Screening of catalytic oxygen reduction reaction activity of 2, 9-dihalo-1, 10-phenanthroline metal complexes: The role of transition metals and halogen substitution

Yizhen Zhang; Xin Chen; Hui Zhang; Xingbo Ge

doi:10.1016/j.jcis.2021.11.148

Screening of catalytic oxygen reduction reaction activity of 2, 9-dihalo-1, 10-phenanthroline metal complexes: The role of transition metals and halogen substitution

J Colloid Interface Sci. 2022 Mar:609:130-138. doi: 10.1016/j.jcis.2021.11.148. Epub 2021 Nov 26.

Authors

Yizhen Zhang¹, Xin Chen², Hui Zhang¹, Xingbo Ge¹

Affiliations

¹ Center for Computational Chemistry and Molecular Simulation, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu, 610500, PR. China.
² Center for Computational Chemistry and Molecular Simulation, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu, 610500, PR. China; State Key Laboratory of Oil & Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, PR. China; Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu, 610500, PR. China. Electronic address: chenxin830107@pku.edu.cn.

PMID: 34894547
DOI: 10.1016/j.jcis.2021.11.148

Abstract

The sluggish kinetics of oxygen reduction reaction (ORR) restricts the employment of fuel cells, it is urgent to design ORR catalysts with excellent performance. The ORR performances of 2, 9-dihalo-1, 10-phenanthroline metal complexes (named as TM-X, X = Cl, Br, I) are comprehensively studied by the density functional theory methods. From the stability point of view, chlorine is more suitable for substitution. The adsorption free energy reveals that the liner relationship between adsorption free energy of *OOH and *OH is changed positively by the steric hindrance caused by the orthogonal TM-X structures. The Ni-Br stands out with the lowest overpotential of 0.34 V, and many other TM-X also show the promising ORR activity. Combining with the analysis of the Gibbs free energy diagrams and d-band center results, the substitution of halogen can improve the electronic structures of TM-X, thus enhancing their ORR activities and changing the ORR mechanism possibly.

Keywords: Density functional theory; Halogen substitution; Oxygen reduction reaction; Transition metal.