Ni3C/Ni3S2 Heterojunction Electrocatalyst for Efficient Methanol Oxidation via Dual Anion Co‐modulation Strategy

Abstract Enhancing active states on the catalyst surface by modulating the adsorption–desorption properties of reactant species is crucial to optimizing the electrocatalytic activity of transition metal‐based nanostructured materials. In this work, an efficient optimization strategy is proposed by co‐modulating the dual anions (C and S) in Ni 3 C/Ni 3 S 2 , the heterostructured electrocatalyst, which is prepared via a simple hot‐injection method. The presence of Ni 3 C/Ni 3 S 2 heterojunctions accelerates the charge carrier transfer and promotes the generation of active sites, enabling the heterostructured electrocatalyst to achieve current densities of 10/100 mA cm −2 at 1.37 V/1.53 V. The Faradaic efficiencies for formate production coupled with hydrogen evolution approach 100%, accompanied with a stability record of 350 h. Additionally, operando electrochemical impedance spectroscopy (EIS), in situ Raman spectroscopy, and density functional theory (DFT) calculations further demonstrate that the creation of Ni 3 C/Ni 3 S 2 heterointerfaces originating from dual anions’ (C and S) differentiation is effective in adjusting the d ‐band center of active Ni atoms, promoting the generation of active sites, as well as optimizing the adsorption and desorption of reaction intermediates. This dual anions co‐modulation strategy to stable heterostructure provides a general route for constructing high‐performance transition metal‐based electrocatalysts.