Highly selective supported gold catalyst for CO-driven reduction of furfural in aqueous media

Article abstract of DOI:10.1016/S1872-2067(16)62458-0

The reductive transformation of furfural (FAL) into furfuryl alcohol (FOL) is an attractive route for the use of renewable bio-sources but it suffers from the heavy use of H₂. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO₂ support with a gold catalyst (Au/TiO₂-R) that used CO/H₂O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel-derived H₂, our process has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.

Full text of DOI:10.1016/S1872-2067(16)62458-0

ChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1669–1675
ꢀ
ꢀ ꢀ ꢀ
ꢀ ꢀ ꢀ ꢀ
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
ꢀ
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
ꢀ
ꢀ
Article (Special Issue on Gold Catalysis)
HighlyꢀselectiveꢀsupportedꢀgoldꢀcatalystꢀforꢀCO‐drivenꢀreductionꢀofꢀ
furfuralꢀinꢀaqueousꢀmediaꢀ
a,b
a
a
ꢀa
a,
b
JingꢀDongꢀ ,ꢀMingmingꢀZhuꢀ ,ꢀGaoshuoꢀZhangꢀ ,ꢀYongmeiꢀLiu ,ꢀYongꢀCaoꢀ *,ꢀSuꢀLiuꢀ ,ꢀ ꢀ
b,#
YangdongꢀWangꢀ
ꢀ
aꢀShanghaiꢀKeyꢀLaboratoryꢀofꢀMolecularꢀCatalysisꢀandꢀInnovativeꢀMaterials,ꢀDepartmentꢀofꢀChemistry,ꢀFudanꢀUniversity,ꢀShanghaiꢀ200433,ꢀChinaꢀ
bꢀSINOPECꢀShanghaiꢀResearchꢀInstituteꢀofꢀPetrochemicalꢀTechnology,ꢀShanghaiꢀ201208,ꢀChinaꢀ
A R T I C L E ꢀ I N F O ꢀ
A B S T R A C T ꢀ
Articleꢀhistory:ꢀ
Theꢀreductiveꢀtransformationꢀofꢀfurfuralꢀ(FAL)ꢀintoꢀfurfurylꢀalcoholꢀ(FOL)ꢀisꢀanꢀattractiveꢀrouteꢀforꢀ
Receivedꢀ14ꢀAprilꢀ2016ꢀ
Acceptedꢀ10ꢀMayꢀ2016ꢀ
Publishedꢀ5ꢀOctoberꢀ2016ꢀ
theꢀuseꢀofꢀrenewableꢀbio‐sourcesꢀbutꢀitꢀsuffersꢀfromꢀtheꢀheavyꢀuseꢀofꢀH
efficientꢀreductionꢀprotocolꢀforꢀconvertingꢀaqueousꢀFALꢀtoꢀFOL.ꢀAꢀsingleꢀphaseꢀrutileꢀTiO
withꢀaꢀgoldꢀcatalystꢀ(Au/TiO ‐R)ꢀthatꢀusedꢀCO/H Oꢀasꢀtheꢀhydrogenꢀsourceꢀcatalyzeꢀthisꢀreductionꢀ
efficientlyꢀunderꢀmildꢀconditions.ꢀByꢀeliminatingꢀtheꢀconsumptionꢀofꢀfossilꢀfuel‐derivedꢀH ,ꢀourꢀpro‐
cessꢀhasꢀtheꢀbenefitꢀaffordedꢀbyꢀusingꢀCOꢀasꢀaꢀconvenientꢀandꢀcostꢀcompetitiveꢀreducingꢀreagent.ꢀ
2
.ꢀWeꢀdescribeꢀhereꢀaꢀhighlyꢀ
2
ꢀsupportꢀ
2
2
2
Keywords:ꢀ
Furfuralꢀ
Reductionꢀ
©ꢀ2016,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences.
PublishedꢀbyꢀElsevierꢀB.V.ꢀAllꢀrightsꢀreserved.
Supportedꢀgoldꢀcatalystꢀ
Carbonꢀmonoxideꢀ
Aqueous
1.ꢀ ꢀ Introductionꢀ
stratedꢀtheꢀpotentialꢀofꢀthisꢀapproachꢀinꢀsettingꢀupꢀaꢀbiobasedꢀ
economyꢀ[11–17].ꢀHowever,ꢀH
ꢀisꢀmainlyꢀproducedꢀfromꢀfossilꢀ
2
Theꢀsearchꢀforꢀchemicalꢀprocessesꢀtoꢀconvertꢀbiogenicꢀfeed‐
fuels,ꢀwhichꢀinꢀturnꢀmakeꢀtheꢀprocessꢀdependentꢀonꢀfossilꢀcar‐
bon.ꢀMoreover,ꢀtheꢀnecessityꢀofꢀspecialꢀhandlingꢀforꢀtheꢀhighlyꢀ
stocksꢀtoꢀrenewableꢀchemicalsꢀandꢀfuelsꢀhasꢀdrivenꢀeffortsꢀtoꢀ
discoverꢀ andꢀ developꢀ newꢀ effectiveꢀ reactionsꢀ thatꢀ enableꢀ theꢀ
selectiveꢀ refunctionalizationꢀ ofꢀ theseꢀ polyoxygenateꢀ materialsꢀ
flammableꢀH ꢀgasꢀandꢀtheꢀrequirementꢀofꢀanꢀorganicꢀsolventꢀtoꢀ
2
achieveꢀaꢀhighꢀselectivityꢀhaveꢀdiminishedꢀtheꢀappealꢀofꢀtheseꢀ
proceduresꢀ[12–15].ꢀAnyꢀstrategyꢀandꢀconditionsꢀthatꢀcanꢀad‐
dressꢀtheseꢀissuesꢀwillꢀbeꢀadvantageousꢀnotꢀonlyꢀforꢀFALꢀreduc‐
tionꢀbutꢀalsoꢀforꢀtheꢀreductionꢀofꢀbiomassꢀintermediatesꢀsuchꢀasꢀ
5‐hydroxymethylfurfuralꢀ(HMF).ꢀ ꢀ ꢀ
[
1–5].ꢀ Inꢀ thisꢀ context,ꢀ furfuralꢀ (FAL)ꢀ representsꢀ aꢀ promisingꢀ
biogenicꢀbuildingꢀblockꢀandꢀtheꢀdirectꢀconversionꢀofꢀFALꢀintoꢀ
furfurylꢀalcoholꢀ(FOL)ꢀbyꢀcatalyticꢀreductionꢀhasꢀbeenꢀidentifiedꢀ
asꢀaꢀreliableꢀ feedstockꢀsourceꢀ toꢀopenꢀnewꢀ scenariosꢀforꢀ sus‐
