Dual function photocatalysis of cyano-bridged heteronuclear metal complexes for water oxidation and two-electron reduction of dioxygen to produce hydrogen peroxide as a solar fuel

Article abstract of DOI:10.1039/C7CC00621G

The photocatalytic production of hydrogen peroxide from water and dioxygen under visible light irradiation was made possible by using polymeric cyano-bridged heteronuclear metal complexes (M^II[Ru^II(CN)₄(bpy)]; M^II = Ni^II, Fe^II and Mn^II), where the photocatalytic two-electron reduction of O₂ and water oxidation were catalysed by the Ru and M^II moieties, respectively.

Full text of DOI:10.1039/C7CC00621G

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
first methanofullerene derivatives of Sc
3
N@C2n (2n
=
68 and 80). Synthesis of the
3
N@D5h-C80
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Pleaseꢀd Co hꢀ ne omt ꢀ Ca do j mu s mt ꢀmarginsꢀ
View Article Online
DOI: 10.1039/C7CC00621G
ꢀ
JournalꢀNameꢀ
COMMUNICATIONꢀ
ꢀ
Dualꢀfunctionꢀphotocatalysisꢀofꢀcyano-bridgedꢀheteronuclearꢀ
metalꢀcomplexesꢀforꢀwaterꢀoxidationꢀandꢀtwo-electronꢀreductionꢀ
ofꢀdioxygenꢀtoꢀproduceꢀhydrogenꢀperoxideꢀasꢀaꢀsolarꢀfuelꢀ
Receivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
a
a
a
b
cd
YusukeꢀAratani, ꢀTomoyoshiꢀSuenobu, ꢀKeiꢀOhkubo, ꢀYusukeꢀYamada* ꢀandꢀShunichiꢀFukuzumi* ꢀ
DOI:ꢀ10.1039/x0xx00000xꢀ
www.rsc.org/ꢀ
Photocatalyticꢀ productionꢀ ofꢀ hydrogenꢀ peroxideꢀ fromꢀ waterꢀ coordinationꢀ polymersꢀ includingꢀ metalꢀ organicꢀ frameworksꢀ
andꢀdioxygenꢀunderꢀvisibleꢀlightꢀirradiationꢀwasꢀmadeꢀpossibleꢀ haveꢀemergedꢀasꢀaꢀclassꢀofꢀheterogeneousꢀcatalystsꢀpossessingꢀ
1
1
byꢀ usingꢀ polymericꢀ cyano-bridgedꢀ heteronuclearꢀ metalꢀ theꢀ advantageꢀ ofꢀ homogeneousꢀ catalysts. ꢀ Theꢀ highlyꢀ
II
II
II
II
II
II
complexesꢀ(M [Ru (CN)
4
(bpy)];ꢀM ꢀ=ꢀNi ,ꢀFe ꢀandꢀMn ),ꢀwhereꢀ designableꢀ natureꢀ ofꢀ theꢀ coordinationꢀ polymersꢀ allowꢀ toꢀ
ꢀ andꢀ waterꢀ designꢀ dualꢀ functionꢀ catalystsꢀ usedꢀ forꢀ solarꢀ fuelꢀ productionꢀ
theꢀ photocatalyticꢀ two-electronꢀ reductionꢀ ofꢀ O
oxidationꢀ wereꢀ catalysedꢀ byꢀ theꢀ Ruꢀ andꢀ M ꢀ moieties,ꢀ withꢀenergyꢀinputꢀfromꢀsunlight. ꢀꢀ
2
II
12
respectively.ꢀ
ꢀ
Weꢀ reportꢀ hereinꢀ thatꢀ polymericꢀ cyanoꢀ (CN)-bridgedꢀ
II
II
II
II
4
heteronuclearꢀmetalꢀcomplexesꢀ(M [Ru (CN) (bpy)];ꢀM ꢀ=ꢀNi ,ꢀ
II
Fe ꢀ andꢀ Mn )ꢀ actꢀ asꢀ dualꢀ functionꢀ catalysts.ꢀ Theꢀ catalystsꢀ
II
Theꢀ productionꢀ ofꢀ solarꢀ fuelꢀ throughꢀ artificialꢀ photosynthesisꢀ
hasꢀ attractedꢀ considerableꢀ attentionꢀ becauseꢀ ofꢀ theꢀ globalꢀ
incorporateꢀbothꢀaꢀvisible-lightꢀresponsibleꢀphotosensitiserꢀandꢀ
1
-3
energyꢀ shortageꢀ andꢀ growingꢀ environmentalꢀ concerns.
