Unraveling Surface Reconstruction of MOF‐Derived La, P‐Co 3 O 4 for Energy‐Efficient Water and Urea Electrolysis

Abstract Constructing robust electrocatalysts and shedding light on the processes of surface reconstruction is crucial for sustained hydrogen production and a deeper understanding of catalytic behavior. Here, a novel ZIF‐67‐derived lanthanum‐ and phosphorus‐co‐doped Co 3 O 4 catalyst (La, P‐Co 3 O 4 ) has been reported. X‐ray absorption spectroscopy (XAS) confirms that the La and P co‐doping reduces the coordination number (CN), improves oxygen vacancies (O v ), and leads to lattice distortion. Soft XAS confirms that Co 2+ exists predominantly in La, P‐Co 3 O 4 than in Co 3 O 4 . Investigation of surface reconstruction with in situ Raman spectroscopy , revealing that La, P‐Co 3 O 4 reconstructs earlier into catalytically active γ‐CoOOH during the oxygen evolution reaction (OER) process. As a result, La, P‐Co 3 O 4 exhibits commendable electrocatalytic performance with minimal overpotentials of 351 mV for the OER, 222 mV for the hydrogen evolution reaction (HER), and 1.46 V for the urea oxidation reaction (UOR) to achieve a current density of 50 mA cm −2 . A two‐electrode electrolyzer using La, P‐Co 3 O 4 as anode and cathode, achieving 19.4% energy savings during urea electrolysis compared to overall water electrolysis while maintaining stability for 72 h. This study provides a new perspective for understanding the mechanism and co‐doping impact on the physicochemical properties of spinel Co 3 O 4 for sustainable energy conversion.