The Zehui Zhang team's work on iron-modified TiO₂ photocatalysis has been published at Journal of the American Chemical Society. Congratulations!

In this paper, a green system consisting of Fe/TiO₂ photocatalyst and NH₄Br has been developed, which is used to catalyze the ammoxidation of alcohol to produce nitriles at room temperature using O₂ and NH₃. It has excellent yield of nitriles. The new mechanism found in this study is of great significance for the design of other photocatalytic systems (using catalysts and additives from rich materials to produce fine chemicals). The well-dispersed Fe (III) species in TiO₂ lattice will not reduce the oxidation potential of alcohol, but will effectively enhance the adsorption of NH₃ and intermediate, and promote the cyanidation of aldehyde intermediate. The Br^– of NH₄Br additive is oxidized to produce living Br^• free radicals under light irradiation. These consume the strong oxidant produced in the photocatalysis system, avoid the excessive oxidation of alcohol, and increase the adsorption of NH₃ and intermediate. Br^• Radical acceleration C α– cleavage of H bond which is the key step in the ammoxidation of alcohol to produce nitrile. This study provides a new strategy for the green synthesis of nitriles and provides ideas for the synthesis of more value-added products through the selective oxidation process.

Read more: https://doi.org/10.1021/jacs.2c07061