Efficient Methylamine Electrosynthesis Enabled by Coupling Heterometallic MOF Catalyst With Integrated Reaction System

Electrochemical C‐N coupling offers a sustainable pathway for organonitrogen synthesis but faces kinetic challenges in reactant activation and C‐N coupling for target product generation. Herein, we report a heterometallic metal‐organic framework (MOF), Cu‐MIL‐125, as a high‐performance catalyst for selective methylamine synthesis from co‐electrolysis of CO 2 and NO 3 − . In situ spectroscopic experiments and theoretical calculations unravel that the constructed heterometallic Cu–Ti sites on Cu‐MIL‐125 synergistically promote key * HCHO/ * NH 2 OH intermediate generation and boost their C‐N coupling and hydrogenation energetics, while simultaneously facilitating reactant accumulation and side reaction suppression. Moreover, by integrating plasma‐assisted nitrogen fixation, cathodic methylamine electrosynthesis coupled with anodic glycerol oxidation in a zero‐gap MEA electrolyzer, we achieve an unprecedented Faradaic efficiency of 86.28% with a methylamine yield rate of 132.02 mmol h −1 g −1 , representing one of the best performances thus far. Our strategy establishes a scalable, economically viable, and carbon‐neutral paradigm for the decentralized synthesis of organonitrogen chemicals.