ꢀ
catalysisꢀunitsꢀforꢀphotocatalyticꢀreductionꢀofꢀO
2
ꢀtoꢀH
ꢀhasꢀmeritedꢀincreasingꢀattentionꢀasꢀanꢀ
idealꢀ solarꢀ fuelꢀ alternativeꢀ toꢀ gaseousꢀ hydrogen,ꢀ becauseꢀ anꢀ
2 2
O ꢀandꢀ
Artificialꢀphotosynthesisꢀisꢀcomposedꢀofꢀseveralꢀprocessesꢀsuchꢀ
asꢀ light-harvesting,ꢀ charge-separation,ꢀ waterꢀ oxidationꢀ andꢀ
2 2 2
forꢀH Oꢀoxidation.ꢀH O
protonꢀ orꢀ CO
systemsꢀ possessingꢀ multi-catalyticꢀ functions.
2
ꢀ reduction,ꢀ whichꢀ requireꢀ hybridꢀ catalyticꢀ
aqueousꢀ solutionꢀ ofꢀ H
2 2
O ꢀ canꢀ beꢀ usedꢀ asꢀ aꢀ fuelꢀ inꢀ aꢀ one-
4
-7ꢀ
1
3-15
Metalꢀ
compartmentꢀ fuelꢀ cellꢀ toꢀ generateꢀ electricity.
ꢀ Inꢀ thisꢀ
ꢀbyꢀreductionꢀofꢀO
withꢀ water,ꢀ bothꢀ ofꢀ whichꢀ areꢀ earthꢀ abundant,ꢀ hasꢀ beenꢀ
complexesꢀ oftenꢀ usedꢀ asꢀ homogeneousꢀ catalystsꢀ areꢀ
advantageousꢀ forꢀ designingꢀ andꢀ synthesisingꢀ heteronuclearꢀ
metalꢀ complexesꢀ toꢀ exhibitꢀ theꢀ multifunctionalꢀ catalysis.ꢀ
However,ꢀ theꢀ synthesisꢀ ofꢀ suchꢀ multifunctionalꢀ catalystsꢀ hasꢀ
beenꢀ veryꢀ difficultꢀ andꢀ theꢀ lowꢀ stabilityꢀ ofꢀ homogeneousꢀ
context,ꢀphotocatalyticꢀproductionꢀofꢀH
2
O
2
2
ꢀ
1
6-18
studied.
usuallyꢀ employedꢀ aꢀ waterꢀ oxidationꢀ catalystꢀ togetherꢀ withꢀ aꢀ
solubleꢀ photosensitiser,ꢀ whichꢀ alsoꢀ actsꢀ asꢀ anꢀ O ꢀ reductionꢀ
catalyst,ꢀ toꢀ utiliseꢀ visibleꢀ lightꢀ efficiently. ꢀ ꢀ Incorporationꢀ ofꢀ
2 2
ꢀReportedꢀphotocatalyticꢀH O ꢀproductionꢀsystemsꢀ
2
8
1
8
catalystsꢀ oftenꢀ causesꢀ aꢀ problemꢀ aboutꢀ trulyꢀ activeꢀ species. ꢀ
Onꢀ theꢀ otherꢀ hand,ꢀ heterogeneousꢀ metalꢀ andꢀ metalꢀ oxideꢀ
nanoparticlesꢀ haveꢀ beenꢀ extensivelyꢀ studiedꢀ asꢀ robustꢀ
photocatalystsꢀ asꢀ wellꢀ asꢀ catalystsꢀ forꢀ waterꢀ reductionꢀ andꢀ
2
suchꢀaꢀphotosensitiserꢀactingꢀasꢀanꢀO ꢀreductionꢀcatalystꢀtoꢀaꢀ
waterꢀoxidationꢀcatalystꢀcanꢀconstructꢀefficientꢀphotocatalystsꢀ
byꢀfacilitatingꢀelectronꢀtransfer.ꢀ
8
ꢀ
II
[Ru (CN)
oxidation. However,ꢀtheꢀdifficultyꢀtoꢀclarifyꢀtheꢀmechanismꢀofꢀ
theꢀheterogeneousꢀcatalysisꢀhasꢀprecludedꢀrationalꢀdesignꢀforꢀ
ꢀ
K
2
4
(bpy)]ꢀ (bpyꢀ =ꢀ 2,2’-bipyridine)ꢀ wasꢀ synthesisedꢀ
1
andꢀ characterisedꢀ asꢀ reportedꢀ inꢀ theꢀ literature. ꢀ Theꢀ K ꢀ ionꢀ
9
+
9
,10
2
+
II
II
wasꢀ replacedꢀ byꢀ Fe ꢀ ionꢀ toꢀ produceꢀ Fe [Ru (CN)
20
(bpy)]. ꢀ
heterogeneousꢀ multifunctionalꢀ catalysts.
