Theoretical Screening of Highly Efficient Single-Atom Catalysts Based on Covalent Triazine Frameworks for Oxygen Reduction

Xin Chen; Liang Luo; Yizhen Zhang; Xiuyun Zhao

doi:10.1021/acs.langmuir.3c00563

Theoretical Screening of Highly Efficient Single-Atom Catalysts Based on Covalent Triazine Frameworks for Oxygen Reduction

Langmuir. 2023 May 16;39(19):6905-6913. doi: 10.1021/acs.langmuir.3c00563. Epub 2023 May 3.

Authors

Xin Chen^{1

2

3}, Liang Luo¹, Yizhen Zhang¹, Xiuyun Zhao⁴

Affiliations

¹ Center for Computational Chemistry and Molecular Simulation, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China.
² Key Laboratory of Fine Chemical Application Technology of Luzhou, Luzhou 646099, China.
³ State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China.
⁴ Department of Technical Physics, University of Eastern Finland, Kuopio 70211, Finland.

PMID: 37134210
DOI: 10.1021/acs.langmuir.3c00563

Abstract

Covalent triazine frameworks (CTFs) obtained from the trimerization of aromatic nitriles are expected to be the preferred carrier for single-atom catalysts (SACs). Using density functional theory methods, the oxygen reduction reaction (ORR) performance of a series of 3d, 4d, and 5d transition metals supported on the 6N or 9N pore of the CTF system [M-CTF(6N) or M-CTF(9N)] is explored. At first, 32 kinds of M-CTF(6N) and M-CTF(9N) are screened out with high thermodynamic and electrochemical stability. The binding energy of ORR intermediates and the change of Gibbs free energy in each step of the ORR are calculated. The overpotential of Pd-CTF(6N) is the lowest, which is 0.38 V. Considering that the ORR activity of M-CTFs is mainly limited by the strong binding of *OH, M-CTF(6N) and M-CTF(9N) are further modified by the OH ligand, namely, M-OH-CTF(6N) and M-OH-CTF(9N). After being modified by the OH ligand, due to the weakened binding strength of *OH, all these screened M-CTFs exhibit better ORR activity. Among them, the η values of Cu-OH-CTF(6N), Pd-OH-CTF(6N), Rh-OH-CTF(6N), Ir-OH-CTF(6N), Rh-OH-CTF(9N), and Ir-OH-CTF(9N) are 0.39, 0.38, 0.24, 0.30, 0.31, and 0.33 V, respectively, which possess better ORR activity than the Pt(111) surface (η = 0.45 V). This work highlights the great potential of CTFs as an efficient carrier for SACs.