HER 计算!俞书宏 Mo2C@ N-C for HER 计算参考 001

SupplementaryInformationfor:Mo2Cnanoparticlesembeddedwithinbacterialcellulose-derived3DN-dopedcarbonnanofibernetworksforefficienthydrogenevolutionZhen-YuWu1,3,Bi-ChengHu1,3,PingWu2,3,Hai-WeiLiang1,Zhi-LongYu1,YueLin1,Ya-RongZheng1,ZhenyuLi2*,andShu-HongYu1*1DivisionofNanomaterials&Chemistry,HefeiNationalLaboratoryforPhysicalSciencesattheMicroscale,CollaborativeInnovationCenterofSuzhouNanoScienceandTechnology,DepartmentofChemistry,CASCenterforExcellenceinNanoscience,HefeiScienceCenterofCAS,UniversityofScienceandTechnologyofChina,Hefei230026,China.2HefeiNationalLaboratoryforPhysicalSciencesattheMicroscale,SynergeticInnovationCenterofQuantumInformationandQuantumPhysics,UniversityofScienceandTechnologyofChina,Hefei230026,China.3Theseauthorscontributedequallytothiswork.Correspondence:ProfessorS-HYu,DivisionofNanomaterials&Chemistry,HefeiNationalLaboratoryforPhysicalSciencesattheMicroscale,DepartmentofChemistry,UniversityofScienceandTechnologyofChina,Hefei230026,China.Email:shyu@orProfessorZ.Y.Li,HefeiNationalLaboratoryforPhysicalSciencesattheMicroscale,SynergeticInnovationCenterofQuantumInformationandQuantumPhysics,UniversityofScienceandTechnologyofChina,Hefei,230026,China.Email:zyli@FigureS1.ThesimulatedmodelsintheDFTcalculationsandtheH*adsorptionsitesonthesurfaceofthesemodels.(a)CNFs,(b)N-CNFs,(c)Mo2C,(d)Mo2C@CNFs,and(e)Mo2C@N-CNFs.FigureS2.XRDpatternsofvariousMo2C@N-CNFssamplesobtainedatdifferentconcentrationsof724solution.(NH4)6MoOFigureS3.ThecrystalstructureofhexagonalMo2C.FigureS4.(a)ElectrocatalyticHERperformanceofvariousMo2C@N-CNFssamplesobtainedatdifferent724solution.(b)NyquistplotsofvariousMoC@N-CNFssamplescollectedatconcentrationsof(NH4)6MoO2180mVoverpotentials.FigureS5.(a)Ramanspectrumand(b)TGAcurveofMo2C@N-CNFscatalyst,indicatingthepresenceofcarbonmaterialinMo2C@N-CNFs.IntheTGAcurve,theinitialweightgainbelow350oCisattributedtothegradualoxidationofMo2CtoMoO3,followedbyasignificantweightlosscausedbythecombustionofN-CNFs.1WhenMo2C@N-CNFsisheatedto700oC,itistransformedtoMoO3.2Therefore,theMo2Ccontentisestimatedtobe50.6wt.%inMo2C@N-CNFsbasedonthefollowingequation:m(Mo2C)=71.4wt.%*M(Mo2C)/2M(MoO3)=71.4wt.%*204/288=50.6wt.%,andtheN-CNFscontentis49.4wt.%.FigureS6.XPSspectraofMo2C@N-CNFselectrocatalyst.(a)SurveyXPSspectrum,high-resolution(b)N1s,(c)C1s,and(d)Mo3dspectra.FigureS7.ThemagnifiedSAEDpatternofMo2C@N-CNFselectrocatalyst.TheredcirclesarethepolycrystallineringsofMo2C,andthegreencirclescorrespondtothepolycrystallineringsofcarbon.FigureS8.(a)Nitrogensorptionisothermsand(b)poresizedistributionofMo2C@N-CNFselectrocatalyst.FigureS9.ThepolarizationcurvesofMo2C@N-CNFselectrocatalystwithdifferentloadingamounts.FigureS10.CVfor(a)Mo2C@N-CNFsand(b)Pt/Celectrocatalystsatdifferentscanratesfrom5to100mVs-1,respectively.(c)Thecapacitivecurrentsat0.22Vvs.RHEasafunctionofscanrateforMo2C@N-CNFsandPt/C.FigureS11.CalculatedexchangecurrentdensityforMo2C@N-CNFsin0.5MH2SO4.FigureS12.(a)EquivalentcircuitusedforfittingtheNyquistplotsinFigure3c.