Ni-Doped MnO₂ Nanosheet Arrays for Efficient Urea Oxidation

Urea oxidation reaction (UOR), with a low thermodynamic potential, offers great promise for replacing anodic oxygen evolution reaction of electrolysis systems such as water splitting, carbon dioxide reduction, etc., thus reducing the overall energy consumption. To promote the sluggish kinetics of UOR, highly efficient electrocatalysts are required, and Ni-based materials have been widely investigated. However, most of these reported Ni-based catalysts suffer from large overpotentials, as they generally undergo self-oxidation to form NiOOH species at high potentials, which act as catalytically active sites for UOR. Herein, Ni-doped MnO₂ (Ni-MnO₂) nanosheet arrays were successfully prepared on nickel foam. The as-fabricated Ni-MnO₂ shows distinct UOR behavior with most of the previously reported Ni-based catalysts, as urea oxidation on Ni-MnO₂ proceeds before the formation of NiOOH. Notably, a low potential of 1.388 V vs reversible hydrogen electrode was required to achieve a high current density of 100 mA cm^-2 on Ni-MnO₂. It is suggested that both Ni doping and nanosheet array configuration are responsible for the high UOR activities on Ni-MnO₂. The introduction of Ni modifies the electronic structure of Mn atoms, and more Mn³⁺ species are generated in Ni-MnO₂, contributing to its outstanding UOR performance.