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

Electrocatalytic nitric oxide reduction reaction (NORR) is a feasible strategy for ammonia (NH₃) 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 NH₃ 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.