Understanding the promotional effect of Au on Pt/WO3 in hydrogenolysis of glycerol to 1,3-propanediol

Article abstract of DOI:10.1016/S1872-2067(18)63103-1

Pt/Au/WO₃ bimetallic catalysts were prepared by impregnation of Pt onto preformed Au/WO₃, obtained by a hexadecyl trmethyl ammonium bromide (CTAB)-assisted one-pot synthesis method. The resulting Pt/Au/WO₃ catalysts exhibited remarkable synergistic effects for selective hydrogenolysis of glycerol to 1,3-propanediol. The characterization results showed that doping of Au promoted the reduction of both Pt and W at low temperatures and uniform dispersion of Pt on the WO₃ support. Furthermore, more low-valence Pt species were produced on the WO₃ surface after introduction of Au. These changes in electronic properties resulted in enhancement of both glycerol conversion and selectivity for 1,3-propanediol.

Full text of DOI:10.1016/S1872-2067(18)63103-1

ChineseꢀJournalꢀofꢀCatalysisꢀ39ꢀ(2018)ꢀ1366–1372
ꢀ
ꢀ ꢀ ꢀ
ꢀ ꢀ ꢀ ꢀ
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
UnderstandingꢀtheꢀpromotionalꢀeffectꢀofꢀAuꢀonꢀPt/WO
hydrogenolysisꢀofꢀglycerolꢀtoꢀ1,3‐propanediolꢀ
3
ꢀinꢀ ꢀ
a,b,†
a,b,†
a,b
ꢀa,b
a
a
a
ChaojunꢀYangꢀ ,ꢀFanꢀZhangꢀ ,ꢀNianꢀLeiꢀ ,ꢀManꢀYang ,ꢀFeiꢀLiuꢀ ,ꢀZhiliꢀMiaoꢀ ,ꢀYongnanꢀSunꢀ ,ꢀ
a
a,
XiaochenꢀZhaoꢀ ,ꢀAiqinꢀWangꢀ *
ꢀ
aꢀStateꢀKeyꢀLaboratoryꢀofꢀCatalysis,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences,ꢀDalianꢀ116023,ꢀLiaoning,ꢀChinaꢀ
bꢀUniversityꢀofꢀChineseꢀAcademyꢀofꢀSciences,ꢀBeijingꢀ100049,ꢀChinaꢀ
A R T I C L E ꢀ I N F O ꢀ
A B S T R A C T ꢀ
Articleꢀhistory:ꢀ
Pt/Au/WO
obtainedꢀbyꢀaꢀhexadecylꢀtrmethylꢀammoniumꢀbromideꢀ(CTAB)‐assistedꢀone‐potꢀsynthesisꢀmethod.ꢀ
TheꢀresultingꢀPt/Au/WO ꢀcatalystsꢀexhibitedꢀremarkableꢀsynergisticꢀeffectsꢀforꢀselectiveꢀhydrogen‐
olysisꢀofꢀglycerolꢀtoꢀ1,3‐propanediol.ꢀTheꢀcharacterizationꢀresultsꢀshowedꢀthatꢀdopingꢀofꢀAuꢀpro‐
motedꢀtheꢀreductionꢀofꢀbothꢀPtꢀandꢀWꢀatꢀlowꢀtemperaturesꢀandꢀuniformꢀdispersionꢀofꢀPtꢀonꢀtheꢀWO
support.ꢀFurthermore,ꢀmoreꢀlow‐valenceꢀPtꢀspeciesꢀwereꢀproducedꢀonꢀtheꢀWO ꢀsurfaceꢀafterꢀintro‐
3
ꢀ bimetallicꢀ catalystsꢀ wereꢀ preparedꢀ byꢀ impregnationꢀ ofꢀ Ptꢀ ontoꢀ preformedꢀ Au/WO ,ꢀ
3
Receivedꢀ6ꢀAprilꢀ2018ꢀ
Acceptedꢀ7ꢀMayꢀ2018ꢀ
Publishedꢀ5ꢀAugustꢀ2018ꢀ
3
3
3
Keywords:ꢀ
Bimetallicꢀ
Pt/Au/WO3ꢀ
Glycerolꢀ
ductionꢀ ofꢀ Au.ꢀ Theseꢀ changesꢀ inꢀ electronicꢀ propertiesꢀ resultedꢀ inꢀ enhancementꢀ ofꢀ bothꢀ glycerolꢀ
conversionꢀandꢀselectivityꢀforꢀ1,3‐propanediol.ꢀ
©ꢀ2018,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences.
PublishedꢀbyꢀElsevierꢀB.V.ꢀAllꢀrightsꢀreserved.
1,3‐Propanediolꢀ
Hydrogenolysis
1
.ꢀ ꢀ Introductionꢀ
similarꢀhydrodeoxygenationꢀ(HDO)ꢀstrategyꢀshouldꢀhaveꢀwideꢀ
applicationsꢀinꢀtheꢀupgradingꢀofꢀbiomassꢀ[16,17].ꢀHowever,ꢀtheꢀ
selectiveꢀ formationꢀ ofꢀ 1,3‐PDOꢀ fromꢀ glycerolꢀ remainsꢀ aꢀ chal‐
lengeꢀ becauseꢀ ofꢀ theꢀ unfavorableꢀ thermodynamicsꢀ andꢀ stericꢀ
hindrance.ꢀ Amongꢀ variousꢀ catalystꢀ compositions,ꢀ onlyꢀ Pt‐Wꢀ
[1–7]ꢀandꢀIr‐Reꢀ[8–11]ꢀbifunctionalꢀsystemsꢀareꢀableꢀtoꢀprovideꢀ
moderate‐to‐goodꢀselectivityꢀ(30–70%),ꢀdependingꢀonꢀtheꢀre‐
actionꢀ conditionsꢀ andꢀ theꢀ natureꢀ ofꢀ theꢀ catalystꢀ support.ꢀ Theꢀ
