Niobium phytate prepared from phytic acid and NbCl5: A highly efficient and heterogeneous acid catalyst

Article abstract of DOI:10.1039/c5cy01123j

The preparation of functional catalysts using naturally-occurring building blocks is of great importance. In this work, we designed a functional heterogeneous acid catalyst, niobium phytate, using phytic acid, which could be obtained from the seeds and grains of plants, as the building block to react with NbCl₅. The prepared niobium phytate was characterized by XRD, FT-IR, XPS, SEM, TEM, NH₃-TPD and N₂ adsorption-desorption examinations. Niobium phytate showed very high activity for both cyanosilylation of carbonyl compounds and dehydration of carbohydrates. It was also found that niobium phytate had higher activity than commercial Nb₂O₅. In addition, niobium phytate could be easily recovered and reused without reducing the reaction activity considerably. Further study indicated that both higher acidity and lower crystallinity contributed significantly to the excellent catalytic performance of niobium phytate. The findings in this work provide insights into the design of new functional catalysts using naturally-occurring building blocks for various organic reactions.

Full text of DOI:10.1039/c5cy01123j

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Ca Pt al el ya ss ies ꢀ dSo cꢀ ni eo nt ꢀca ed j&u sTt ꢀemc ah rng oi nl os ꢀg y
View Article Online
DOI: 10.1039/C5CY01123J
JournalꢀNameꢀ
ꢀ
ARTICLEꢀ
NiobiumꢀphyticꢀpreparedꢀfromꢀphyticꢀacidꢀandꢀNbCl :ꢀHighlyꢀ
5
efficientꢀandꢀheterogeneousꢀacidꢀcatalystsꢀꢀ
Receivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
a
b
b
b
b
b ꢀ
ZhiminꢀXue, *ꢀYuweiꢀZhang, ꢀGuofengꢀLi, ꢀJinfangꢀWang, ꢀWanchengꢀZhao, ꢀandꢀTianchengꢀMu, *
DOI:ꢀ10.1039/x0xx00000xꢀ
Preparationꢀ ofꢀ functionalꢀ catalystsꢀ usingꢀ naturally-occurredꢀ buildingꢀ blocksꢀ isꢀ ofꢀ greatꢀ importance.ꢀ Inꢀ thisꢀ work,ꢀ weꢀ
designedꢀaꢀfunctionalꢀheterogeneousꢀacidꢀcatalyst,ꢀniobiumꢀphytic,ꢀusingꢀphyticꢀacid,ꢀwhichꢀcouldꢀbeꢀobtainedꢀfromꢀtheꢀ
www.rsc.org/ꢀ
seedsꢀandꢀgrainsꢀofꢀplants,ꢀasꢀtheꢀbuildingꢀblockꢀtoꢀreactꢀwithꢀNbCl
XRD,ꢀFT-IR,ꢀXPS,ꢀSEM,ꢀTEM,ꢀNH -TPDꢀandꢀN ꢀadsorption-desorptionꢀexaminations.ꢀTheꢀniobiumꢀphyticꢀshowedꢀveryꢀhighꢀ
activityꢀforꢀbothꢀcyanosilylationꢀofꢀcarbonylꢀcompoundsꢀandꢀdehydrationꢀofꢀcarbohydrates.ꢀItꢀwasꢀalsoꢀfoundꢀthatꢀniobiumꢀ
phyticꢀ hadꢀ higherꢀ activityꢀ thanꢀ commercialꢀ Nb .ꢀ Inꢀ addition,ꢀ niobiumꢀ phyticꢀ couldꢀ beꢀ easilyꢀ recoveredꢀ andꢀ reusedꢀ
5
.ꢀTheꢀpreparedꢀniobiumꢀphyticꢀwasꢀcharacterizedꢀbyꢀ
3
2
2
O
5
withoutꢀreducingꢀtheꢀreactionꢀactivityꢀconsiderably.ꢀFurtherꢀstudyꢀindicatedꢀthatꢀbothꢀhigherꢀacidityꢀandꢀlowerꢀcrystallinityꢀ
contributedꢀsignificantlyꢀtoꢀtheꢀexcellentꢀcatalyticꢀperformanceꢀofꢀniobiumꢀphytic.ꢀTheꢀfindingsꢀinꢀthisꢀworkꢀprovideꢀtheꢀ
viewꢀ ofꢀ designingꢀ newꢀ functionalꢀ catalystꢀ usingꢀ naturally-occurredꢀ buildingꢀ blocksꢀ forꢀ variousꢀ organicꢀ reactions.ꢀ
7
performanceꢀ forꢀ theꢀ hydrogenationꢀ ofꢀ quinolone. ꢀ Theseꢀ
Introductionꢀ
developmentsꢀonꢀcatalystꢀpreparationꢀfromꢀnaturally-occurredꢀ
buildingꢀ blocksꢀ provideꢀ aꢀ widerꢀ viewꢀ forꢀ designingꢀ efficientꢀ
catalysts,ꢀwhichꢀisꢀinterestingꢀandꢀattractive.ꢀ
Withꢀ theꢀ increasingꢀ attentionꢀ onꢀ theꢀ utilizationꢀ andꢀ
1
transformationꢀofꢀbiomass, ꢀdesignꢀofꢀefficientꢀcatalystsꢀbasedꢀ
Phyticꢀ acid,ꢀ aꢀ majorꢀ phosphorusꢀ reservoirꢀ inꢀ plants,ꢀ canꢀ
beꢀ obtainedꢀ fromꢀ theꢀ seedsꢀ andꢀ grainsꢀ ofꢀ plantsꢀ andꢀ widelyꢀ
8
usedꢀ asꢀ aꢀ chelatingꢀ agent,ꢀ foodꢀ additive,ꢀ andꢀ antioxidant. ꢀ
onꢀnaturally-occurredꢀbuildingꢀblocksꢀhasꢀbecomingꢀaꢀhotꢀtopicꢀ
2
inꢀ recentꢀ years. ꢀ Aꢀ salientꢀ featureꢀ ofꢀ naturally-occurredꢀ
buildingꢀblocksꢀisꢀtheirꢀdiversityꢀtoꢀprovideꢀmoreꢀopportunitiesꢀ
forꢀdesigningꢀnovelꢀcatalystsꢀwithꢀspecificꢀfunctionsꢀtoꢀcatalyzeꢀ
variousꢀreactions.ꢀ
Becauseꢀ thereꢀ areꢀ sixꢀ phosphinicꢀ groupsꢀ inꢀ itsꢀ structureꢀ
(
Schemeꢀ S1),ꢀ phyticꢀ acidꢀ canꢀ beꢀ usedꢀ asꢀ theꢀ sourceꢀ ofꢀ
phosphoricꢀacidꢀtoꢀcoordinateꢀwithꢀvariousꢀmetalꢀionsꢀtoꢀformꢀ
aꢀ novelꢀ metalꢀ phosphonate.ꢀ Metalꢀ phosphonatesꢀ areꢀ veryꢀ
usefulꢀfunctionalꢀmaterials,ꢀwhichꢀhaveꢀgainedꢀmuchꢀattentionꢀ
