Assembly of Amorphizing Porous Bimetallic Metal‐Organic Frameworks Spheres with Zn─O─Fe Cluster and Coordination Deficiency via Ligand Competition for Efficient Electro‐Fenton Catalysis

Electro‐Fenton process stands out as a highly promising approach for generating reactive oxygen‐containing radicals to address the escalating issue of environmental pollution. However, the long‐term goal of application necessitates ongoing pursuit of high‐quality catalysts with both sufficient activity and stability. Herein, a general route is reported for large‐scale synthesis of amorphizing porous bimetallic metal‐organic framework (MOF) spheres with Zn─O─Fe structure and coordination deficiency through facile and low‐cost synthesis of ligand competition. Assisted by a coordination modulator, deprotonation of terephthalic acid is accelerated and rapid synthesis of amorphous bimetallic MOF spheres is successfully achieved at room temperature. As inactive metal Zn is introduced into metal clusters of MOFs, the cycling efficiency of Fe3+/Fe2+ is improved and a secondary building unit of Zn─O─Fe is constructed, greatly accelerating electron conduction rate. Compared to crystalline spindle cMIL‐88B(Fe2Zn) by traditional solvothermal route, amorphous aMIL‐88B(Fe2Zn) has a unique spherical porous structure with larger surface area, higher conductivity, and more exposed active sites. Endowed with unique textural and surface chemistry, aMIL‐88B(Fe2Zn) exhibits superior catalytic activity in the degradation of refractory organic pollutants. The progress offers a feasible way to rational design of iron‐based hybrid MOF materials with tunable structures and enhance properties for various applications. Assembly of amorphizing porous bimetallic MOF spheres with Zn─O─Fe cluster and coordination deficiency is achieved by an innovative and facile methodology of ligand competition at room temperature. Unique Zn─O─Fe structure and coordination chemistry led amorphous aMIL‐88B(Fe2Zn) to exhibit superior catalytic activity to degradation of refractory organic pollutants with accelerated Fe3+/Fe2+ cycle.