Optimizing Intermediate Adsorption Through Frustrated Electron Transfer Strategy for Enhanced NO Reduction to Ammonia

ABSTRACT Employing highly active electrocatalysts to convert NO to ammonia (NH ₃ ) under ambient conditions offers a valuable waste‐to‐wealth strategy and a more efficient complementary pathway to the industrially challenged Haber–Bosch process for NH ₃ synthesis, surpassing N ₂ electroreduction. However, highly active NO reduction reaction (NORR) electrocatalysts often face two major challenges: excessively strong NO adsorption (limited by scaling relations, hindering product desorption and active site recycling) and preferential metal–H bond formation (impeding the target reaction on active metal surfaces). Here, capitalizing on their high selectivity in suppressing the hydrogen evolution reaction (HER), we systematically investigated the application of thirteen transition metal diborides (TMB ₂ ) in NORR and proposed a frustrated electron transfer strategy to optimize intermediate adsorption, thereby facilitating the desorption of the target product NH ₃ . The results demonstrate that Pd ₁ /FeB ₂ , modified using this strategy, maintains high reactivity toward NO while significantly lowering the thermodynamic and kinetic energy barriers for NH ₃ (g) formation, thus circumventing the limitation of scaling relations. This fully validates the effectiveness of the proposed strategy, offering new insights for the rational design of NORR electrocatalysts to achieve green and effective NH ₃ synthesis in practical applications.