Electronic modulation towards MOFs as template derived CoP via engineered heteroatom defect for a highly efficient overall water splitting

The reasonable design of material morphology and eco-friendly electrocatalysts are essential to highly efficient water splitting. It is proposed that a promising strategy effectively regulates the electronic structure of the d‐orbitals of CoP using cerium doping in this paper, thus significantly improving the intrinsic property and conductivity of CoP for water splitting. As a result, the as-synthesize porous Ce-doped CoP micro-polyhedron composite derived from Ce-ZIF-67 as bifunctional electrocatalytic materials exhibits excellent electrocatalytic performance in both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), overpotentials of about 152 mV for HER at 10 mA cm⁻² and about 352 mV for OER at 50 mA cm⁻², and especially it shows outstanding long-term stability. Besides, an alkaline electrolyzer, using Ce_0.04Co_0.96P electrocatalyst as both the anode and cathode, delivers a cell voltage value of 1.55 V at the current density of 10 mA cm⁻². The calculation results of the density functional theory (DFT) demonstrate that the introduction of an appropriate amount of Ce into CoP can enhance the conductivity, and can induce the electronic modulation to regulate the selective adsorption of reaction intermediates on catalytic surface and the formation of O* intermediates (CoOOH), which exhibits an excellent electrocatalytic performance. This study provides novel insights into the design of an extraordinary performance water-splitting of the multicomponent electrocatalysts.