owingꢀ toꢀ theirꢀ diverseꢀ potentialꢀ applicationsꢀ inꢀ adsorption,ꢀ
catalysis,ꢀ separation,ꢀ energyꢀ storage,ꢀ biology,ꢀ ionꢀ exchange,ꢀ
Differentꢀ naturally-occurredꢀ buildingꢀ blocksꢀ haveꢀ beenꢀ
usedꢀ toꢀ generateꢀ efficientꢀ catalysts.ꢀ Amongꢀ variousꢀ naturallyꢀ
occurringꢀ compounds,ꢀ aminoꢀ acidsꢀ areꢀ theꢀ mostꢀ usedꢀ
compoundsꢀ forꢀ theꢀ preparationꢀ ofꢀ bio-basedꢀ catalysts.ꢀ Forꢀ
example,ꢀaminoꢀacidsꢀsupportedꢀonꢀpolystyreneꢀcouldꢀbeꢀusedꢀ
9
3
andꢀ functionalꢀ materials. ꢀ Inꢀ particular,ꢀ metalꢀ phosphonatesꢀ
asꢀ efficientꢀ catalystꢀ forꢀ chemicalꢀ fixationꢀ ofꢀ carbonꢀ dioxide. ꢀ
II
Cu -complexesꢀ derivedꢀ fromꢀ aminoꢀ acidsꢀ couldꢀ catalyzeꢀ theꢀ
4
asymmetricꢀoxidativeꢀcouplingꢀofꢀ2-naphthol. ꢀAminoꢀacidꢀionicꢀ
haveꢀ recentlyꢀ emergedꢀ asꢀ aꢀ classꢀ ofꢀ promisingꢀ catalystsꢀ orꢀ
catalyst-supportsꢀ forꢀ aꢀ wideꢀ rangeꢀ ofꢀ chemicalꢀ reactions,ꢀ
10
11
includingꢀ asymmetricꢀ hydrogenations, ꢀ diverseꢀ oxidations, ꢀ
liquidsꢀ wereꢀ successfullyꢀ synthesizedꢀ andꢀ showedꢀ eminentꢀ
catalyticꢀactivitiesꢀtowardsꢀAldolꢀreactionsꢀandꢀtheꢀsynthesisꢀofꢀ
5
styreneꢀcarbonateꢀfromꢀstyreneꢀoxideꢀandꢀCO2. ꢀBesidesꢀaminoꢀ
12
13
polymerizations, ꢀ Aldolꢀ andꢀ Knoevenagelꢀ condensations, ꢀ
andꢀsoꢀon.ꢀVeryꢀrecently,ꢀaꢀporousꢀzirconium-phyticꢀacidꢀhybridꢀ
hadꢀ beenꢀ preparedꢀ andꢀ usedꢀ asꢀ theꢀ efficientꢀ catalystꢀ forꢀ
acids,ꢀ chitosanꢀ couldꢀ beꢀ convertedꢀ intoꢀ chitosan-Schiffꢀ baseꢀ
6
complexesꢀ forꢀ aerobicꢀ oxidationꢀ ofꢀ cyclohexene. ꢀ Recently,ꢀ
14
Meerwein-Ponndorf-Verleyꢀreductions. ꢀ
Inspiredꢀbyꢀtheseꢀachievements,ꢀweꢀdesignedꢀaꢀnovelꢀNb-
containingꢀ heterogeneousꢀ catalyst,ꢀ niobiumꢀ phytic,ꢀ byꢀ usingꢀ
phyticꢀ acidꢀ asꢀ theꢀ buildingꢀ blocks.ꢀ Theꢀ niobiumꢀ phyticꢀ wasꢀ
Guoꢀ andꢀ co-workersꢀ foundꢀ thatꢀ tannicꢀ acidꢀ (TA)ꢀ couldꢀ
III
III
coordinateꢀ withꢀ Rh ꢀ toꢀ formꢀ Rh -TAꢀ capsulesꢀ throughꢀ theꢀ
chelationꢀabilityꢀofꢀphenolicꢀstructure,ꢀwhichꢀshowedꢀexcellentꢀ
5+
formedꢀbyꢀtheꢀcoordinationꢀbetweenꢀNb ꢀandꢀtheꢀphosphateꢀ
groupsꢀ inꢀ phyticꢀ acid.ꢀ Asꢀ examplesꢀ ofꢀ applications,ꢀ theꢀ
synthesizedꢀ niobiumꢀ phyticꢀ wasꢀ usedꢀ asꢀ anꢀ effectiveꢀ
heterogeneousꢀ acid-catalystꢀ forꢀ bothꢀ cyanosilylationꢀ ofꢀ
carbonylꢀ compoundsꢀ andꢀ dehydrationꢀ ofꢀ carbohydratesꢀ toꢀ
formꢀ 5-hydroxymethylfurfuralꢀ (HMF),ꢀ whichꢀ areꢀ typicalꢀ acid-
catalyzedꢀ reactions.ꢀ Theꢀ as-preparedꢀ niobiumꢀ phyticꢀ showedꢀ
highꢀ catalyticꢀ activityꢀ forꢀ theꢀ twoꢀ reactions.ꢀ Inꢀ addition,ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
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Ca Pt al el ya ss ies ꢀ dSo cꢀ ni eo nt ꢀca ed j&u sTt ꢀemc ah rng oi nl os ꢀg y
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ARTICLEꢀ
JournalꢀNameꢀ
niobiumꢀ phyticꢀ canꢀ beꢀ easilyꢀ recoveredꢀ andꢀ reusedꢀ withoutꢀ composedꢀofꢀtwoꢀsingleꢀpeaksꢀlocatedꢀatꢀ207.5ꢀeVꢀforꢀNbꢀ3d5/2ꢀ
View Article Online
+ 16
considerableꢀ decreaseꢀ inꢀ catalyticꢀ activityꢀ forꢀ bothꢀ reactions.ꢀ andꢀ210.2ꢀeVꢀforꢀNbꢀ3d3/2,ꢀwhichꢀwereꢀcharacteristicꢀofꢀNb . ꢀ
5
DOI: 10.1039/C5CY01123J
5+
Phyticꢀ acid,ꢀ asꢀ buildingꢀ blocks,ꢀ hasꢀ greatꢀ potentialꢀ inꢀ theꢀ TheꢀbindingꢀenergyꢀofꢀPꢀ2pꢀatꢀ133.6ꢀeVꢀwasꢀcharacteristicꢀofꢀP ꢀ
5+
5
+
preparationꢀofꢀfunctionalꢀheterogeneousꢀcatalysts.ꢀ
(Fig.ꢀ3b).ꢀTheseꢀresultsꢀsuggestedꢀtheꢀpresenceꢀofꢀNb ꢀandꢀP ꢀ
inꢀtheꢀpreparedꢀcatalyst.ꢀ
Resultsꢀandꢀdiscussionꢀ
Catalystꢀcharacterizationꢀ
Theꢀsyntheticꢀprocedureꢀforꢀniobiumꢀphyticꢀwasꢀpresentedꢀinꢀ
detailꢀinꢀtheꢀExperimentalꢀsection.ꢀTheꢀpowderꢀXRDꢀpatternꢀofꢀ
theꢀsynthesizedꢀniobiumꢀphyticꢀwasꢀshownꢀinꢀFig.ꢀ1a.ꢀItꢀcouldꢀ
beꢀ seenꢀ thatꢀ theꢀ catalystꢀ hadꢀ noꢀ X-rayꢀ crystalꢀ structure.ꢀ
Furthermore,ꢀ theꢀ XRDꢀ patternꢀ showedꢀ oneꢀ broadꢀ diffractionꢀ
peak,ꢀ indicatingꢀ thatꢀ theꢀ obtainedꢀ catalystꢀ wasꢀ amorphous.ꢀ
Theꢀ scanningꢀ electronꢀ microscopyꢀ (SEM)ꢀ andꢀ transmissionꢀ Fig.ꢀ3.ꢀTheꢀXPSꢀspectraꢀofꢀNbꢀ3dꢀ(a)ꢀandꢀPꢀ2pꢀ(b)ꢀinꢀtheꢀniobiumꢀ
electronꢀmicroscopyꢀ(TEM)ꢀdemonstratedꢀthatꢀtheꢀcatalystꢀwasꢀ phytic.ꢀ
formedꢀfromꢀparticlesꢀwithꢀaꢀsizeꢀofꢀaboutꢀ60ꢀnmꢀ(Figs.ꢀ1bꢀandꢀ
1
c).ꢀ
Theꢀ texturalꢀ parametersꢀ ofꢀ theꢀ synthesizedꢀ niobiumꢀ
phyticꢀ wereꢀ investigatedꢀ byꢀ theꢀ N2ꢀ adsorption-desorptionꢀ
o
methodꢀafterꢀtheꢀsampleꢀwasꢀdegassedꢀatꢀ100ꢀ Cꢀforꢀ24ꢀhours.ꢀ
