How Nitrogen Doping Affects Hydrogen Spillover on Carbon-Supported Pd Nanoparticles New Insights from DFT H ¨ uckel calculations - War

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HowNitrogenDopingAectsHydrogenSpilloveronCarbon-SupportedPdNanoparticles:NewInsightsfromDFTLisaWarczinskiandChristofH•attigRuhr-UniversityBochum,Universit•atsstrae150,44780Bochum,GermanyE-mail:lisa.warczinski@rub.deH•uckelcalculationsFortheH•uckelcalculationsweusedtwosetsofparameterstoaccountforthetwotypesofNatoms:•pyridinicnitrogens,N1:N1C=1:00CCandN1=+0:50•graphiticnitrogens,N2:N2C=0:89CCandN2=+1:37whereistheatomicorbitalenergyofCatomsandarethereducedresonanceintegralsbetweentwoCatoms.S1

1120100ade80c-160bm40E(DFT)/kJmol20p0o-2000.10.20.30.40.5E(HMO)/|β|FigureS1:CorrelationbetweentheDFTandH•uckelbindingenergiesforspilloverhydrogenforthedierentpositionswithrespecttographiticN(cmp.Table1ofthemaintext).Thedashedlineshowstheresultofaleastsquaretof
E(DFT)=c+
E(HMO)thatresultedinc=8:6kJmol1and=179:8kJmol1.S2

2FigureS2:SketchofH•uckelorbitals:(a)onespilloverhydrogenconnectedtoonecarbonatomofthegraphenesheet;(b)onespilloverhydrogenconnectedtoonecarbonatomdirectlynexttoagraphiticNatom.S3

3StabilitywithrespecttoDFTfunctionalandbasissetTableS1:ComparisonofactivationenergiesforthehydrogenspilloverfromPd21ontodif-ferentsupportmaterialsonthebasisofTPSS/def2-SVPgeometries.TPSS/PBE/TPSS/modelsystemdef2-SVPdef2-SVPdef2-TZVPPd21ongraphenesupport;trianglesite130.8130.7127.5Pd21ongraphiticNsupport;bridgesite46.845.546.3TableS2:ComparisonofactivationenergiesforspilloverhydrogendiusionondierentsupportmaterialsonthebasisofTPSS/def2-SVPgeometries.TPSS/PBE/TPSS/pathwaydef2-SVPdef2-SVPdef2-TZVPa105.094.3106.6b121.5114.5120.1TableS3:ComparisonofactivationenergiesforthechangefromthechemisorbedtothephysisorbedstateonthebasisofTPSS/def2-SVPgeometries.TPSS/PBE/TPSS/modelsystemdef2-SVPdef2-SVPdef2-TZVPpuregraphenesupport68.576.666.5graphiticNsupport107.6114.0106.5S4

4ElectrondensitydierencesFigureS3:ElectrondensitydierenceplotsforspilloverhydrogenonthegraphiticNsupportmaterial:(a)twographiticNatoms;(b)sixgraphiticNatoms.Densitygainiscoloredingreen;densitylossiscoloredingrey.(isosurfacevalues:0.0025)S5

5SpindensityFigureS4:Plotofthespindensityforspilloverhydrogeninthephysisorptionminimum.(isosurfacevalues:0.0002)S6

6AdditionalreactionpathwaysFigureS5:ReactionpathwayforspilloverhydrogendiusionviatheGrotthusmechanism.TableS4:EnergiesandfreeactivationenthalpydierencesforspilloverhydrogendiusionviatheGrotthusmechanism.
E/kJmol-1
G/kJmol-1React.-TS1+66.2+77.7TS1-Min.-6.1-1.4Min.-TS2+5.9+0.4TS2-Prod.-59.9-73.4S7

7FigureS6:Hydrogendesorptionpathwayonthepuregraphenesupport.FigureS7:HydrogendesorptionpathwaynexttoagraphiticNatom.S8

8FigureS8:HydrogendesorptionpathwaynexttoapyridinicNatom.DierentenergycontributionsTableS5:Dierentenergycontributionstothebindingenergyofhydrogenoncarboninthephysisorptionminimum.ThedispersioncontributionhasbeentakenastheD3correctionthatisincludedinthetotalDFT-D3bindingenergies(attheDFT-D3geometries).E/kJmol-1totalbindingenergy-10.2ZPVEcorrection+4.5Dispersioncorrection-9.0S9