cooperativeꢀ mechanismꢀ involvingꢀ theꢀ metallicꢀ componentꢀ (Ptꢀ
Selectiveꢀ hydrogenolysisꢀ ofꢀ glycerolꢀ toꢀ 1,3‐propanediolꢀ
(1,3‐PDO)ꢀisꢀanꢀimportantꢀreactionꢀinꢀtermsꢀofꢀbothꢀfundamen‐
talꢀandꢀappliedꢀcatalysisꢀ[1–15].ꢀOnꢀoneꢀhand,ꢀthisꢀreactionꢀin‐
volvesꢀ selectiveꢀ cleavageꢀ ofꢀ secondaryꢀ C–Oꢀ bondsꢀ inꢀ polyols,ꢀ
whichꢀ requiresꢀ sophisticatedꢀ designꢀ ofꢀ anꢀ acid‐metalꢀ bifunc‐
tionalꢀcatalystꢀinꢀorderꢀtoꢀengineerꢀtheꢀactivationꢀenergyꢀsuchꢀ
thatꢀ theꢀ reactionꢀ proceedsꢀ towardsꢀ 1,3‐PDOꢀ ratherꢀ thanꢀ theꢀ
parallelꢀreactionꢀtoꢀ1,2‐PDOꢀorꢀtheꢀsequentialꢀoneꢀtoꢀ1‐propanolꢀ
orꢀIr)ꢀandꢀtheꢀoxophilicꢀmetalꢀoxideꢀ(low‐valenceꢀWO
x
ꢀorꢀReO )ꢀ
x
(
1‐PO).ꢀOnꢀtheꢀotherꢀhand,ꢀtheꢀreactionꢀallowsꢀtheꢀconversionꢀofꢀ
isꢀ yetꢀ toꢀ beꢀ clarified,ꢀ althoughꢀ thereꢀ haveꢀ beenꢀ experimentalꢀ
reportsꢀimplyingꢀthatꢀglycerolꢀisꢀadsorbedꢀandꢀactivatedꢀonꢀtheꢀ
surfaceꢀofꢀtheꢀoxophilicꢀmetalꢀoxides,ꢀwhileꢀhydrogenꢀisꢀheter‐
olyticallyꢀ dissociatedꢀ atꢀ theꢀ interfaceꢀ ofꢀ theꢀ metalꢀ andꢀ oxideꢀ
cheapꢀandꢀsurplusꢀglycerolꢀtoꢀhighlyꢀvaluedꢀ1,3‐PDO,ꢀwhichꢀisꢀ
widelyꢀusedꢀasꢀtheꢀmonomerꢀforꢀtheꢀproductionꢀofꢀhigh‐qualityꢀ
polyesterꢀpolytrimethyleneꢀterephthalateꢀ(PTT).ꢀMoreover,ꢀtheꢀ
*
ꢀCorrespondingꢀauthor.ꢀTel:ꢀ+86‐411‐84379348;ꢀFax:ꢀ+86‐411‐84685940;ꢀE‐mail:ꢀaqwang@dicp.ac.cnꢀ
Theseꢀauthorsꢀcontributedꢀequallyꢀtoꢀthisꢀwork.ꢀ
†
ꢀ
ThisꢀworkꢀwasꢀsupportedꢀbyꢀtheꢀNationalꢀNaturalꢀScienceꢀFoundationꢀofꢀChinaꢀ(21690080,ꢀ21690084,ꢀ21721004,ꢀ21673228),ꢀtheꢀStrategicꢀPriorityꢀ
ResearchꢀProgramꢀofꢀtheꢀChineseꢀAcademyꢀofꢀSciencesꢀ(XDB17020100),ꢀandꢀtheꢀNationalꢀKeyꢀProjectsꢀforꢀFundamentalꢀResearchꢀandꢀDevelopmentꢀofꢀ
Chinaꢀ(2016YFA0202801).ꢀ
DOI:ꢀ10.1016/S1872‐2067(18)63103‐1ꢀ|ꢀhttp://www.sciencedirect.com/science/journal/18722067ꢀ|ꢀChin.ꢀJ.ꢀCatal.,ꢀVol.ꢀ39,ꢀNo.ꢀ8,ꢀAugustꢀ2018ꢀ ꢀ ꢀ

ꢀ
ChaojunꢀYangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ39ꢀ(2018)ꢀ1366–1372ꢀ
1367ꢀ
[
18,19].ꢀ
Inꢀourꢀearlierꢀstudiesꢀ[20–24],ꢀweꢀsynthesizedꢀmesoporousꢀ
WO ꢀ(2.5ꢀ<ꢀxꢀ<ꢀ3.0),ꢀwhichꢀhasꢀabundantꢀoxygenꢀvacancies,ꢀandꢀ
foundꢀ thatꢀ theꢀ WO ‐supportedꢀ Ptꢀ catalystꢀ wasꢀ superiorꢀ toꢀ
WO ‐supportedꢀ oneꢀ forꢀ theꢀ hydrogenolysisꢀ ofꢀ glycerolꢀ toꢀ
,3‐PDOꢀbecauseꢀofꢀtheꢀimprovedꢀdispersionꢀofꢀPtꢀonꢀtheꢀWO
support.ꢀInꢀtheꢀPt/WO ꢀsystem,ꢀPtꢀwasꢀprobablyꢀdispersedꢀasꢀ
stainlessꢀsteelꢀautoclave.ꢀ12ꢀgꢀofꢀglycerolꢀaqueousꢀsolutionꢀ(5ꢀ
wt%)ꢀandꢀ0.3ꢀgꢀofꢀcatalystꢀwereꢀloadedꢀintoꢀtheꢀreactor.ꢀTheꢀ
x
autoclaveꢀwasꢀpurgedꢀthreeꢀtimesꢀwithꢀH ,ꢀthenꢀpressurizedꢀtoꢀ
2
x
5ꢀMPa,ꢀandꢀheatedꢀtoꢀaꢀcertainꢀreactionꢀtemperature.ꢀAfterꢀtheꢀ
reaction,ꢀ theꢀ autoclaveꢀ wasꢀ cooledꢀ toꢀ roomꢀ temperatureꢀ andꢀ
theꢀliquidꢀwasꢀcollectedꢀforꢀanalysisꢀusingꢀaꢀgasꢀchromatographꢀ
(Agilentꢀ 7890ꢀ B)ꢀ equippedꢀ withꢀ aꢀ flameꢀ ionizationꢀ detectorꢀ
(FID)ꢀandꢀaꢀFFAPꢀcapillaryꢀcolumn.ꢀn‐Butanolꢀwasꢀusedꢀasꢀanꢀ
internalꢀstandardꢀforꢀanalysisꢀ ꢀ
3
1
x
ꢀ
x
singleꢀatomsꢀorꢀfineꢀclustersꢀofꢀonlyꢀaꢀfewꢀatomsꢀbecauseꢀofꢀtheꢀ
stabilizationꢀ effectꢀ ofꢀ oxygenꢀ vacancyꢀ onꢀ Ptꢀ atoms.ꢀ Moreover,ꢀ
byꢀ introducingꢀ aꢀ smallꢀ amountꢀ ofꢀ Auꢀ (0.1%–0.2%)ꢀ toꢀ theꢀ
x
pre‐formedꢀ Pt/WO ,ꢀ bothꢀ glycerolꢀ conversionꢀ andꢀ 1,3‐PDOꢀ
2.3.ꢀ ꢀ Characterizationꢀ ꢀ
selectivityꢀwereꢀgreatlyꢀenhancedꢀ[24].ꢀTheꢀpromotionalꢀeffectꢀ
