Phosphorus‐Driven Bimetallic Site Regulation in MOFs for Photocatalytic Hydrogen Production

Developing efficient and stable photocatalysts for solar‐driven hydrogen production is fundamentally limited by inefficient charge separation and weak electronic coupling between active sites, particularly in bimetallic metal–organic frameworks (MOFs). Here, we address these challenges by introducing phosphorus into a bimetallic cobalt–zinc MOF constructed from 2‐methylimidazole, aiming to electronically couple dual‐metal centers and simultaneously optimize surface reaction kinetics. The optimized P‐modified Co–Zn MOF achieves a high hydrogen evolution rate of 4099 µmol·h −1 ·g −1 under visible‐light irradiation, corresponding to an approximately sixfold enhancement over the pristine material, together with excellent cycling stability. Mechanistic studies reveal that phosphorus incorporation reconstructs the local electronic environment of Co and Zn centers, forming P‐bridged bimetallic motifs that promote efficient photogenerated charge separation and accelerate interfacial charge transfer. In parallel, the phosphorus‐mediated electronic modulation optimizes proton adsorption and hydrogen‐reduction kinetics, enabling a synergistic improvement in photocatalytic performance. This work demonstrates that electronic‐structure regulation via phosphorus provides an effective solution to the long‐standing challenge of activating bimetallic synergy in MOF‐based photocatalysts, offering new insights into the rational design of high‐performance systems for photocatalytic hydrogen evolution.