资源描述：
《Atom-Pair Catalysts Supported by N-doped Graphene for Nitrogen Reduction Reaction d -band Center Based - Deng et al. - Unknown - Unknow》由会员上传分享，免费在线阅读，更多相关内容在学术论文-天天文库。
SupportingInformationAtom-PairCatalystsSupportedbyN-dopedGrapheneforNitrogenReductionReaction:d-bandCenterBasedDescriptorTingDeng1,ChaoCen1,2,HujunShen2,ShuyiWang1,2,JingdongGuo2,ShaohongCai3,andMingsenDeng2,3*1SchoolofPhysics,GuizhouUniversity,Guiyang,550025,China2GuizhouProvincialKeyLaboratoryofComputationalNano-materialScience,GuizhouEducationUniversity,Guiyang,550018,China3SchoolofInformation,GuizhouUniversityofFinanceandEconomics,Guiyang,550025,China*correspondingauthor:deng@gznc.edu.cn
1(a)(b)Fig.S1.(a)TheoptimizedgeometrystructuresofN-dopedgraphene.(b)themeansquaredisplacement(MSD)ofmetalatom-pairwhiletheTM2-N6@Gsystemshadbeenheatedto500KwiththeNosé−Hooverthermostatandthermalizedfor6ps.(c)thetotalenergyofAPCmodelsat15psduringAIMDat500KwithNosé−Hoovermethod.
2Tab.S1.ThevibrationmodesassociatedwithNatomsofN-dopedgrapheneshowninFig.S1(a).No.12345Freq.(meV)158.210577156.901218134.456435132.892987110.380864No.678910Freq.(meV)108.621532100.181010100.15535586.50469784.687839No.1112131415Freq.(meV)76.65575076.43584164.40835764.32256749.888958No.161718Freq.(meV)49.49776024.35249121.108622Fig.S2.TheoptimizedgeometrystructuresofAPCsupportedbyN-dopedgraphene.ThecoordinationmodesofN2andTM2atompairsarerespectivelydenotedas?2―?1:?1(end-on/end-on),?2―?2:?1(side-on/side-on),?2―?2:?2(side-on/side-on),?2―?2(Bridgesite)and?1―?1(Topsite),respectively.
3Tab.S2.CalculatedfreeenergyG∗H,theadsorptionenergiesoftheresultantTM2-N6@G(?ads)withthecohesiveenergyofatom-paircatalysts(?coh),Badercharge(),*NNbondlength(Enzymaticpathway),d-bandcenter(???(0―2)),theadsorptionenergyof*N(∆?∗N)andthefreeenergychangeofN2adsorption(∆?∗N2)(Enzymaticpathway).G∗H(eV)?ads(eV)?coh(eV)?(eV)*NNbondlength(Å)??(0―2)(eV)∆?∗N(eV)∆?∗N2(eV)V2-N6@G-1.16-5.57-0.231.191.240.31-2.37-2.06Mn2-N6@G-0.66-4.24-0.171.221.200.77-1.010.02Fe2-N6@G-0.55-5.30-0.080.991.20-1.13-0.510.21Co2-N6@G-0.65-5.63-0.300.761.18-1.050.050.23Ni2-N6@G0.35-6.07-0.950.74-1.082.11Cu2-N6@G1.05-3.83-0.280.801.16-3.063.450.47Nb2-N6@G-1.34-7.850.831.091.450.28-2.66-2.45Mo2-N6@G-1.27-4.911.460.981.26-0.73-1.95-1.96Tc2-N6@G-1.27-5.441.550.861.21-0.69-2.06-1.29Ru2-N6@G-1.24-5.641.580.721.21-1.30-1.56-0.42Rh2-N6@G-1.05-5.290.780.551.18-1.70-0.16-0.23Pd2-N6@G0.04-3.560.200.56-2.172.55Ag2-N6@G-0.23-1.620.900.611.15-3.703.740.34Ta2-N6@G-1.47-7.071.311.311.280.46-3.60-2.83W2-N6@G-1.64-6.112.291.031.26-0.12-2.17-2.12Re2-N6@G-1.62-5.252.510.911.33-0.45-2.09-1.13Os2-N6@G-1.23-5.852.191.071.24-1.56-1.64-0.26Ir2-N6@G-1.25-6.262.090.751.20-2.07-0.460.16Pt2-N6@G-0.37-5.060.500.58-2.483.67Au2-N6@G-0.23-1.471.570.651.17-5.181.590.07
