Dual cation-modified hierarchical nickel hydroxide nanosheet arrays as efficient and robust electrocatalysts for the urea oxidation reaction

Abstract

The rational modification of electronic structures to create catalytically active sites has been proved to be a promising strategy to efficiently facilitate the urea oxidation reaction (UOR). Herein, a well-defined nanosheet arrays catalyst of Ni(OH)₂ doped with dual cations of Co and Mn on Ni foam (NF) (Co/Mn–Ni(OH)₂) is synthesized through a simple hydrothermal process. Benefiting from the advantages of unique structures and modified binding strengths, it is found experimentally that the obtained Co/Mn–Ni(OH)₂ catalyst only requires a potential of 1.38 V to deliver a current density of 100 mA cm⁻² and exhibits a small Tafel slope of 35 mV dec⁻¹, outperforming single-component-incorporated Ni(OH)₂. Moreover, the catalyst has shown excellent stability for 25 h at a current density of 50 mA cm⁻². Additionally, first-principles calculations demonstrate that the co-incorporation of Co and Mn remarkably lowers the adsorption barrier of CO(NH₂)₂* on the catalyst surface, and accelerates the dissociation of the CO(NH₂)₂* intermediate into CO* and NH* intermediates, which synergistically improve the UOR reaction kinetics. This work provides a generic paradigm for designing advanced and effective catalysts toward the UOR.