tainableꢀchemicalꢀproductionꢀ[6–10].ꢀHistorically,ꢀtheꢀreductionꢀ
ofꢀfurfuralꢀunderꢀanꢀaggressiveꢀhydrogenꢀatmosphereꢀhasꢀbeenꢀ
theꢀ focusꢀ ofꢀ extensiveꢀ efforts.ꢀ Recentꢀ progressꢀ hasꢀ demon‐
DueꢀtoꢀtheꢀpotentialꢀforꢀtheꢀuseꢀofꢀCOꢀasꢀaꢀkeyꢀintermediateꢀ
1
inꢀtheꢀchemicalꢀindustry,ꢀmainlyꢀasꢀaꢀC ꢀbuildingꢀblock,ꢀthereꢀisꢀ
continuousꢀinterestꢀinꢀtheꢀdevelopmentꢀofꢀtransformationsꢀforꢀ
*
ꢀ
ꢀCorrespondingꢀauthor.ꢀTel:ꢀ+86‐21‐55665287;ꢀFax:ꢀ+86‐21‐65643774;ꢀE‐mail:ꢀyongcao@fudan.edu.cnꢀ ꢀ
Correspondingꢀauthor.ꢀTel:ꢀ+86‐21‐68462947;ꢀFax:ꢀ+86‐21‐68462283;ꢀE‐mail:ꢀwangyd.sshy@sinopec.comꢀ ꢀ
#
ThisꢀworkꢀwasꢀsupportedꢀbyꢀtheꢀNationalꢀNaturalꢀScienceꢀFoundationꢀofꢀChinaꢀ(21273044,ꢀ21473035,ꢀ91545108),ꢀtheꢀResearchꢀFundꢀforꢀtheꢀDoctoralꢀ
ProgramꢀofꢀHigherꢀEducationꢀ(2012007000011),ꢀSINOPECꢀ(X514005),ꢀScienceꢀ&ꢀTechnologyꢀCommissionꢀofꢀShanghaiꢀMunicipalityꢀ(08DZ2270500),
andꢀtheꢀOpenꢀProjectꢀofꢀStateꢀKeyꢀLaboratoryꢀofꢀChemicalꢀEngineeringꢀ(SKL‐ChE‐15C02).ꢀ
DOI:ꢀ10.1016/S1872‐2067(16)62458‐0ꢀ|ꢀhttp://www.sciencedirect.com/science/journal/18722067ꢀ|ꢀChin.ꢀJ.ꢀCatal.,ꢀVol.ꢀ37,ꢀNo.ꢀ10,ꢀOctoberꢀ2016ꢀ ꢀ ꢀ

1670ꢀ
JingꢀDongꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1669–1675ꢀ
COꢀ valorization.ꢀ Theꢀ useꢀ ofꢀ COꢀ insteadꢀ ofꢀ hydrogenꢀ orꢀ otherꢀ
hydrogenꢀ donorꢀ agentsꢀ isꢀ particularlyꢀ interestingꢀ sinceꢀ COꢀ isꢀ
currentlyꢀ producedꢀ inꢀ multi‐tonꢀ quantitiesꢀ asꢀ aꢀ byproductꢀ ofꢀ
theꢀsteelꢀindustryꢀ[18]ꢀandꢀthusꢀrepresentsꢀanꢀabundantꢀsourceꢀ
forꢀ chemicalꢀ reductionꢀ [19,20].ꢀ Oneꢀ conceptuallyꢀ straightfor‐
Theꢀ0.6ꢀwt%ꢀAu/TiO
deposition‐precipitationꢀ (DP)ꢀ methodꢀ [30,31].ꢀ Inꢀ brief,ꢀ anꢀ
aqueousꢀsolutionꢀofꢀHAuCl ꢀwasꢀaddedꢀtoꢀ100ꢀmLꢀofꢀdeionizedꢀ
waterꢀatꢀ80ꢀ°Cꢀunderꢀvigorousꢀstirring.ꢀTheꢀpHꢀwasꢀadjustedꢀtoꢀ
7.0ꢀandꢀ1.0ꢀgꢀTiO ‐RꢀwasꢀdispersedꢀinꢀtheꢀsolutionꢀwithꢀtheꢀpHꢀ
2
‐Rꢀsampleꢀwasꢀpreparedꢀbyꢀaꢀroutineꢀ
4
2
wardꢀwayꢀisꢀtoꢀuseꢀaꢀCO/H
2
Oꢀcoupleꢀasꢀaꢀsourceꢀofꢀhydrogen,ꢀ
keptꢀconstantꢀatꢀ6.5–7.0.ꢀTheꢀmixtureꢀwasꢀstirredꢀforꢀ2ꢀhꢀatꢀ80ꢀ
°C.ꢀAfterꢀthat,ꢀtheꢀsuspensionꢀwasꢀcooledꢀtoꢀ25ꢀ°C.ꢀAfterꢀthor‐
oughꢀ washingꢀ withꢀ deionisedꢀ water,ꢀ theꢀ samplesꢀ wereꢀ driedꢀ
underꢀvacuumꢀatꢀ25ꢀ°Cꢀforꢀ12ꢀhꢀandꢀthenꢀcalcinedꢀinꢀaꢀmuffleꢀ
althoughꢀtheꢀmostꢀidealꢀscenarioꢀwouldꢀbeꢀCOꢀasꢀsoleꢀreductantꢀ
withoutꢀanꢀexternalꢀhydrogenꢀsourceꢀ[19].ꢀWeꢀhaveꢀcontribut‐
edꢀ toꢀ thisꢀ fieldꢀ byꢀ discoveringꢀ anꢀ excellentꢀ Au‐catalyzedꢀ
2
CO/H O‐drivenꢀstrategyꢀthatꢀallowedꢀrapidꢀandꢀchemoselectiveꢀ
2
ovenꢀ atꢀ 350ꢀ °Cꢀ forꢀ 2ꢀ h.ꢀ 0.6ꢀ wt%ꢀ Au/TiO ‐A,ꢀ 0.6ꢀ wt%ꢀ
reductionꢀofꢀsubstitutedꢀnitroꢀandꢀcarbonylꢀgroupsꢀunderꢀveryꢀ
mildꢀconditionsꢀ[20,21].ꢀOurꢀsubsequentꢀstudiesꢀrevealedꢀthatꢀ
theꢀAu‐CO‐assistedꢀreductionꢀstrategyꢀcouldꢀbeꢀusedꢀforꢀreduc‐
tiveꢀiminationꢀandꢀcarbonylativeꢀalkyneꢀsemireductionꢀ[22,23].ꢀ
Ourꢀ continuingꢀ interestꢀ inꢀ theꢀ developmentꢀ ofꢀ innovativeꢀ
CO‐basedꢀcatalyticꢀreductionꢀtechnologiesꢀledꢀusꢀtoꢀinvestigateꢀ
Au/TiO ‐P25,ꢀandꢀ0.6ꢀwt%ꢀAu/TiO ‐P90ꢀwereꢀpreparedꢀbyꢀtheꢀ
2
2
sameꢀmethod.ꢀ
0.6ꢀwt%ꢀIr/TiO
2
‐R,ꢀ0.6ꢀwt%ꢀPd/TiO
‐Rꢀcatalystsꢀwereꢀpreparedꢀbyꢀincipientꢀwet‐
nessꢀimpregnationꢀ(IWI)ꢀofꢀtheꢀsupportꢀwithꢀaqueousꢀsolutionsꢀ
ofꢀ H IrCl ·6H O,ꢀ PdCl ,ꢀ H PtCl ·6H Oꢀ orꢀ RuCl ꢀ precursors,ꢀ re‐
2
‐R,ꢀ0.6ꢀwt%ꢀPt/TiO ‐R,ꢀ
2
0.6ꢀwt%ꢀRu/TiO
2
2
6
2
2
2
6
2
3
theꢀ reductionꢀ efficiencyꢀ ofꢀ theꢀ Au‐CO/H
2
Oꢀ protocolꢀ forꢀ theꢀ
spectivelyꢀ [31].ꢀ Afterꢀ mixingꢀ theꢀ correspondingꢀ slurries,ꢀ theꢀ