4Tab.S3.LimitingpotentialofTM2-N6@Gviaenzymaticpathway??(enzy),distalpathway(bridgesite??(Brid)andtopsite??(Top))??(enzy)(V)??(Brid)(V)??(Top)(V)V2-N6@G-1.56Mn2-N6@G-0.77-0.77Fe2-N6@G-0.46-0.89Co2-N6@G-0.77-0.87-1.02Ni2-N6@G-1.66Cu2-N6@G-1.34-1.97Nb2-N6@G-1.05Mo2-N6@G-0.90-1.63Tc2-N6@G-0.91-1.44Ru2-N6@G-0.36-1.30-1.30Rh2-N6@G-0.88-0.92-0.89Pd2-N6@G-1.55Ag2-N6@G-1.58-1.85-2.00Ta2-N6@G-1.21W2-N6@G-1.33Re2-N6@G-0.82-1.49Os2-N6@G-0.50-1.42Ir2-N6@G-0.53-0.64-1.04Pt2-N6@G-1.58Au2-N6@G-0.78-0.85
5Fig.S3Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonFe2-N6@Gviatheenzymaticanddistalpathway.Fig.S4Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonRu2-N6@Gviatheenzymaticanddistalpathway.
6Fig.S5Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonRh2-N6@Gviatheenzymaticanddistalpathway.Fig.S6Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonOs2-N6@Gviatheenzymaticanddistalpathway.
7Fig.S7Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonIr2-N6@Gviatheenzymaticanddistalpathway.Fig.S8Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonMn2-N6@Gviatheenzymaticanddistalpathway.
8Fig.S9Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonCo2-N6@Gviatheenzymaticanddistalpathway.Fig.S10Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonCu2-N6@Gviatheenzymaticanddistalpathway.
9Fig.S11Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonMo2-N6@Gviatheenzymaticanddistalpathway.Fig.S12Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonTc2-N6@Gviatheenzymaticanddistalpathway.
10Fig.S13Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonAg2-N6@Gviatheenzymaticanddistalpathway.Fig.S14Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonRe2-N6@Gviatheenzymaticanddistalpathway.
11Fig.S15Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonAu2-N6@Gviatheenzymaticanddistalpathway.Fig.S16Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonV2-N6@Gviatheenzymaticpathway.
12Fig.S17Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonNi2-N6@Gviathedistalpathway.Fig.S18Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonNb2-N6@Gviatheenzymaticpathway.
13Fig.S19Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonPd2-N6@Gviathedistalpathway.Fig.S20Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonTa2-N6@Gviatheenzymaticpathway.
14Fig.S21Optimizedgeometricstructuresofvariousintermediates(upperpart)andfreeenergydiagrams(lowerpart)forNRRonW2-N6@Gviatheenzymaticpathway.Fig.S22Thecorrelationbetweenthechangeoffreeenergyofproton-coupledelectrontransfer(PCET)step∆?(∗NH2∗NH3→∗NH3+NH3(g))with(a)d-bandbasedcenter??(0,2)and(b)theadsorptionenergyof*N?∗N.Thecorrelationbetweenthechangeoffreeenergyofproton-coupledelectrontransfer(PCET)step∆?(∗+N(g)+H++?―→∗NNH)with(c)d-bandbasedcenter??(0,2)and(d)the2adsorptionenergyof*N?∗N.
15Fig.S23ThevolcanicdiagramoflimitingpotentialandtheN2H*adsorptionenergy.
