Regulating the coordination environment of single-atom catalysts for electrocatalytic CO2 reduction

Song Lu; Fengliu Lou; Yafei Zhao; Zhixin Yu

doi:10.1016/j.jcis.2023.05.064

Regulating the coordination environment of single-atom catalysts for electrocatalytic CO₂ reduction

J Colloid Interface Sci. 2023 Sep 15:646:301-310. doi: 10.1016/j.jcis.2023.05.064. Epub 2023 May 13.

Authors

Song Lu¹, Fengliu Lou², Yafei Zhao³, Zhixin Yu⁴

Affiliations

¹ Department of Energy and Petroleum Engineering, University of Stavanger, 4036 Stavanger, Norway.
² Beyonder AS, 4033 Stavanger, Norway.
³ School of Physics and Engineering, Henan University of Science and Technology, Luoyang 471023, China. Electronic address: zhaoyafei@haust.edu.cn.
⁴ Department of Energy and Petroleum Engineering, University of Stavanger, 4036 Stavanger, Norway; Institute of New Energy, School of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing 312000, China. Electronic address: zhixin.yu@uis.no.

PMID: 37201458
DOI: 10.1016/j.jcis.2023.05.064

Abstract

Electrochemical CO₂ reduction (ECR) through single-atom catalysts (SACs) consisting of transition metals (TMs) anchored on nitrogenated carbon (TM-N-C) has shown promise for carbon neutralization. However, high overpotentials and low selectivity are still issues. Regulating the coordination environment of anchored TM atom is important to address these problems. In this study, we evaluated nonmetal atom (NM = B, O, F, Si, P, S, Cl, As and Se) modified TM (TM = Fe, Co, Ni, Cu and Zn)@N₄-C catalysts for their ECR to CO performance using density functional theory (DFT) calculations. NM dopants can induce active center distortion and tune electron structure, promoting intermediate formation. Doping heteroatoms can improve ECR to CO activity on Ni and Cu@N₄ but worsen it on Co@N₄ catalysts. Fe@N₄-F₁(I), Ni@N₃-B₁, Cu@N₄-O₁(III), and Zn@N₄-Cl₁(II) have excellent activity for ECR to CO, with overpotentials of 0.75, 0.49, 0.43, and 0.15 V, respectively, and improved selectivity. The catalytic performance is related to the intermediate binding strength, as evidenced by d band center, charge density difference, crystal orbital Hamilton population (COHP), and integrated COHP (ICOHP). It is expected that our work can be used as the design principle to guide the synthesis of the high-performance heteroatoms modified SACs for ECR to CO.

Keywords: DFT calculations; Electrochemical CO(2) reduction; Heteroatom doping; Single-atom catalysts.