theꢀ depletionꢀ ofꢀ absorptionꢀ atꢀ 400-500ꢀ nmꢀ withꢀ anꢀ isos-
besticꢀpointꢀatꢀ539ꢀnm,ꢀsuggestingꢀthatꢀsuchꢀspectralꢀevo-
lutionꢀ correspondsꢀ toꢀ theꢀ sameꢀ process.ꢀ Whileꢀ similarꢀꢀ
suggestsꢀ theꢀ feasibilityꢀ ofꢀ Re-COFꢀ asꢀ photocatalystsꢀ forꢀ
solarꢀfuelꢀconversion.ꢀAccordingly,ꢀweꢀproceededꢀtoꢀexam-
ineꢀitsꢀphotocatalyticꢀactivityꢀforꢀCO
asꢀtheꢀsacrificialꢀdonorꢀandꢀXeꢀlampꢀ(cut-offꢀwavelengthꢀ=ꢀ
20ꢀ nm)ꢀ asꢀ lightꢀ source.ꢀ Underꢀ theꢀ optimizedꢀ conditionsꢀ
SIꢀ andꢀ Figureꢀ S5),ꢀ Theꢀ systemꢀ canꢀ generateꢀ ~15ꢀ mmolꢀ
2
ꢀreductionꢀusingꢀTEOAꢀ
evolutionꢀwasꢀobservedꢀinꢀtheꢀsystemꢀwithoutꢀCO ,ꢀsignifi-
2
4
(
cantlyꢀlessꢀevolutionꢀwasꢀobservedꢀinꢀtheꢀabsenceꢀofꢀTEOAꢀ
(Figureꢀ S7),ꢀ suggestingꢀ thatꢀ reductionꢀ quenchingꢀ ofꢀ Re-
+
CO/gꢀofꢀRe-COFꢀsteadilyꢀforꢀ>20ꢀhꢀafterꢀ� ꢀ15ꢀminꢀinductionꢀ
periodꢀ (Figureꢀ 3a),ꢀ accountingꢀ forꢀ aꢀ TONꢀ ofꢀ 48ꢀ andꢀ 22ꢀ
timesꢀbetterꢀthanꢀitsꢀhomogeneousꢀcounterpartꢀ(FigureꢀS5).ꢀ
COFꢀbyꢀTEOAꢀwithꢀtheꢀformationꢀofꢀaꢀformalꢀTEOA -(COF-
-
Re) ꢀ CSꢀ stateꢀ contributesꢀ toꢀ theꢀ evolution.ꢀ Theꢀ timeꢀ win-
dowꢀforꢀthisꢀspectralꢀevolutionꢀagreesꢀwithꢀtheꢀinductionꢀ
periodꢀandꢀcanꢀthusꢀbeꢀattributedꢀtoꢀtheꢀaccumulationꢀofꢀ
Sinceꢀonlyꢀ2%ꢀH
S5),ꢀ thisꢀ systemꢀ hasꢀ highꢀ selectivityꢀ forꢀ CO
generateꢀ COꢀ (98%).ꢀ Isotopicꢀ experimentꢀ usingꢀ 13CO
2
ꢀwasꢀproducedꢀinꢀtheꢀgasꢀphaseꢀ(Figureꢀ
ꢀ reductionꢀ toꢀ
ꢀ wasꢀ
+
-
2
TEOA -(COF-Re) ꢀCSꢀstateꢀbeforeꢀcatalysisꢀinitiatesꢀ(StepꢀI,ꢀ
Figureꢀ3a).ꢀ
2
performedꢀ underꢀ theꢀ sameꢀ catalyticꢀ conditions.ꢀ Theꢀ pro-
ducedꢀ 13COꢀ (m/zꢀ =ꢀ 29)ꢀ shownꢀ byꢀ gasꢀ chromatographyꢀ
massꢀspectrometryꢀ(FigureꢀS6)ꢀconfirmsꢀthatꢀtheꢀgenerat-
Afterꢀ theꢀ inductionꢀ period,ꢀ theꢀ absorptionꢀ atꢀ 550-800ꢀ
nmꢀdecreasesꢀsignificantlyꢀwithinꢀ3ꢀhꢀwhileꢀtheꢀfeatureꢀatꢀ<ꢀ