ofꢀ goldꢀ wasꢀ attributedꢀ toꢀ theꢀ productionꢀ ofꢀ moreꢀ in‐situꢀ
Brønstedꢀacidꢀsitesꢀandꢀhydridesꢀdueꢀtoꢀgoldꢀdeposition.ꢀInꢀthisꢀ
case,ꢀ goldꢀ isꢀ supposedꢀ toꢀ depositꢀ onꢀ theꢀ Ptꢀ atomsꢀ becauseꢀ itꢀ
Theꢀ crystallineꢀ phaseꢀ ofꢀ theꢀ catalystꢀ wasꢀ identifiedꢀ withꢀ
X‐rayꢀdiffractionꢀ(XRD)ꢀonꢀaꢀPANalyticalꢀX’pertꢀProꢀSuperꢀX‐rayꢀ
diffractometerꢀ usingꢀ Cuꢀ K ꢀ radiationꢀ (λꢀ =ꢀ 0.15418ꢀ nm).ꢀ Theꢀ
α
couldꢀnotꢀbeꢀdepositedꢀonꢀtheꢀsurfaceꢀofꢀacidicꢀWO
x
ꢀwithoutꢀPt.ꢀ
tubeꢀvoltageꢀandꢀcurrentꢀwereꢀ40ꢀkVꢀandꢀ40ꢀmA,ꢀrespectively,ꢀ
andꢀtheꢀscanningꢀangleꢀrangedꢀbetweenꢀ10°ꢀandꢀ80°.ꢀ ꢀ
However,ꢀ ifꢀ itꢀ wasꢀ true,ꢀ theꢀ exposedꢀ Ptꢀ surfaceꢀ wouldꢀ beꢀ re‐
duced,ꢀwhichꢀwouldꢀhinderꢀtheꢀdissociationꢀofꢀhydrogen,ꢀwhichꢀ
conflictedꢀwithꢀtheꢀexperimentalꢀresults.ꢀTherefore,ꢀthereꢀmightꢀ
beꢀanotherꢀpathwayꢀexplainingꢀtheꢀpromotionalꢀeffectꢀofꢀgold.ꢀ ꢀ ꢀ
Toꢀprovideꢀanꢀinsightfulꢀunderstandingꢀofꢀtheꢀpromotionalꢀ
effectꢀ ofꢀ gold,ꢀ weꢀ reportꢀ hereꢀ anꢀ inverseꢀ catalystꢀ system,ꢀ
Hydrogenꢀ temperature‐programmedꢀ reductionꢀ (H ‐TPR)ꢀ
2
wasꢀperformedꢀonꢀaꢀMicromeriticsꢀAutochemꢀIIꢀ2920.ꢀ100ꢀmgꢀ
ofꢀtheꢀcalcinedꢀsampleꢀwasꢀplacedꢀinꢀtheꢀU‐shapedꢀquartzꢀreac‐
torꢀandꢀheatedꢀtoꢀ120ꢀCꢀinꢀArꢀforꢀ30ꢀminꢀtoꢀremoveꢀtheꢀphysi‐
callyꢀadsorbedꢀwaterꢀandꢀotherꢀcontaminates.ꢀAfterꢀcoolingꢀtoꢀ
Pt/Au/WO
Au/WO .ꢀ Theꢀ Pt/Au/WO
creaseꢀinꢀspaceꢀtimeꢀyieldꢀ(STY)ꢀofꢀ1,3‐PDOꢀcomparedꢀwithꢀtheꢀ
Au‐Pt/WO ꢀ catalystꢀ weꢀ reportedꢀ earlierꢀ [24],ꢀ andꢀ 4‐foldꢀ in‐
creaseꢀ inꢀ STYꢀ comparedꢀ withꢀ theꢀ Pt/WO ꢀ catalystꢀ [20].ꢀ Theꢀ
3
,ꢀ inꢀ whichꢀ Ptꢀ wasꢀ depositedꢀ onꢀ theꢀ pre‐formedꢀ
–50ꢀ C,ꢀ theꢀ gasꢀ wasꢀ switchedꢀ toꢀ 10%ꢀ H
wasꢀheatedꢀtoꢀ800Cꢀatꢀaꢀrampꢀrateꢀofꢀ10ꢀC/minꢀforꢀreduction.ꢀ
2
/Ar,ꢀ andꢀ theꢀ sampleꢀ
ꢀ
3
3
ꢀ systemꢀ providesꢀ almostꢀ 2‐foldꢀ in‐
Theꢀ H ꢀ consumptionꢀ duringꢀ theꢀ sampleꢀ reductionꢀ wasꢀ moni‐
2
x
toredꢀwithꢀTCD.ꢀ
3
Transmissionꢀelectronꢀmicroscopyꢀ(TEM)ꢀimagesꢀwereꢀob‐
tainedꢀ onꢀ aꢀ JEM‐2100Fꢀ microscopeꢀ operatingꢀ atꢀ accelerationꢀ
voltageꢀofꢀ200ꢀkV.ꢀ ꢀ
superiorꢀ performanceꢀ isꢀ attributedꢀ toꢀ theꢀ higherꢀ dispersion,ꢀ
higherꢀsurfaceꢀenrichmentꢀandꢀincreasedꢀelectronꢀdensityꢀofꢀPtꢀ
dueꢀtoꢀtheꢀdopingꢀofꢀAuꢀintoꢀtheꢀWO
.ꢀ ꢀ Experimentalꢀ ꢀ ꢀ
.1.ꢀ ꢀ Catalystꢀpreparationꢀ
Theꢀ Au/WO ꢀ catalystꢀ wasꢀ preparedꢀ byꢀ aꢀ surface‐modifiedꢀ
3
.ꢀ
X‐rayꢀphotoelectronꢀspectroscopyꢀ(XPS)ꢀwasꢀperformedꢀonꢀ
anꢀESCALABꢀ250ꢀinstrumentꢀequippedꢀwithꢀanꢀAlꢀK ꢀX‐rayꢀra‐
α
2
diationꢀ sourceꢀ (1486.6ꢀ eV).ꢀ Bindingꢀ energiesꢀ wereꢀ calibratedꢀ
usingꢀtheꢀCꢀ1sꢀpeakꢀatꢀ284.6ꢀeV.ꢀ
Surfaceꢀ areasꢀ ofꢀ theꢀ catalystsꢀ wereꢀ measuredꢀ onꢀ aꢀ Mi‐
cromeriticsꢀASAPꢀ2460ꢀinstrument.ꢀBeforeꢀtheꢀmeasurements,ꢀ
theꢀsamplesꢀwereꢀdegassedꢀatꢀ110ꢀCꢀforꢀ1ꢀh,ꢀfollowedꢀbyꢀ300ꢀ
2
3
depositionꢀmethod.ꢀInꢀdetail,ꢀ2.7ꢀgꢀofꢀammoniumꢀparatungstateꢀ
wasꢀfirstꢀdissolvedꢀinꢀ90ꢀmLꢀofꢀwaterꢀatꢀ90ꢀ°Cꢀandꢀstirredꢀmag‐
netically.ꢀ Afterꢀ coolingꢀ downꢀ toꢀ roomꢀ temperature,ꢀ aꢀ certainꢀ
amountꢀofꢀaqueousꢀsolutionꢀofꢀHClꢀwasꢀaddedꢀdropwiseꢀtoꢀad‐
justꢀtheꢀsolutionꢀpHꢀtoꢀ0.9.ꢀAfterꢀcontinuousꢀstirringꢀforꢀ0.5ꢀh,ꢀ
Cꢀforꢀ4ꢀh.ꢀTheꢀN ꢀadsorptionꢀwasꢀperformedꢀatꢀ−196ꢀC.ꢀTheꢀ
specificꢀ surfaceꢀ areaꢀ wasꢀ calculatedꢀ byꢀ theꢀ Brunau‐
