The non-noble Mn coordinated N,P co-doping graphene materials were investigated theoretically in this work based on density functional theory calculation.The electronic structure is effectively tuned after the introdu...The non-noble Mn coordinated N,P co-doping graphene materials were investigated theoretically in this work based on density functional theory calculation.The electronic structure is effectively tuned after the introduction of P heteroatom.The moderate d band center and density of states at Fermi energy of MnN_(4)-P1-G indicate that it is ofmodest adsorption ability for these O-containing intermediates.The rank of adsorption energies ofO-containing intermediates for MnN_(4)-P1-G is OH*>2OH*>OOH*>O*>O2*>H2O*,whereas the MnN_(4)-P1-G favors a four-electron process instead of two-electron process.The doping of P on MnN_(4)-P1-G can increase the kinetic activity for the rate-determining step as well as the Ulim for MnN_(4)-P1-G significantly increases from 0.38 to 0.45 V compared with MnN_(4)-G.The spin density and magnetic moments of Mn are effectively tuned by d,p hybridization to lower the adsorption energy ofOHintermediates(rate-determining step[RDS])so as to improve the catalytic activity.It is concluded that the P-doped MnN_(4)catalysts with excellent oxygen reduction reaction activity can be obtained and this study can provide theoretical guidance for the rational design of high-performanceMn-based carbonmaterials catalysts.展开更多
基金State Key Laboratory of UrbanWater Resource and Environment,Harbin Institute of Technology,China,Grant/Award Number:2021TS07。
文摘The non-noble Mn coordinated N,P co-doping graphene materials were investigated theoretically in this work based on density functional theory calculation.The electronic structure is effectively tuned after the introduction of P heteroatom.The moderate d band center and density of states at Fermi energy of MnN_(4)-P1-G indicate that it is ofmodest adsorption ability for these O-containing intermediates.The rank of adsorption energies ofO-containing intermediates for MnN_(4)-P1-G is OH*>2OH*>OOH*>O*>O2*>H2O*,whereas the MnN_(4)-P1-G favors a four-electron process instead of two-electron process.The doping of P on MnN_(4)-P1-G can increase the kinetic activity for the rate-determining step as well as the Ulim for MnN_(4)-P1-G significantly increases from 0.38 to 0.45 V compared with MnN_(4)-G.The spin density and magnetic moments of Mn are effectively tuned by d,p hybridization to lower the adsorption energy ofOHintermediates(rate-determining step[RDS])so as to improve the catalytic activity.It is concluded that the P-doped MnN_(4)catalysts with excellent oxygen reduction reaction activity can be obtained and this study can provide theoretical guidance for the rational design of high-performanceMn-based carbonmaterials catalysts.