ꢀ
Recently,ꢀ
4
II
II
SimilarlyꢀNi [Ru (CN)
II
II
(bpy)],ꢀMn [Ru (CN)
II
II
(bpy)],ꢀCo [Ru (CN)
4
4
4
-
II
bpy)],ꢀ Cu [Ru (CN)
II
II
(bpy)],ꢀ Fe [Ru (CN)
II
(
4
4 2
(Me phen)]ꢀ andꢀ
II
Fe [Ru (CN) {(MeO) bpy}]ꢀwereꢀsynthesisedꢀandꢀcharacterisedꢀ
II
4 2
byꢀ powderꢀ X-rayꢀ diffractionꢀ patterns,ꢀ IRꢀ andꢀ diffusedꢀ
reflectanceꢀ UV-visꢀ spectraꢀ (seeꢀ Figs.ꢀ S1-S3†).ꢀ Powderꢀ XRDꢀ
patternsꢀ showꢀ thatꢀ theꢀ structureꢀ ofꢀ theꢀ complexesꢀ isꢀ 4,2-
2
1
ribbonꢀ likeꢀ chainꢀ (Fig.ꢀ 1). ꢀ IRꢀ spectraꢀ shiftingꢀ toꢀ higherꢀ
wavenumberꢀindicateꢀtheꢀincorporationꢀofꢀdivalentꢀmetalꢀionsꢀ
II
II
intoꢀ theꢀ frameworks.ꢀ Fe [Ru (CN)
photocatalystꢀforꢀproductionꢀofꢀH
presenceꢀofꢀSc(NO ,ꢀwhichꢀisꢀexpectedꢀtoꢀenhanceꢀH
byꢀstabilisingꢀaꢀreactiveꢀintermediate,ꢀO
4
(bpy)]ꢀ actsꢀ asꢀ anꢀ effectiveꢀ
ꢀfromꢀH OꢀandꢀO ꢀinꢀtheꢀ
ꢀyieldꢀ
2
O
2
2
2
3
)
3
2 2
O
•
–
2
ꢀandꢀthus,ꢀbyꢀꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
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COMMUNICATIONꢀ
JournalꢀNameꢀ
View Article Online
DOI: 10.1039/C7CC00621G
N
N
N
N
N
N
C
N
N
C
C
C
C
N
N
N
N
RuII
C
C
C
RuII
RuII
C
C
C
C
N
N
N
N
N
N
N
N
OH2
OH
2
OH2
OH2
MII
MII
MII
MII
H2
N
O
H2O
C
H2O
N
H2O
N
N
N
N
N
N
C
C
C
C
C
C
RuII
RuII
RuII
N
C
N
C
N
N
N
N
C
C
C
N
N
N
N
N
N
ꢀ
ꢀ
Fig.ꢀ1.ꢀSchematicꢀdrawingꢀofꢀ4,2-ribbonꢀlikeꢀchainꢀstructure.ꢀ
Time / hꢀ
ꢀ fromꢀ H Oꢀ andꢀ O
II
ꢀ II
Fig.ꢀ 3ꢀ Timeꢀ profilesꢀ ofꢀ productionꢀ ofꢀ H
2
O
2
2
2
ꢀ withꢀ M [Ru (CN)
4
(bpy)]ꢀ
(
(
0.12ꢀmM;ꢀMꢀ=ꢀNiꢀ(▼),ꢀMnꢀ(■),ꢀFeꢀ(●),ꢀCoꢀ(▲)ꢀandꢀCuꢀ(◆))ꢀinꢀtheꢀpresenceꢀofꢀSc(NO
3 3
) ꢀ
0.10ꢀM)ꢀinꢀO -saturatedꢀH Oꢀ(2.0ꢀmL)ꢀunderꢀvisibleꢀlightꢀirradiationꢀwithꢀaꢀXenonꢀlampꢀ
2
2
usingꢀaꢀUVꢀcut-offꢀfilterꢀ(l >ꢀ390ꢀnm)ꢀatꢀ298ꢀK.ꢀ
II
ꢀ withꢀ Ni [Ru (CN)
II
oxidationꢀ ofꢀ H
significantlyꢀasꢀcomparedꢀwithꢀthoseꢀinꢀonlyꢀH
2
Oꢀ byꢀ O
2
