Evaluating the catalytic activity of transition metal dimers for the oxygen reduction reaction

Zhao Liang; Mingming Luo; Mingwei Chen; Chao Liu; S Gouse Peera; Xiaopeng Qi; Juan Liu; U Pramod Kumar; Tongxiang Liang Tongxiang Liang

doi:10.1016/j.jcis.2020.02.034

Evaluating the catalytic activity of transition metal dimers for the oxygen reduction reaction

J Colloid Interface Sci. 2020 May 15:568:54-62. doi: 10.1016/j.jcis.2020.02.034. Epub 2020 Feb 12.

Authors

Zhao Liang¹, Mingming Luo¹, Mingwei Chen¹, Chao Liu², S Gouse Peera³, Xiaopeng Qi¹, Juan Liu⁴, U Pramod Kumar¹, Tongxiang Liang Tongxiang Liang⁵

Affiliations

¹ Engineering Research Center for Hydrogen Energy Materials and Devices, Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China.
² Engineering Research Center for Hydrogen Energy Materials and Devices, Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China; State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China. Electronic address: liuchao198967@126.com.
³ Department of Environmental Science and Engineering, Keimyung University, Daegu 42601, Republic of Korea.
⁴ Department of Mining and Materials Engineering, McGill University, Montreal, QC, H3A 0C5, Canada.
⁵ Engineering Research Center for Hydrogen Energy Materials and Devices, Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China. Electronic address: liang_tx@126.com.

PMID: 32078938
DOI: 10.1016/j.jcis.2020.02.034

Abstract

Various experimental investigation had proved that metal dimers possess excellent oxygen reduction reaction (ORR) activity compared to single metal atom catalysts, due to the synergistic effect exerted by two metal atoms. However, it is still unclear how the electrocatalytic activity is enhanced in a fundamental aspect. In this study, we systematically investigated five 3d transition metals (Fe, Co, Ni, Cu and Zn) by density functional theory (DFT) to explore the ability of metal dimers to catalyze the ORR. It is found that different combinations of different metal atoms have different adsorption strengths to oxygenated intermediates, which helps to screen suitable catalyst materials. The scaling relationship of the free energy of adsorption of oxygen-containing species was calculated for various metal-dimer systems. The classical volcanic diagram is derived, and it is found that the CoZnOH embedded nitrogen-doped graphene (the overpotential is 0.61 V) shows the best catalytic properties, and it is predicted that when the adsorption free energy of OH is equal to 0.95 eV, the optimal overpotential is 0.29 V. Electronic structure calculations show that the pairing of different metal atoms alters the d-band center which in turn change the adsorption properties and hence ORR catalytic performance.

Keywords: Density functional theory; Oxygen reduction reaction; Transition metal dimer; Volcano plot.