mixtureꢀwasꢀvigorouslyꢀstirredꢀatꢀ80ꢀ°Cꢀforꢀ4ꢀh.ꢀThenꢀsamplesꢀ
wereꢀdriedꢀunderꢀvacuumꢀatꢀ25ꢀ°Cꢀforꢀ12ꢀhꢀandꢀthenꢀreducedꢀinꢀ
transformationꢀ ofꢀ biogenicꢀ platformꢀ chemicalsꢀ [24].ꢀ Weꢀ dis‐
closeꢀhereꢀtheꢀversatileꢀcatalyticꢀbehaviorꢀofꢀsupportedꢀAuꢀna‐
noparticlesꢀ(NPs)ꢀinꢀtheꢀreductiveꢀtransformationꢀofꢀFALꢀtoꢀFOLꢀ
5ꢀvol%ꢀH /Arꢀ(80ꢀmL/min)ꢀatꢀ400ꢀ°Cꢀforꢀ2ꢀh.ꢀ
2
2
withoutꢀtheꢀuseꢀofꢀH .ꢀWeꢀdemonstrateꢀthatꢀadoptingꢀaꢀsuitableꢀ
inorganicꢀ supportꢀ suchꢀ asꢀ singleꢀ phaseꢀ rutileꢀ TiO
2
ꢀ toꢀ anchorꢀ
2.2.ꢀ ꢀ Characterizationꢀ
finelyꢀdispersedꢀAuꢀNPsꢀenabledꢀaꢀhighlyꢀselectiveꢀandꢀefficientꢀ
transformationꢀofꢀFALꢀtoꢀFOLꢀinꢀwaterꢀunderꢀaꢀmildꢀCOꢀatmos‐
phereꢀ (Schemeꢀ 1).ꢀ Asꢀ opposedꢀ toꢀ previousꢀ procedures,ꢀ thisꢀ
X‐rayꢀdiffractionꢀ(XRD)ꢀ analysisꢀ wasꢀcarriedꢀoutꢀonꢀ aꢀGer‐
manꢀ Brukerꢀ D8Advanceꢀ X‐rayꢀ diffractometerꢀ usingꢀ nickelꢀ fil‐
teredꢀCuꢀKαꢀradiationꢀwithꢀaꢀscanningꢀangleꢀ(2θ)ꢀofꢀ10°–80°,ꢀaꢀ
scanningꢀspeedꢀofꢀ2°/min,ꢀandꢀaꢀvoltageꢀandꢀcurrentꢀofꢀ40ꢀkVꢀ
andꢀ20ꢀmA.ꢀTransmissionꢀelectronꢀmicroscopeꢀ (TEM)ꢀimagesꢀ
wereꢀtakenꢀwithꢀaꢀJEOLꢀ2011ꢀelectronꢀmicroscopeꢀoperatingꢀatꢀ
200ꢀ kV.ꢀ Beforeꢀ beingꢀ transferredꢀ intoꢀ theꢀ TEMꢀ chamber,ꢀ theꢀ
samplesꢀwereꢀdispersedꢀinꢀethanolꢀandꢀdepositedꢀontoꢀaꢀcar‐
bon‐coatedꢀcopperꢀgridꢀandꢀthenꢀquicklyꢀmovedꢀintoꢀtheꢀvac‐
uumꢀ evaporator.ꢀ Theꢀ sizeꢀ distributionꢀ ofꢀ theꢀ metalꢀ particlesꢀ
wasꢀdeterminedꢀbyꢀmeasuringꢀaboutꢀ200ꢀrandomꢀparticlesꢀinꢀ
theꢀimages.ꢀCOꢀtemperatureꢀprogrammedꢀreductionꢀ(CO‐TPR)ꢀ
experimentsꢀ wereꢀ carriedꢀ outꢀ onꢀ aꢀ homemadeꢀ apparatusꢀ de‐
scribedꢀ elsewhereꢀ [32].ꢀ X‐rayꢀ photoelectronꢀ spectroscopyꢀ
Au‐CO/H O‐mediatedꢀreductionꢀsystemꢀcanꢀdeliverꢀhighꢀselec‐
2
tivityꢀinꢀtheꢀreductionꢀofꢀaqueousꢀFAL,ꢀaffordingꢀexclusivelyꢀtheꢀ
correspondingꢀ FOLꢀ inꢀ aꢀ mild,ꢀ economicalꢀ andꢀ greenꢀ manner.ꢀ
Thisꢀreductionꢀusingꢀaꢀsimpleꢀandꢀrobustꢀgoldꢀcatalystꢀcoupledꢀ
withꢀCO/H Oꢀasꢀtheꢀhydrogenꢀsourceꢀunderꢀmildꢀconditionsꢀcanꢀ
2
makeꢀ aꢀ significantꢀ contributionꢀ toꢀ theꢀ catalyticꢀ potentialꢀ ofꢀ
supportedꢀAuꢀNPsꢀandꢀtoꢀestablishꢀanꢀapproachꢀforꢀmoreꢀeffi‐
cientꢀFALꢀreduction.ꢀ
2
.ꢀ ꢀ Experimentalꢀ
.1.ꢀ ꢀ Preparationꢀ
Anataseꢀ (TiO
2
(
XPS)ꢀanalysisꢀwasꢀperformedꢀusingꢀaꢀPerkinꢀElmerꢀPHIꢀ5000Cꢀ
systemꢀequippedꢀwithꢀaꢀhemisphericalꢀelectronꢀenergyꢀanalyz‐
er.ꢀTheꢀMgꢀΚ
ꢀ(hνꢀ=ꢀ1253.6ꢀeV)ꢀwasꢀoperatedꢀatꢀ15ꢀkVꢀandꢀ20ꢀ
2
2
‐A,ꢀ surfaceꢀ areaꢀ ofꢀ154ꢀm /g),ꢀrutileꢀ(TiO
2
‐R,ꢀ
2
surfaceꢀ areaꢀ ofꢀ 65ꢀ m /g),ꢀ Au/ZrO
2
ꢀ(ZrO
2
,ꢀ surfaceꢀ areaꢀ ofꢀ 115ꢀ
m /g),ꢀAu/TiO2ꢀ(P25,ꢀsurfaceꢀareaꢀofꢀ45ꢀm /g;ꢀP90,ꢀsurfaceꢀareaꢀ
α
2
2
mA.ꢀTheꢀenergyꢀscaleꢀwasꢀinternallyꢀcalibratedꢀbyꢀsettingꢀtheꢀCꢀ
1sꢀpeakꢀatꢀ284.6ꢀeV.ꢀTheꢀsolutionꢀafterꢀreactionꢀwasꢀmeasuredꢀ
byꢀ inductivelyꢀ coupledꢀ plasmaꢀ atomicꢀ emissionꢀ spectroscopyꢀ
(ICP‐AES)ꢀusingꢀaꢀThermoꢀElectronꢀIRISꢀIntrepidꢀIIꢀXSPꢀspec‐
trometer.ꢀ
2
2
ofꢀ 95ꢀ m /g),ꢀ Au/CeO
2
ꢀ (CeO
2
,ꢀ surfaceꢀ areaꢀ ofꢀ 139ꢀ m /g)ꢀ andꢀ
2
Au/HTꢀ (HT,ꢀ surfaceꢀ areaꢀ ofꢀ 118ꢀ m /g).ꢀ Allꢀ theꢀ supportsꢀ andꢀ
catalystsꢀ wereꢀ preparedꢀ byꢀ usingꢀ previouslyꢀ describedꢀ meth‐
odsꢀ[23–30].ꢀ
2.3.ꢀ ꢀ ReductionꢀofꢀFALꢀtoꢀFOLꢀ
Previous work
using H [11-17]
2
Aꢀ25‐mLꢀHastelloy‐CꢀhighꢀpressureꢀParrꢀreactorꢀwasꢀusedꢀtoꢀ
O
OH
O
carryꢀoutꢀtheꢀliquidꢀphaseꢀreductionꢀreaction.ꢀAꢀmixtureꢀofꢀFALꢀ
2.6ꢀmmol,ꢀfreshꢀdistilled),ꢀsupportedꢀmetalꢀcatalysts,ꢀwaterꢀ(20ꢀ
mL)ꢀwereꢀloadedꢀintoꢀtheꢀreactor.ꢀTheꢀreactorꢀwasꢀstirredꢀatꢀaꢀ
rateꢀofꢀ800ꢀr/minꢀunderꢀ4ꢀMPaꢀCOꢀ(syngas,ꢀorꢀH )ꢀforꢀaꢀspecificꢀ
Cat.