4
(bpy)]ꢀ increasedꢀ
Oꢀtoꢀaffordꢀtheꢀ
2
apparentꢀturnoverꢀnumberꢀ(TON)ꢀofꢀ247ꢀbasedꢀonꢀtheꢀnumberꢀ
ofꢀtheꢀmonomerꢀunitꢀafterꢀ70ꢀhꢀ(Fig.ꢀ4).ꢀTheꢀparticleꢀsizesꢀofꢀ
II
II
4
Ni [Ru (CN) (bpy)]ꢀhaveꢀnotꢀbeenꢀsignificantlyꢀchangedꢀduringꢀ
theꢀreactionꢀ(Fig.ꢀS6†).ꢀTheꢀbetterꢀphotocatalyticꢀperformanceꢀ
inꢀtheꢀmixedꢀsolventꢀthanꢀthatꢀinꢀpureꢀwaterꢀcanꢀbeꢀexplainedꢀ
byꢀ theꢀ lowerꢀ dielectricꢀ constantꢀ ofꢀ theꢀ mixedꢀ solvent.ꢀ Theꢀ
lowerꢀdielectricꢀconstantꢀisꢀbeneficialꢀtoꢀelongateꢀtheꢀlifetimeꢀ
Time / hꢀ
ꢀfromꢀH OꢀandꢀO
ꢀ
II
II
Fig.ꢀ2ꢀTimeꢀprofilesꢀofꢀproductionꢀofꢀH
2
O
2
2
2
ꢀwithꢀFe [Ru (CN)
4
(bpy)]ꢀ(1.2ꢀ
bpy}]ꢀ (1.0ꢀ mM,ꢀ ▲)ꢀ
ꢀ(0.10ꢀM)ꢀinꢀO
•
–
3+
II
II
II
II
ofꢀO
•–
2
ꢀbyꢀenhancingꢀelectrostaticꢀinteractionꢀbetweenꢀSc ꢀandꢀ
mM,ꢀ ●),ꢀ Fe [Ru (CN)
4
(Me
2
phen)]ꢀ (1.1ꢀ mM,ꢀ ■),ꢀ Fe [Ru (CN)
]ꢀ(1.4ꢀmM,ꢀ◆),ꢀinꢀtheꢀpresenceꢀofꢀSc(NO
4
{(MeO)
2
II
II
andꢀFe
2
[Ru (CN)
6
3
)
3
2
-saturatedꢀ O2 ,ꢀresultingꢀinꢀincreasingꢀH O ꢀyields.ꢀNoꢀH O ꢀproductionꢀinꢀ
2
2
2 2
H
2
Oꢀ(2.0ꢀmL)ꢀunderꢀvisibleꢀlightꢀirradiationꢀwithꢀaꢀXenonꢀlampꢀusingꢀaꢀUVꢀcut-offꢀfilterꢀ(lꢀ
pureꢀ CH
electronꢀsourceꢀofꢀO
3
OHꢀ asꢀ shownꢀ inꢀ Fig.ꢀ 4ꢀ manifestedꢀ thatꢀ waterꢀ isꢀ theꢀ
ꢀreduction.ꢀ
>
ꢀ390ꢀnm)ꢀatꢀ298ꢀK.ꢀ
2
ꢀ
Nanosecondꢀlaser-inducedꢀtransientꢀabsorptionꢀspectraꢀofꢀ
II
[Ru (CN)
1
8a
prohibitingꢀbackꢀelectronꢀtransfer, ꢀinꢀH
2
Oꢀunderꢀirradiationꢀ
ꢀ>ꢀ390ꢀnm)ꢀasꢀshownꢀinꢀFig.ꢀ2ꢀ[Eq.ꢀ(1)].ꢀTheꢀ
K
2
4
(bpy)]ꢀinꢀCH
2–
3
OH/H
(bpy)] ꢀ moiety.ꢀ Theꢀ lifetimeꢀ ofꢀ theꢀ excitedꢀ stateꢀ ofꢀ
2
Oꢀ(5:1,ꢀv/v)ꢀwereꢀmeasuredꢀforꢀ
ofꢀvisibleꢀlightꢀ(
ꢀ
l
ꢀ
II
Ru (CN)
[
[
(
[
4
4
II
Ru (CN)
2–ꢀ
3 2
(bpy)] wasꢀdeterminedꢀtoꢀbeꢀ0.23ꢀµsꢀinꢀCH OH/H Oꢀ
hν
2
ꢀ
H
2
Oꢀ+ꢀO
2
ꢀ
ꢀ
2H
2
O
2
ꢀ ꢀ
ꢀ
ꢀ
ꢀ
ꢀ(1)ꢀ
5:1,ꢀ v/v)ꢀ (Fig.ꢀ 5a).ꢀ Theꢀ lifetimeꢀ ofꢀ theꢀ excitedꢀ stateꢀ ofꢀ
II
Ru (CN)
II
II
Fe [Ru (CN)
(bpy)]