er‐Emmett‐Tellerꢀ(BET)ꢀmethod.ꢀ
2
3.ꢀ ꢀ Resultsꢀandꢀdiscussionꢀ ꢀ ꢀ
1.2ꢀgꢀofꢀCTABꢀwasꢀaddedꢀandꢀstirredꢀforꢀanotherꢀ30ꢀmin.ꢀThen,ꢀ
anꢀaqueousꢀsolutionꢀofꢀHAuCl ꢀwasꢀaddedꢀtoꢀtheꢀaboveꢀsolution.ꢀ
Theꢀsuspensionꢀwasꢀagedꢀforꢀ24ꢀhꢀbeforeꢀtheꢀsolidꢀwasꢀrecov‐
eredꢀbyꢀ filteringꢀandꢀwashing.ꢀTheꢀ solidꢀ wasꢀ furtherꢀ driedꢀ atꢀ
4
Usually,ꢀ Auꢀ isꢀ difficultꢀ toꢀ depositꢀ onꢀ theꢀ WO
conventionalꢀ deposition‐precipitationꢀ orꢀ co‐precipitationꢀ
methodꢀ becauseꢀ ofꢀ lowꢀ isoelectricꢀ pointꢀ ofꢀ WO ꢀ (<ꢀ 2)ꢀ [25].ꢀ
Hereinꢀ weꢀ developedꢀ aꢀ newꢀ CTAB‐assistedꢀ depositionꢀ ap‐
proachꢀ(Fig.ꢀ1),ꢀwhichꢀresultedꢀinꢀquantitativeꢀdepositionꢀofꢀAuꢀ
upꢀtoꢀanꢀamountꢀofꢀ0.5ꢀwt%.ꢀ
3
ꢀ surfaceꢀ viaꢀ
3
ꢀ
1
10Cꢀovernight,ꢀandꢀcalcinedꢀatꢀ500–650ꢀCꢀforꢀ3ꢀhꢀtoꢀobtainꢀ
Au/WO
whereꢀtheꢀAuꢀcontentꢀwasꢀfixedꢀatꢀ0.1ꢀwt%.ꢀSubsequently,ꢀtheꢀ
Au/WO ‐Tꢀ samplesꢀ wereꢀ impregnatedꢀ withꢀ anꢀ aqueousꢀ solu‐
tionꢀofꢀH PtCl ·6H O,ꢀfollowedꢀbyꢀcalcinationꢀatꢀ300ꢀCꢀforꢀ1ꢀhꢀ
andꢀ reductionꢀ inꢀ flowingꢀ H ꢀ atꢀ 300ꢀ Cꢀ forꢀ 1ꢀ hꢀ toꢀ obtainꢀ theꢀ
‐Tꢀ catalysts,ꢀ whereꢀ theꢀ Ptꢀ contentꢀ wasꢀ fixedꢀ atꢀ 2ꢀ
3
‐Tꢀ (Tꢀ refersꢀ toꢀ calcinationꢀ temperature,ꢀ C)ꢀ samplesꢀ
3
Tableꢀ1ꢀshowsꢀtheꢀperformanceꢀofꢀtheꢀPt/Au/WO ꢀinꢀcom‐
3
2
6
2
2
Pt/Au/WO
3
wt%.ꢀ ꢀ
2.2.ꢀ ꢀ Reactionꢀtestꢀ
Fig.ꢀ1.ꢀAꢀnewꢀCTAB‐assistedꢀdepositionꢀapproachꢀtoꢀprepareꢀAu/WO .
3
TheꢀreactionꢀtestsꢀwereꢀperformedꢀinꢀaꢀTeflon‐linedꢀ75‐mLꢀ

1368ꢀ
ChaojunꢀYangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ39ꢀ(2018)ꢀ1366–1372ꢀ
Tableꢀ1ꢀ
3
CatalyticꢀperformancesꢀofꢀPt/Au/WO ꢀcatalystsꢀinꢀcomparisonꢀwithꢀreferenceꢀsamples.ꢀ
Reactionꢀtemperatureꢀ
Selectivityꢀ(%)ꢀ
STYꢀ
(g1,3‐PDO/(gcath))
Catalystꢀ
Conv.ꢀ(%)
Ref.ꢀ
o
(
C)‐Timeꢀ(h)ꢀ
1,3‐PDOꢀ
39.3ꢀ
28.1ꢀ
56.9ꢀ
56.3ꢀ
32.4ꢀ
43.2ꢀ
37.8ꢀ
54.3ꢀ
54.4ꢀ
1‐POꢀ
33.8ꢀ
52.3ꢀ
29.7ꢀ
33.7ꢀ
46.3ꢀ
36.0ꢀ
51.2ꢀ
34.8ꢀ
43.8ꢀ
1,2‐PDOꢀ
2‐POꢀ
7.1ꢀ
4.1ꢀ
3.0ꢀ
3.8ꢀ
6.4ꢀ
5.4ꢀ
9.3ꢀ
5.0ꢀ
6.5ꢀ
Pt/m‐WO3ꢀaꢀ
180‐12ꢀ
160‐12ꢀ
160‐12ꢀ
140‐12ꢀ
155‐12ꢀ
155‐7ꢀ
155‐5.3ꢀ
155‐7.5ꢀ
155‐9ꢀ
18.0ꢀ
49.5ꢀ
33.7ꢀ
52.0ꢀ
37.5ꢀ
30.0ꢀ
33.1ꢀ
30.7ꢀ
17.8ꢀ
4.1ꢀ
6.5ꢀ
2.9ꢀ
5.4ꢀ
4.0ꢀ
2.2ꢀ
3.2ꢀ
3.3ꢀ
0ꢀ
0.019ꢀ
0.019ꢀ
0.026ꢀ
0.040ꢀ
0.033ꢀ
0.061ꢀ
0.078ꢀ
0.073ꢀ
0.036ꢀ
[20]ꢀ
[23]ꢀ
Thisꢀwork
[24]ꢀ
Thisꢀwork
Thisꢀwork
Thisꢀwork
Thisꢀwork
Thisꢀwork
b
Pt/WOxꢀ
ꢀ
ꢀ
bꢀ
Pt/WO
3
0
.1Au‐Pt/WOxꢀbꢀ
c
Pt/WO3ꢀ
ꢀ
c
Pt/Au/WO
Pt/Au/WO
Pt/Au/WO
Pt/Au/WO
aꢀ
3
3
3
3
‐500ꢀ ꢀ
c
‐550ꢀ ꢀ
c
‐600ꢀ ꢀ
c
‐650ꢀ ꢀ
Reactionꢀconditions:ꢀ1.0ꢀgꢀcatalyst,ꢀ40ꢀgꢀglycerolꢀaqueousꢀsolutionꢀ(10ꢀwt%),ꢀH
Reactionꢀconditions:ꢀ0.3ꢀgꢀcatalyst,ꢀ12ꢀgꢀglycerolꢀaqueousꢀsolutionꢀ(5ꢀwt%),ꢀH
Reactionꢀconditions:ꢀ0.3ꢀgꢀcatalyst,ꢀ12ꢀgꢀglycerolꢀaqueousꢀsolutionꢀ(10ꢀwt%),ꢀH
2
ꢀpressureꢀ5.5ꢀMPa.ꢀ ꢀ
ꢀpressureꢀ1.0ꢀMPa.ꢀ
ꢀpressureꢀ5.0ꢀMPa.ꢀ
bꢀ
2
cꢀ
2
ꢀ
parisonꢀwithꢀtheꢀreferenceꢀsamplesꢀforꢀtheꢀglycerolꢀhydrogen‐
olysis.ꢀTheꢀPt/WO ꢀcatalystꢀprovidedꢀaꢀglycerolꢀconversionꢀofꢀ
3.7%ꢀandꢀ1,3‐PDOꢀselectivityꢀofꢀ56.9%ꢀafterꢀreactionꢀatꢀ160ꢀCꢀ
forꢀ12ꢀ h,ꢀ whileꢀ theꢀPt/WO ꢀcatalystꢀgaveꢀ49.5%ꢀglycerolꢀcon‐
versionꢀ andꢀ 28.1%ꢀ 1,3‐PDOꢀ selectivityꢀ underꢀ identicalꢀ condi‐
tionsꢀ[23].ꢀClearly,ꢀtheꢀPt/WO ꢀcatalystꢀisꢀlessꢀactiveꢀbutꢀmoreꢀ
selectiveꢀthanꢀtheꢀPt/WO ꢀcatalystꢀweꢀreportedꢀearlierꢀforꢀtheꢀ
