Synergistic Spatial Confining Effect and O Vacancy in WO3 Hollow Sphere for Enhanced N2 Reduction

Visible-light-driven N2 reduction into NH3 in pure H2O provides an energy-saving alternative to the Haber–Bosch process for ammonia synthesizing. However, the thermodynamic stability of N≡N and low water solubility of N2 remain the key bottlenecks. Here, we propose a solution by developing a WO3−x hollow sphere with oxygen vacancies. Experimental analysis reveals that the hollow sphere structure greatly promotes the enrichment of N2 molecules in the inner cavity and facilitates the chemisorption of N2 onto WO3−x-HS. The outer layer’s thin shell facilitates the photogenerated charge transfer and the full exposure of O vacancies as active sites. O vacancies exposed on the surface accelerate the activation of N≡N triple bonds. As such, the optimized catalyst shows a NH3 generation rate of 140.08 μmol g−1 h−1, which is 7.94 times higher than the counterpart WO3-bulk.