2–
(bpy)] ꢀwasꢀshortenedꢀbyꢀincreasingꢀconcentrationꢀofꢀꢀ
4
4
ꢀ
originꢀ ofꢀ oxygenꢀ inꢀ theꢀ producedꢀ H
labellingꢀ experimentsꢀ usingꢀ gaseousꢀ
2
1
O
2
ꢀ wasꢀ confirmedꢀ byꢀ
8
O
2
ꢀ (Fig.ꢀ S4†).ꢀ Itꢀ wasꢀ
confirmedꢀ thatꢀ noꢀ
H
2
O
2
ꢀ
(bpy)]ꢀwasꢀreplacedꢀbyꢀFe
wasꢀ producedꢀ whenꢀ
II
II
Fe [Ru (CN)
II
II
[Ru (CN)
4
2
6
],ꢀwhichꢀdoesꢀ
2
notꢀabsorbꢀvisibleꢀlightꢀ(Fig.ꢀ2). ꢀꢀ
2
II
Amongꢀ variousꢀ metal-substitutedꢀ M [Ru (CN)
II
ꢀ
4
(bpy)],ꢀ
II
II
Ni [Ru (CN)
theꢀproductionꢀofꢀH
2 4
ꢀ formationꢀ wasꢀ observedꢀ whenꢀ K [Ru (CN) (bpy)]ꢀ wasꢀ
4
(bpy)]ꢀexhibitedꢀtheꢀhighestꢀcatalyticꢀreactivityꢀforꢀ
2
O
2
ꢀfromꢀH OꢀandꢀO ꢀasꢀshownꢀinꢀFig.ꢀ3.ꢀNoꢀ
2
2
II
H
2
O
2
usedꢀ asꢀ aꢀ homogeneousꢀ catalystꢀ (Fig.ꢀ S5†).ꢀ Theꢀ catalyticꢀ
II
activityꢀhighlyꢀinfluencedꢀbyꢀN-boundꢀM ꢀspeciesꢀsuggestsꢀthatꢀ
II
M ꢀ ionsꢀ offerꢀ theꢀ activeꢀ sitesꢀ forꢀ theꢀ photocatalyticꢀ waterꢀ
Time / hꢀ
ꢀ
oxidationꢀasꢀreportedꢀforꢀconventionalꢀPrussianꢀblueꢀanaloguesꢀ
II
II
Fig.ꢀ4ꢀTimeꢀprofileꢀofꢀproductionꢀofꢀH
mM)ꢀinꢀtheꢀpresenceꢀofꢀSc(NO ꢀ(67ꢀmM)ꢀinꢀO
ribbonꢀ likeꢀ structureꢀ mayꢀ haveꢀ aꢀ coordinationꢀ structureꢀ orꢀ underꢀvisibleꢀlightꢀirradiationꢀwithꢀaꢀXenonꢀlampꢀusingꢀaꢀUVꢀcut-offꢀfilterꢀ(l >ꢀ390ꢀnm)ꢀatꢀ
98ꢀKꢀ(●).ꢀTimeꢀprofileꢀinꢀCH OHꢀwithoutꢀH Oꢀunderꢀotherwiseꢀtheꢀsameꢀexperimentalꢀ
conditionsꢀisꢀalsoꢀshownꢀforꢀcomparisonꢀ(■).ꢀ
2
O
2
ꢀfromꢀH
2
OꢀandꢀO
2
ꢀwithꢀNi [Ru (CN)
4
(bpy)]ꢀ(9.6ꢀ
2
3
usedꢀasꢀwaterꢀoxidationꢀcatalysts. ꢀThus,ꢀaꢀNiꢀionꢀinꢀtheꢀ4,2-
3
)
3
2
-saturatedꢀCH
3
OH/H Oꢀ(3.0ꢀmL;ꢀ5:1,ꢀv/v)ꢀ
2
2
3
2
bondsꢀwithꢀaquaꢀligandsꢀsuitableꢀforꢀwaterꢀoxidation.ꢀ
ꢀ
WhenꢀH
2
OꢀwasꢀreplacedꢀbyꢀaꢀmixedꢀsolventꢀofꢀCH
3 2
OH/H Oꢀ
(
5:1,ꢀv/v),ꢀtheꢀamountꢀofꢀH O
2 2
ꢀproducedꢀinꢀtheꢀphotocatalyticꢀꢀ
2
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
