Unconventional Phase Synergies with Doping Engineering Over Ni Electrocatalyst Featuring Regulated Electronic State for Accelerated Urea Oxidation

Exploring high-performing Ni-based electrocatalysts for the urea oxidation reaction (UOR) is crucial for developing urea-related energy technologies yet remains a daunting challenge. In this study, a synergistic anomalous hcp phase and heteroatom doping engineering over metallic Ni are found to enhance the UOR. A metal-organic framework-mediated approach is proposed to construct Ni nanoparticles (NPs) with designated crystal phase embedded in N-doped carbon (fcc-Ni/NC and hcp-Ni/NC). Significant crystal phase-dependent catalytic activity for the UOR is observed; hcp-Ni/NC, featuring unusual hcp phase, outperforms fcc-Ni/NC with conventional fcc phase. Moreover, incorporating foreign Mn species in hcp-Ni/NC can further dramatically promote UOR, making it among the best UOR catalysts reported to date. From experimental results and DFT calculations, the specific nanoarchitecture, involving an anomalous hcp phase together with Mn doping engineering, endows hcp-MnNi/NC with abundant exposed active sites, facile charge transfer, and more significantly, optimized electronic state, giving rise to enriched Ni3+ active species and oxygen vacancies on the catalyst surface during electrocatalysis. These features collectively contribute to the enhanced UOR activity. This work highlights a potent design strategy to develop advanced catalysts with regulated electronic state through synergistic crystal phase and doping engineering.