CHO + hydrogen source
(
This work
2
using CO/H O
reactionꢀ timeꢀ atꢀ aꢀ givenꢀ temperature.ꢀ Afterꢀ reaction,ꢀ theꢀ COꢀ
atmosphereꢀ wasꢀ removedꢀ andꢀ theꢀ resultantꢀ productꢀ mixtureꢀ
wasꢀ transferredꢀ withꢀ 5ꢀ mLꢀ ofꢀ ethanol.ꢀ Anꢀ amountꢀ ofꢀ
N,N‐dimethylformamideꢀ(DMF)ꢀwasꢀthenꢀaddedꢀasꢀanꢀinternalꢀ
2
Schemeꢀ1.ꢀ Reductiveꢀ transformationꢀ ofꢀ FALꢀ toꢀ FOLꢀ withꢀ variousꢀ hy‐
drogenꢀsources.ꢀ

ꢀ
JingꢀDongꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1669–1675ꢀ
1671ꢀ
standardꢀ substance.ꢀ Theꢀ samplesꢀ wereꢀ analyzedꢀ onꢀ aꢀ Agilentꢀ
GC‐6820ꢀgasꢀchromatographꢀequippedꢀwithꢀaꢀcapillaryꢀcolumnꢀ
DB‐Waxꢀ(30ꢀmꢀ×ꢀ0.25ꢀmm)ꢀandꢀFIDꢀdetector.ꢀTheꢀidentificationꢀ
ofꢀtheꢀproductsꢀwasꢀperformedꢀbyꢀusingꢀaꢀGC‐MSꢀspectrometer.ꢀ
100
80
FOL
60
40
20
0
3
.ꢀ ꢀ Resultsꢀandꢀdiscussionꢀ
Atꢀfirst,ꢀtheꢀreactionꢀwasꢀevaluatedꢀusingꢀaꢀdilutedꢀaqueousꢀ
solutionꢀofꢀfreshlyꢀdistilledꢀFALꢀ(0.13ꢀmol/L)ꢀandꢀAuꢀNPsꢀ(av‐
erageꢀdiameterꢀofꢀca.ꢀ2.2ꢀnm)ꢀdepositedꢀonꢀsomeꢀcommonꢀin‐
organicꢀoxidesꢀwithꢀaꢀsubstrate‐to‐goldꢀ(nFAL/nAu)ꢀratioꢀofꢀ200:1ꢀ
underꢀmildꢀconditionsꢀ(4ꢀMPaꢀofꢀCOꢀpressureꢀinꢀneatꢀwaterꢀatꢀ
FAL
0
1
2
3
4
9
0ꢀ°C).ꢀWeꢀinitiallyꢀfocusedꢀourꢀattentionꢀonꢀAu/CeO
2
ꢀbecauseꢀ
Time (h)
ofꢀ theꢀ successfulꢀ applicationꢀ ofꢀ thisꢀ Au‐basedꢀ catalystꢀ forꢀ theꢀ
chemoselectiveꢀreductionꢀofꢀaꢀrangeꢀofꢀa,ꢀβ‐unsaturatedꢀalde‐
hydes,ꢀe.g.,ꢀcrotonaldehydeꢀandꢀcinnamaldehyde,ꢀtoꢀtheirꢀallylꢀ
Fig.ꢀ1.ꢀTimeꢀprofilesꢀofꢀFALꢀreductionꢀoverꢀAu/TiO
2
‐R.ꢀReactionꢀcondi‐
tions:ꢀFALꢀ2.6ꢀmmol,ꢀwaterꢀ20ꢀmL,ꢀnFAL/n ꢀ=ꢀ200,ꢀ90ꢀ°C,ꢀp(CO)ꢀ=ꢀ4ꢀMPa.
Au
alcoholsꢀinꢀtheꢀpresenceꢀofꢀCOꢀandꢀH
terialꢀ affordedꢀ onlyꢀ modestꢀ activityꢀ forꢀ theꢀ CO/H
FALꢀtoꢀFOLꢀreductionꢀunderꢀtheꢀscreeningꢀconditionsꢀemployedꢀ
Tableꢀ1,ꢀentryꢀ1).ꢀWeꢀthenꢀturnedꢀourꢀattentionꢀtoꢀtheꢀselectionꢀ
ofꢀ otherꢀ commonlyꢀ usedꢀ Au‐supportꢀ combinationsꢀ thatꢀ haveꢀ
provenꢀ effectiveꢀ inꢀ theꢀ Au‐CO/H O‐mediatedꢀ reductiveꢀ trans‐
formation,ꢀ includingꢀ Au/TiO ‐P25,ꢀ Au/Al ,ꢀ Au/ZrO ꢀ andꢀ
2
Oꢀ[21].ꢀHowever,ꢀthisꢀma‐
ingꢀ theꢀ TiO
–8).ꢀ Eventually,ꢀ theꢀ optimizedꢀ Au/TiO
depositedꢀonꢀsingleꢀphaseꢀrutileꢀTiO ꢀ(Au/TiO
2
ꢀ phaseꢀ duringꢀ theꢀ preparationꢀ (Tableꢀ 1,ꢀ entryꢀ 1,ꢀ
‐Rꢀ comprisingꢀ goldꢀ
‐R)ꢀwasꢀtheꢀmostꢀ
2
O‐mediatedꢀ
6
2
2
2
(
efficient,ꢀwhichꢀaccomplishedꢀquantitativeꢀFAL‐to‐FOLꢀconver‐
sionꢀwithinꢀonlyꢀ4ꢀhꢀatꢀ90ꢀ°Cꢀ(Tableꢀ1,ꢀentryꢀ9).ꢀAꢀplotꢀofꢀtheꢀ
timeꢀ dependentꢀ conversionꢀ ofꢀ FALꢀ (Fig.ꢀ 1)ꢀ revealedꢀ thatꢀ theꢀ
reactionꢀ proceededꢀ smoothlyꢀ andꢀ FOLꢀ wasꢀ theꢀ onlyꢀ product,ꢀ
thatꢀis,ꢀweꢀdidꢀnotꢀdetectꢀanyꢀotherꢀproductꢀduringꢀtheꢀwholeꢀ
reaction.ꢀFurthermore,ꢀinꢀaꢀseriesꢀofꢀstudiesꢀexaminingꢀtheꢀef‐
fectꢀofꢀpressure,ꢀtheꢀreactionꢀtimeꢀwasꢀshortenedꢀfromꢀ4ꢀtoꢀ2.5ꢀ
hꢀasꢀtheꢀpCOꢀwasꢀraisedꢀfromꢀ4ꢀtoꢀ6ꢀMPaꢀ(Tableꢀ1,ꢀentriesꢀ9ꢀandꢀ
2
2
O
2 3
2
Au/Mg‐Alꢀhydrotalciteꢀ(Tableꢀ1,ꢀentriesꢀ2–5).ꢀWhileꢀnoneꢀwereꢀ
foundꢀtoꢀbeꢀparticularlyꢀactiveꢀforꢀFALꢀreduction,ꢀtheꢀmodestꢀ
successꢀachievedꢀwithꢀAu/TiO
surveyꢀofꢀstructurallyꢀrelatedꢀAu‐TiO
WeꢀsubsequentlyꢀoptimizedꢀtheꢀAu‐TiO
