N-doping TiO₂ hollow microspheres with abundant oxygen vacancies for highly photocatalytic nitrogen fixation

Photocatalytic fixation of nitrogen to ammonia (NH₃) is a green but low-efficiency technology due to the high recombination of photo-generated carriers and poor light absorption of photocatalysts. Generally, the adsorption capacity for N₂ and the band position of TiO₂ are responsible for bandgap, light-adsorption, and the separation of photocarriers. Therefore, they play crucial roles to improve catalytic activity. Herein, N-doping TiO₂ hollow microspheres (NTO-0.5) with oxygen vacancies were synthesized via a hydrothermal method using phenolic resin microsphere as a template. The obtained NTO-0.5 achieves an impressive ammonia yield of 80.09 μmol g_cat^-1h^-1. Oxygen vacancies of NTO-0.5 were confirmed by ESR, Raman, XPS, Zeta potential, and H₂O₂ treatment for reducing oxygen vacancies. The ammonia yield of NTO-0.5 decreases to 34.78 μmol g_cat^-1h^-1 after reducing oxygen vacancies by H₂O₂ treatment, which demonstrates the importance of oxygen vacancies. The oxygen vacancies narrow the bandgap from 3.18 eV to 2.83 eV and impede the recombination of photo-generated carriers. The hollow microspheres structure is conducive to light absorption and utilization. Therefore, the synergistic effect between the oxygen vacancies and the hollow microspheres structure boosts the efficiency of photocatalytic nitrogen fixation. After four cycles, the ammonia production yield still maintains at 76.52 μmol g_cat^-1h^-1, meaning high stability. This work provides a new insight into the construction of catalysts with oxygen vacancies to enhance photocatalytic nitrogen fixation performance.