Synergy of Photogenerated Electrons and Holes toward Efficient Photocatalytic Urea Synthesis from CO2 and N2

Directly coupling N2 and CO2 to synthesize urea by photocatalysis paves a sustainable route for urea synthesis, but its performance is limited by the competition of photogenerated electrons between N2 and CO2, as well as the underutilized photogenerated holes. Herein, we report an efficient urea synthesis process involving photogenerated electrons and holes in respectively converting CO2 and N2 over a redox heterojunction consisting of WO3 and Ni single‐atom‐decorated CdS (Ni1‐CdS/WO3). For the photocatalytic urea synthesis from N2 and CO2 in pure water, Ni1‐CdS/WO3 attained a urea yield rate of 78 μM h−1 and an apparent quantum yield of 0.15 % at 385 nm, which ranked among the best photocatalytic urea synthesis performance reported. Mechanistic studies reveal that the N2 was converted into NO species by ⋅OH radicals generated from photogenerated holes over the WO3 component, meanwhile, the CO2 was transformed into *CO species over the Ni site by photogenerated electrons. The generated NO and *CO species were further coupled to form *OCNO intermediate, then gradually transformed into urea. This work emphasizes the importance of reasonably utilizing photogenerated holes in photocatalytic reduction reactions. For a catalyst consisting of WO3 and Ni single‐atom‐decorated CdS, the N2 is converted into NO species by ⋅OH radicals generated from photogenerated holes, meanwhile the CO2 is transformed into *CO species by photogenerated electrons. The generated NO and *CO species are further coupled and gradually transformed into urea.