4
30ꢀ nmꢀgrowsꢀ andꢀ aꢀ newꢀ isosbesticꢀ pointꢀ isꢀ observedꢀ atꢀ
edꢀ COꢀ comesꢀ fromꢀ CO .ꢀ Theꢀ recyclingꢀ experimentsꢀ afterꢀ
2
430ꢀnmꢀ(StepꢀII,ꢀFigureꢀ3c),ꢀwhichꢀresultsꢀinꢀaꢀdistinctꢀfea-
tureꢀfromꢀStepꢀIꢀandꢀsuggestsꢀtheꢀformationꢀofꢀaꢀnewꢀin-
termediateꢀspecies.ꢀNoteꢀthatꢀnegligibleꢀorꢀveryꢀslightꢀevo-
lutionꢀcorrespondingꢀtoꢀStepꢀIIꢀwasꢀobservedꢀinꢀtheꢀsystemꢀ
everyꢀthreeꢀhoursꢀofꢀreactionꢀshowꢀthatꢀtheꢀcatalyticꢀactivi-
tyꢀpersistsꢀforꢀatꢀleastꢀ3ꢀcyclesꢀ(lowerꢀrightꢀinsetꢀofꢀFigureꢀ
3
a).ꢀꢀ
Toꢀgainꢀmoreꢀmechanisticꢀinsight,ꢀweꢀcollectedꢀtheꢀinꢀsituꢀ
withoutꢀ CO
suggestingꢀ thatꢀ theꢀ intermediateꢀ speciesꢀ formedꢀ duringꢀ
StepꢀIIꢀisꢀassociatedꢀwithꢀCO ꢀandꢀRe-moiety.ꢀAfterꢀStepꢀII,ꢀ
2
ꢀ orꢀ byꢀ replacingꢀ Re-COFꢀ byꢀ COFꢀ (Figureꢀ S8),ꢀ
diffuseꢀreflectanceꢀ UV-visibleꢀspectraꢀofꢀtheꢀcatalyticꢀsys-
temꢀunderꢀtheꢀcatalyticꢀconditions.ꢀImmediatelyꢀfollowingꢀ
illumination,ꢀprominentꢀabsorptionꢀinꢀ550-800ꢀnmꢀregionꢀ
thatꢀresemblesꢀtheꢀbroadꢀabsorptionꢀofꢀtheꢀICTꢀbandꢀinꢀTAꢀ
wasꢀ observedꢀ (Figureꢀ 3b),ꢀ andꢀ canꢀ thusꢀ beꢀ attributedꢀ toꢀ
theꢀformationꢀofꢀtheꢀexcitedꢀICTꢀstate.ꢀTheꢀintensityꢀofꢀthisꢀ
2
theꢀspectralꢀevolutionꢀstopsꢀ(StepꢀIII,ꢀFigureꢀ3c),ꢀconsistentꢀ
withꢀ theꢀ timeꢀ windowꢀ forꢀ steadyꢀ generationꢀ ofꢀ CO,ꢀ sug-
gestingꢀthatꢀtheꢀsystemꢀreachesꢀanꢀequilibriumꢀstate.ꢀ
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 6
Takingꢀ together,ꢀ theseꢀ spectroscopicꢀ resultsꢀ pointꢀ toꢀ aꢀ
3.ꢀ
Appel,ꢀ A.ꢀ M.;ꢀ Bercaw,ꢀ J.ꢀ E.;ꢀ Bocarsly,ꢀ A.ꢀ B.;ꢀ Dobbek,ꢀ H.;ꢀ
1
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7
8
9
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6
mechanisticꢀ pathwayꢀ proposedꢀ inꢀ Schemeꢀ 1d.ꢀ Uponꢀ illu-
mination,ꢀtheꢀcatalyticꢀcycleꢀinitiatesꢀwithꢀtheꢀformationꢀofꢀ
