Structural and electronic modulation of conductive MOFs for efficient oxygen evolution reaction electrocatalysis

Abstract

Conductive metal–organic frameworks (MOFs) have been developed as a superior platform for heterogeneous catalysis. Particularly, the tunable composition and structure of conductive MOFs provide an opportunity to probe the structure–activity relationship toward electrocatalysis. Herein, we exemplify an alternative strategy to modulate the electronic structure in conductive MOFs for efficient oxygen evolution reaction (OER). By replacing an appropriate number of Ni–O₄ sites with Fe–O₄ sites in NiPc–Ni, the optimal bimetallic conductive MOF has a low overpotential of 300 mV at 10 mA cm⁻² and an ultra-high TOF value of 1.943 s⁻¹ at η = 300 mV. DFT calculations reveal that the electronic interaction between Ni–O₄ and Fe–O₄ notably enhances the intrinsic activity of bimetallic conductive MOFs. This work highlights the importance of modulating the electronic structure of conductive MOFs with great promise for water-splitting and other promising applications.