ItꢀcanꢀbeꢀseenꢀthatꢀtheꢀN2ꢀadsorption-desorptionꢀisothermꢀofꢀ
theꢀ catalystꢀ wasꢀ similarꢀ toꢀ theꢀ typeꢀ IVꢀ mode,ꢀ showingꢀ poreꢀ
condensationꢀ withꢀ pronouncedꢀ adsorption-desorptionꢀ
hysteresisꢀ (Fig.ꢀ 4).ꢀ Theꢀ resultꢀ inꢀ Fig.ꢀ 4ꢀ indicatesꢀ thatꢀ theꢀ
niobiumꢀphyticꢀpreparedꢀwasꢀporous.ꢀTheꢀporosityꢀofꢀniobiumꢀ
phyticꢀ couldꢀ resultꢀ fromꢀ theꢀ networksꢀ formedꢀ byꢀ theꢀ
5+
Fig.ꢀ1.ꢀPowderꢀXRDꢀpatternsꢀ(a),ꢀSEMꢀimageꢀ(b)ꢀandꢀTEMꢀimageꢀ coordinationꢀbetweenꢀNb ꢀandꢀphyticꢀacid.ꢀXRDꢀpatternꢀ(Fig.ꢀ
(
c)ꢀofꢀtheꢀpreparedꢀniobiumꢀphytic.ꢀ
1a)ꢀ indicatedꢀ thatꢀ niobiumꢀ phyticꢀ wasꢀ poorlyꢀ ordered.ꢀ
Therefore,ꢀitꢀcanꢀbeꢀdeducedꢀthatꢀthereꢀwereꢀmanyꢀirregularꢀ
TheꢀFourierꢀtransform-infraredꢀ(FT-IR)ꢀtechniqueꢀwasꢀalsoꢀ connectivityꢀinꢀniobiumꢀphytic,ꢀwhichꢀwasꢀconsistentꢀwithꢀtheꢀ
usedꢀtoꢀcharacterizeꢀtheꢀsynthesizedꢀcatalystꢀ(Fig.ꢀ2).ꢀTheꢀbandꢀ factꢀthatꢀtheꢀporeꢀsizeꢀdistributionꢀwasꢀrelativelyꢀwideꢀ(Fig.ꢀ4).ꢀ
-1
-1
atꢀ3400ꢀcm ꢀandꢀ1630ꢀcm ꢀcanꢀbeꢀassociatedꢀtoꢀtheꢀsurface- Theꢀaverageꢀporeꢀdiameter,ꢀtheꢀBrunauer-Emmett-Tellerꢀ(BET)ꢀ
15
adsorbedꢀmolecularꢀwater. ꢀItꢀcouldꢀbeꢀfoundꢀthatꢀthereꢀwasꢀ surfaceꢀ area,ꢀ andꢀ theꢀ poreꢀ volumeꢀ calculatedꢀ fromꢀ theꢀ N ꢀ
2
-
1
2 -1
oneꢀ bandꢀ atꢀ 1020ꢀ cm ,ꢀ suggestingꢀ theꢀ formationꢀ ofꢀ Nb-O-Pꢀ adsorption-desorptionꢀ wereꢀ 12.4ꢀ nm,ꢀ 30.9ꢀ m g ,ꢀ andꢀ 0.11ꢀ
3
-1
networksꢀ inꢀ theꢀ synthesizedꢀ catalyst.ꢀ Anꢀ additionalꢀ strongꢀ cm g ,ꢀrespectively.ꢀ
bandꢀwasꢀalsoꢀfoundꢀatꢀ625ꢀcm ,ꢀwhichꢀwasꢀassignedꢀtoꢀNb-Oꢀ
-1
1
4
stretchingꢀ modes. ꢀ UV-Visꢀ analysisꢀ forꢀ niobiumꢀ phyticꢀ andꢀ
Nb2O5ꢀ foundꢀ thatꢀ theyꢀ hadꢀ similarꢀ spectraꢀ (Fig.ꢀ S1),ꢀ whichꢀ
5
+
indicatedꢀthatꢀNb ꢀinꢀniobiumꢀphyticꢀhadꢀsimilarꢀcoordinationꢀ
patternꢀwithꢀNb2O5.ꢀ
Fig.ꢀ4.ꢀN2ꢀadsorption-desorptionꢀisothermꢀforꢀtheꢀsynthesizedꢀ
niobiumꢀphytic.ꢀ
Examinationꢀofꢀcatalyticꢀactivityꢀꢀ
Theꢀ as-preparedꢀ niobiumꢀ phyticꢀ mayꢀ findꢀ wide-rangingꢀ
applicationsꢀ inꢀ differentꢀ fields.ꢀ Itꢀ isꢀ veryꢀ stableꢀ andꢀ isꢀ notꢀ
solubleꢀinꢀwaterꢀandꢀcommonꢀorganicꢀsolvents,ꢀwhichꢀareꢀtheꢀ
Fig.ꢀ2.ꢀFT-IRꢀspectraꢀofꢀniobiumꢀphytic.ꢀ
X-rayꢀ photoelectronꢀ spectroscopyꢀ (XPS)ꢀ wasꢀ takenꢀ toꢀ excellentꢀcharacteristicsꢀofꢀheterogeneousꢀcatalysts.ꢀGenerallyꢀ
investigateꢀtheꢀchemicalꢀstateꢀofꢀtheꢀpreparedꢀcatalystꢀ(Fig.ꢀ3).ꢀ speaking,ꢀ Nb-containingꢀ compoundsꢀ couldꢀ beꢀ usedꢀ asꢀ acidꢀ
Asꢀ shownꢀ inꢀ Fig.ꢀ 3a,ꢀ theꢀ Nbꢀ 3dꢀ signalꢀ inꢀ niobiumꢀ phyticꢀ wasꢀ catalystsꢀ forꢀ variousꢀ organicꢀ reactions.ꢀ Asꢀ examplesꢀ ofꢀ
2
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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Ca Pt al el ya ss ies ꢀ dSo cꢀ ni eo nt ꢀca ed j&u sTt ꢀemc ah rng oi nl os ꢀg y
JournalꢀNameꢀ
ꢀARTICLEꢀ
3
ꢀ
Niobiumꢀphyticꢀ
Niobiumꢀphyticꢀ
15ꢀ
96ꢀ
applications,ꢀweꢀusedꢀtheꢀniobiumꢀphyticꢀasꢀaꢀheterogeneousꢀ
catalystꢀ toꢀ catalyzeꢀ bothꢀ cyanosilylationꢀ ofꢀ carbonylꢀ
compoundsꢀ andꢀ dehydrationꢀ ofꢀ carbohydratesꢀ toꢀ formꢀ 5-
hydroxymethylfurfuralꢀ (HMF),ꢀ whichꢀ areꢀ bothꢀ acid-catalyzedꢀ
reactions.ꢀꢀ
O
ꢀ
View Article Online
O
O
DOI: 10.1039/C5CY01123J
4ꢀ
15ꢀ
100ꢀ
ꢀ
O
5
6
ꢀ
ꢀ
Niobiumꢀphyticꢀ
15ꢀ
98ꢀ
ꢀ
Cyanosilylationꢀ ofꢀ carbonylꢀ compoundsꢀ isꢀ aꢀ convenientꢀ
reactionꢀ toꢀ synthesizeꢀ cyanohydrins,ꢀ whichꢀ areꢀ importantꢀ
intermediatesꢀ inꢀ theꢀ synthesisꢀ ofꢀ fineꢀ chemicalsꢀ andꢀ
O
Commercialꢀ
Nb O ꢀ
2 5
30ꢀ
16ꢀ
ꢀ
17
O
O
pharmaceuticals. ꢀ Theꢀ synthesizedꢀ niobiumꢀ phyticꢀ wasꢀ usedꢀ
asꢀaꢀheterogeneousꢀcatalystꢀforꢀtheꢀcyanosilylationꢀreactionꢀofꢀ
carbonylꢀcompounds,ꢀincludingꢀvariousꢀaldehydesꢀandꢀketones,ꢀ
withꢀtrimethylsilylꢀcyanideꢀ(TMSCN)ꢀtoꢀproduceꢀcyanohydrins,ꢀ
andꢀ theꢀ resultsꢀ areꢀ givenꢀ inꢀ Tableꢀ 1.ꢀ Itꢀ isꢀ obviousꢀ thatꢀ theꢀ
reactionꢀdidꢀnotꢀproceedꢀwithoutꢀanyꢀcatalystꢀ(Tableꢀ1,ꢀentryꢀ1).ꢀ
Toꢀ ourꢀ delight,ꢀ theꢀ niobiumꢀ phyticꢀ catalystꢀ showedꢀ excellentꢀ
performanceꢀ forꢀ theꢀ cyanosilylationꢀ reactionsꢀ atꢀ roomꢀ
temperature.ꢀ Weꢀ alsoꢀ studiedꢀ theꢀ activityꢀ ofꢀ commercialꢀ
Nb2O5ꢀforꢀtheꢀcyanosilylationꢀofꢀcyclohexanoneꢀ(Tableꢀ1,ꢀentryꢀ
c
13 ꢀ
7ꢀ
Phyticꢀacidꢀ
20ꢀ
30ꢀ
ꢀ
ꢀ
Amorphousꢀ
Nb
8
ꢀ
d
37ꢀ
2
O
5
ꢀ
a
Reactionꢀconditions:ꢀcarbonylꢀcompound,ꢀ2ꢀmmol;ꢀTMSCN,ꢀ4ꢀmmol;ꢀcatalyst,ꢀ
b
,ꢀ4ꢀg.ꢀ YieldsꢀwereꢀdeterminedꢀbyꢀGCꢀusingꢀethylbenzeneꢀasꢀtheꢀ