ICTꢀ stateꢀ whichꢀ isꢀ quicklyꢀ reducedꢀ byꢀ TEOA,ꢀ formingꢀ aꢀ
DuBois,ꢀD.ꢀL.;ꢀDupuis,ꢀM.;ꢀFerry,ꢀJ.ꢀG.;ꢀFujita,ꢀE.;ꢀHille,ꢀR.;ꢀKenis,ꢀP.ꢀJ.ꢀ
A.;ꢀ Kerfeld,ꢀ C.ꢀ A.;ꢀ Morris,ꢀ R.ꢀ H.;ꢀ Peden,ꢀ C.ꢀ H.ꢀ F.;ꢀ Portis,ꢀ A.ꢀ R.;ꢀ
Ragsdale,ꢀ S.ꢀ W.;ꢀ Rauchfuss,ꢀ T.ꢀ B.;ꢀ Reek,ꢀ J.ꢀ N.ꢀ H.;ꢀ Seefeldt,ꢀ L.ꢀ C.;ꢀ
Thauer,ꢀ R.ꢀ K.;ꢀ Waldrop,ꢀ G.ꢀ L.,ꢀ Frontiers,ꢀ Opportunities,ꢀ andꢀ
ChallengesꢀinꢀBiochemicalꢀandꢀChemicalꢀCatalysisꢀofꢀCO2ꢀFixation.ꢀ
Chem.ꢀRev.ꢀ2013,ꢀ113,ꢀ6621-6658.ꢀ
+
-
TEOA -(COF-Re) ꢀ CSꢀ stateꢀ (Stepꢀ I).ꢀ Thisꢀ formalꢀ CSꢀ stateꢀ
withꢀreducedꢀRe-COFꢀisꢀthenꢀableꢀtoꢀcaptureꢀCO ꢀtoꢀformꢀ
2
theꢀnextꢀintermediateꢀspeciesꢀ(StepꢀII).ꢀAccordingꢀtoꢀprevi-
ousꢀliterature,6,ꢀ36-38,ꢀ45-46ꢀthisꢀintermediateꢀspeciesꢀisꢀlikelyꢀ
4.ꢀ
Thoi,ꢀ V.ꢀ S.;ꢀ Kornienko,ꢀ N.;ꢀ Margarit,ꢀ C.ꢀ G.;ꢀ Yang,ꢀ P.ꢀ D.;ꢀ
Chang,ꢀ C.ꢀ J.,ꢀ Visible-Lightꢀ Photoredoxꢀ Catalysis:ꢀ Selectiveꢀ
ReductionꢀofꢀCarbonꢀDioxideꢀtoꢀCarbonꢀMonoxideꢀbyꢀaꢀNickelꢀN-
Heterocyclicꢀ Carbene-Isoquinolineꢀ Complex.ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.ꢀ
2013,ꢀ135,ꢀ14413-14424.ꢀ
+
-
theꢀ CO
TEOA -(COF-Re[CO
2
ꢀ adductsꢀ suchꢀ asꢀ TEOA -(COF-Re[CO
2
]) ꢀ or/andꢀ
+
-
2
H]) ,ꢀwhichꢀisꢀformedꢀafterꢀtheꢀdissoci-
ationꢀofꢀCl ꢀfromꢀRe-moiety.ꢀAsꢀtheꢀspectraꢀpersistꢀduringꢀ
–
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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5.ꢀ
Barton,ꢀE.ꢀE.;ꢀRampulla,ꢀD.ꢀM.;ꢀBocarsly,ꢀA.ꢀB.,ꢀSelectiveꢀ
steadyꢀgenerationꢀofꢀCOꢀ(StepꢀIII),ꢀtheꢀconsumptionꢀofꢀtheꢀ
Solar-DrivenꢀReductionꢀofꢀCO2ꢀtoꢀMethanolꢀUsingꢀaꢀCatalyzedꢀp-
GaPꢀBasedꢀPhotoelectrochemicalꢀCell.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2008,ꢀ130,ꢀ
ꢀ
CO
2
ꢀadductstoꢀeventuallyꢀformꢀCOꢀrepresentsꢀtheꢀrateꢀlim-
34-36,ꢀ43-44
itingꢀstepꢀofꢀtheꢀcatalyticꢀreaction.
