Exploring Spin Dynamics in Diatomic Co2 Catalysts on Graphyne for Enhanced Co Electroreduction

Abstract Investigating spin dynamics in electrocatalysis is crucial for the rational design of magnetically heterogeneous catalysts. Utilizing spin‐polarized density functional theory calculation, herein, the spin dynamic of diatomic Co₂‐supported γ‐graphyne (Co 2 ‐GY) catalysts during the process of CO electroreduction (eCORR) is identified, focusing on the effect of the applied potential and acidity on spin dynamic and catalytic performance. In particular, the obtained Co 2 ‐GY shows a new efficient C 2 pathway of CH 2 * + CHO* coupling mechanism, resulting in the optimal CH 3 CH 2 OH product with ∆G of 0.50 eV and the selectivity of 99.99% under alkaline conditions. Under acidic media, Co 2 ‐GY exhibits the optimal C 1 product (CH 3 OH) with ∆G of 0.27 eV and a selectivity of 99.99%. During CO electroreduction, the reaction environment (pH and applied potential) influences spin dynamics in catalyst‐reactant systems, affecting the spin transition of diatomic Co 2 active sites among four magnetic states: ferromagnetic, antiferromagnetic, paramagnetic, and diamagnetic. These findings will be helpful for the rational design of transition‐metal heterogeneous catalysts.