Programmable Active Phase Reconstruction in Metal–Organic Framework Toward High‐Efficient Oxygen Evolution

Abstract Orchestrated manipulation of the dynamic structural evolution of catalytic materials in service represents an effective approach to rationally architect the active phase for highly efficient catalysis. Herein, this study reports a 2D ultrathin nickel‐based metal–organic framework (MOF) pre‐catalyst, where multimetallic electronic cooperativity enables on‐demand hierarchical regulation of the structural evolution as well as the catalytic process of the reconstruction‐derived active phase, delivering oxygen evolution reaction (OER) performance superior to benchmark RuO 2 . Tailored cobalt‐iron co‐substitution in nickel‐based MOF strategically engineers the overall structural flexibility, controllably promoting the reconstruction process in alkaline media into ligand‐anchored nickel oxyhydroxide active phases. Crucially, the controlled modulation of the structural state of reconstructed phases induces targeted metal‐oxygen electronic interplay, steering active oxygen intermediate reconfiguration and reducing the thermodynamic bottleneck of the rate‐determining step, ultimately achieving optimized catalytic pathways. This work precisely constructs MOF‐derived reconstructed active phases and elucidates a programmed optimization mechanism governed by multimetallic electronic interplay, which dynamically bridges structural transformation and catalytic activity enhancement. A promising approach is showcased to accurately design high‐efficiency electrocatalysts through programming dynamic structural evolution.