Structure and Electron Engineering for Nitrate Electrocatalysis to Ammonia: Identification and Modification of Active Sites in Spinel Oxides

Abstract Cobalt spinel oxides, which consist of tetrahedral site (AO 4 ) and octahedral site (BO 6 ), are a potential group of transition metal oxides (TMO) for electrocatalytic nitrate reduction reactions to ammonia (NRA). Identifying the true active site in spinel oxides is crucial to designing advanced catalysts. This work reveals that the CoO 6 site is the dominant site for NRA through the site substitution strategy. The suitable electronic configuration of Co at the octahedral site leads to a stronger interaction between the Co d‐orbital and the O p‐orbital in O‐containing intermediates, resulting in a high‐efficiency nitrate‐to‐ammonia reduction. Furthermore, the substitution of metallic elements at the AO 4 site can affect the charge density at the BO 6 site via the structure of A‐O‐B. Thereafter, Ni and Cu are introduced to replace the tetrahedral site in spinel oxides and optimize the electronic structure of CoO 6 . As a result, NiCo 2 O 4 exhibits the best activity for NRA with an outstanding yield of NH 3 (15.49 mg cm −2 h −1 ) and FE (99.89%). This study introduces a novel paradigm for identifying the active site and proposes an approach for constructing high‐efficiency electrocatalysts for NRA.