Bi₂Ti₂O₇ Quantum Dots for Efficient Photocatalytic Fixation of Nitrogen to Ammonia: Impacts of Shallow Energy Levels

Photocatalytic fixation of nitrogen to ammonia represents an attractive alternative to the Haber-Bosch process under ambient conditions, and the performance can be enhanced by defect engineering of the photocatalysts, in particular, formation of shallow energy levels due to oxygen vacancies that can significantly facilitate the adsorption and activation of nitrogen. This calls for deliberate size engineering of the photocatalysts. In the present study, pyrochlore Bi₂Ti₂O₇ quantum dots and (bulk-like) nanosheets are prepared hydrothermally by using bismuth nitrate and titanium sulfate as the precursors. Despite a similar oxygen vacancy concentration, the quantum dots exhibit a drastically enhanced photocatalytic performance toward nitrogen fixation, at a rate of 332.03 µmol g^-1 h^-1, which is 77 times higher than that of the nanosheet counterpart. Spectroscopic and computational studies based on density functional theory calculations show that the shallow levels arising from oxygen vacancies in the Bi₂Ti₂O₇ quantum dots, in conjunction with the moderately constrained quantum confinement effect, facilitate the chemical adsorption and activation of nitrogen.