Modulating Coordination Environment of Ni‐MOF by Graphitic Carbon Nitride to Promote Methanol Oxidation

ABSTRACT Regulating the coordination microenvironment of catalytic active centers is crucial for enhancing catalyst performance. Ni‐based metal‐organic frameworks (Ni‐MOFs) are promising anode catalysts for direct methanol fuel cells (DMFCs), owing to their high activity, excellent stability, and low cost. The metal coordination center (the tunability of the electronic structure and coordination environment of the nickel center) is generally considered to be an effective catalytic activity center in the study of the electrocatalytic performance of the nickel metal organic framework (Ni‐MOF). In this work, the g‐C 3 N 4 nanosheets were introduced to modulate the coordination environment of Ni active sites to further optimize the Ni‐MOF structure and improve the catalytic activity. A Ni‐MOF/g‐C 3 N 4 nanoflower heterostructure was synthesized via ultrasonic mixing and calcination, which exhibited significantly enhanced methanol oxidation activity with the geometric activity of 280.96 mA cm −2 and mass activity of 5514.65 mA mg −1 at 1.723 V, and it was twice higher than that of pure Ni‐MOF. XPS confirmed electron transfer from Ni‐MOF to g‐C 3 N 4 , optimizing the electronic state of Ni and intermediate adsorption. In‐situ Raman and XPS revealed that g‐C 3 N 4 promotes NiOOH formation, thereby improving electrocatalytic efficiency. This work provides deeper insight into the methanol oxidation reaction mechanism.