Inꢀ conclusion,ꢀ weꢀ reportꢀ aꢀ newlyꢀ designedꢀ COFꢀ hybridꢀ
catalystꢀbyꢀincorporatingꢀRe(bpy)(CO) Clꢀintoꢀ2Dꢀtriazineꢀ
COFꢀviaꢀpostsyntheticꢀmodification.ꢀWeꢀshowꢀthatꢀthisꢀsys-
temꢀcanꢀefficientlyꢀreduceꢀCO ꢀwithꢀbetterꢀactivityꢀthanꢀitsꢀ
ꢀ
6
342-6344.ꢀ
6.ꢀ Smieja,ꢀJ.ꢀM.;ꢀBenson,ꢀE.ꢀE.;ꢀKumar,ꢀB.;ꢀGrice,ꢀK.ꢀA.;ꢀSeu,ꢀC.ꢀ
S.;ꢀMiller,ꢀA.ꢀJ.ꢀM.;ꢀMayer,ꢀJ.ꢀM.;ꢀKubiak,ꢀC.ꢀP.,ꢀKineticꢀandꢀStructuralꢀ
Studies,ꢀOriginsꢀofꢀSelectivity,ꢀandꢀInterfacialꢀChargeꢀTransferꢀinꢀ
theꢀ Artificialꢀ Photosynthesisꢀ ofꢀ CO.ꢀ PNAS.ꢀ 2012,ꢀ 109,ꢀ 15646-
3
2
1
7
5650.ꢀ
.ꢀ
homogenousꢀcounterpartꢀandꢀhighꢀselectivityꢀandꢀstability.ꢀ
UsingꢀTAꢀandꢀXTAꢀspectroscopy,ꢀweꢀshowꢀthatꢀthisꢀsystemꢀ
canꢀundergoꢀfacileꢀICTꢀthroughꢀETꢀfromꢀphotoexcitedꢀCOFꢀ
toꢀ Reꢀ moiety.ꢀ Usingꢀ inꢀ situꢀ diffuseꢀ reflectanceꢀ UV-visibleꢀ
spectroscopy,ꢀ weꢀ unraveledꢀ threeꢀ keyꢀ intermediateꢀ spe-
ciesꢀthatꢀareꢀresponsibleꢀforꢀCS,ꢀinductionꢀperiod,ꢀandꢀrateꢀ
White,ꢀ J.ꢀ L.;ꢀ Baruch,ꢀ M.ꢀ F.;ꢀ Pander,ꢀ J.ꢀ E.;ꢀ Hu,ꢀ Y.;ꢀ
Fortmeyer,ꢀI.ꢀC.;ꢀPark,ꢀJ.ꢀE.;ꢀZhang,ꢀT.;ꢀLiao,ꢀK.;ꢀGu,ꢀJ.;ꢀYan,ꢀY.;ꢀShaw,ꢀ
T.ꢀ W.;ꢀ Abelev,ꢀ E.;ꢀ Bocarsly,ꢀ A.ꢀ B.,ꢀ Light-Drivenꢀ Heterogeneousꢀ
Reductionꢀ ofꢀ Carbonꢀ Dioxide:ꢀ Photocatalystsꢀ andꢀ
Photoelectrodes.ꢀChem.ꢀRev.ꢀ2015,ꢀ115,ꢀ12888-12935.ꢀ
8.ꢀ
Wang,ꢀS.ꢀB.;ꢀYao,ꢀW.ꢀS.;ꢀLin,ꢀJ.ꢀL.;ꢀDing,ꢀZ.ꢀX.;ꢀWang,ꢀX.ꢀC.,ꢀ
Cobaltꢀ Imidazolateꢀ Metal-Organicꢀ Frameworksꢀ Photosplitꢀ CO2ꢀ
underꢀMildꢀReactionꢀConditions.ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2014,ꢀ53,ꢀ
limitingꢀ stepꢀ inꢀ CO ꢀ reduction.ꢀ Theseꢀ resultsꢀ notꢀ onlyꢀ
2
demonstratedꢀtheꢀgreatꢀpotentialꢀofꢀCOFsꢀasꢀeffectiveꢀsolarꢀ
fuelꢀphotocatalystsꢀbutꢀalsoꢀprovidedꢀunprecedentedꢀnewꢀ
1
034-1038.ꢀ
