Electrocatalytic Coupling Conversion of Methane by Dual‐Site Control in Nickel Oxyhydroxide

Methane (CH 4 ), as both a carbon resource and greenhouse gas, requires an effective and ecologically friendly catalysis to accomplish the conversion into valued‐added chemicals or fuels, wherein the establishment of a proper multi‐site active structure to boost the C─H dissociation and C─C coupling demands further exploration. Herein, we disclose a facile and general approach by controlling the electronic property of Ni to preserve a moderate orbital hybridization (d‐p) with O, and thereby induce a synergistic Ni─O dual‐site for the expected electrocatalysis of CH 4 toward C 2 product. Specifically, along the d band shifting downwards via the Ni valence increase, the optimal NiOOH not only affords sufficient capability for the CH 4 oxygenation relative to the Ni(OH) 2 , but also minimizes the probability of O detachment compared with the NiO 2 . The resultant NiOOH catalyst exhibits the highest Faradaic efficiency of 53.5% with a production rate of 401.6 µmol g cat. −1 h −1 or 1.61 µmol h ‒1 cm ‒2 for acetic acid, and a long‐term stability for over 50 h without detectable structural deterioration. This study develops an efficient electrocatalytic CH 4 process, and could arouse extensive attention to the new materials and routes meeting the economicity and sustainability.