Progress of Experimental and Computational Catalyst Design for Electrochemical Nitrogen Fixation

Large-scale ammonia synthesis via the electrochemical nitrogen reduction reaction (eNRR) under mild reaction conditions represents a green prospect for agriculture, industry, and energy. This bioinspired and carbon-free reaction has been proposed as an ideal alternative to the Haber–Bosch process. However, the yield and selectivity of the current eNRR have not met the requirements for industrialization. Mechanistic understanding and catalysts' design are still long-term pursuits in this field, where theoretical simulations will have significant contributions. In this Review, we will start with the natural N2 fixation enzymes, the nitrogenases, followed by a summary of the key experimental eNRR performances on hundreds of recently reported catalysts, and we analyze the general trend and challenges before eNRR can significantly impact the ammonia industry. Then, we will systematically review the recent progress and contributions of computational studies in understanding the reaction mechanism and rational catalyst design for eNRR. The fundamental principles, reaction mechanisms, crucial theoretical criteria, modeling methods, and computationally predicted catalysts for eNRR are systematically summarized and discussed. Finally, we outline the current challenges and future opportunities for experimental and computational studies of electrochemical N2 reduction.