Exploring the ORR activity of S-doped CuN4 materials in vacuum and constant potential solvent environments

Abstract

The advancement of efficient and cost-effective electrocatalysts for fuel cells and metal-air batteries holds significant commercial importance. Utilizing Density Functional Theory (DFT), we calculated various properties of CuN₄SN catalysts, with the number of sulfur atoms (N) ranging from 0 to 3, including their formation energy, binding energy, state density, Bader charge, and redox reactions. Our findings revealed that CuN₄SN catalysts possess a high formation energy, facilitating their ease of preparation. By studying the adsorption behavior of oxygen-containing intermediates on the catalyst surface, we observed that under vacuum settings, CuN₄S1 exhibits the lowest η_ORR (overpotential for oxygen reduction reaction) and reaction energy barrier among the four models, with values of 0.95 V and 0.74 eV, respectively. Furthermore, we investigated the ORR activity of CuN₄S1 under a constant potential implicit solvent model and found that CuN₄S1 demonstrates superior performance in alkaline environments for ORR. Specifically, its η_ORR and reaction energy barrier were 0.36 V and 0.56 eV in alkaline conditions, respectively.