Efficient Nitrogen Fixation to Ammonia through Integration of Plasma Oxidation with Electrocatalytic Reduction

Abstract Present one‐step N 2 fixation is impeded by tough activation of the N≡N bond and low selectivity to NH 3 . Here we report fixation of N 2 ‐to‐NH 3 can be decoupled to a two‐step process with one problem effectively solved in each step, including: 1) facile activation of N 2 to NO x − by a non‐thermal plasma technique, and 2) highly selective conversion of NO x − to NH 3 by electrocatalytic reduction. Importantly, this process uses air and water as low‐cost raw materials for scalable ammonia production under ambient conditions. For NO x − reduction to NH 3 , we present a surface boron‐rich core–shell nickel boride electrocatalyst. The surface boron‐rich feature is the key to boosting activity, selectivity, and stability via enhanced NO x − adsorption, and suppression of hydrogen evolution and surface Ni oxidation. A significant ammonia production of 198.3 μmol cm −2 h −1 was achieved, together with nearly 100 % Faradaic efficiency.