Regulating Local Reaction Environments for Efficient Nitric Oxide Reduction to Ammonia via Strengthening Interactions Between Heteroatom‐Doped Carbon and Metallic Alloys

Abstract Electrocatalytic nitric oxide reduction reaction (NORR) is a feasible strategy for ammonia (NH 3 ) synthesis and restoring the nitrogen cycle. Electronic structure modulation of metal sites through strengthening metal‐support interactions represents a plausible approach to enhance NORR yield and Faradaic efficiency (FE), primarily by facilitating NO hydrogenation and inhibiting the hydrogen evolution reaction (HER). In this work, a boron and nitrogen co‐doped carbon‐supported CuNi alloy (CuNi@BCN) catalyst is designed and fabricated, which achieved a high NH 3 yield rate of 573.70 µmol cm −2 h −1 in a flow cell and a FE of 95.13% in an H‐cell. These newly achieved performances are outperforming the most recently developed NORR electrocatalysts. Theoretical calculations and in situ tests clarify that heteroatom‐doped carbon can lead to an electron‐rich alloy and thus facilitate NO hydrogenation with efficient participation of proton (*H) and inhibition of HER. The precise modulation of the alloy's electronic structure originates from heteroatom doping, which regulates the local reaction environments and successfully strengthens the alloy‐support interaction. This work demonstrates a route for optimizing the catalyst's electrocatalytic performance by regulating the local reaction environments of the metal active center.