The Enhanced CO2RR Performance of Co13 Cluster Supported Defective Graphene: A DFT Investigation

Transition metal cluster catalysts (TMCCs) play a vital role in the carbon dioxide reduction reaction (CO2RR), due to their superior activity and selectivity. In this work, density functional theory (DFT) calculations were performed to investigate the catalytic performance of Co13 clusters anchored on defective graphene (Co13@NxC/OyC (x = 1, 2, 3, 4, 5 and y = 1, 2, 3, 4, 5)) for CO2 reduction to methane. Among the constructed catalysts, the Co13@NxC/OyC (x = 1-5 and y = 1-3) catalysts exhibits excellent structural stability. Catalytic performance analysis indicates that, except for Co13@O2C, the rate-determining step (RDS) energy barriers of the other catalysts range from 0.574 to 1.074 eV. Notably, Co13@N3C (0.574 eV) owns excellent performance not only with lowest energy barriers but also with favorable catalysitc select against HER. Additionally, Co13@NxC (x = 1, 4, 5) catalysts follow a unique reaction pathway: *CO2 → *CO*OH → *COH*OH → *C*OH → *CH*OH → *CH2*OH → *CH3*OH → CH4(g) *OH → CH4(g). This study provides a nanoscale exploration of the CO2RR catalytic performance of Co13 cluster, facilitating efficient catalyst synthesis with reduced experimental trials.