Density Functional Theory Study of the Oxygen Reduction Reaction Mechanism on Graphene Doped with Nitrogen and a Transition Metal

Kirill Yurievich Vinogradov; Anzhela Vladimirovna Bulanova; Roman Vladimirovich Shafigulin; Elena Olegovna Tokranova; Alexander Moiseevich Mebel; Hong Zhu

doi:10.1021/acsomega.1c06768

Density Functional Theory Study of the Oxygen Reduction Reaction Mechanism on Graphene Doped with Nitrogen and a Transition Metal

ACS Omega. 2022 Feb 17;7(8):7066-7073. doi: 10.1021/acsomega.1c06768. eCollection 2022 Mar 1.

Authors

Kirill Yurievich Vinogradov¹, Anzhela Vladimirovna Bulanova¹, Roman Vladimirovich Shafigulin¹, Elena Olegovna Tokranova¹, Alexander Moiseevich Mebel^{1

2}, Hong Zhu³

Affiliations

¹ Samara University, Samara 443086, Russia.
² Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, United States.
³ State Key Laboratory of Chemical Resource Engineering, Institute of Modern Catalysis, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, P.R. China.

Abstract

The active centers of carbon nonplatinum catalysts doped with cobalt, iron, nickel, and copper have been simulated by quantum-chemical density functional theory methods. The thermodynamics of the electrochemical oxygen reduction reaction (ORR) on model catalysts has been determined. It was found that among the studied catalysts, graphene doped with cobalt and iron showed the best properties. A two-state reactivity effect has been found on a cobalt-containing catalyst, and a more detailed reaction mechanism has been proposed, including the stages of charging by an extra electron and association with water. The proposed mechanism explains several effects that have arisen during the modeling in relation to the classical mechanism.