byꢀtheꢀshorterꢀreactionꢀtime)ꢀandꢀ1,3‐PDOꢀselectivity,ꢀandꢀtheꢀ
STYꢀwasꢀalmostꢀdoubled.ꢀMoreover,ꢀtheꢀperformanceꢀcouldꢀbeꢀ
furtherꢀtailoredꢀbyꢀchangingꢀtheꢀcalcinationꢀtemperatureꢀofꢀtheꢀ
3
3
x
Au/WO
andꢀtheꢀ1,3‐PDOꢀselectivityꢀincreasedꢀwithꢀincreasingꢀcalcina‐
tionꢀtemperatureꢀofꢀtheꢀAu/WO ꢀprecursorꢀ(asꢀindicatedꢀbyꢀaꢀ
3
.ꢀ Theꢀ activityꢀ ofꢀ theꢀ resultantꢀ Pt/Au/WO ꢀ decreasedꢀ
3
3
3
x
longerꢀreactionꢀtimeꢀtoꢀreachꢀcomparableꢀconversionꢀofꢀglycer‐
glycerolꢀ conversionꢀ toꢀ 1,3‐PDO,ꢀ whichꢀ agreesꢀ wellꢀ withꢀ theꢀ
ol).ꢀSuchꢀ aꢀtrendꢀcanꢀbeꢀexplainedꢀ byꢀtheꢀ decreaseꢀinꢀ surfaceꢀ
2
2
muchꢀlowerꢀsurfaceꢀareaꢀofꢀWO
3
ꢀthanꢀWO
x
ꢀ(17.7ꢀm /gꢀvs.ꢀ126ꢀ
areaꢀ(14.0,ꢀ10.6,ꢀ11.2ꢀm /gꢀforꢀAu/WO
3
‐500,ꢀAu/WO ‐550,ꢀandꢀ
3
2
m /g).ꢀInꢀtermsꢀofꢀSTYꢀofꢀ1,3‐PDO,ꢀhowever,ꢀtheꢀPt/WO
3
ꢀcata‐
ꢀ(0.026ꢀvs.ꢀ0.019ꢀg1,3‐PDO/(gcath)).ꢀTheꢀ
superiorꢀ performanceꢀ ofꢀ theꢀ Pt/WO ꢀ catalystꢀ mayꢀ ariseꢀ fromꢀ
theꢀsuitableꢀinteractionꢀbetweenꢀPtꢀandꢀWO .ꢀConsideringꢀthatꢀ
Au/WO
perature.ꢀ Consequently,ꢀ theꢀ dispersionꢀ ofꢀ Ptꢀ mayꢀ decrease,ꢀ
whichꢀinꢀturnꢀresultsꢀinꢀdecreaseꢀinꢀactivity.ꢀWhenꢀAu/WO ꢀwasꢀ
calcinedꢀatꢀ600ꢀC,ꢀtheꢀresultantꢀPt/Au/WO ꢀgaveꢀtheꢀhighestꢀ
1,3‐PDOꢀselectivityꢀ(54.3%),ꢀandꢀtheꢀSTYꢀwasꢀhigherꢀthanꢀthatꢀ
ofꢀ theꢀ Au‐Pt/WO ꢀ catalystꢀ reportedꢀ earlierꢀ [24].ꢀ Furtherꢀ in‐
3
‐600,ꢀ respectively)ꢀ withꢀ increasingꢀ calcinationꢀ tem‐
lystꢀisꢀsuperiorꢀtoꢀPt/WO
x
3
3
3
3
theꢀ hydrogenolysisꢀ ofꢀ glycerolꢀ isꢀ aꢀ consecutiveꢀ reaction,ꢀ weꢀ
controlledꢀtheꢀglycerolꢀconversionꢀatꢀ~30%ꢀbyꢀvaryingꢀtheꢀre‐
actionꢀtimeꢀandꢀthenꢀcomparedꢀtheꢀ1,3‐PDOꢀselectivityꢀbetweenꢀ
differentꢀ catalysts.ꢀ Asꢀ shownꢀ inꢀ Tableꢀ 1,ꢀ whenꢀ theꢀ reactionꢀ
temperatureꢀwasꢀfixedꢀatꢀ155ꢀCꢀandꢀtheꢀglycerolꢀfeedꢀconcen‐
x
creasingꢀ ofꢀ theꢀ calcinationꢀ temperatureꢀ toꢀ 650ꢀ Cꢀ ledꢀ toꢀ theꢀ
decreaseꢀ inꢀ activity,ꢀ thoughꢀ theꢀ 1,3‐PDOꢀ selectivityꢀ remainedꢀ
unchanged.ꢀ
trationꢀwasꢀraisedꢀtoꢀ10ꢀwt%,ꢀtheꢀPt/WO
glycerolꢀconversionꢀofꢀ37.5%ꢀandꢀ1,3‐PDOꢀselectivityꢀofꢀ32.4%ꢀ
afterꢀ reactionꢀ forꢀ 12ꢀ h.ꢀ Comparedꢀ withꢀ Pt/WO ,ꢀ theꢀ
Pt/Au/WO ‐500ꢀcatalystꢀgaveꢀriseꢀtoꢀbothꢀactivityꢀ(asꢀindicatedꢀ
3
ꢀcatalystꢀprovidedꢀaꢀ
Fig.ꢀ2ꢀillustratesꢀtheꢀglycerolꢀconversionꢀandꢀproductꢀselec‐
tivityꢀasꢀaꢀfunctionꢀofꢀtemperatureꢀandꢀH ꢀpressure.ꢀTheꢀglycer‐
2
3
olꢀconversionꢀincreasesꢀwithꢀincreasingꢀreactionꢀtemperature;ꢀ
concomitantly,ꢀtheꢀ1,3‐PDOꢀselectivityꢀ decreases,ꢀdemonstrat‐
3
1
00
100
Conv.
,3-PDO
1-PO
(b)
Conv.
1,3-PDO
1-PO
1,2-PDO
2-PO
(a)
1
80
60
40
20
0
8
6
4
2
0
0
0
0
0
1
2
,2-PDO
-PO
1
3
5
150
160
170
180
o
PH2 (MPa)
Temperature ( C)
Fig.ꢀ2.ꢀCatalyticꢀperformanceꢀofꢀPt/Au/WO
3
‐500ꢀatꢀdifferentꢀreactionꢀtemperaturesꢀandꢀH ꢀpressures.ꢀReactionꢀconditions:ꢀ0.3ꢀgꢀcatalyst,ꢀ12ꢀgꢀglycerolꢀ
2
solutionꢀ(5ꢀwt%),ꢀPꢀ=ꢀ5ꢀMPaꢀ(a)ꢀandꢀTꢀ=ꢀ155ꢀ°Cꢀ(b).ꢀ

ꢀ
ChaojunꢀYangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ39ꢀ(2018)ꢀ1366–1372ꢀ
1369ꢀ
Pt/WO
Pt/Au/WO
WO
3
Pt/WO
Pt/Au/WO
3
PtO/WO -500
3
3
3
PtO/Au/WO -500
3
3
30.7
PtO/Au/WO -550
3
PtO/Au/WO -600
3
21
22
23
24
25
76.6
o
2
/( )
22.8
90.1
0
100 200 300 400 500 600 700 800
1
0
20
30
40
2
50
/( )
60
70
80
o
o
Temperature ( C)
Fig.ꢀ4.ꢀH
2
‐TPRꢀprofilesꢀofꢀtheꢀcalcinedꢀPt/WO
3
ꢀandꢀPt/Au/WO ꢀsamples.
