Photo‐Excited High‐Spin State Ni (III) Species in Mo‐Doped Ni3S2 for Efficient Urea Oxidation Reaction

Designing robust catalysts for increasing the sluggish kinetics of the urea oxidation reaction (UOR) is challenging. Herein, the regulation of spin states for metal active sites by photoexcitation to facilitate the adsorption of urea and intermediates is demonstrated. Mo‐doped nickel sulfide nanoribbon arrays (Mo‐Ni3S2@NMF) with excellent light‐trapping capacity are successfully prepared. Under AM 1.5G illumination, the activity of the Mo‐Ni3S2@NMF exhibits a 50% improvement in the UOR current. Compared with those under dark conditions, Mo‐Ni3S2@NMF achieve 10 mA cm−2 at 1.315 VRHE for UOR and 1.32 Vcell for urea electrolysis, which are decreases of 15 and 80 mV, respectively. The electron spin resonance, in situ Fourier transform infrared spectroscopy analysis and density functional theory calculations reveal that illumination led to the formation of Ni3+ active sites in a high‐spin state, which strengthens the d‐p orbital hybridization of Ni‐N, hence facilitating the adsorption of urea. C─N cleavage of the *CONN intermediate is further inhibited, which promotes the oxidation of urea molecules via the active N2 pathway, thereby accelerating the UOR rate. A novel illumination‐assisted strategy is reported to boost UOR, which leads to the formation of high‐spin state Ni3+ sites and facilitates the adsorption of urea. By utilizing AM1.5G illumination, the UOR current of Mo‐Ni3S2@NMF is significantly improved by 50%, and the onset potential for UOR and urea electrolysis is 1.315 and 1.32 V, which are decreased by 15 and 80 mV respectively compared to dark conditions.