Synergistic etching of nickel foam by Fe3+ and Cl- ions to synthesize nickel-iron-layered double hydroxide nanolayers with abundant oxygen vacancies for superior urea oxidation.

Urea electrolysis is an appealing topic for hydrogen production due to its ability to extract hydrogen at a lower potential. However, it is plagued by sluggish kinetics and noble-metal catalyst requirements. Herein, we developed nickel-iron-layered double hydroxide (NiFe-LDH) nanolayers with abundant oxygen vacancies (OV) via synergistically etching nickel foam with Fe3+ and Cl- ions, enabling the efficient conversion of urea into H2 and N2. The synthesized OV-NiFe-LDH exhibits a lower potential (1.30 vs. reversible hydrogen electrode, RHE) for achieving 10 mA cm-2 in the urea oxidation reaction (UOR), surpassing most recently reported Ni-based electrodes. OV provides favorable conductivity and a large surface area, which results in a 4.1-fold in electron transport and a 5.1-fold increase in catalyst reactive sites. Density Functional Theory (DFT) calculations indicate that OV can lower the adsorption energy of urea, and enhance the bonding strength of *CONHNH, giving rise to improved UOR. This study provides a viable path toward economical and efficient production of high-purity hydrogen.