0
.1ꢀg;ꢀCH
2
Cl
2
c
internalꢀ standard.ꢀ Theꢀ conversionꢀ ofꢀ cyclohexanoneꢀ wasꢀ 18%ꢀ andꢀ theꢀ
d
selectivityꢀ wasꢀ aboutꢀ 72%ꢀ withꢀ someꢀ unidentifiedꢀ by-products.ꢀ Theꢀ
2 5
amorphousꢀNb O ꢀwasꢀpreparedꢀbyꢀhydrolysisꢀofꢀniobium(V)ꢀethoxide.ꢀꢀ
6
),ꢀ andꢀ theꢀ activityꢀ wasꢀ lowerꢀ thanꢀ theꢀ as-preparedꢀ niobiumꢀ
ꢀ
phyticꢀ(Tableꢀ1,ꢀentryꢀ2).ꢀTheꢀhigherꢀactivityꢀofꢀniobiumꢀphyticꢀ
couldꢀ beꢀ causedꢀ byꢀ itsꢀ higherꢀ acidityꢀ andꢀ lowerꢀ crystallinity,ꢀ
whichꢀwillꢀbeꢀdiscussedꢀinꢀdetailꢀinꢀtheꢀfollowingꢀsection.ꢀTheꢀ
reusabilityꢀ ofꢀ theꢀ as-preparedꢀ niobiumꢀ phyticꢀ forꢀ theꢀ
cyanosilylationꢀreactionꢀofꢀcyclohexanoneꢀwasꢀalsoꢀstudied.ꢀItꢀ
wasꢀ indicatedꢀ thatꢀ theꢀ catalystꢀ couldꢀ beꢀ reusedꢀ atꢀ leastꢀ fiveꢀ
timesꢀwithoutꢀreducingꢀtheꢀcatalyticꢀactivity,ꢀasꢀshownꢀinꢀFig.ꢀ5.ꢀ
Theꢀ niobiumꢀ phyticꢀ recoveredꢀ afterꢀ reusedꢀ fiveꢀ timesꢀ wasꢀ
characterizedꢀbyꢀFT-IR,ꢀXRD,ꢀXPS,ꢀSEM,ꢀandꢀTEM.ꢀAsꢀshownꢀinꢀ
theꢀpatternsꢀofꢀFT-IRꢀ(Fig.ꢀ6a),ꢀXRDꢀ(Fig.ꢀ6b),ꢀandꢀXPSꢀ(Figs.ꢀS2ꢀ
andꢀS3),ꢀitꢀcanꢀbeꢀseenꢀthatꢀtheꢀrecoveredꢀcatalystꢀshowedꢀtheꢀ
characteristicsꢀpeaks,ꢀwhichꢀindicatedꢀthatꢀtheꢀstructureꢀofꢀtheꢀ
recoveredꢀ catalystꢀ wasꢀ notꢀ changed.ꢀ Meanwhile,ꢀ fromꢀ theꢀ
imagesꢀofꢀSEMꢀ(Fig.ꢀ6c)ꢀandꢀTEMꢀ(Fig.ꢀ6d),ꢀitꢀisꢀobviousꢀthatꢀtheꢀ Fig.ꢀ 5.ꢀ Reusabilityꢀ ofꢀ niobiumꢀ phyticꢀ forꢀ theꢀ cyanosilylationꢀ
recoveredꢀcatalystꢀdidꢀnotꢀcollapseꢀandꢀtheꢀparticleꢀshowedꢀnoꢀ reactionꢀ
ofꢀ cyclohexanone.ꢀ Reactionꢀ conditions:ꢀ
obviousꢀ aggregationsꢀ comparedꢀ withꢀ theꢀ freshꢀ catalyst.ꢀ XPSꢀ cyclohexanone,ꢀ 20ꢀ mmol;ꢀ TMSCN,ꢀ 40ꢀ mmol;ꢀ niobiumꢀ phytic,ꢀ
examinationsꢀshowedꢀthatꢀtheꢀconcentrationsꢀofꢀNb,ꢀP,ꢀCꢀandꢀ 0.1ꢀg;ꢀCH Cl ,ꢀ4ꢀg,ꢀreactionꢀtime,ꢀ15ꢀmin;ꢀreactionꢀtemperature,ꢀ
2
2
Oꢀonꢀtheꢀsurfaceꢀofꢀfreshꢀandꢀusedꢀniobiumꢀphyticꢀwereꢀnotꢀ roomꢀtemperature.ꢀ
nearlyꢀchangedꢀ(TableꢀS1)ꢀafterꢀfiveꢀcatalyticꢀrecycles.ꢀFurther,ꢀ
theꢀthermogravimetricꢀanalysisꢀinꢀthisꢀworkꢀindicatedꢀthatꢀtheꢀ
decompositionꢀ temperatureꢀ ofꢀ theꢀ as-preparedꢀ catalystꢀ wasꢀ
ꢀ
o
aboutꢀ 300 Cꢀ (Fig.ꢀ S4),ꢀ whichꢀ wasꢀ muchꢀ higherꢀ thanꢀ theꢀ
reactionꢀ temperature.ꢀ Theꢀ aboveꢀ examinationsꢀ provedꢀ thatꢀ
niobiumꢀ phyticꢀ wasꢀ stableꢀ inꢀ theꢀ catalyticꢀ processꢀ andꢀ itsꢀ
propertiesꢀwereꢀnotꢀchangedꢀnoticeablyꢀafterꢀused.ꢀ
Tableꢀ1.ꢀCyanosilylationꢀreactionꢀofꢀcarbonylꢀcompoundsꢀusingꢀ
a
TMSCN. ꢀ
O
TMSO CN
Catalyst
rt, CH Cl
+
TMSCN
2
2
R
2
R
1
R
2
R
1
ꢀ
Reactionꢀ
timeꢀ(min)ꢀ
Yieldꢀ
(%) ꢀ
Entryꢀ
Reactantꢀ
Catalystꢀ
Noneꢀ
b
O
1
2
ꢀ
ꢀ
20ꢀ
0ꢀ
ꢀ
O
Fig.ꢀ6.ꢀTheꢀcharacterizationꢀofꢀniobiumꢀphyticꢀafterꢀreusedꢀfiveꢀ
times.ꢀFT-IRꢀspectrumꢀ(a),ꢀXRDꢀpatternꢀ(b),ꢀSEMꢀimageꢀ(c),ꢀandꢀ
TEMꢀimageꢀ(d).ꢀ
Niobiumꢀphyticꢀ
20ꢀ
98ꢀ
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ca Pt al el ya ss ies ꢀ dSo cꢀ ni eo nt ꢀca ed j&u sTt ꢀemc ah rng oi nl os ꢀg y
Page 4 of 8
ARTICLEꢀ
JournalꢀNameꢀ
Niobiumꢀphyticꢀ
Weꢀ alsoꢀ usedꢀ theꢀ niobiumꢀ phyticꢀ asꢀ anꢀ acidicꢀ
View Article Online
DOI: 10.1039/C5CY01123J
Fructoseꢀ
1ꢀ
97.8ꢀ
74.3ꢀ
5
ꢀ
d
heterogeneousꢀ catalystꢀ forꢀ dehydrationꢀ ofꢀ carbohydratesꢀ toꢀ
formꢀ HMFꢀ inꢀ theꢀ ionicꢀ liquidꢀ 1-butyl-3-methylimidazoliumꢀ
chlorideꢀ ([Bmim]Cl),ꢀ whichꢀ isꢀ aꢀ veryꢀ importantꢀ reactionꢀ forꢀ
(5th) ꢀ
Inulinꢀ
Niobiumꢀphyticꢀ
Niobiumꢀphyticꢀ
3ꢀ
3ꢀ
100ꢀ
100ꢀ
56.4(±2.9)ꢀ
45.4(±3.5)ꢀ
6
7
ꢀ
ꢀ
Sucroseꢀ
18
biomassꢀ conversion. ꢀ Weꢀ conductedꢀ theꢀ reactionꢀ usingꢀ theꢀ
synthesizedꢀ niobiumꢀ phytic,ꢀ NbCl5,ꢀ andꢀ commercialꢀ Nb2O5ꢀ asꢀ
theꢀcatalystsꢀatꢀtheꢀsameꢀreactionꢀconditions,ꢀandꢀtheꢀresultsꢀ
areꢀ shownꢀ inꢀ Tableꢀ 2.ꢀ Althoughꢀ theꢀ dehydrationꢀ ofꢀ fructoseꢀ
couldꢀbeꢀproceededꢀwithoutꢀcatalystsꢀinꢀ[Bmim]Cl,ꢀtheꢀyieldꢀofꢀ
HMFꢀ wasꢀ veryꢀ lowꢀ (Entryꢀ 1,ꢀ Tableꢀ 2),ꢀ indicatingꢀ thatꢀ theꢀ
catalystꢀwasꢀnecessaryꢀtoꢀachieveꢀhighꢀreactionꢀactivity.ꢀItꢀwasꢀ
foundꢀ thatꢀ niobiumꢀ phyticꢀ showedꢀ theꢀ highestꢀ HMFꢀ yieldꢀ
a
Reactionꢀ conditions:ꢀ reactantꢀ 0.1ꢀ g;ꢀ catalystꢀ 0.1ꢀ g;ꢀ [Bmim]Clꢀ 1ꢀ g;ꢀ reactionꢀ
o
b
temperatureꢀ100ꢀ C.ꢀ TheꢀyieldsꢀwereꢀdeterminedꢀbyꢀHPLCꢀusingꢀanꢀexternalꢀ
c
d
standardꢀmethod.ꢀ Theꢀdataꢀinꢀparenthesesꢀwasꢀtheꢀerrorꢀbars.ꢀ Theꢀniobiumꢀ
phyticꢀwasꢀresuedꢀforꢀtheꢀfifthꢀtime.ꢀ
ꢀ
Explanationꢀofꢀtheꢀhigherꢀcatalyticꢀactivityꢀofꢀniobiumꢀphyticꢀ