2
‐P25ꢀpromptedꢀaꢀmoreꢀdetailedꢀ
‐basedꢀsystems.ꢀ ꢀ
ꢀcatalystsꢀbyꢀalter‐
2
2
1
1).ꢀFurtherꢀexperimentsꢀonꢀtheꢀeffectꢀofꢀtemperatureꢀindicatedꢀ
thatꢀtheꢀAu/TiO ‐Rꢀcatalystꢀexhibitedꢀratherꢀlowꢀactivityꢀatꢀ30ꢀ
Cꢀ(Tableꢀ1,ꢀentryꢀ13).ꢀAtꢀ120ꢀ°C,ꢀquantitativeꢀformationꢀofꢀFOLꢀ
wasꢀattainedꢀatꢀ4ꢀMPaꢀwithinꢀ2ꢀhꢀ(Tableꢀ1,ꢀentryꢀ12).ꢀ ꢀ
Inꢀ lineꢀ withꢀ severalꢀ otherꢀ CO/H O‐mediatedꢀ reductionꢀ
20–23],ꢀ weꢀ foundꢀ thatꢀ Auꢀ wasꢀ asꢀ activeꢀ forꢀ theꢀ reductionꢀ ofꢀ
FALꢀwithꢀCO/H Oꢀasꢀtraditionalꢀnobleꢀmetalsꢀ(Tableꢀ1,ꢀentriesꢀ
7–20).ꢀ Theseꢀ resultsꢀ confirmedꢀ thatꢀ theꢀ combinationꢀ ofꢀ Auꢀ
NPsꢀ withꢀaꢀ suitableꢀTiO ꢀphaseꢀcouldꢀachieveꢀaꢀhighꢀcatalyticꢀ
2
Tableꢀ1ꢀ
°
FALꢀconversionꢀandꢀFOLꢀselectivityꢀwithꢀdifferentꢀcatalysts.ꢀ
a
a
pꢀ ꢀ
Tꢀ ꢀ
tꢀ ꢀ Conversionꢀ ꢀ Selectivityꢀ
Entryꢀ
Catalystꢀ
Au/CeO
2
(
MPa)ꢀ (°C)ꢀ (h)ꢀ
(%)ꢀ
ꢀ 21ꢀ
ꢀ 53ꢀ
ꢀ 15ꢀ
ꢀ ꢀ 1ꢀ
ꢀ 18ꢀ
ꢀ 52ꢀ
ꢀ 67ꢀ
ꢀ 48ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
ꢀ 19ꢀ
100ꢀ
ꢀ 99ꢀ
100ꢀ
ꢀ ꢀ 8ꢀ
ꢀ ꢀ 1ꢀ
ꢀ ꢀ 1ꢀ
ꢀ ꢀ 1ꢀ
100ꢀ
(%)ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
[
1
ꢀ
2
ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
2ꢀ
6ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
4ꢀ
ꢀ 90ꢀ 2ꢀ
ꢀ 90ꢀ 2ꢀ
ꢀ 90ꢀ 2ꢀ
ꢀ 90ꢀ 2ꢀ
ꢀ 90ꢀ 2ꢀ
ꢀ 90ꢀ 2ꢀ
ꢀ 90ꢀ 2ꢀ
ꢀ 90ꢀ 2ꢀ
ꢀ 90ꢀ 4ꢀ
ꢀ 90ꢀ 7ꢀ
ꢀ 90ꢀ 2.5ꢀ
120ꢀ 2ꢀ
ꢀ 30ꢀ 4ꢀ
ꢀ 90ꢀ 23ꢀ
ꢀ 90ꢀ 61ꢀ
ꢀ 90ꢀ 4.5ꢀ
ꢀ 90ꢀ 4ꢀ
ꢀ 90ꢀ 4ꢀ
ꢀ 90ꢀ 4ꢀ
ꢀ 90ꢀ 4ꢀ
ꢀ 90ꢀ 4ꢀ
2
ꢀ
Au/TiO ‐P25ꢀ
Au/ZrO
Au/Al
Au/HTꢀ
Au/TiO ‐P90ꢀ
‐Rꢀ
‐Aꢀ
2
2
3
ꢀ
2
ꢀ
1
4
ꢀ
2 3
O ꢀ
2
5
ꢀ
activityꢀ forꢀ theꢀ selectiveꢀ reductionꢀ ofꢀ FALꢀ intoꢀ FOL.ꢀ Afterꢀ theꢀ
6
ꢀ
2
7
ꢀ
Au/TiO
Au/TiO
Au/TiO
Au/TiO
Au/TiO
Au/TiO
Au/TiO
Au/TiO
Au/TiO
Au/TiO
2
8
ꢀ
2
2.00E-009
9
ꢀ
2
‐Rꢀ
2
‐Rꢀ
2
‐Rꢀ
2
‐Rꢀ
2
‐Rꢀ
2
‐Rꢀ
2
‐Rꢀ
2
‐Rꢀ
ꢀ
1
1
1
1
1
1
1
1
1
1
2
2
0 ꢀ
Au-TiO -R
2
1ꢀ
2ꢀ
3ꢀ
4 ꢀ
5 ꢀ
6 ꢀ
7ꢀ
8ꢀ
9ꢀ
0ꢀ
1.50E-009
Au-TiO -P25
2
ꢀb
ꢀc
1.00E-009
5.00E-010
Au-TiO -A
2
ꢀd
2
Ir/TiO ‐Rꢀ
Au-CeO2
Pd/TiO
2
‐Rꢀ
‐Rꢀ
Pt/TiO
Ru/TiO
Au/TiO
2
Au-Al O
2
3
2
‐Rꢀ
‐Rꢀ
e
1ꢀ ꢀ
2
0.00E+000
Reactionꢀconditions:ꢀFALꢀ2.6ꢀmmol,ꢀwaterꢀ20ꢀmL,ꢀnFAL/nAuꢀ=ꢀ200,ꢀ90ꢀ°C,ꢀ
0
100
200
300
400
500
p(CO)ꢀ=ꢀ4ꢀMPa,ꢀ2ꢀh.ꢀ
o
Temperature ( C)
a
ꢀ
Conversionꢀ andꢀ selectivityꢀwereꢀ determinedꢀbyꢀ GCꢀ andꢀ GC‐MSꢀwithꢀ
N,N‐dimethylformamideꢀasꢀtheꢀinternalꢀstandard.ꢀ
Fig.ꢀ 2.ꢀ COꢀ TPRꢀ profilesꢀ (1%ꢀ COꢀ inꢀ He,ꢀ 20ꢀ mL/min;ꢀ heatingꢀ rate:ꢀ 5ꢀ
°C/min;ꢀ 100ꢀ mgꢀ sample)ꢀ forꢀ differentꢀ Auꢀ catalysts.ꢀ Eachꢀ sampleꢀ wasꢀ
purgedꢀwithꢀ20ꢀmL/minꢀHeꢀatꢀ100ꢀ°Cꢀforꢀ30ꢀminꢀandꢀthenꢀcooledꢀtoꢀ30ꢀ
°CꢀinꢀHe.ꢀBeforeꢀbeingꢀheatedꢀfromꢀ30ꢀtoꢀ550ꢀ°C,ꢀtheꢀsampleꢀwasꢀstabi‐
lizedꢀinꢀ1%ꢀCOꢀinꢀHeꢀforꢀ30ꢀmin.ꢀ
b
ꢀ
n
FAL/nAuꢀ=ꢀ2000.ꢀ ꢀ
c
ꢀ
ꢀ
n
FAL/nAuꢀ=ꢀ5000.ꢀ ꢀ
d
th
Theꢀ5 ꢀreuseꢀofꢀtheꢀcatalystꢀrecoveredꢀfromꢀentryꢀ10.ꢀ ꢀ
eꢀUsingꢀagedꢀdistillatesꢀofꢀFALꢀasꢀfeedstock.ꢀ

1672ꢀ
JingꢀDongꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1669–1675ꢀ
reductionꢀofꢀFAL,ꢀAu/TiO ‐Rꢀcanꢀbeꢀseparatedꢀfromꢀtheꢀreactionꢀ
mixtureꢀandꢀreusedꢀwithoutꢀlossꢀofꢀcatalyticꢀefficiencyꢀ(Tableꢀ1,ꢀ
entriesꢀ 16).ꢀ Toꢀ gainꢀ insightꢀ intoꢀ theꢀ originꢀ ofꢀ theꢀ enhancedꢀ
