Ammonia (NH3) plays a significant role in the manufacture of fertilizers, nitrogen-containing chemical production, and hydrogen storage. The electrochemical nitrogen reduction reaction (e-NRR) is an attractive prospect for achieving clean and sustainable NH3 production, under mild conditions driven by renewable energy. The sluggish cleavage of N≡N bonds and poor selectivity of e-NRR are the primary challenges for e-NRR, over the competitive hydrogen evolution reaction (HER). The rational design of e-NRR electrocatalysts is of vital significance and should be based on a thorough understanding of the structure-activity relationship and mechanism. Among the various explored e-NRR catalysts, metal-based electrocatalysts have drawn increasing attention due to their remarkable performances. This review highlighted the recent progress and developments in metal-based electrocatalysts for e-NRR. Different kinds of metal-based electrocatalysts used in NH3 synthesis (including noble-metal-based catalysts, non-noble-metal-based catalysts, and metal compound catalysts) were introduced. The theoretical screening and the experimental practice of rational metal-based electrocatalyst design with different strategies were systematically summarized. Additionally, the structure-function relationship to improve the NH3 yield was evaluated. Finally, current challenges and perspectives of this burgeoning area were provided. The objective of this review is to provide a comprehensive understanding of metal-based e-NRR electrocatalysts with a focus on enhancing their efficiency in the future.
Keywords: NH3 synthesis; electrochemical nitrogen reduction reaction; metal compound catalysts; noble-metal-based catalysts; non-noble-metal-based catalysts.