(b)Dependenceofthecharge-transferresistance(Rct)ontheoverpotential.(c)Plotsofoverpotentialvs.logRct-1forMo2C@N-CNFs.FigureS13.(a,b)TEMimages,(c)HRTEMimage,andSAEDpatternofMo2C@N-CNFselectrocatalystafter2000CVcyclesin0.5MH2SO4solution.FigureS14.(a)TEMimage,and(b)correspondingelementmappingsofMo2C@N-CNFselectrocatalystafter2000CVcyclesin0.5MH2SO4solution.FigureS15.(a)Polarizationcurvesand(b)TafelcurvesofMo2C@N-CNFsin1MKOHsolution(pH14).(c)Polarizationcurvesand(d)TafelcurvesofMo2C@N-CNFsin0.1MPBSsolution(pH7).Theloadingamountofthecatalystsis0.255mgcm-2.FigureS16.StabilitytestsforMo2C@N-CNFsbyCVscanningfor2000cyclesin(a)1MKOHsolutionand(b)0.1MPBSsolution.TableS1.Thelatticeparametersofthesupercellforallthemodels.Modelsa(Å)7.38b(Å)7.38c(Å)12GrapheneN-dopedGrapheneMo2C(001)12.306.0712.306.071225Mo2C(001)@Graphene12.30Mo2C(001)@N-doped12.30Graphene12.3012.302525TableS2.TheΔE(H*),EZPE(H*),ΔEZPEandΔG(H*)valuesoftheH*adsorbedonthegivensurfaces.ΔEH*(eV)EZPE(H*)(eV)ΔEZPE(eV)ModelsAdsorptionSiteΔG(H*)(eV)CGraphene1.4640.522-1.070.2950.3120.1730.1530.171.822N-dopedGrapheneMo2C(001)0.8970.031-0.834Mo2C(001)@GrapheneMo2C(001)@0.150.3080.3170.1660.1750.5210.54N-0.162C1dopedGrapheneC2C3C4C5-0.05-0.020.1691.040.3150.3170.3080.3340.1730.1750.1660.1920.330.360.541.44TableS3.ComparisonofHERperformanceofMo2C@N-CNFswithvariousnon-preciousHERelectrocatalytsreportedintheliteraturein0.5MH2SO4electrolyte.Loadingdensity(mgcm-2)η@j=10mAcm-2(mVvsRHE)J0(exchangecurrentdensity)(mAcm-2)Ref.porousMoCxnano-octahedronsMo2C/GCSs0.81420.023Nat.Commun.2015,6,65120.36~210~1402100.01250.0013ACSCatal.2014,4,2658J.Am.Chem.Soc.2015,137,110Angew.Chem.Int.Ed.2012,51,12703PDAP-MoCN-CO2Mo2C0.4(pH=1)1.4(1MH2SO4)β-Mo0.06W0.94C/CBβ-Mo2C0.7220Angew.Chem.Int.Ed.2014,53,51310.28(0.1MHClO4)0.35205(1mAcm-2)~4000.017290.00023Angew.Chem.Int.Ed.2014,126,6525.ultrathinWS2nanoflakesFe-WCNAngew.Chem.Int.Ed.2014,53,7860020.282220Angew.Chem.Int.Ed.2013,52,13638J.Am.Chem.Soc.2013,135,19186J.Mater.Chem.A2015,3,8361Angew.Chem.Int.Ed.2014,53,4372Nat.Commun.2015,6,7992Co0.6Mo1.4N2Mo2CnanoparticlesCo-NRCNTs2001982600.010.07CoNx/C133CoNi@NC0.32224Angew.Chem.Int.Ed.2015,54,2100MoSe2/CP2500.000480.18NanoLett.,2013,13,3426Angew.Chem.Int.Ed.2014,53,9577Chem.Mater.2015,27,4281CuPNWs/CufoilFe-dopedβ-Mo2C15.20.28161~290(0.1MHClO4)N,S-3DnanoporousgrapheneCoS2/RGO-CNT280142Angew.Chem.Int.Ed.2015,54,2131Angew.Chem.Int.Ed.2014,53,12594Angew.Chem.Int.Ed.2013,52,13756260.0028WS2/rGO~260CoS2NW1.7±0.3145J.Am.Chem.Soc.2014,136,10053Angew.Chem.Int.Ed.2014,53,13934g-C3N4nanoribbon-GMo2C@N-CNFs0.1432071.020192167Thiswork0.2550.0473TableS4.ComparisonofHERperformanceofMo2C@N-CNFswithvariousnon-preciousHERelectrocatalytsreportedintheliteraturein1MKOHelectrolyte.Loadingdensity(mgcm-2)η@j=10mAcm-2(mVvsRHE)Tafelslope(mVdec-1)Ref.Mo2C1.419054Angew.Chem.Int.Ed.2012,51,12703Nat.Commun.2015,6,6512porousMoCxnano-octahedrons2-cycleNiFeOx/CFP0.815159481.60.1020.86388176~140257Nat.Commun.2015,6,7261J.Mater.Chem.A2015,3,8361E