2
O
H
O
O
OH
CO/H
TiO ꢀasꢀtheꢀsupport,ꢀCO‐TPRꢀwasꢀperformedꢀforꢀAuꢀdepositedꢀ
onꢀdifferentꢀsupportsꢀ(Fig.ꢀ2).ꢀThisꢀrevealedꢀthatꢀtheꢀlowerꢀper‐
formanceꢀ observedꢀ withꢀ Au/TiO ‐A,ꢀ Au/Al ꢀ andꢀ Au/CeO
wereꢀdueꢀtoꢀthatꢀtheꢀH ꢀformationꢀratesꢀcatalyzedꢀbyꢀtheseꢀcat‐
alystsꢀ wereꢀ significantlyꢀ lowerꢀ thanꢀ thatꢀ overꢀ theꢀ Au/TiO ‐Rꢀ
sample.ꢀ Thisꢀ wasꢀ reinforcedꢀ byꢀ theꢀ observationꢀ thatꢀ theꢀ lowꢀ
temperatureꢀH ꢀproductionꢀrateꢀoverꢀAu/TiO ‐Rꢀalsoꢀoccurredꢀ
atꢀaꢀmuchꢀhigherꢀrateꢀthanꢀthatꢀoverꢀTiO ‐P25ꢀsupportedꢀAu.ꢀ
Takenꢀ together,ꢀ theseꢀ resultsꢀ demonstratedꢀ thatꢀ theꢀ
Au‐catalyzedꢀCO/H O‐mediatedꢀFALꢀreductionꢀproceededꢀbyꢀaꢀ
2
O‐mediatedꢀ reductionꢀ activityꢀ achievedꢀ byꢀ usingꢀ rutileꢀ
CO2
2
Step 3
[
H ]
2
2
O
2 3
2
ꢀ
H O
2
X
2
Step 2
Step 4
2
CO
2
2
2
Step 1
2
sequentialꢀwater‐gas‐shift/FAL‐reductionꢀpathwayꢀ(Schemeꢀ2),ꢀ
inꢀwhichꢀtheꢀgenerationꢀofꢀaꢀtransientꢀAu ‐Hꢀspeciesꢀformedꢀbyꢀ
CO
0
Schemeꢀ2.ꢀMechanismꢀforꢀtheꢀAu/TiO
byꢀCO/H O.ꢀ
2
‐R‐catalyzedꢀreductionꢀofꢀHMFꢀ
CO‐inducedꢀH Oꢀactivationꢀwasꢀtheꢀmainꢀstep.ꢀ
2
2
Theseꢀresultsꢀ showedꢀthatꢀtheꢀAu/rutile‐basedꢀcatalystꢀ fa‐
cilitatedꢀ efficientꢀ FAL‐to‐FOLꢀ conversionꢀ withoutꢀ anꢀ externalꢀ
confirmedꢀthatꢀtheꢀaverageꢀdiameterꢀofꢀtheꢀAuꢀparticlesꢀwasꢀ2.2ꢀ
nmꢀinꢀtheꢀfreshꢀandꢀusedꢀAu/TiO ‐Rꢀcatalysts,ꢀverifyingꢀthereꢀ
wasꢀnoꢀAuꢀNPsꢀaggregationꢀduringꢀtheꢀreactionꢀ(Fig.ꢀ3(c)ꢀandꢀ
d)).ꢀ Theseꢀ resultsꢀ accountedꢀ forꢀ theꢀ remarkableꢀ stabilityꢀ ofꢀ
Au/TiO ‐Rꢀinꢀtheꢀrecyclingꢀtests.ꢀ
H
2
ꢀsupply.ꢀByꢀinvestigatingꢀtheꢀphysicochemicalꢀ propertiesꢀofꢀ
2
theꢀAu/TiO ‐Rꢀcatalyst,ꢀtheꢀfollowingꢀinformationꢀwasꢀcollected.ꢀ
2
FromꢀtheꢀXPSꢀresults,ꢀitꢀwasꢀseenꢀthatꢀthereꢀwasꢀonlyꢀmetallicꢀ
AuꢀonꢀtheꢀAu/rutileꢀsampleꢀ(Fig.ꢀ3(a)).ꢀICP‐AESꢀdataꢀrevealedꢀ
thatꢀthereꢀwasꢀnoꢀAuꢀspeciesꢀinꢀtheꢀsolutionꢀafterꢀtheꢀreaction,ꢀ
whichꢀindicatedꢀtheꢀabsenceꢀofꢀAuꢀleachingꢀduringꢀtheꢀreaction.ꢀ
(
2
Asꢀaꢀfurtherꢀillustrationꢀofꢀtheꢀeffectivenessꢀofꢀtheꢀaboveꢀre‐
duction,ꢀ fullꢀ conversionꢀ ofꢀ FALꢀ wasꢀ readilyꢀ obtainedꢀ atꢀ aꢀ
XRDꢀanalysisꢀdisplayedꢀthatꢀbothꢀtheꢀfreshꢀandꢀusedꢀAu/TiO ‐Rꢀ
2
n
FAL/nAu
ꢀ
ratioꢀ ofꢀ 2000ꢀ (Tableꢀ 1,ꢀ entryꢀ 14).ꢀ Thisꢀ
O‐mediatedꢀ reductionꢀ stillꢀ occurredꢀ withꢀ onlyꢀ 0.02ꢀ
catalystsꢀshowedꢀtheꢀsameꢀcrystalꢀphase,ꢀwithꢀnoꢀobviousꢀAuꢀ
featureꢀbeingꢀidentifiedꢀinꢀtheseꢀtwoꢀsamples,ꢀwhichꢀsuggestedꢀ
thatꢀtheꢀparticleꢀsizesꢀofꢀAuꢀwereꢀquiteꢀsmallꢀ(Fig.ꢀ3(b)).ꢀTEMꢀ
Au‐CO/H
2
2
mol%ꢀofꢀtheꢀAu/TiO ‐R,ꢀalbeitꢀanꢀextendedꢀreactionꢀtimeꢀofꢀ61ꢀ
(
a)
(
b)
Reused
Fresh
8
3.4 ev
80
82
84
86
88
90
10
20
30
40
2/( )
50
60
70
80
o
Binding energy (eV)
(
c)
(
d)
60
50
40
30
20
10
0
50
<
Dp>~2.2 nm
<Dp>~2.2 nm
40
30
20
10
0
0
1
2
3
4
0
1
2
3
4
particle size ( nm)
particle size (nm)
Fig.ꢀ3. (a)ꢀXPSꢀspectrumꢀofꢀAu/TiO
2
‐R;ꢀ(b)ꢀXRDꢀpatternsꢀofꢀfreshꢀandꢀusedꢀAu/TiO
2
‐R;ꢀTEMꢀimagesꢀofꢀfreshꢀ(c)ꢀandꢀusedꢀ(d)ꢀAu/TiO ‐R.ꢀ
2

ꢀ
JingꢀDongꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1669–1675ꢀ
1673ꢀ
4.ꢀ ꢀ Conclusionsꢀ
Au/TiO -R