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g = 2.0163
(
a)
2
0 G
Magnetic field / Gauss
Fig.ꢀ6ꢀEPRꢀspectrumꢀobservedꢀunderꢀphotoirradiationꢀofꢀanꢀO
2
-saturatedꢀCH
3
OH/H
2
Oꢀ
II
II
(
5:1,ꢀv/v)ꢀsolutionꢀ(2.0ꢀmL)ꢀcontainingꢀNi [Ru (CN)
4
(bpy)]ꢀ(0.50ꢀmM)ꢀandꢀSc(NO ) ꢀ(0.10ꢀ
3 3
M)ꢀwithꢀanꢀHgꢀlampꢀ(lꢀ>ꢀ310ꢀnm)ꢀatꢀ298ꢀK.ꢀ
Time / µs
Ni [Ru (CN) (bpy•–)]*
II
III
2–
S O
8
(
b)
4
2
hν
k
q
= 2.3 x 10 M s-1
9
-1
O + 4H+
II
II
SO4•– + SO42–
2
Ni [Ru (CN) (bpy)]
4
II
II
Ni [Ru (CN) (bpy)]
x 4
{
4
III
II
+
Ni [Ru (CN) (bpy)] }
2
H O
4
2
II
III
+
Ni [Ru (CN) (bpy)]
4
SO42–
II
III
+
Ni [Ru (CN) (bpy)]
4
Schemeꢀ 1ꢀ Catalyticꢀ cycleꢀ ofꢀ visible-lightꢀ drivenꢀ waterꢀ oxidationꢀ byꢀ persulphateꢀ withꢀ
II
II
4
Ni [Ru (CN) (bpy)]ꢀ
[
O
2
] / mM
ꢀ
Fig.ꢀ5ꢀ(a)ꢀDecayꢀtimeꢀprofilesꢀofꢀabsorbanceꢀatꢀ660ꢀnmꢀobservedꢀinꢀCH
3
OH/H
(bpy)]ꢀ(0.29ꢀmM)ꢀandꢀvariousꢀconcentrationsꢀofꢀO ꢀ([O
black),ꢀ 1.5ꢀ (red)ꢀ andꢀ 7.6ꢀ (blue)ꢀ mM).ꢀ (b)ꢀ Plotꢀ ofꢀ theꢀ decayꢀ rateꢀ constantꢀ vs.ꢀ
concentrationꢀofꢀO .ꢀ
2
Oꢀ(5:1,ꢀ
methanol.ꢀTheꢀphotocatalyticꢀcycleꢀisꢀgivenꢀinꢀSchemeꢀ1,ꢀwhereꢀ
II
v/v)ꢀcontainingꢀK
2
[Ru (CN)
4
2
2
]:ꢀ0ꢀ
II
II
theꢀ excitedꢀ stateꢀ ofꢀ Ni [Ru (CN)
4
(bpy)]ꢀ wasꢀ oxidativelyꢀ
(
II
III
+
quenchedꢀ byꢀ Na ꢀ toꢀ produceꢀ Ni [Ru (CN)
2
S
2
O
8
4
(bpy)] ꢀ and,ꢀ
(bpy)]} ꢀthatꢀoxidisesꢀwaterꢀtoꢀevolveꢀO .ꢀ
TheꢀmechanismꢀofꢀphotocatalyticꢀproductionꢀofꢀH ꢀfromꢀ
2
III
II
+
then,ꢀ{Ni [Ru (CN)
4
2
ꢀ
2 2
O
2
O ꢀ (Fig.ꢀ 5b).ꢀ Thisꢀ suggestsꢀ thatꢀ electronꢀ transferꢀ fromꢀ theꢀ
II
II
3+
II
excitedꢀ stateꢀ ofꢀ [Ru (CN)
2–
(bpy)] ꢀ toꢀ O
H
2 2 4
OꢀandꢀO ꢀwithꢀNi [Ru (CN) (bpy)]ꢀinꢀtheꢀpresenceꢀofꢀSc ꢀisꢀ
4
2
ꢀ occursꢀ toꢀ produceꢀ
II
II
III
–
•–
3+
•– shownꢀ inꢀ Schemeꢀ 2.ꢀ Photoexcitationꢀ ofꢀ Ni [Ru (CN) (bpy)]ꢀ
resultedꢀ inꢀ electronꢀ transferꢀ fromꢀ theꢀ excitedꢀ stateꢀ ofꢀ
4
[
Ru (CN)
