First-Principles Study on Oxygen Evolution Reaction Activity of CoPS₃ Quantum Dot Edge States Modified with Oxygen

doi:10.15541/jim20250092

Abstract

Abstract: The two-dimensional CoPS₃ electrocatalyst suffers from scarcity of in-plane metal active sites, resulting in the slow kinetics for the oxygen evolution reaction (OER) at the anode, thereby limiting the overall efficiency of hydrogen production via water splitting. To address this issue, this study proposes a new strategy to enhance the catalytic activity through the synergistic effects of quantum confinements and edge chemical modification. Initially, two typical CoPS₃ quantum dots (CoPS₃-QDs) structures with high edge-site densities were constructed. Through the binding and bond energy calculations, the thermodynamically stable CoPS₃-QDs1 structure was identified, with its edge Co2 site exhibiting the best OER activity among other edge sites (Gibbs free energy change for the rate-determining step, ΔG=1.68 eV). Subsequently, oxygen modification was introduced at the Co2 site of CoPS₃-QDs1 and its neighboring sulfur atoms, obtaining five O-CoPS₃-QDs models. Theoretical calculations revealed that the M4 model (with O modification at the S3 site) has an overpotential (η^OER) of only 0.32 V, which is 29% lower than that of the unmodified system and significantly better than the noble metal catalyst RuO₂ reported in the literature. Partial density of states analysis further revealed that O modification optimized the charge redistribution around the Co sites, enabling moderate adsorptions of oxygen intermediates (*OH, *O, *OOH). This study elucidates the crucial role of edge-site modification of quantum dots in regulating electronic structure and reaction kinetics, providing a theoretical basis for designing efficient and low-cost OER electrocatalysts.

Key words: CoPS₃, quantum dot, oxygen evolution reaction, edge states

CLC Number:

TQ151

HU Xuemin, ZHANG Xingjian, JIANG Zhihao, HUANG Liwen, DING Kaining, ZHANG Shengli. First-Principles Study on Oxygen Evolution Reaction Activity of CoPS₃ Quantum Dot Edge States Modified with Oxygen[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250092.

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