OH
O
2
OH
OH
(
0.6 mol% Au)
O
O
TiO ꢀ supportedꢀ Auꢀ catalysts,ꢀ inꢀ particularꢀ theꢀ Au/TiO ‐Rꢀ
2
2
o
9
0 C, 3 h
system,ꢀ wereꢀ veryꢀ promisingꢀ forꢀ theꢀ selectiveꢀ reductionꢀ ofꢀ
bio‐derivedꢀfurfuralꢀusingꢀCOꢀasꢀaꢀconvenientꢀandꢀcostꢀcompet‐
itiveꢀhydrogenꢀsource.ꢀThisꢀAu‐basedꢀcatalyticꢀprotocolꢀconsti‐
tutesꢀtheꢀfirstꢀfurfuralꢀreductionꢀsystemꢀthatꢀdirectlyꢀusedꢀsyn‐
gasꢀasꢀaꢀhydrogenꢀsourceꢀandꢀwouldꢀfurnishꢀaꢀnewꢀapplicationꢀ
ofꢀ syngas.ꢀ Asꢀ controlledꢀ hydrogenationꢀ andꢀ reductiveꢀ trans‐
formationꢀ isꢀ aꢀ veryꢀ generalꢀ issueꢀ inꢀ theꢀ conversionꢀ ofꢀ
bio‐derivedꢀfeedstocks,ꢀtheꢀprocedureꢀhereꢀisꢀexpectedꢀtoꢀbeꢀofꢀ
broadꢀapplicabilityꢀinꢀtheꢀutilizationꢀofꢀbiomass.ꢀ
2.6 mmol
Yield 100%
Schemeꢀ3.ꢀReductionꢀofꢀHMFꢀbyꢀCO/H O.ꢀ
2
hꢀ wasꢀ requiredꢀ (Tableꢀ 1,ꢀ entryꢀ 15).ꢀ Underꢀ theseꢀ conditions,ꢀ
remarkableꢀvaluesꢀofꢀtheꢀturnoverꢀnumberꢀ(TONꢀ=ꢀ5000)ꢀandꢀ
averageꢀ turnoverꢀ frequencyꢀ (TOFꢀ =ꢀ 91ꢀ h )ꢀ wereꢀ calculatedꢀ
Tableꢀ1,ꢀentryꢀ15).ꢀPerhapsꢀtheꢀmostꢀnotableꢀfindingꢀwasꢀtheꢀ
abilityꢀofꢀtheꢀAu‐CO/H O‐basedꢀprotocolꢀtoꢀconvertꢀagedꢀdistil‐
–1
(
2
latesꢀ ofꢀ FALꢀ toꢀ valueꢀ addedꢀ material.ꢀ Alongꢀ theseꢀ lines,ꢀ weꢀ
demonstratedꢀ thatꢀ theꢀ presentꢀ Au‐basedꢀ technologyꢀ couldꢀ beꢀ
usedꢀtoꢀconvertꢀFALꢀthatꢀwasꢀsetꢀasideꢀforꢀmoreꢀthanꢀaꢀmonthꢀ
intoꢀFOLꢀwithꢀhighꢀefficiencyꢀ(Tableꢀ1,ꢀentryꢀ21).ꢀTheseꢀresultsꢀ
wereꢀextremelyꢀencouragingꢀbecauseꢀtheyꢀshowedꢀthatꢀcrudeꢀ
FOLꢀcouldꢀbeꢀusedꢀdirectlyꢀasꢀaꢀfeedstockꢀforꢀindustriallyꢀrele‐
Referencesꢀ
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2
O‐
ꢀ
[
4] J.ꢀ C.ꢀ Serrano‐Ruiz,ꢀ R.ꢀ Luque,ꢀ A.ꢀ Sepulveda‐Escribano,ꢀ Chem.ꢀ Soc.ꢀ
mediatedꢀ reductionꢀ processꢀ wasꢀ notꢀ limitedꢀ toꢀ FAL.ꢀ Whenꢀ
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Rev.,ꢀ2011,ꢀ40,ꢀ5266–5281.ꢀ
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subjectedꢀ toꢀ theꢀ reductionꢀ inꢀ theꢀ presenceꢀ ofꢀ theꢀ Au/TiO
sample,ꢀtheꢀreactionꢀalsoꢀproceededꢀefficiently.ꢀInꢀthisꢀcase,ꢀ2,ꢀ
‐bis‐(hydroxymethyl)ꢀ furanꢀ (BHMF),ꢀ anꢀimportantꢀmonomerꢀ
2
‐Rꢀ
[
5
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forꢀ industrialꢀ processes,ꢀ wasꢀ exclusivelyꢀ obtainedꢀ underꢀ theꢀ
standardꢀreactionꢀconditionsꢀ(Schemeꢀ3).ꢀ ꢀ
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GivenꢀtheꢀfactꢀthatꢀproducingꢀCOꢀandꢀH ꢀ(syngas)ꢀfromꢀbio‐
2
1002–1016.ꢀ
massꢀisꢀaꢀcrucialꢀstepꢀinꢀtheꢀproductionꢀofꢀmostꢀsecondꢀgenera‐
tionꢀ biofuels,ꢀ weꢀ exploredꢀ theꢀ possibilityꢀ toꢀ produceꢀ FOLꢀ byꢀ
aqueousꢀFALꢀreductionꢀusingꢀsimulatedꢀsyngasꢀwithꢀaꢀvaryingꢀ
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[
[
[
[
[
H /COꢀ feedꢀ ratio.ꢀ Threeꢀ differentꢀ volumetricꢀ compositionsꢀ ofꢀ
2
syngasꢀwereꢀexamined.ꢀAsꢀshownꢀinꢀTableꢀ2,ꢀinꢀallꢀcases,ꢀFALꢀ
wasꢀ quantitativelyꢀ convertedꢀ intoꢀ FOLꢀ butꢀ differentꢀ reactionꢀ
2
009,ꢀ10,ꢀ1665–1669.ꢀ
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013,ꢀ454,ꢀ127–136.ꢀ
timesꢀwereꢀrequired.ꢀTheꢀreactionꢀinvolvingꢀtheꢀH ‐richꢀsyngasꢀ
2
