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SupplementaryInformation

PhosphatemodifiedceriaasaBrønstedacidic/redoxmultifunctionalcatalyst

NicholasC.Nelson,ZhuoranWang,PranjaliNaik,J.SebastiánManzano,MarekPruski,IgorI.Slowing*

USDOEAmesLaboratory,Ames,Iowa50011,UnitedStatesDepartmentofChemistry,IowaStateUniversity,Ames,Iowa50011,UnitedStates

Fig.S1MeasuredP:CemoleratioaftertrimethylphosphatedepositionontoCeO2followedbycalcinationversusthenominalP:Cemoleratio.

Fig.S2STEMimageandcorrespondingEDSelementalmapsforCeO2-0.1POx.STEManalysisofCeO2-0.2POxisexpectedtobesimilar.STEMimagesofCeO2havebeenreportedpreviously.1

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2017

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Fig.S3DRIFTspectraofthematerialswithnopretreatment(i.e.as-synthesized)andnobaselinecorrectioninthe(a)carbonate/phosphateand(b)hydroxylregions.Thebandaround2100cm-1forCeO2hasbeenproposedaseitheranelectrontransitionfromdonorlevelslocatedneartheconductionbandsuchasCe3+oroxygenvacanciesortheforbidden2F5/2à2F7/2electronictransitionofCe3+locatedatsubsurface(orbulk)defectivelatticesites.2-4

Fig.S4XPSspectrainthe(a)O1sspectralregionforCeO2,CeO2-0.1POx,andCeO2-0.2POx.(b)P2pspectralregionforphosphatefunctionalizedmaterials.

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Fig.S531P{1H}CPMASspectraofCeO2-0.1POxandCeO2-0.2POx.Thespectrawereobtainedat9.4TusingvR=18kHz,tCP=2.1ms,vRF(1HCP)=96kHz,vRF(31PCP)=78kHz,vRF(1HSPINAL-64)=96kHzand1024scans.

Fig.S61HDPMASspectrumofCeO2,obtainedat14.1TusingvR=38kHz,vRF(1H90˚)=83.3kHz,trd=3sand16scans.Theprobebackgroundwassubtracted.

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Fig.S71HDPMASHahnechospectraof(a)CeO2-0.1POxand(b)CeO2-0.2POx.Thespectrawereobtainedat9.4TusingvR=18kHz,vRF(1H90˚)=96kHz,trd=7s,64scans/delay,andechodelaysindicatedinthefigure.

100 80 60 40 20 0 -20 -40 -60 -80 -100

111222333444555666777888999111012211332144315541665

echo

dea

ly (µ

s)

d 1H (ppm)

100 80 60 40 20 0 -20 -40 -60 -80 -100

111222333444555666777888999111012211332144315541665

ech

o de

lay

(µ s

)

δ 1H (ppm)

-40-30-20-1001020304050

d 1H (ppm)

-40-30-20-1001020304050

d 1H (ppm)

(a)

(b)

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Fig.S8Comparisonbetween31PDPMAS(black)and31PDQ-filteredDPMAS(red)spectraofCeO2-0.2POxmeasuredat9.4T.The31PDPMASspectrumwasobtainedusingvR=18kHz,vRF(31P90˚)=83.3kHz,vRF(1HSPINAL-64)=100kHz,and128scanswithtrd=6s.31PDQ-filteredDPMASspectrumwasobtainedusingvR=18kHz,vRF(31P90˚)=83.3kHz,vRF(1HSPINAL-64)=100kHz,and2048scanswithtrd=5s.

Fig.S9ExperimentalDQbuild-upcurvesmeasuredat9.4Tfor(a)CeO2-0.1POxand(b)CeO2-0.2POx,usingvR=18kHz,vRF(31P90˚)=83.3kHz,vRF(1HSPINAL-64)=100kHz,and2048scanswithtrd=10sforCeO2-0.1POxandtrd=5sforCeO2-0.2POx.SIMPSONsimulationsoftheDQbuild-upcurvesfor2-spinmodel,without(c)andwith(d)takingintoaccounttheeffectofspin-spinrelaxation(forthemain31PpeakinCeO2-0.2POx,aT2`valueof5.6mswasmeasuredatvR=18kHz).

