Modulation effect in adjacent dual metal single atom catalysts for electrochemical nitrogen reduction reaction

Nitrogen reduction reaction (NRR) is a clean mode of energy conversion and the development of highly efficient NRR electrocatalysts under ambient conditions for industrial application is still a big challenge. Metal-nitrogen-carbon (M-N-C) has emerged as a class of single atom catalyst due to the unique geometric structure, high catalytic activity, and clear selectivity. Herein, we designed a series of dual metal single atom catalysts containing adjacent M-N-C dual active centers (MN4/M'N-4-C) as NRR electrocatalysts to uncover the structure-activity relationship. By evaluating structural stability, catalytic activity, and selectivity using density functional theory (DFT) calculations, 5 catalysts, such as CrN4/M'N-4-C (M' = Cr, Mn, Fe, Cu and Zn), were determined to exhibit the best NRR catalytic performance with the limiting potential ranging from -0.64 V to -0.62 V. The CrN4 center acted as the main catalytic site and the adjacent M'N-4 center could enhance the NRR catalytic activity by modulation effect based on the analysis of the electronic properties including the charge density difference, partial density of states (PDOS), and Bader charge variation. This study offers useful insights on understanding the structure-activity relationship of dual metal single atom catalysts for electrochemical NRR. (C) 2021 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.