Asꢀdiscussedꢀabove,ꢀniobiumꢀphyticꢀshowedꢀhigherꢀactivityꢀforꢀ
theꢀtwoꢀexaminedꢀreactionsꢀthanꢀNb2O5,ꢀwhichꢀwasꢀinducedꢀbyꢀ
twoꢀ possibleꢀ reasons,ꢀ includingꢀ higherꢀ acidityꢀ andꢀ lowerꢀ
crystallinity.ꢀ Firstly,ꢀ weꢀ determinedꢀ theꢀ localꢀ environmentꢀ ofꢀ
theꢀNbꢀspeciesꢀinꢀniobiumꢀphyticꢀandꢀNb2O5ꢀbyꢀXPSꢀmethodꢀofꢀ
Nbꢀ3d.ꢀAsꢀshownꢀinꢀFig.ꢀ7a,ꢀtheꢀbindingꢀenergyꢀvaluesꢀofꢀNbꢀinꢀ
niobiumꢀphyticꢀcorrespondingꢀtoꢀNbꢀ3d5/2ꢀandꢀNbꢀ3d3/2ꢀwereꢀ
(
87.5%)ꢀ(Entryꢀ2,ꢀTableꢀ2)ꢀwithꢀfullꢀconversionꢀofꢀfructose.ꢀInꢀ
contrast,ꢀ althoughꢀ theꢀ conversionꢀ ofꢀ fructoseꢀ wasꢀ alsoꢀ 100%ꢀ
overꢀNbCl5,ꢀtheꢀyieldꢀofꢀHMFꢀwasꢀonlyꢀ73.6%ꢀ(Entryꢀ3,ꢀTableꢀ2)ꢀ
dueꢀ toꢀ theꢀ sideꢀ reaction.ꢀ Whenꢀ usingꢀ Nb2O5ꢀ asꢀ theꢀ catalyst,ꢀ
longerꢀ reactionꢀ timeꢀ (1.5ꢀ h)ꢀ wasꢀ neededꢀ toꢀ convertꢀ fructoseꢀ
completelyꢀ(Entryꢀ4,ꢀTableꢀ2).ꢀBut,ꢀtheꢀyieldꢀofꢀHMFꢀwasꢀstillꢀ
lowerꢀ thanꢀ theꢀ resultꢀ obtainedꢀ overꢀ niobiumꢀ phyticꢀ becauseꢀ
longerꢀreactionꢀtimeꢀcouldꢀcauseꢀsideꢀreactionsꢀofꢀHMF.ꢀTheseꢀ
resultsꢀ indicatedꢀ thatꢀ niobiumꢀ phyticꢀ wasꢀ theꢀ betterꢀ catalystꢀ
forꢀdehydrationꢀofꢀfructose,ꢀwhichꢀwasꢀcomparableꢀwithꢀmanyꢀ
resultsꢀ reportedꢀ inꢀ theꢀ literaturesꢀ usingꢀ heterogeneousꢀ
2
07.5ꢀ andꢀ 210.2ꢀ eV,ꢀ whichꢀ wereꢀ higherꢀ thanꢀ theꢀ resultsꢀ ofꢀ
Nb2O5ꢀ(207.2ꢀandꢀ209.9ꢀeV).ꢀTheꢀhigherꢀbindingꢀenergyꢀofꢀNbꢀ
dꢀinꢀniobiumꢀphyticꢀcausedꢀbyꢀthatꢀtheꢀformationꢀofꢀP-O-Nbꢀ
bondsꢀinꢀitsꢀstructureꢀcouldꢀresultꢀinꢀaꢀhigherꢀpositiveꢀchargeꢀ
3
19
onꢀNbꢀatoms,ꢀwhichꢀcouldꢀincreaseꢀtheꢀacidityꢀofꢀNb. ꢀFurther,ꢀ
theꢀ acidityꢀ ofꢀ niobiumꢀ phyticꢀ andꢀ commercialꢀ Nb2O5ꢀ wasꢀ
examinedꢀbyꢀNH3-TPDꢀmethod.ꢀAsꢀshownꢀinꢀFig.ꢀ7b,ꢀniobiumꢀ
17
catalystsꢀ inꢀ variousꢀ solvents. ꢀ Recyclableꢀ experimentsꢀ
indicatedꢀthatꢀniobiumꢀphyticꢀcouldꢀalsoꢀbeꢀreusedꢀfiveꢀtimesꢀ
forꢀ theꢀ dehydrationꢀ ofꢀ fructoseꢀ withꢀ aꢀ slightꢀ reductionꢀ inꢀ
catalyticꢀ efficiency.ꢀ Theꢀ slightꢀ decreaseꢀ inꢀ catalyticꢀ activityꢀ
maybeꢀresultedꢀfromꢀtheꢀleachingꢀofꢀNbꢀ(aboutꢀ21ꢀppm)ꢀinꢀtheꢀ
reactionꢀmixturesꢀdueꢀtoꢀtheꢀstrongꢀsolventꢀpowerꢀofꢀ[Bmim]Cl,ꢀ
whichꢀ couldꢀ beꢀ examinedꢀ byꢀ ICPꢀ method.ꢀ Furthermore,ꢀ theꢀ
niobiumꢀphyticꢀcouldꢀalsoꢀbeꢀusedꢀtoꢀcatalyzeꢀtheꢀdehydrationꢀ
ofꢀinulinꢀandꢀsucroseꢀinꢀ[Bmim]ClꢀtoꢀproduceꢀHMF,ꢀandꢀyieldsꢀ
ofꢀ 56.4%ꢀ andꢀ 45.4%ꢀ (Entriesꢀ 5ꢀ andꢀ 6,ꢀ Tableꢀ 2),ꢀ respectively,ꢀ
couldꢀ beꢀ obtainedꢀ withꢀ aꢀ prolongedꢀ reactionꢀ timeꢀ (3ꢀ h).ꢀ
Comparedꢀ withꢀ fructose,ꢀ inulinꢀ andꢀ sucroseꢀ onlyꢀ gaveꢀ
moderateꢀ HMFꢀ yields.ꢀ Thereꢀ wereꢀ twoꢀ reasonsꢀ forꢀ thisꢀ
phenomenon.ꢀ Firstly,ꢀ theꢀ reactionꢀ processꢀ ofꢀ inulinꢀ andꢀ
sucroseꢀ toꢀ produceꢀ HMFꢀ wasꢀ aꢀ two-stepꢀ reactionꢀ involvingꢀ
hydrolysisꢀ andꢀ dehydration,ꢀ whichꢀ couldꢀ increaseꢀ sideꢀ
reactionsꢀandꢀthusꢀloweredꢀtheꢀreactionꢀyield.ꢀSecondly,ꢀthereꢀ
wereꢀglucoseꢀunitsꢀinꢀtheꢀstructureꢀofꢀinulinꢀandꢀsucroseꢀandꢀ
theꢀ niobiumꢀ phyticꢀ showedꢀ noꢀ activityꢀ forꢀ glucose.ꢀ Afterꢀ theꢀ
reaction,ꢀ glucoseꢀ wasꢀ remainedꢀ detectedꢀ byꢀ HPLCꢀ withꢀ aꢀ
refractiveꢀ detectorꢀ (Shimadzuꢀ RID-10A).ꢀ Onlyꢀ fructoseꢀ unitsꢀ
couldꢀ beꢀ convertedꢀ intoꢀ HMFꢀ overꢀ niobiumꢀ phytic,ꢀ andꢀ thusꢀ
HMFꢀyieldꢀwasꢀmoderateꢀwhenꢀinulinꢀandꢀsucroseꢀwereꢀusedꢀ
asꢀtheꢀsubstrates.ꢀ
o
phyticꢀshowedꢀaꢀpeakꢀatꢀaboutꢀ220ꢀ C,ꢀwhichꢀwasꢀrelatedꢀtoꢀ
5+
theꢀ weakꢀ acidꢀ sitesꢀ (mainlyꢀ resultedꢀ fromꢀ Nb ).ꢀ However,ꢀ
commercialꢀNb2O5ꢀshowedꢀnoꢀobviousꢀpeaks.ꢀTheꢀresultsꢀinꢀFig.ꢀ
7
bꢀindicatedꢀthatꢀtheꢀamountꢀofꢀNH3ꢀdesorbedꢀfromꢀniobiumꢀ
phyticꢀ wasꢀ muchꢀ moreꢀ thanꢀ commercialꢀ Nb2O5,ꢀ whichꢀ wasꢀ
consistentꢀwithꢀtheirꢀacidity.ꢀWeꢀalsoꢀconductedꢀtheꢀpyridineꢀ
absorptionꢀ FT-IRꢀ analysisꢀ toꢀ identifyꢀ theꢀ kindꢀ andꢀ numberꢀ ofꢀ
acidꢀ sitesꢀ forꢀ niobiumꢀ phyticꢀ andꢀ Nb2O5ꢀ (Fig.ꢀ 7c).ꢀ Fromꢀ theꢀ
figure,ꢀ weꢀ couldꢀ seeꢀ thatꢀ theꢀ characteristicꢀ ofꢀ Lewisꢀ acidꢀ sitesꢀ atꢀ
-
1
aboutꢀ 1606ꢀ andꢀ 1445ꢀ cm ꢀ wereꢀ observedꢀ inꢀ theꢀ spectraꢀ ofꢀ bothꢀ
20
niobiumꢀ phyticꢀ andꢀ Nb
2 5
O . ꢀ Theꢀ numberꢀ ofꢀ Lewisꢀ acidꢀ sitesꢀ inꢀ
niobiumꢀphyticꢀwasꢀaboutꢀ196ꢀμmol/g,ꢀwhichꢀwasꢀhigherꢀthanꢀthatꢀ
-
1
inꢀ Nb
2 5
O ꢀ (78ꢀ μmol/g).ꢀ Theꢀ bandꢀ atꢀ aboutꢀ 1487ꢀ cm ꢀ isꢀ normallyꢀ
attributedꢀ toꢀ aꢀ combinationꢀ bandꢀ associatedꢀ withꢀ bothꢀ Brønstedꢀ
21
-1
acidꢀandꢀLewisꢀacidꢀsites.