3
Fig.ꢀ3.ꢀXRDꢀpatternsꢀofꢀtheꢀfreshlyꢀreducedꢀandꢀpassivatedꢀPt/WO
Pt/Au/WO ꢀcatalysts.ꢀ
3
ꢀandꢀ
3
wasꢀdetectedꢀbyꢀXRD,ꢀsuggestingꢀthatꢀbothꢀcomponentsꢀwereꢀ
highlyꢀdispersedꢀonꢀtheꢀWO ꢀsupport.ꢀFurthermore,ꢀcomparedꢀ
withꢀtheꢀPt/WO ꢀcatalyst,ꢀtheꢀPt/Au/WO ꢀXRDꢀpeaksꢀareꢀshift‐
edꢀtowardsꢀlowerꢀangles.ꢀConsideringꢀthatꢀAu3+ꢀisꢀbiggerꢀthanꢀ
6+ꢀ(0.85ꢀvs.ꢀ0.60ꢀÅ),ꢀtheꢀpeakꢀshiftꢀofꢀtheꢀPt/Au/WO
ꢀcatalystꢀ
mayꢀbeꢀdueꢀtoꢀtheꢀreplacementꢀofꢀW6+ꢀwithꢀAu3+.ꢀInꢀfact,ꢀinꢀtheꢀ
ingꢀtheꢀtypicalꢀfeatureꢀofꢀconsecutiveꢀreactions.ꢀTheꢀmajorꢀsideꢀ
productꢀ thatꢀ competesꢀ withꢀ 1,3‐PDOꢀ isꢀ 1‐PO,ꢀ whichꢀ couldꢀ beꢀ
producedꢀfromꢀfurtherꢀhydrogenolysisꢀofꢀdiolsꢀorꢀdirectlyꢀfromꢀ
theꢀ hydrogenolysisꢀ ofꢀ glycerol,ꢀ basedꢀ onꢀ previousꢀ reportsꢀ
3
3
3
W
3
[4,26].ꢀInꢀcontrastꢀtoꢀ1‐PO,ꢀonlyꢀaꢀmarginalꢀamountꢀofꢀ1,2‐PDOꢀ
wasꢀ formedꢀ usingꢀ thisꢀ catalystꢀ system.ꢀ Theꢀ pres‐
sure‐dependenceꢀ ofꢀ theꢀ glycerolꢀ conversionꢀ isꢀ similarꢀ toꢀ theꢀ
fieldꢀofꢀsemiconductors,ꢀdopingꢀofꢀAuꢀintoꢀWO
modifyꢀtheꢀpropertiesꢀ[27].ꢀ
3
ꢀwasꢀalsoꢀusedꢀtoꢀ
temperatureꢀ dependence,ꢀ increasingꢀ withꢀ increasingꢀ H
sure,ꢀwhileꢀtheꢀ1,3‐PDOꢀselectivityꢀdoesꢀnotꢀchangeꢀmuchꢀwithꢀ
increasingꢀ H ꢀ pressure.ꢀThisꢀtrendꢀisꢀquiteꢀdifferentꢀ fromꢀtheꢀ
inverseꢀ dependenceꢀ onꢀ H ꢀ pressureꢀ observedꢀ forꢀ theꢀ
Au‐Pt/WO ꢀcatalystꢀ[24].ꢀTheꢀunderlyingꢀreasonꢀmightꢀbeꢀtheꢀ
2
ꢀpres‐
TheꢀH ‐TPRꢀprofilesꢀshowꢀthatꢀtheꢀintroductionꢀofꢀAuꢀfacili‐
tatedꢀtheꢀreductionꢀofꢀbothꢀPt4+ꢀandꢀW6+,ꢀshiftingꢀtheirꢀreduc‐
tionꢀ peakꢀ temperatureꢀ towardsꢀ lowerꢀ temperaturesꢀ (Fig.ꢀ 4).ꢀ
Theꢀ calculationꢀ ofꢀ theꢀ amountꢀ ofꢀ hydrogenꢀ consumedꢀ belowꢀ
2
2
2
x
300ꢀCꢀindicatesꢀWO
ꢀWO2.91ꢀinꢀtheꢀPt/Au/WO
moreꢀ oxygenꢀ vacanciesꢀ inꢀ theꢀ reducedꢀ Pt/Au/WO
thanꢀinꢀtheꢀPt/WO ꢀsample.ꢀ
Fig.ꢀ5ꢀpresentsꢀtheꢀtypicalꢀTEMꢀimagesꢀofꢀtheꢀtwoꢀcatalysts.ꢀ
WhileꢀtheꢀPtꢀparticlesꢀinꢀtheꢀPt/WO ꢀcatalystꢀareꢀirregular,ꢀtheyꢀ
areꢀnearlyꢀsphericalꢀandꢀmoreꢀfinelyꢀandꢀuniformlyꢀdispersedꢀinꢀ
3
ꢀꢀWO2.96ꢀinꢀtheꢀPt/WO
‐600ꢀcatalyst.ꢀTherefore,ꢀthereꢀareꢀ
ꢀ catalystꢀ
3
ꢀcatalystꢀandꢀWO
3
ꢀ
structuralꢀdifferenceꢀbetweenꢀtheꢀtwoꢀcatalysts.ꢀ
3
ToꢀunderstandꢀtheꢀsuperiorꢀperformanceꢀofꢀtheꢀPt/Au/WO
3
ꢀ
3
catalyst,ꢀweꢀperformedꢀextensiveꢀcharacterizationsꢀusingꢀXRD,ꢀ
TEM,ꢀ H ‐TPR,ꢀ andꢀ XPS.ꢀ Fig.ꢀ 3ꢀ showsꢀ thatꢀ bothꢀ theꢀ freshlyꢀ re‐
ducedꢀ andꢀ passivatedꢀ Pt/WO ꢀ andꢀ Pt/Au/WO ‐600ꢀ catalystsꢀ
presentedꢀtheꢀtypicalꢀXRDꢀpatternꢀofꢀWO ;ꢀnoꢀPtꢀorꢀAuꢀphaseꢀ
3
2
3
3
3
3
Fig.ꢀ5.ꢀTEMꢀimagesꢀofꢀPt/WO
3
ꢀ(a)ꢀandꢀPt/Au/WO ꢀ(b)ꢀcatalyst.ꢀ
3

1370ꢀ
ChaojunꢀYangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ39ꢀ(2018)ꢀ1366–1372ꢀ
Pt3 Pt2 Pt1
W3 W2
W1
Pt/WO3
Pt/WO3
Pt/Au/WO3
Pt/Au/WO3
40
39
38
37
36
35
34
33
32
77
76
75
74
73
72
71
70
69
Binding energy (eV)
Binding energy (eV)
Fig.ꢀ6.ꢀWꢀ4fꢀandꢀPtꢀ4fꢀXPSꢀspectraꢀofꢀfreshlyꢀreducedꢀandꢀpassivatedꢀPt/WO