isꢀboundꢀtoꢀaꢀSc ꢀionꢀtoꢀaffordꢀtheꢀO
wasꢀdetectedꢀbyꢀEPRꢀafterꢀphotoirradiationꢀofꢀanꢀO
4
(bpy)] ꢀandꢀO
2
.ꢀ InꢀtheꢀpresenceꢀofꢀSc ꢀions,ꢀO ꢀ
2
3
+
•–
3+
2
–Sc ꢀcomplex,ꢀwhichꢀꢀ
-saturatedꢀ
II
II
3+
4
Ni [Ru (CN) (bpy)]ꢀ toꢀ O2ꢀ inꢀ theꢀ presenceꢀ ofꢀ Sc ꢀ toꢀ produceꢀ
2
II
Ni [Ru (CN)
III
+
(bpy)] ꢀ andꢀ O
•–
3+
–Sc .ꢀ Theꢀ O
•–
3+
–Sc ꢀ complexꢀ
II
II
4
2
2
CH
3 2 4
OH/H Oꢀ(5:1,ꢀv/v)ꢀsolutionꢀofꢀNi [Ru (CN) (bpy)]ꢀasꢀshownꢀ
+
disproportionatesꢀinꢀtheꢀpresenceꢀofꢀH ꢀto produceꢀH
12
. ꢀOnꢀ
2
O
2
inꢀ Fig.ꢀ 6ꢀ andꢀ Fig.ꢀ S7†,ꢀ whereꢀ theꢀ superhyperfineꢀ dueꢀ toꢀ Scꢀ
II
III
+
2
nucleusꢀ (8ꢀ lines,ꢀ Iꢀ =ꢀ 7/2)ꢀ is observed. ꢀ Theꢀ rateꢀ constantꢀ ofꢀ
4
4
theꢀ otherꢀ hand,ꢀ fourꢀ equivalentsꢀ ofꢀ Ni [Ru (CN) (bpy)] ꢀ
+
ꢀandꢀfourꢀequivalentsꢀofꢀH .ꢀ
II
2–
oxidisesꢀwaterꢀtoꢀproduceꢀO
2
4
electronꢀtransferꢀfromꢀtheꢀexcitedꢀstateꢀofꢀ[Ru (CN) (bpy)] ꢀtoꢀ
ꢀ
Inꢀ conclusion,ꢀ polymericꢀ cyano-bridgedꢀ heteronuclearꢀ
O
2ꢀ wasꢀ determinedꢀ fromꢀ theꢀ linearꢀ plotꢀ ofꢀ theꢀ decayꢀ rateꢀ
II
II
IIꢀ
II
II
II
9
–1 –1
metalꢀ complexesꢀ (M [Ru (CN)
4
(bpy)];ꢀ M =ꢀ Ni ,ꢀ Fe ꢀ andꢀ Mn )ꢀ
exhibitedꢀ dualꢀ functionꢀ photocatalysisꢀ forꢀ H Oꢀ oxidationꢀ andꢀ
ꢀinꢀphotocatalyticꢀproductionꢀofꢀH ꢀfromꢀ
.ꢀ Theꢀ highestꢀ apparentꢀ TONꢀ ofꢀ 247ꢀ basedꢀ onꢀ theꢀ
2
constantꢀvs.ꢀconcentrationꢀofꢀO ꢀtoꢀbeꢀ2.3(±0.2)ꢀ×ꢀ10 ꢀM ꢀs ,ꢀ
2
whichꢀ isꢀ diffusion-limitedꢀ andꢀ consistsꢀ theꢀ rateꢀ constantꢀ ofꢀ
electronꢀ transferꢀ determinedꢀ fromꢀ aꢀ slopeꢀ ofꢀ Stern–Volmerꢀ
O
H
2
ꢀreductionꢀtoꢀH
Oꢀ andꢀ O
2
O
2
2 2
O
II
*
2
2
plotꢀandꢀtheꢀlifetimeꢀofꢀ[Ru (CN)
TheꢀcapabilityꢀofꢀH OꢀoxidationꢀofꢀNi [Ru (CN)
confirmedꢀ inꢀ theꢀ photocatalyticꢀ oxidationꢀ ofꢀ H
4
(bpy)] ꢀ(Fig.ꢀS8†).ꢀ
II
III
+
numberꢀ ofꢀ monomerꢀ unitꢀ wasꢀ obtainedꢀ withꢀ
II
ꢀ
2
4
(bpy)] ꢀwasꢀ
II
Ni [Ru (CN)
ꢀ
4 2 2 2 2