222 444 666 888 1110 1332 τDQ (µs) =" 222 444 666 888 1110 1332 τDQ (µs) ="

(a) (b)

(c) (d)

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Fig.S10DeconvolutedNH3-TPDprofilesfor(a)CeO2,(b)CeO2-0.1POx,(c)CeO2-0.2POx,whichcorrespondtoNH3integratedvaluesof0.61,0.57,0.68mmolg-1,respectively.Thedeconvolutedpeakswithmaximaaround110°Cand160°C(thetwolowesttemperaturedeconvolutedpeaks)werecommontoallthreematerials.ThisindicatesthatthetypeofadsorbedNH3speciesisthesameforallthreematerialsandthelowdesorptiontemperaturesuggeststheyaremultilayerand/orphysisorbedspecies.Thesepeaksweresubtractedtodeterminethetotalnumberofacidsites.Aftercorrectingforphysisorption,theacidsitedensityforCeO2was2.0μmolm-2.ThisvalueagreeswellwithpriorstudiesusingNH3adsorptionmicrocalorimetry(1.9±0.3μmolm-2).5-8ThesimilaritybetweenthecorrectedCeO2acidsitedensitytotheliteraturevaluesforceriasuggestthiscorrectionmethodisagoodapproximationtothetrueacidsitedensity.Themethodwasextendedtothephosphatefunctionalizedmaterialssincethelowtemperaturedeconvolutedpeaksarecommontoallmaterials.Aftercorrectingforphysisorbed/multilayerNH3theintegratedvaluesforCeO2,CeO2-0.1POx,andCeO2-0.2POxwere0.44,0.41,0.44mmolg-1,respectively.

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Fig.S11RecyclingexperimentsusingCeO2-0.2POxcatalystforthehydrolysisofpropyleneoxide.Conditions:~40mgcatalyst,T=60°C,D2O(1mL),propyleneoxide=~2.4mmol,t=1h.Thecatalyst:substrateratiowasmaintainedat16.7mgmmol-1.

Fig.S12PXRDpatternsofthecatalystsusedforeugenolhydrogenolysisreaction.

TableS1Physicochemicalpropertiesofcatalystsforeugenolhydrogenolysis.

Sample BETSurfaceArea(m2g-1)aCeO2Crystallite

Size(nm)bPdDispersion

(%)cPdLoading(wt.

%)dPd/CeO2 121 7 64 1.0

Pd/CeO2-0.1POx 111 9 7 1.0Pd/CeO2-0.2POx 112 10 9 1.1

aSurfaceareascalculatedusingBETapproximation.bObtainedfromPXRDdatausingScherrerequation.cCalculatedfromH2chemisorptiondata.dLoadingsobtainedfromICPanalysis.

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Fig.S13ProductdistributionforthehydrogenolysisofeugenoloverPd/CeO2,Pd/CeO2-0.1POx,andPd/CeO2-0.2POx.Theerrorbarsrepresentthestandarddeviationfromthreeseparatereactions.Conditions:T=100°C,t=4h,PH2=10bar,Pd:Eugenol=5mol.%,25mLH2O.

TableS2Productdistributionforthehydrogenolysisofeugenoloverthethreecatalysts.a

Reaction

Allylhydrogenation Allyl+aromatichydrogenationAllyl+aromatic+methoxyhydrogenation/lysis

Product

Catalyst

4-propyl-2-methoxyphenolYield(%)

4-propyl-2-methoxycyclohexanolYield(%)

4-propylcyclohexanolYield(%)

Pd/CeO2 16±1 59±4 25±3Pd/CeO2-0.1POx 9.1±2.5 36±3 55±4Pd/CeO2-0.2POx 37±5 27±3 36±3aErrorbarsrepresentthestandarddeviationfromthreeseparatereactions.Conditions:T=100°C,t=4h,PH2=10bar,Pd:Eugenol=5mol.%,25mLH2O.

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Fig.S14CyclohexanolyieldforthehydrogenolysisofguaiacoloverPd/CeO2,Pd/CeO2-0.1POx,andPd/CeO2-0.2POx.Conditions:T=100°C,t=4h,PH2=10bar,Pd:Guaiacol=5mol.%,25mLH2O.

Table S3 Conversion and selectivity data for guaiacol hydrogenolysis over the three catalysts. Reaction

Aromatichydrogenation Aromatic+methoxyhydrogenation/lysis

Reactant Products

Catalyst

Conversion

2-methoxycyclohexanolYield

CyclohexanolYield(%)Pd/CeO2 84 59 25

Pd/CeO2-0.1POx 97 46 50Pd/CeO2-0.2POx 89 53 36

REFERENCES

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