LAUSR

Transition metals have been recognized as excellent and efficient catalysts for the electrochemical nitric oxide reduction reaction (NORR) to value‐added chemicals. In this work, a class of core–shell electrocatalysts that utilize nickel nanoparticles in the core and nitrogen‐doped porous carbon architecture in the shell (Ni@NC) for the efficient electroreduction of NO to ammonia (NH3) is reported. In Ni@NC, the NC prevents the dissolution of Ni nanoparticles and ensures the long‐term stability of the catalyst. The Ni nanoparticles involve in the catalytic reduction of NO to NH3 during electrolysis. As a result, the Ni@NC achieves a faradaic efficiency (FE) of 72.3% at 0.16 VRHE. The full‐cell electrolyzer is constructed by coupling Ni@NC as cathode for NORR and RuO2 as an anode for oxygen evolution reaction (OER), which delivers a stable performance over 20 cycles at 1.5 V. While integrating this setup with a PV‐electrolyzer cell, and it demonstrates an appreciable FE of >50%. Thus, the results exemplify that the core–shell catalyst based electrolyzer is a promising approach for the stable NO to NH3 electroconversion.