Surface Charge and Electrostatic Spin Crossover Effects in CoN4 Electrocatalysts

• Published in: ACS catalysis Vol. 10; no. 20
• Main Authors: Duan, Zhiyao, Henkelman, Graeme
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society (ACS) 16.10.2020
• Subjects: binding energy; Co- and N-doped carbon; constant-potential condition; density functional theory; electrical properties; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oxygen evolution reaction; oxygen reduction reaction; pH-dependent activity; quantum mechanics; radiology; redox reactions; spin crossover effect
• ISSN: 2155-5435; 2155-5435
• DOI: 10.1021/acscatal.0c02458

Carbon materials doped with nitrogen and 3d transition metals have attracted a great deal of interest for catalyzing electrochemical reactions such as water splitting, oxygen reduction, and carbon dioxide reduction. Here, we employed density functional theory to study Co–N-doped carbon as electrocatalysts for the oxygen reduction and oxygen evolution reactions. Specifically, we investigated the interplay among adsorption energies, the spin state of the CoN4 active center, and the applied potential. We found that adsorption energies strongly depend on both the applied potential and the spin state of the Co center. Furthermore, spin state transitions induced by the applied potential also play an important role in determining the adsorption energies. Here, this effect originates from a different potential of zero charge and capacitance of each spin state.