3
ꢀandꢀPt/Au/WO ꢀcatalysts.ꢀ
3
Tableꢀ2ꢀ
3 3
XPSꢀanalysisꢀresultꢀforꢀPt/WO ꢀandꢀPt/Au/WO ꢀcatalysts.ꢀ
Wꢀ4f7/2
ꢀ
Ptꢀ4f7/2
Pt2ꢀ
71.5ꢀ
40.7ꢀ
71.6ꢀ
35.6ꢀ
ꢀ
Catalystꢀ
XPSꢀ
Pt/Wꢀ
W1ꢀ
34.0ꢀ
12.1ꢀ
34.0ꢀ
16.5ꢀ
W2ꢀ
35.5ꢀ
79.1ꢀ
35.5ꢀ
74.6ꢀ
W3ꢀ
36.2ꢀ
ꢀ 8.8ꢀ
36.2ꢀ
ꢀ 8.9ꢀ
Pt1ꢀ
70.9ꢀ
39.0ꢀ
71.0ꢀ
48.2ꢀ
Pt3ꢀ
Bindingꢀenergyꢀ(eV)ꢀ
Contentꢀ(%)ꢀ
Bindingꢀenergyꢀ(eV)ꢀ
Contentꢀ(%)ꢀ
72.3ꢀ
20.3ꢀ
72.4ꢀ
16.2ꢀ
1/8.3ꢀ
ꢀ
1/7.9ꢀ
ꢀ
Pt/WO
3
ꢀ
Pt/Au/WO
3
ꢀ
theꢀPt/Au/WO
ThisꢀresultꢀindicatesꢀthatꢀtheꢀdopingꢀofꢀAuꢀonꢀWO
theꢀdispersionꢀofꢀtheꢀactiveꢀcomponent,ꢀPt.ꢀ ꢀ
Theꢀ electronicꢀ propertiesꢀ ofꢀ Ptꢀ andꢀ Wꢀ wereꢀ studiedꢀ withꢀ
XPS.ꢀ Asꢀ shownꢀ inꢀ Fig.ꢀ 6ꢀ andꢀ Tableꢀ 2,ꢀ inꢀ comparisonꢀ withꢀ theꢀ
3
ꢀcatalyst,ꢀwithꢀaꢀmeanꢀparticleꢀsizeꢀofꢀ2.36ꢀnm.ꢀ
eVꢀ(W2)ꢀandꢀ36.2ꢀeVꢀ(W3),ꢀwhichꢀcanꢀbeꢀascribedꢀtoꢀW5‐δ,ꢀW6+,ꢀ
andꢀ W6+δꢀ [31],ꢀ respectively.ꢀ Inꢀ comparisonꢀ withꢀ Pt/WO
,ꢀ theꢀ
percentageꢀofꢀW5‐δꢀinꢀtheꢀPt/Au/WO
ꢀisꢀmuchꢀhigher,ꢀinꢀagree‐
mentꢀwithꢀtheꢀH ‐TPRꢀresultꢀthatꢀAuꢀfacilitatedꢀW ꢀreduction.ꢀ
ForꢀtheꢀoxidationꢀstateꢀofꢀPt,ꢀaꢀtrendꢀsimilarꢀtoꢀthatꢀofꢀWꢀwasꢀ
obtained,ꢀ i.e.ꢀ low‐valenceꢀ stateꢀ ofꢀ Ptꢀ isꢀ moreꢀ abundantꢀ onꢀ
3
ꢀpromotesꢀ
3
3
6+
2
Pt/WO
enrichmentꢀofꢀPt;ꢀtheꢀsurfaceꢀratioꢀofꢀPtꢀtoꢀWꢀisꢀ1/8.3ꢀinꢀPt/WO
whileꢀ itꢀ isꢀ 1/7.9ꢀ inꢀ theꢀ Pt/Au/WO ꢀ catalyst.ꢀ Auꢀ inducesꢀ thisꢀ
effectꢀbecauseꢀitꢀweakensꢀtheꢀinteractionꢀbetweenꢀPtꢀandꢀWO .ꢀ
Pt/WO ꢀ isꢀ aꢀ typicalꢀ strongꢀ metal‐supportꢀ interactionꢀ (SMSI)ꢀ
systemꢀ [28–30],ꢀ andꢀ theꢀ factꢀ thatꢀ bothꢀ Ptꢀ andꢀ WO ꢀ couldꢀ beꢀ
3
,ꢀtheꢀPt/Au/WO
3
ꢀcatalystꢀshowedꢀaꢀremarkableꢀsurfaceꢀ
3
ꢀ
3 3
Pt/Au/WO ꢀthanꢀthatꢀonꢀPt/WO .ꢀTheꢀincreasedꢀelectronꢀden‐
3
2
sityꢀ ofꢀ Ptꢀ favorsꢀ theꢀ dissociationꢀ ofꢀ H ꢀ inꢀ aꢀ heterolyticꢀ way,ꢀ
3
providingꢀmoreꢀprotonsꢀandꢀhydridesꢀforꢀtheꢀselectiveꢀhydro‐
genolysisꢀofꢀglycerolꢀtoꢀ1,3‐PDOꢀbasedꢀonꢀourꢀpreviousꢀstudiesꢀ
[20–24].ꢀ
3
3
reducedꢀsimultaneouslyꢀ(Fig.ꢀ4)ꢀprovidesꢀevidenceꢀforꢀtheꢀSMSI.ꢀ
However,ꢀAuꢀbelongsꢀtoꢀtheꢀIBꢀgroupꢀonꢀtheꢀperiodicꢀtableꢀandꢀ
itsꢀ dopingꢀ willꢀ inevitablyꢀ weakenꢀ theꢀ interactionꢀ betweenꢀ Ptꢀ
4.ꢀ ꢀ Conclusionsꢀ ꢀ
andꢀWO
3
.ꢀMoreꢀthanꢀoneꢀpeakꢀbelowꢀ300ꢀCꢀinꢀtheꢀH
2
‐TPRꢀpro‐
3
Pt/Au/WO ꢀ catalystsꢀ wereꢀ successfullyꢀ preparedꢀ viaꢀ aꢀ
filesꢀofꢀtheꢀthreeꢀPt/Au/WO
TheꢀXPSꢀspectrumꢀofꢀW4fꢀcanꢀbeꢀdeconvolutedꢀintoꢀthreeꢀsetsꢀofꢀ
doubletsꢀwithꢀtheꢀW4f7/2ꢀbindingꢀenergiesꢀatꢀ34.0ꢀeVꢀ(W1),ꢀ35.5ꢀ
3
ꢀsamplesꢀsupportsꢀthisꢀconclusion.ꢀ
CTAB‐assistedꢀdepositionꢀmethod.ꢀTheꢀdopingꢀwithꢀAuꢀresultedꢀ
6+
3+
inꢀpartialꢀreplacementꢀofꢀW ꢀwithꢀAu ,ꢀwhichꢀalteredꢀtheꢀsur‐
faceꢀpropertiesꢀofꢀWO .ꢀConsequently,ꢀtheꢀinteractionꢀbetweenꢀ
3

ꢀ
ChaojunꢀYangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ39ꢀ(2018)ꢀ1366–1372ꢀ
GraphicalꢀAbstractꢀ
1371ꢀ
Chin.ꢀJ.ꢀCatal.,ꢀ2018,ꢀ39:ꢀ1366–1372ꢀ ꢀ ꢀ doi:ꢀ10.1016/S1872‐2067(18)63103‐1
