In this research,we present a comprehensive investigation on the catalyst screening,reaction mechanism,and electrocatalytic properties of two-dimensional monoatomic metalloporphyrinoid(MPor)materials for the oxygen re...In this research,we present a comprehensive investigation on the catalyst screening,reaction mechanism,and electrocatalytic properties of two-dimensional monoatomic metalloporphyrinoid(MPor)materials for the oxygen reduction reaction(ORR).Through a combination of high-throughput screening,first-principles DFT calculations,and molecular dynamics simulations,we uncovered some promising oxygen reduction catalysts with limiting potentials of 0.60,0.57,0.56 V under acidic medium,and-0.17,-0.20,-0.21 V under basic medium for M=Co,Fe,Mn,respectively.Full reaction pathway search demonstrates that Co Por is a special case with 2e^(–)and 4e^(–)paths under both acidic and basic media,and for Fe Por and Mn Por,only 4e^(–)path is viable.In-depth analyses indicate that the adsorption free energy of OH and limiting potential shows the volcano curve relationship,which can guide the design and optimization of the ORR catalysts.The crystal orbital Hamiltonian population(COHP)between M and O in O_(2)-MPor can well explain why only Co Por has a 2e^(–)path,while other metals do not,because the Co–O bond is much weaker compared to other M–O bonds.Our research will shed some insights on designing efficient ORR catalysts,and stimulate the experimental efforts in this direction.展开更多
基金financially supported by the National Key Research and Development Program of China(No.2021YFA1600800)the National Natural Science Foundation of China(Nos.22073033,21873032,21673087,and 21903032)+3 种基金the startup fund(Nos.2006013118 and 3004013105)from Huazhong University of Science and Technologythe Fundamental Research Funds for the Central Universities(No.2019kfy RCPY116)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(No.B21003)support from the Guangdong Basic and Applied Basic Research Foundation(No.2021A1515010382)。
文摘In this research,we present a comprehensive investigation on the catalyst screening,reaction mechanism,and electrocatalytic properties of two-dimensional monoatomic metalloporphyrinoid(MPor)materials for the oxygen reduction reaction(ORR).Through a combination of high-throughput screening,first-principles DFT calculations,and molecular dynamics simulations,we uncovered some promising oxygen reduction catalysts with limiting potentials of 0.60,0.57,0.56 V under acidic medium,and-0.17,-0.20,-0.21 V under basic medium for M=Co,Fe,Mn,respectively.Full reaction pathway search demonstrates that Co Por is a special case with 2e^(–)and 4e^(–)paths under both acidic and basic media,and for Fe Por and Mn Por,only 4e^(–)path is viable.In-depth analyses indicate that the adsorption free energy of OH and limiting potential shows the volcano curve relationship,which can guide the design and optimization of the ORR catalysts.The crystal orbital Hamiltonian population(COHP)between M and O in O_(2)-MPor can well explain why only Co Por has a 2e^(–)path,while other metals do not,because the Co–O bond is much weaker compared to other M–O bonds.Our research will shed some insights on designing efficient ORR catalysts,and stimulate the experimental efforts in this direction.
