Single-Atom Doping and High-Valence State for Synergistic Enhancement of NiO Electrocatalytic Water Oxidation.

Abstract

The NiO-based electrocatalytic oxygen evolution reaction (OER) of water splitting is recognized as a promising approach to produce clean H2 fuel. However, the OER performance is still low, and especially, the overpotential is larger than 200mV at the current density of 10mA cm-2 . Herein, an Ir@IrNiO sample is prepared with single-atom (SA) Ir4+ doping and surface metallic Ir nanoparticles loaded onto the NiO. Owing to the bonding of the loaded Ir with surface-exposed Ni2+ , the nearby Ni atoms exist in the +3valence state, that is, the surface-loaded Ir particles behave like a stabilizer for the Ni3+ sites. Under the synergistic effect of SA Ir4+ and high-valance-state Ni3+ , the Ir@IrNiO nanostructure effectively reduces the overpotential to 195mV at acurrent density of 10mA cm-2 . Moreover, it gives an Ir-content-normalized current density of 0.0457 A mgIr -1 , 72.1 times higher than that of the best commercialized IrO2 (6.33 × 10-4 A mgIr -1 ), under the condition of 1.5V versus reversible hydrogen electrode. Operando Raman and X-ray absorption fine-structure (XAFS) measurements reveal that there are more surface-active species of Ni3+ , which adsorb and activate water molecules to form Ni3+ -*OH at low voltage, the intermediate of Ni4+ -•O is then formed at a relatively high bias voltage, and then the •O is transferred to the SA Ir4+ sites to generate Ir4+ -O-O with OH at increased voltage. This work can help design more SA-based highly active OER materials.