Ferric Oxide Nanocrystals‐Embedded Co/Fe‐MOF with Self‐Tuned d‐Band Centers for Boosting Urea‐Assisted Overall Water Splitting

A novel semiconductive Co/Fe-MOF embedded with Fe₂ O₃ nanocrystals (Fe₂ O₃ @CoFe-MOF) is developed as a trifunctional electrocatalyst for the urea oxidation reaction (UOR), oxygen evolution reaction (OER), and hydrogen evolution reaction for enhancing the efficiency of the hydrogen production via the urea-assisted overall water splitting. Fe₂ O₃ @CoFe-TPyP-MOF comprises unsaturated metal-nitrogen coordination sites, affording enriched defects, self-tuned d-band centers, and efficient π-π interaction between different layers. Density functional theory calculation confirms that the adsorption of urea can be optimized at Fe₂ O₃ @CoFe-TPyP-MOF, realizing the efficient adsorption of intermediates and desorption of the final product of CO₂ and N₂ characterized by the in situ Fourier transform infrared spectroscopy. The two-electrode urea-assisted water splitting device-assembled with Fe₂ O₃ @CoFe-TPyP-MOF illustrates a low cell voltage of 1.41 V versus the reversible hydrogen electrode at the current density of 10 mA cm^-2 , attaining the hydrogen production rate of 13.13 µmol min^-1 in 1 m KOH with 0.33 m urea. The in situ electrochemical Raman spectra and other basic characterizations of the used electrocatalyst uncover that Fe₂ O₃ @CoFe-TPyP-MOF undergoes the reversible structural reconstruction after the UOR test, while it demonstrates the irreversible reconstruction after the OER measurement. This work redounds the progress of urea-assisted water spitting for hydrogen production.