existedꢀ inꢀ theꢀ spectraꢀ ofꢀ niobiumꢀ phytic,ꢀ whichꢀ wasꢀ theꢀ
ꢀMeanwhile,ꢀaꢀbandꢀofꢀaboutꢀ1540ꢀcm ꢀ
2
2
characteristicꢀ ofꢀ Brønstedꢀ acidꢀ site. ꢀ Thisꢀ Brønstedꢀ acidꢀ siteꢀ wasꢀ
resultedꢀfromꢀtheꢀsmallꢀamountꢀofꢀP-OHꢀspeciesꢀofꢀtheꢀphosphateꢀ
2
3
5+
2 5
groups, ꢀ whichꢀ didꢀ notꢀ coordinateꢀ withꢀ Nb .ꢀ Inꢀ contrast,ꢀ Nb O ꢀ
showedꢀ noꢀ characteristicꢀ ofꢀ Brønstedꢀ acidꢀ site.ꢀ Theꢀ Brønstedꢀ acidꢀ
sitesꢀ existedꢀ inꢀ niobiumꢀ phyticꢀ couldꢀ alsoꢀ promoteꢀ theꢀ reactions.ꢀ
However,ꢀ whenꢀ phyticꢀ acidꢀ wasꢀ usedꢀ asꢀ theꢀ catalystꢀ forꢀ theꢀ
cyanosilylationꢀreactionꢀofꢀcyclohexanone,ꢀtheꢀyieldꢀofꢀtheꢀdesiredꢀ
productꢀwasꢀonlyꢀ13%ꢀwithꢀaꢀselectivityꢀofꢀaboutꢀ72%ꢀ(Entryꢀ7,ꢀTableꢀ
a
Tableꢀ2.ꢀDehydrationꢀofꢀcarbohydratesꢀtoꢀproduceꢀHMF. ꢀ
1
).ꢀThisꢀresultꢀindicatedꢀthatꢀtheꢀLewisꢀcenterꢀ(Nb)ꢀwasꢀveryꢀcrucialꢀ
Timeꢀ
Conversionꢀ
Yieldꢀ
Reactantꢀ
Catalystꢀ
Entryꢀ
b,c
(%) ꢀ
forꢀtheꢀhighꢀcatalyticꢀactivityꢀofꢀniobiumꢀphytic.ꢀTherefore,ꢀbasedꢀ
onꢀ theꢀ resultsꢀ obtainedꢀ fromꢀ XPS,ꢀ NH3-TPDꢀ andꢀ pyridineꢀ
absorptionꢀ FT-IRꢀ examinations,ꢀ itꢀ canꢀ beꢀ concludedꢀ thatꢀ theꢀ
acidityꢀ ofꢀ niobiumꢀ phyticꢀ isꢀ muchꢀ strongerꢀ thanꢀ commercialꢀ
Nb2O5.ꢀBecauseꢀtheꢀtwoꢀexaminedꢀreactionsꢀwereꢀbothꢀacid-
catalyzedꢀ reaction,ꢀ theꢀ higherꢀ acidityꢀ ofꢀ niobiumꢀ phyticꢀ wasꢀ
beneficialꢀtoꢀincreaseꢀtheꢀrateꢀofꢀtheꢀtwoꢀreactions.ꢀ
(
h)ꢀ
1ꢀ
(%)ꢀ
Fructoseꢀ
Fructoseꢀ
Fructoseꢀ
Noneꢀ
18.4ꢀ
12.7(±1.3)ꢀ
87.5(±1.9)ꢀ
73.6(±4.5)ꢀ
76.8(±2.6)ꢀ
81.6(±1.7)ꢀ
1
2
3
ꢀ
ꢀ
ꢀ
Niobiumꢀphyticꢀ
1ꢀ
100ꢀ
NbCl
5
ꢀ
1ꢀ
100ꢀ
1
ꢀ
90.5ꢀ
Fructoseꢀ
Nb
2
O
5
ꢀ
4
ꢀ
1
.5ꢀ
100ꢀ
4
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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Page 5 of 8
Ca Pt al el ya ss ies ꢀ dSo cꢀ ni eo nt ꢀca ed j&u sTt ꢀemc ah rng oi nl os ꢀg y
JournalꢀNameꢀ
ꢀARTICLEꢀ
ꢀ
carbohydratesꢀtoꢀproduceꢀHMF,ꢀwhichꢀareꢀbothꢀaVcieidw-AcratictlaelOynzleindeꢀ
DOI: 10.1039/C5CY01123J
reactions.ꢀ Niobiumꢀ phyticꢀ couldꢀ beꢀ easilyꢀ recoveredꢀ andꢀ
reusedꢀ atꢀ leastꢀ fiveꢀ timesꢀ withoutꢀ decreasingꢀ theꢀ reactionꢀ
activityꢀ andꢀ selectivity.ꢀ Furtherꢀ studyꢀ indicatedꢀ thatꢀ niobiumꢀ
phyticꢀhadꢀhigherꢀactivityꢀthanꢀcommercialꢀNb2O5,ꢀwhichꢀcouldꢀ
beꢀ resultedꢀ fromꢀ theꢀ higherꢀ acidityꢀ andꢀ lowerꢀ crystallinityꢀ ofꢀ
niobiumꢀphytic.ꢀTheꢀfindingsꢀinꢀthisꢀworkꢀprovideꢀtheꢀviewꢀofꢀ
designingꢀ newꢀ functionalꢀ catalystꢀ derivedꢀ fromꢀ naturally-
Fig.ꢀ 7.ꢀ XPSꢀ ofꢀ Nbꢀ 3dꢀ (a),ꢀ NH3-TPDꢀ spectraꢀ (b),ꢀ andꢀ pyridineꢀ occurredꢀbuildingꢀblocksꢀforꢀvariousꢀorganicꢀreactions.ꢀ
absorptionꢀFT-IRꢀanalysisꢀ(c)ꢀforꢀniobiumꢀphyticꢀandꢀNb2O5.ꢀ
Lowerꢀ crystallinityꢀ wasꢀ anotherꢀ reasonꢀ forꢀ theꢀ higherꢀ Experimentalꢀ
activityꢀ ofꢀ niobiumꢀ phytic.ꢀ Niobiumꢀ phyticꢀ synthesizedꢀ andꢀ
Materialsꢀ
commercialꢀ Nb2O5ꢀ wereꢀ characterizedꢀ byꢀ XRDꢀ (Fig.ꢀ 8).ꢀ Itꢀ isꢀ
Fructoseꢀ(99%),ꢀsucroseꢀ(99%)ꢀandꢀ1-hexaldehydeꢀ(>95%)ꢀwereꢀ
obviousꢀ thatꢀ theꢀ synthesizedꢀ niobiumꢀ phyticꢀ wasꢀ amorphousꢀ
purchasedꢀ fromꢀ Alfaꢀ Aesar.ꢀ Inulinꢀ (95%),ꢀ Nb2O5ꢀ (99.5%),ꢀ
withꢀ aꢀ veryꢀ lowꢀ crystallinity.ꢀ Inꢀ contrast,ꢀ commercialꢀ Nb2O5ꢀ
niobiumꢀ (V)ꢀ chlorideꢀ (99+%),ꢀ trimethylsilylꢀ cyanideꢀ (TMSCN,ꢀ
showedꢀbetterꢀcrystallinity.ꢀTheꢀlowerꢀcrystallinityꢀofꢀniobiumꢀ
9
7%)ꢀandꢀfurfuralꢀ(98%)ꢀwereꢀprovidedꢀbyꢀJ&KꢀScientificꢀLtd.ꢀ
phyticꢀ couldꢀ beꢀ favourableꢀ forꢀ theꢀ reactantsꢀ toꢀ contactꢀ withꢀ
theꢀ acidꢀ centerꢀ (Nb)ꢀ ofꢀ theꢀ catalyst,ꢀ andꢀ thusꢀ promotedꢀ theꢀ
reactionꢀwithꢀaꢀhigherꢀactivity.ꢀItꢀwasꢀfoundꢀthatꢀanꢀamorphousꢀ
Nb2O5ꢀ(Fig.ꢀ8)ꢀpreparedꢀbyꢀhydrolysisꢀofꢀniobium(V)ꢀethoxide,ꢀ
