High-density electron transfer in Ni-metal-organic framework@FeNi-layered double hydroxide for efficient electrocatalytic oxygen evolution

The electrochemical oxygen evolution reaction is a bottleneck reaction in hydrolysis and electrolysis because the four-step electron transfer leads to slow reaction kinetics and large overpotentials. This situation can be improved by fast charge transfer by optimizing the interfacial electronic structure and enhancing polarization. Herein, a unique metal (Ni) organic (diphenylalanine, DPA) framework Ni(DPA)₂ (Ni-MOF) with tunable polarization is designed to bond with FeNi-LDH (layered double hydroxides) nanoflakes. The Ni-MOF@FeNi-LDH heterostructure delivers excellent oxygen evolution performance exemplified by an ultralow overpotential of 198 mV at 100 mA cm^-2 compared to other (FeNi-LDH)-based catalysts. Experiments and theoretical calculations show that FeNi-LDH exists in an electron-rich state in Ni-MOF@FeNi-LDH due to polarization enhancement caused by interfacial bonding with Ni-MOF. This effectively changes the local electronic structure of the metal Fe/Ni active sites and optimizes adsorption of the oxygen-containing intermediates. Polarization and electron transfer of Ni-MOF are further enhanced by magnetoelectric coupling consequently giving rise to better electrocatalytic properties as a result of high-density electron transfer to active sites. These findings reveal a promising interface and polarization modulation strategy to improve electrocatalysis.