Accelerated Dynamic Reconstruction in Metal–Organic Frameworks with Ligand Defects for Selective Electrooxidation of Amines to Azos Coupling with Hydrogen Production

Abstract Electrosynthesis coupled hydrogen production (ESHP) mostly involves catalyst reconstruction in aqueous phase, but accurately identifying and controlling the process is still a challenge. Herein, we modulated the electronic structure and exposed unsaturated sites of metal–organic frameworks (MOFs) via ligand defect to promote the reconstruction of catalyst for azo electrosynthesis (ESA) coupled with hydrogen production overall reaction. The monolayer Ni‐MOFs achieved 89.8 % Faraday efficiency and 90.8 % selectivity for the electrooxidation of 1‐methyl‐1H‐pyrazol‐3‐amine (Pyr−NH 2 ) to azo, and an 18.5‐fold increase in H 2 production compared to overall water splitting. Operando X‐ray absorption fine spectroscopy (XAFS) and various in situ spectroscopy confirm that the ligand defect promotes the potential dependent dynamic reconstruction of Ni(OH) 2 and NiOOH, and the reabsorption of ligand significantly lowers the energy barrier of rate‐determining step (*Pyr−NH to *Pyr−N). This work provides theoretical guidance for modulation of electrocatalyst reconstruction to achieve highly selective ESHP.