In situ evolution of highly dispersed amorphous CoOx clusters for oxygen evolution reaction

Abstract

Electrocatalytic water splitting is a key technique to produce hydrogen fuels, which can be considered as an efficient strategy to store renewable energy. Oxygen evolution reaction (OER) that occurs at the anode side requires a four-electron transfer under highly oxidizing conditions. OER has a large overpotential and therefore determines the overall efficiency. Certain electrocatalysts can efficiently help to improve the reaction kinetics. Owing to the high cost of precious metals such as Pt, Ru, and Ir, non-precious metal oxide catalysts have been vigorously investigated under alkaline conditions. Herein, we synthesized novel highly dispersed amorphous CoO_xfor the first time in the form of a cluster favorable to enhance the OER activity using a facile method via the air dielectric barrier discharge (DBD) plasma. Compared with the pristine biopolymer–cobalt complex, the amorphous CoO_x cluster exhibits a much higher current density and a lower overpotential for OER, e.g., the overpotential of 290 mV at 10 mA cm⁻² and the overpotential of only 350 mV at 300 mA cm⁻¹. The excellent electrocatalytic OER activity was attributed to the unsaturated catalytic sites on the amorphous CoO_x cluster. In addition, we studied the reaction mechanism, and it was observed that pure O₂ DBD plasma could lead to the evolution of crystalline CoO_x; however, the presence of N₂ and O₂ in DBD plasma could ensure the facile evolution of amorphous CoO_x clusters. This study provides a new strategy to design amorphous materials for electrocatalysis and beyond.