9.ꢀ Wang,ꢀ S.ꢀ B.;ꢀ Wang,ꢀ X.ꢀ C.,ꢀ Imidazoliumꢀ Ionicꢀ Liquids,ꢀ
insightꢀintoꢀtheꢀcatalyticꢀmechanismꢀforꢀCO ꢀreduction.ꢀꢀ
2
Imidazolylideneꢀ Heterocyclicꢀ Carbenes,ꢀ andꢀ Zeoliticꢀ Imidazolateꢀ
Frameworksꢀ forꢀ CO2ꢀ Captureꢀ andꢀ Photochemicalꢀ Reduction.ꢀ
Angew.ꢀChem.ꢀInt.ꢀEd.ꢀ2016,ꢀ55,ꢀ2308-2320.ꢀ
ASSOCIATEDꢀCONTENTꢀꢀ
SupportingꢀInformation.ꢀTheꢀsynthesisꢀandꢀstandardꢀcharac-
terizationꢀ ofꢀ Re(bpy)(CO) Cl,ꢀ COF,ꢀ Re-COF,ꢀ experimentalꢀ de-
10.ꢀ
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AUTHORꢀINFORMATIONꢀ
CorrespondingꢀAuthorꢀ
Hanusch,ꢀ F.ꢀ C.;ꢀ Auras,ꢀ F.;ꢀ Bein,ꢀ T.,ꢀ Oligothiophene-Bridgedꢀ
ConjugatedꢀCovalentꢀOrganicꢀFrameworks.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2017,ꢀ
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39,ꢀ8194-8199.ꢀ
*JierꢀHuangꢀ(jier.huang@marquette.edu)ꢀ
*JianꢀZhangꢀ(jzhang3@unl.edu)ꢀ
ꢀ
14.ꢀ Dalapati,ꢀS.;ꢀJin,ꢀE.ꢀQ.;ꢀAddicoat,ꢀM.;ꢀHeine,ꢀT.;ꢀJiang,ꢀD.ꢀL.,ꢀ
HighlyꢀEmissiveꢀCovalentꢀOrganicꢀFrameworks.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ
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Wan,ꢀS.;ꢀGandara,ꢀF.;ꢀAsano,ꢀA.;ꢀFurukawa,ꢀH.;ꢀSaeki,ꢀA.;ꢀ
Notesꢀ
Dey,ꢀS.ꢀK.;ꢀLiao,ꢀL.;ꢀAmbrogio,ꢀM.ꢀW.;ꢀBotros,ꢀY.ꢀY.;ꢀDuan,ꢀX.ꢀF.;ꢀSeki,ꢀ
S.;ꢀStoddart,ꢀJ.ꢀF.;ꢀYaghi,ꢀO.ꢀM.,ꢀCovalentꢀOrganicꢀFrameworksꢀwithꢀ
HighꢀChargeꢀCarrierꢀMobility.ꢀChem.ꢀMater.ꢀ2011,ꢀ23,ꢀ4094-4097.ꢀ
Theꢀauthorsꢀdeclareꢀnoꢀcompetingꢀfinancialꢀinterests.ꢀ
ACKNOWLEDGMENTꢀꢀ
16.ꢀ
Patra,ꢀ B.ꢀ C.;ꢀ Khilari,ꢀ S.;ꢀ Manna,ꢀ R.ꢀ N.;ꢀ Mondal,ꢀ S.;ꢀ
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Energy,ꢀOfficeꢀofꢀScience,ꢀOfficeꢀofꢀBasicꢀEnergyꢀSciences,ꢀun-
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