whichꢀ hadꢀ similarꢀ acidityꢀ withꢀ commercialꢀ Nb2O5ꢀ (Fig.ꢀ S5),ꢀ
showedꢀ betterꢀ catalyticꢀ activityꢀ (Entryꢀ 8,ꢀ Tableꢀ 1)ꢀ forꢀ
cyanosilylationꢀreactionꢀofꢀcyclohexanoneꢀthanꢀtheꢀcommercialꢀ
Nb2O5,ꢀ whichꢀ indicatedꢀ thatꢀ lowerꢀ crystallinityꢀ wasꢀ indeedꢀ
beneficialꢀ toꢀ theꢀ reaction.ꢀ Inꢀ addition,ꢀ asꢀ shownꢀ inꢀ Tableꢀ S2,ꢀ
niobiumꢀ phyticꢀ hadꢀ higherꢀ BETꢀ surfaceꢀ area,ꢀ largerꢀ poreꢀ
diameter,ꢀ andꢀ largerꢀ poreꢀ volumeꢀ thanꢀ commercialꢀ Nb2O5,ꢀ
whichꢀwereꢀalsoꢀhelpfulꢀtoꢀincreaseꢀtheꢀdiffusionꢀofꢀreactantsꢀ
toꢀtheꢀactivityꢀcenterꢀtoꢀpromoteꢀtheꢀreactionsꢀproceed.ꢀLowerꢀ
crystallinityꢀcombinedꢀwithꢀhigherꢀacidityꢀtogetherꢀresultedꢀinꢀ
theꢀhigherꢀcatalyticꢀactivityꢀofꢀniobiumꢀphytic.ꢀ
N,N-Dimethylformamideꢀ (DMF),ꢀ CH2Cl2,ꢀ ethylꢀ ether,ꢀ ethanol,ꢀ
methanolꢀ andꢀ cyclohexanoneꢀ wereꢀ A.ꢀ R.ꢀ gradeꢀ andꢀ wereꢀ
obtainedꢀ fromꢀ Sinopharmꢀ Chemicalꢀ Reagentꢀ Beijingꢀ Co.,ꢀ Ltd.ꢀ
Phyticꢀ acidꢀ withꢀ C.ꢀ P.ꢀ gradeꢀ wasꢀ receivedꢀ fromꢀ Sinopharmꢀ
ChemicalꢀReagentꢀBeijingꢀCo.,ꢀLtd.ꢀHere,ꢀweꢀneededꢀtoꢀpointꢀ
outꢀthatꢀphyticꢀacidꢀshouldꢀbeꢀobtainedꢀfromꢀseedsꢀandꢀgrainsꢀ
8
ofꢀ plants. ꢀ However,ꢀ inꢀ thisꢀ work,ꢀ weꢀ mainlyꢀ focusꢀ onꢀ theꢀ
preparationꢀ ofꢀ functionalꢀ catalystsꢀ usingꢀ phyticꢀ acidꢀ asꢀ theꢀ
buildingꢀ blocksꢀ andꢀ thusꢀ weꢀ purchasedꢀ itꢀ fromꢀ chemicalꢀ
company.ꢀ Theꢀ ionicꢀ liquidꢀ [Bmim]Clꢀ usedꢀ inꢀ theꢀ experimentꢀ
wereꢀpurchasedꢀfromꢀLanzhouꢀGreenchemꢀILs,ꢀLICP,ꢀCAS,ꢀChinaꢀ
(Lanzhou,ꢀChina)ꢀwithꢀaꢀpurityꢀoverꢀ99.9%.ꢀ[Bmim]Clꢀwasꢀdriedꢀ
o
atꢀ80ꢀ Cꢀunderꢀvacuumꢀforꢀ96ꢀhꢀbeforeꢀuse.ꢀꢀ
Synthesisꢀofꢀniobiumꢀphyticꢀ
5+
Niobiumꢀchlorideꢀ(theꢀresourceꢀofꢀNb ,ꢀ22ꢀmmol)ꢀandꢀphyticꢀ
acidꢀ(theꢀligand,ꢀ10ꢀmmol)ꢀwereꢀdissolvedꢀinꢀDMFꢀ(400ꢀmL)ꢀinꢀaꢀ
flaskꢀ ofꢀ 1000ꢀ mL.ꢀ Then,ꢀ triethylamineꢀ (theꢀ deprotonationꢀ
reagent,ꢀ 150ꢀ mmol)ꢀ wasꢀ addedꢀ intoꢀ theꢀ solutionꢀ dropwiselyꢀ
withꢀaꢀtimeꢀofꢀ3ꢀh.ꢀAfterꢀthat,ꢀtheꢀmixtureꢀwasꢀfirstlyꢀstirredꢀforꢀ
5
ꢀ hꢀ atꢀ roomꢀ temperatureꢀ andꢀ thenꢀ agedꢀ underꢀ staticꢀ
o
conditionsꢀatꢀ80ꢀ Cꢀforꢀ6ꢀh.ꢀFinally,ꢀtheꢀwhiteꢀprecipitateꢀwasꢀ
separatedꢀ byꢀ filtration,ꢀ thoroughlyꢀ washedꢀ withꢀ DMFꢀ toꢀ
removeꢀ theꢀ unreactedꢀ NbCl5ꢀ andꢀ phyticꢀ acid.ꢀ Beforeꢀ theꢀ
characterizationꢀ andꢀ utilization,ꢀ theꢀ sampleꢀ wasꢀ washedꢀ byꢀ
o
ethanolꢀatꢀ90ꢀ CꢀthroughꢀSoxhletꢀextractionꢀforꢀ72ꢀhꢀtoꢀremoveꢀ
DMFꢀcompletely.ꢀAfterꢀthat,ꢀtheꢀniobiumꢀphyticꢀwasꢀdriedꢀatꢀ
o
0ꢀ Cꢀunderꢀvacuumꢀforꢀ12ꢀh.ꢀTheꢀyieldꢀofꢀniobiumꢀphyticꢀwasꢀ
8
aboutꢀ89%ꢀ(7.85g).ꢀICPꢀanalysisꢀshowedꢀthatꢀtheꢀNb/Pꢀmolarꢀ
ratioꢀinꢀniobiumꢀphyticꢀwasꢀaboutꢀ1:3.ꢀAnal.ꢀFound:ꢀ21.27%ꢀNb,ꢀ
Fig.ꢀ8.ꢀXRDꢀpatternsꢀofꢀniobiumꢀphytic,ꢀcommercialꢀNb2O5,ꢀandꢀ
amorphousꢀ Nb2O5ꢀ preparedꢀ byꢀ hydrolysisꢀ ofꢀ niobium(V)ꢀ
ethoxide.ꢀ
23.59%ꢀP,ꢀ9.13%ꢀC.ꢀCalcd.ꢀforꢀNb2P6C6O24H8ꢀ(835.77):ꢀ22.23%ꢀ
Nb,ꢀ22.23%ꢀP,ꢀ8.62%ꢀC.ꢀ
Cyanosilylationꢀofꢀcarbonylꢀcompoundsꢀ
Inꢀaꢀtypicalꢀexperiment,ꢀcarbonylꢀcompoundꢀ(2ꢀmmol),ꢀTMSCNꢀ
Conclusionsꢀ
(
4ꢀmmol),ꢀCH2Cl2ꢀ(4ꢀg)ꢀandꢀcatalystꢀ(0.1ꢀg)ꢀwereꢀchargedꢀintoꢀaꢀ
Inꢀsummary,ꢀaꢀfunctionalꢀheterogeneousꢀacidꢀcatalyst,ꢀniobiumꢀ
phytic,ꢀ couldꢀ beꢀ designedꢀ usingꢀ phyticꢀ acidꢀ asꢀ theꢀ buildingꢀ
blockꢀ toꢀ reactꢀ withꢀ NbCl5.ꢀ Itꢀ wasꢀ discoveredꢀ thatꢀ niobiumꢀ
phyticꢀ showedꢀ veryꢀ highꢀ activityꢀ forꢀ bothꢀ cyanosilylationꢀ ofꢀ
carbonylꢀ compoundsꢀ withꢀ TMSCNꢀ andꢀ dehydrationꢀ ofꢀ
flaskꢀofꢀ10ꢀmLꢀequippedꢀwithꢀaꢀmagneticꢀstirrer.ꢀTheꢀreactionꢀ
mixtureꢀ wasꢀ stirredꢀ atꢀ roomꢀ temperatureꢀ withꢀ aꢀ desiredꢀ
reactionꢀtime.ꢀAfterꢀtheꢀreaction,ꢀtheꢀproductsꢀwereꢀanalyzedꢀ