proceededꢀ muchꢀ moreꢀ rapidlyꢀ thanꢀ theꢀ reactionꢀ withꢀ theꢀ
CO‐richꢀsyngas.ꢀThisꢀwasꢀinꢀagreementꢀwithꢀthatꢀtheꢀreactionꢀ
2
14] M.ꢀ M.ꢀVillaverde,ꢀ N.ꢀ M.ꢀ Bertero,ꢀT.ꢀ F.ꢀGaretto,ꢀ A.ꢀJ.ꢀ Marchi,ꢀCatal.ꢀ
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58,ꢀ6–10.ꢀ
proceededꢀatꢀaꢀmuchꢀfasterꢀrateꢀwithꢀH
Moreꢀimportant,ꢀthisꢀrevealedꢀthatꢀcheap,ꢀrenewableꢀandꢀeasilyꢀ
accessibleꢀ CO ‐richꢀ bio‐syngasꢀ couldꢀ beꢀ successfullyꢀ usedꢀ forꢀ
2
ꢀasꢀtheꢀsoleꢀreductant.ꢀ
2
FALꢀ reduction.ꢀ Theseꢀ resultsꢀ areꢀ particularlyꢀ relevantꢀ sinceꢀ
flexibleꢀandꢀversatileꢀsyngasꢀcanꢀbeꢀusedꢀasꢀaꢀdirectꢀhydrogenꢀ
sourceꢀforꢀselectiveꢀbiomassꢀconversion.ꢀThisꢀwouldꢀopenꢀtheꢀ
possibilityꢀ toꢀ developꢀ costꢀ effectiveꢀ technologiesꢀ forꢀ theꢀ pro‐
ductionꢀofꢀbio‐renewableꢀchemicalsꢀbasedꢀonꢀCO‐drivenꢀreduc‐
tion.ꢀ
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352–356.ꢀ
[
[
[
[
[
19] H.ꢀQ.ꢀLi,ꢀX.ꢀLiu,ꢀQ.ꢀZhang,ꢀS.ꢀS.ꢀLi,ꢀY.ꢀM.ꢀLiu,ꢀH.ꢀY.ꢀHe,ꢀY.ꢀCao,ꢀChem.ꢀ
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Chem.ꢀInt.ꢀEd.,ꢀ2009,ꢀ48,ꢀ9538ꢀ–9541.ꢀ
Tableꢀ2ꢀ
2
FALꢀreductionꢀusingꢀsyngasꢀwithꢀvaryingꢀH /COꢀfeedꢀratioꢀasꢀhydrogenꢀ
source.ꢀ
21] L.ꢀHe,ꢀF.ꢀJ.ꢀYu,ꢀX.ꢀB.ꢀLou,ꢀY.ꢀCao,ꢀH.ꢀY.ꢀHe,ꢀK.ꢀN.ꢀFan,ꢀChem.ꢀCommun.,ꢀ
2
010,ꢀ46,ꢀ1553–1555.ꢀ
22] J.ꢀHuang,ꢀL.ꢀYu,ꢀL.ꢀHe,ꢀY.ꢀM.ꢀLiu,ꢀY.ꢀCao,ꢀK.ꢀN.ꢀFan,ꢀGreenꢀChem.,ꢀ2011,ꢀ
3,ꢀ2672–2677.ꢀ
23] S.ꢀS.ꢀLi,ꢀX.ꢀLiu,ꢀY.ꢀM.ꢀLiu,ꢀH.ꢀY.ꢀHe,ꢀK.ꢀN.ꢀFan,ꢀY.ꢀCao,ꢀChem.ꢀCommun.,ꢀ
014,ꢀ50,ꢀ5626–5628.ꢀ
H
2
/COꢀ
Timeꢀ(h)ꢀ
2.5ꢀ
1.8ꢀ
Conversionꢀ(%)ꢀ
Selectivityꢀ(%)ꢀ
1
2
:1ꢀ
:1ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
100ꢀ
1
bio‐syngasꢀ*ꢀ
pureꢀH
ꢀ 2ꢀ
ꢀ 1ꢀ
2
2
ꢀ
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ChemSusChem,ꢀ2013,ꢀ6,ꢀ42–46.ꢀ
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Chem.ꢀInt.ꢀEd.,ꢀ2014,ꢀ53,ꢀ7624–7629.ꢀ
Reactionꢀcondition:ꢀFALꢀ2.6ꢀmmol,ꢀwaterꢀ20ꢀmL,ꢀAu/TiO
00,ꢀ90ꢀ°C,ꢀp(CO)ꢀ=ꢀ4ꢀMPa.ꢀ
ꢀH :CO:CO2ꢀ=ꢀ10:5:1.ꢀ
2
‐R,ꢀnFAL/nAuꢀ=ꢀ
2
*
2

1674ꢀ
JingꢀDongꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ37ꢀ(2016)ꢀ1669–1675ꢀ
GraphicalꢀAbstractꢀ
Chin.ꢀJ.ꢀCatal.,ꢀ2016,ꢀ37:ꢀ1669–1675ꢀ ꢀ ꢀ doi:ꢀ10.1016/S1872‐2067(16)62458‐0
HighlyꢀselectiveꢀsupportedꢀgoldꢀcatalystꢀforꢀCO‐drivenꢀreductionꢀofꢀfurfuralꢀinꢀaqueousꢀmediaꢀ
ꢀ
ꢀ
JingꢀDong,ꢀMingmingꢀZhu,ꢀGaoshuoꢀZhang,ꢀYongmeiꢀLiu,ꢀYongꢀCao*,ꢀSuꢀLiu,ꢀYangdongꢀWang*ꢀ
FudanꢀUniversity;ꢀSINOPECꢀShanghaiꢀResearchꢀInstituteꢀofꢀPetrochemicalꢀTechnologyꢀ
CO/H O
CO2
2
o
9
0 C, 4 MPa
Without external H2
Biomass
Au/TiO2
ꢀ
2
Byꢀusingꢀaꢀsingleꢀphaseꢀrutileꢀtitaniaꢀsupportꢀandꢀgoldꢀasꢀtheꢀcatalystꢀ(Au/TiO ‐R),ꢀCOꢀwasꢀusedꢀasꢀhydrogenꢀsourceꢀtoꢀgetꢀfurfurylꢀalcoholꢀ
asꢀtheꢀonlyꢀproductꢀfromꢀfurfuralꢀinꢀaqueousꢀmedia.ꢀ
[
[
[
[
[
[
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Pageꢀnumbersꢀreferꢀtoꢀtheꢀcontentsꢀinꢀtheꢀprintꢀversion,ꢀwhichꢀincludeꢀ
1
bothꢀtheꢀEnglishꢀversionꢀandꢀextendedꢀChineseꢀabstractꢀofꢀtheꢀpaper.ꢀTheꢀ
onlineꢀversionꢀonlyꢀhasꢀtheꢀEnglishꢀversion.ꢀTheꢀpagesꢀwithꢀtheꢀextendedꢀ
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