(bpy)]ꢀforꢀproductionꢀofꢀH O ꢀfromꢀH OꢀandꢀO ꢀinꢀꢀ
2
Oꢀ byꢀ
(bpy)]ꢀ inꢀ theꢀ presenceꢀ ofꢀ
Oꢀ (5:1,ꢀ v/v),ꢀ whereꢀ O ꢀ evolutionꢀ wasꢀ
observedꢀ underꢀ visibleꢀ lightꢀ irradiationꢀ ( ꢀ >ꢀ 390ꢀ nm).ꢀ Waterꢀ
Oꢀwasꢀalsoꢀconductedꢀtoꢀ
II
II
persulphateꢀ withꢀ Ni [Ru (CN)
Sc(NO ꢀ inꢀ CH OH/H
4
*
RuIIꢀ
O2ꢀ
3
)
3
3
2
2
hνꢀ
l
1
8
16
RuIIꢀ
oxidationꢀusingꢀH
2
OꢀinsteadꢀofꢀH
2
H O
2
ꢀ
H+ꢀ
Niꢀ
confirmꢀwhetherꢀevolvedꢀoxygenꢀcomesꢀfromꢀwater.ꢀAfterꢀtheꢀ
reaction,ꢀtheꢀevolvedꢀoxygenꢀwasꢀanalysedꢀbyꢀGC-MSꢀ(Fig.ꢀS9†).ꢀ
RuIIIꢀ
O2ꢀꢁꢀ
/2O + 2H+
ꢀ
1/2H O + 1/2O
2 2 2ꢀ
1
2
Sc3+)ꢀ
(
1
8 18
ꢀ wasꢀ O Oꢀ (>99%),ꢀ indicatingꢀ thatꢀ
II
II
Theꢀ observedꢀ O
2
Ni [Ru (CN)
(bpy)]
4 ꢀ
II
Ni [Ru (CN)
II
Schemeꢀ 2ꢀ Catalyticꢀ cycleꢀ ofꢀ visible-lightꢀ drivenꢀ waterꢀ oxidationꢀ byꢀ O2ꢀ withꢀ
4
(bpy)]ꢀoxidisesꢀwaterꢀevenꢀinꢀtheꢀpresenceꢀofꢀꢀ
II
II
4
Ni [Ru (CN) (bpy)]ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Pleaseꢀd Co hꢀ ne omt ꢀ Ca do j mu s mt ꢀmarginsꢀ
Page 4 of 4
COMMUNICATIONꢀ
JournalꢀNameꢀ
Nguyen,ꢀACSꢀCatal.,ꢀ2011,ꢀ
andꢀF.ꢀX.ꢀLlabrésꢀiꢀXamena,ꢀChem.ꢀRev .D, ꢀ O2 0I : 11 00 .,1ꢀ 0
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theꢀpresenceꢀofꢀSc(NO ) ꢀinꢀCH OH/H Oꢀ(5:1,ꢀv/v)ꢀunderꢀvisibleꢀ
View Article Online
39
110/ ,Cꢀ 47 6C 0C 60 -0 46 62 51 G5 .ꢀ
lightꢀirradiationꢀ(
l
ꢀ>ꢀ390ꢀnm).ꢀTheꢀdualꢀfunctionꢀphotocatalysisꢀ
(bpy)]ꢀ inꢀ aꢀ singleꢀ catalystꢀ providesꢀ aꢀ veryꢀ
efficientꢀintegratedꢀprocessꢀforꢀtheꢀphotocatalyticꢀproductionꢀ
ofꢀH ꢀasꢀaꢀpromisingꢀsolarꢀfuelꢀfromꢀH OꢀandꢀO ꢀusingꢀsolarꢀ
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Theꢀ authorsꢀ acknowledgeꢀ Dr.ꢀ Tatsuoꢀ Nakagawaꢀ forꢀ transientꢀ
absorptionꢀ spectraꢀ measurements.ꢀ Thisꢀ workꢀ wasꢀ supportedꢀ
byꢀtheꢀSENTANꢀprojectꢀfromꢀJapanꢀScienceꢀTechnologyꢀAgencyꢀ
1
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