byꢀgasꢀchromatographyꢀ(GC,ꢀAgilentꢀ7890)ꢀusingꢀethylbenzeneꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ5ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ca Pt al el ya ss ies ꢀ dSo cꢀ ni eo nt ꢀca ed j&u sTt ꢀemc ah rng oi nl os ꢀg y
Page 6 of 8
ARTICLEꢀ
JournalꢀNameꢀ
1,ꢀ2564-2575;ꢀ(e)ꢀQ.ꢀZhang,ꢀX.ꢀWang,ꢀZ.ꢀLi,ꢀW.ꢀVWiewuA,ꢀrJti.cꢀlLeiOun,ꢀliHne.ꢀ
9
Wu,ꢀS.ꢀCuiꢀandꢀK.ꢀGuo,ꢀRSCꢀAdv.,ꢀ2014,ꢀ4,ꢀ19710-19715.ꢀ
asꢀtheꢀinternalꢀstandard,ꢀandꢀidentificationꢀofꢀtheꢀproductsꢀwasꢀ
doneꢀbyꢀGC-MSꢀ(ShimadzuꢀQP2010).ꢀInꢀtheꢀexperimentsꢀtoꢀtestꢀ
theꢀreusabilityꢀofꢀniobiumꢀphytic,ꢀtheꢀcatalystꢀwasꢀrecoveredꢀ
byꢀcentrifugation,ꢀwashedꢀusingꢀethanolꢀandꢀethylꢀether.ꢀAfterꢀ
DOI: 10.1039/C5CY01123J
9
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o
dryingꢀunderꢀvacuumꢀatꢀ80ꢀ Cꢀforꢀ12ꢀh,ꢀtheꢀcatalystꢀwasꢀreusedꢀ
forꢀtheꢀnextꢀrunꢀbyꢀaddingꢀnewꢀreactantsꢀandꢀsolvents.ꢀ
1
1
DehydrationꢀofꢀcarbohydratesꢀtoꢀproduceꢀHMFꢀ
Inꢀaꢀtypicalꢀexperiment,ꢀcarbohydrateꢀ(0.1ꢀg),ꢀcatalystꢀ(0.1ꢀg)ꢀ
andꢀ[Bmim]Clꢀ(1ꢀg)ꢀwereꢀchargedꢀintoꢀaꢀflaskꢀofꢀ5ꢀmLꢀequippedꢀ
o
withꢀaꢀmagneticꢀstirrer.ꢀTheꢀmixtureꢀwasꢀstirredꢀatꢀ100ꢀ Cꢀforꢀ
2
009,ꢀ10,ꢀ1261-1266;ꢀ(c)ꢀJ.ꢀS.ꢀChang,ꢀJ.ꢀS.ꢀHwang,ꢀS.ꢀH.ꢀJhung,ꢀ
theꢀ desiredꢀ time.ꢀ Thenꢀ theꢀ mixtureꢀ wasꢀ cooledꢀ toꢀ roomꢀ
temperatureꢀimmediately.ꢀTheꢀamountꢀofꢀHMFꢀwasꢀanalyzedꢀ
byꢀHPLCꢀusingꢀanꢀexternalꢀstandardꢀmethodꢀwithꢀShimadzuꢀLC-
S.ꢀE.ꢀPark,ꢀG.ꢀFereyꢀandꢀA.ꢀK.ꢀCheetham,ꢀAngew.ꢀChem.ꢀInt.ꢀ
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2 (a)ꢀS.ꢀBeck,ꢀA.ꢀR.ꢀBroughꢀandꢀM.ꢀBochmann,ꢀJ.ꢀMol.ꢀCatal.ꢀA:ꢀ
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1
1
1
5Cꢀ pump,ꢀ Shimadzuꢀ UV-Visꢀ SPD-15Cꢀ detectorꢀ atꢀ 282.0ꢀ nm,ꢀ
o
andꢀaꢀSupelcosilꢀLC-18ꢀ5ìmꢀcolumnꢀatꢀ35ꢀ C.ꢀBeforeꢀanalyzed,ꢀ
theꢀreactionꢀmixtureꢀwasꢀdilutedꢀtoꢀ1000ꢀmL.ꢀMethanol/waterꢀ
solutionꢀ(50/50ꢀV/V)ꢀwasꢀusedꢀasꢀtheꢀmobileꢀphaseꢀatꢀaꢀflowꢀ
rateꢀofꢀ0.8ꢀmL/min.ꢀ
7
99.ꢀ
3 (a)ꢀM.ꢀAngeloni,ꢀO.ꢀPiermatti,ꢀF.ꢀPizzoꢀandꢀL.ꢀVaccaro,ꢀEur.ꢀJ.ꢀ
Org.ꢀChem.,ꢀ2014,ꢀ1716-1726;ꢀ(b)ꢀR.ꢀQ.ꢀZeng,ꢀX.ꢀK.ꢀFu,ꢀC.ꢀB.ꢀ
Gong,ꢀY.ꢀSui,ꢀX.ꢀB.ꢀMaꢀandꢀX.ꢀB.ꢀYang,ꢀJ.ꢀMol.ꢀCatal.ꢀA:ꢀChem.,ꢀ
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4 J.ꢀL.ꢀSong,ꢀB.ꢀW.ꢀZhou,ꢀH.ꢀC.ꢀZhou,ꢀL.ꢀQ.ꢀWu,ꢀQ.ꢀL.ꢀMeng,ꢀZ.ꢀM.ꢀ
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Liuꢀ andꢀ B.ꢀ X.ꢀ Han,ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.,ꢀ 2015,ꢀ 54,ꢀ 9399-
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Wang,ꢀCatal.ꢀSci.ꢀTechnol.,ꢀ2012,ꢀ2,ꢀ2485-2491.ꢀ
1
1
1
TheꢀauthorsꢀthankꢀtheꢀBeijingꢀForestryꢀUniversityꢀFundamentalꢀ
Researchꢀ Fundsꢀ forꢀ theꢀ Centralꢀ Universitiesꢀ BLX2014-40ꢀ andꢀ
Nationalꢀ Naturalꢀ Scienceꢀ Foundationꢀ ofꢀ Chinaꢀ (21473252,ꢀ
6 E.ꢀL.ꢀS.ꢀNgee,ꢀY.ꢀGao,ꢀX.ꢀChen,ꢀT.ꢀM.ꢀLee,ꢀZ.ꢀHu,ꢀD.ꢀZhaoꢀandꢀN.ꢀ
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1503016)ꢀforꢀfinancialꢀsupport.ꢀ
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Ca Pt al el ya ss ies ꢀ dSo cꢀ ni eo nt ꢀca ed j&u sTt ꢀemc ah rng oi nl os ꢀg y
JournalꢀNameꢀ
3 A.ꢀS.ꢀRocha,ꢀA.ꢀM.ꢀS.ꢀForrester,ꢀM.ꢀH.ꢀC.ꢀdeꢀlaꢀCruz,ꢀC.ꢀT.ꢀdaꢀ
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ꢀARTICLEꢀ
2
View Article Online
DOI: 10.1039/C5CY01123J
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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Catalysis Science & Technology
Page 8 of 8
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DOI: 10.1039/C5CY01123J
Graphical abstract
Niobium phytic, designed from phytic acid and NbCl
5
, showed high activity for
cyanosilylation of carbonyl compounds and dehydration of carbohydrates.