Electron repulsion tuned electronic structure of TiO2 by fluorination for efficient and selective photocatalytic ammonia generation.

The photocatalytic conversion of nitrogen into high-value ammonia products holds tremendous potential in the global nitrogen cycle. However, the activation of N2 and competition of hydrogen evolution limit the improvement of nitrogen fixation performance. In this study, we developed a fluorinated TiO2 (F-TiO2) using a hydrothermal-annealing method. The incorporation of F dopants not only enhances the adsorption and activation of N2 through electronic structure regulation, but also facilitates an in situ increase in active sites via the electron repulsion effect between F and Ti atoms. In addition, the presence of F on the surface effectively improved the nitrogen supply problem and optimized the nitrogen fixation selectivity for its hydrophobic modulation. The NH3 yield of the F-TiO2 photocatalyst reached 63.8 µmol h-1 g-1, which was 8.5 times higher than that of pure TiO2. And the selectivity experiment showed that the electronic ratio of NH3 to H2 production reached 0.890. This research offers valuable insights for the design of highly efficient and selective nitrogen-fixing photocatalysts.

Defect-induced charge redistribution of MoO3-x nanometric wires for photocatalytic ammonia synthesis.

Photocatalytic ammonia synthesis technology has become one of the effective methods to replace the Haber method for nitrogen fixation in the future for its low energy consumption and green environment. However, limited by the weak adsorption/activation ability of N2 molecules at the photocatalyst interface, the efficient nitrogen fixation still remains a daunting job. Defect-induced charge redistribution as a catalytic site for N2 molecules is the most prominent strategy to enhance the adsorption/activation of N2 molecules at the interface of catalysts. In this study, MoO3-x nanowires containing asymmetric defects were prepared by a one-step hydrothermal method via using glycine as a defect inducer. It is shown that at the atomic scale, the defect-induced charge reconfiguration can significantly improve the nitrogen adsorption and activation capacity and enhance the nitrogen fixation capacity; at the nanoscale, the charge redistribution induced by asymmetric defects effectively improved the photogenerated charge separation. Given the charge redistribution on the atomic and nanoscale of MoO3-x nanowires, the optimal nitrogen fixation rate of MoO3-x reached 200.35 µmol g-1h-1.