Boosting Electrocatalytic Oxygen Evolution over Ce-Co9 S8 Core-Shell Nanoneedle Arrays by Electronic and Architectural Dual Engineering

Chemistry. 2022 Jun 7;28(32):e202200664. doi: 10.1002/chem.202200664. Epub 2022 Apr 26.

Abstract

An dual electronic and architectural engineering strategy is a good way to rationally design earth-abundant and highly efficient electrocatalysts of the oxygen evolution reaction (OER) for sustainable hydrogen-based energy devices. Here, a Ce-doped Co9 S8 core-shell nanoneedle array (Ce-Co9 S8 @CC) supported on a carbon cloth has been designed and developed to accelerate the sluggish kinetics of the OER. Profiting from valance alternative Ce doping, a fine core-shell structure and vertically aligned nanoneedle arrayed architecture, Ce-Co9 S8 @CC integrates modulated electronic structure, highly exposed active sites, and multidimensional mass diffusion channels; together, these afford a favorable catalyzed OER. Ce-Co9 S8 @CC exhibits remarkable performance in the OER in an alkaline medium, where the overpotential requires only 242 mV to deliver a current density of 10 mA cm-2 for the OER; this is 70 mV superior to that of Ce-free Co9 S8 catalyst and other counterparts. Good stability and impressive selectivity (nearly 100 % Faradic efficiency) are also demonstrated. When integrated into a two-electrode OER//HER electrolyzer, the as-prepared Ce-Co9 S8 @CC displays a low operation potential of 1.54 V at 10 mA cm-2 and long-term stability, thus demonstrating great potential for economical water electrolysis.

Keywords: cerium; cobalt; electronic structure; nanoarrays; nanoneedles; oxygen evolution reaction; water splitting.