UnderstandingꢀtheꢀpromotionalꢀeffectꢀofꢀAuꢀonꢀPt/WO ꢀinꢀhydrogenolysisꢀofꢀglycerolꢀtoꢀ1,3‐propanediolꢀ
3
†
†
ChaojunꢀYangꢀ ,ꢀFanꢀZhangꢀ ,ꢀNieꢀLei,ꢀManꢀYang,ꢀFeiꢀLiu,ꢀZhiliꢀMiao,ꢀYunnanꢀSun,ꢀXiaochenꢀZhao,ꢀAiqinꢀWangꢀ*ꢀ
DalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences;ꢀUniversityꢀofꢀChineseꢀAcademyꢀofꢀSciencesꢀ
ꢀ
ꢀ
ꢀcatalystꢀaffordsꢀalmostꢀ2.4‐foldꢀSTYꢀofꢀ1,3‐propanediolꢀthanꢀtheꢀ
Inꢀselectiveꢀhydrogenolysisꢀofꢀglycerolꢀtoꢀ1,3‐propanediol,ꢀtheꢀPt/Au/WO
Pt/WO ꢀcatalystꢀdueꢀtoꢀAuꢀdoping.ꢀ
3
3
3
PtꢀandꢀWO ꢀwasꢀweakened,ꢀandꢀtheꢀreductionꢀofꢀbothꢀPtꢀandꢀWꢀ
2009,ꢀ131,ꢀ312–320.ꢀ
becameꢀeasier,ꢀresultingꢀinꢀmoreꢀlow‐valenceꢀstateꢀofꢀWꢀandꢀPt.ꢀ
Suchꢀaꢀchangeꢀinꢀtheꢀelectronicꢀstateꢀisꢀbeneficialꢀtoꢀtheꢀconver‐
sionꢀ ofꢀ glycerolꢀ toꢀ 1,3‐PDO,ꢀ leadingꢀ toꢀ enhancementꢀ inꢀ bothꢀ
glycerolꢀ conversionꢀ andꢀ 1,3‐PDOꢀ selectivityꢀ comparedꢀ withꢀ
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Au促进Pt/WO 催化甘油氢解制1,3-丙二醇
3
a,b,†
a,b,†
a,b
a,b
a
a
a
杨超军 , 张 帆 , 雷 念 , 杨 曼 , 刘 菲 , 苗治理 , 孙永南 ,
a
a,*
赵晓晨 , 王爱琴
a
中国科学院大连化学物理研究所催化基础重点实验室, 辽宁大连116023
b
中国科学院大学, 北京100049
摘要: 近年来, 以生物质为基础的生物柴油得到了迅速发展, 导致了粗甘油过剩. 通过甘油选择性氢解制1,3-丙二醇, 进而
被用于合成高价值的聚对苯二甲酸丙二醇酯被认为是最具工业应用潜力的反应之一, 对于提高生物柴油的利用效率有着
极其重要的意义. 但由于反应空间位阻和热力学上的限制给甘油氢解制1,3-丙二醇带来了很大的挑战, 因此需要设计高活
性的金属-酸双功能催化剂以降低甘油第二个C-O键断裂的活化能和减少其他副反应的发生. 目前Pt-W和Ir-Re双功能催化
剂可高选择性制得1,3-丙二醇, 但仍需较严苛的反应条件实现对氢气的活化和解离. 本课题组曾将准单原子/单原子Pt高度
分散于具有大量氧空位和酸位点的WO
加Au可促进B酸产生, 进而提高了甘油转化率和1,3-丙二醇的选择性.
为了进一步研究Au对Pt/WO 催化剂结构和催化性能的影响, 本文利用CTAB辅助吸附法制备了Au/WO
x
载体上, 十分有利于甘油选择性氢解制1,3-丙二醇反应; 在Au-Pt/WO
x
催化剂中添
x
3
, 再浸渍Pt制
得Pt/Au/WO 双金属催化剂. 在甘油选择性氢解制1,3-丙二醇反应中, 所制催化剂表现出比Au-Pt/WO 更好的催化活性, 1,3-
3
x
丙二醇时空收率为0.078 g1,3-PDO/(gcath), 是后者的1.95倍. 值得一提的是, Au-Pt/WO
x
催化剂在低压时活性较高, 而
3
Pt/Au/WO 催化剂活性则在压力的升高而提高; 另外反应温度的升高导致副产物正丙醇的选择性上升, 1,3-丙二醇的选择
o
性降低. 因此, 适宜的反应条件为155 C和5 MPa. 与Pt/WO 和Pt/WO 相比, Pt/Au/WO 表现出了更优异的催化性能, 其1,3-
3
x
3
丙二醇的时空收率是Pt/WO
3
x
的2.36倍和Pt/WO 的4倍.
为了探究Au的掺入对Pt/WO
x
催化剂性能的影响, 通过XRD, TEM, H
2
-TPR和XPS等技术对催化剂进行了深入表征. 结
3
+
6+
果表明, 与Pt/WO 相比, Pt/Au/WO -600催化剂的XRD衍射峰向小角度偏移, 其原因是Au 离子半径(0.85 Å)比W 的(0.60
3
3
3
+
6+
o
Å)大, Au 以取代晶格W 形式进入WO
Pt/Au/WO 可被还原至Pt/Au/WO2.91. 因此与Pt/WO
wt%Au后, 促进了更低价态的Pt均匀分散在WO 载体上, 其平均粒径为2.36 nm.
3
晶格中; 对H
2
-TPR前300 C耗氢量的计算可知：Pt/WO
3
可被还原至Pt/WO2.96, 而
3
3
相比, Pt/Au/WO
3
表面氧空位更加丰富. TEM和XPS表征可知, 添加0.1
3
综上所述, Au的掺杂改变了Pt/Au/WO
作用, 也促进了更低价态的Pt均匀分散于WO
为优异的活性和产物选择性. 该催化剂有望被广泛运用于其他生物质平台化合物加氢脱氧的反应中.
关键词: 双金属; Pt/Au/WO ; 甘油; 1,3-丙二醇; 氢解作用
3
双金属催化剂的结构, 不仅降低了Pt和W的还原温度, 削弱了Pt和W之间的相互
3
载体上, 使得Pt/Au/WO 双金属催化剂在甘油氢解制1,3-丙二醇反应中具有更
3
3
收稿日期: 2018-04-06. 接受日期: 2018-05-07. 出版日期: 2018-08-05.
*
通讯联系人. 电话: (0411)84379348; 传真: (0411)84685940; 电子信箱: aqwang@dicp.ac.cn
†
共同第一作者.
基金来源: 国家自然科学基金(21690080, 21690084, 21721004, 21673228); 中国科学院战略重点研究项目(XDB17020100); 国家
重点基础研究和发展项目(2016YFA0202801).
本文的电子版全文由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18722067).