A Self‐Templated Design Approach toward Multivariate Metal–Organic Frameworks for Enhanced Oxygen Evolution

Abstract Multivariate metal–organic framework (MOF) is an ideal electrocatalytic material due to the synergistic effect of multiple metal active sites. In this study, a series of ternary M‐NiMOF (M = Co, Cu) through a simple self‐templated strategy that the Co/Cu MOF isomorphically grows in situ on the surface of NiMOF is designed. Owing to the electron rearrange of adjacent metals, the ternary CoCu‐NiMOFs demonstrate the improved intrinsic electrocatalytic activity. At optimized conditions, the ternary Co₃Cu‐Ni₂MOFs nanosheets give the excellent oxygen evolution reaction (OER) performance of current density of 10 mA cm⁻² at low overpotential of 288 mV with a Tafel slope of 87 mV dec⁻¹, which is superior to that of bimetallic nanosheet and ternary microflowers. The low free energy change of potential‐determining step identifies that the OER process is favorable at Cu–Co concerted sites along with strong synergistic effect of Ni nodes. Partially oxidized metal sites also reduce the electron density, thus accelerating the OER catalytic rate. The self‐templated strategy provides a universal tool to design multivariate MOF electrocatalysts for highly efficient energy transduction.