Photochemical Ammonia Synthesis over Reduced Polyoxovanadate-Intercalated Defective ZnAl Layered Double Hydroxide Nanosheets

The exploration of efficient and stable N₂ fixation photocatalysts featuring a broad absorption spectrum and N₂ fixation active sites has become specifically conspicuous. Herein, a series of reduced polyoxovanadates (POVs) were intercalated into copper-induced ZnAl layered double hydroxide (0.5%-ZnAl LDH) nanosheets with oxygen vacancies via an anion exchange strategy toward green ammonia production. The intervalence charge transfer arising from mixed-valence POV materials is responsible for its light-harvesting behavior, and the LDHs lay the foundation for the chemical adsorption and activation process of nitrogen molecules; both contributions facilitate the nitrogen photofixation performance of such composite materials. As predicted, the catalytic efficiency of V₃₄/0.5%-ZnAl is 7.0 times higher than 0.5%-ZnAl LDH. Therefore, such an all-inorganic system exhibits an apparent quantum efficiency of 0.3137% at 500 nm. The strategy of "working in tandem" established by POV-based light-absorber species and oxygen vacancies as the sites for N₂ activation is extremely vital for enhanced ammonia formation. This work opens up a versatile insight for the rational design of an efficient photo-driven nitrogen-reduction composite catalyst toward sustainable ammonia production compared to the industrial Haber-Bosch process.