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Photosynthesis of Benzonitriles on BiOBr Nanosheets Promoted by Vacancy Associates |
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| Authors: | Dr Tong Han Dr Xing Cao Dr Hsiao-Chien Chen Junguo Ma Yuan Yu Yuhuan Li Wei Xu Dr Kaian Sun Aijian Huang Dr Zheng Chen Prof Chen Chen Prof Hongjun Zhang Prof Bangjiao Ye Prof Qing Peng Prof Yadong Li |
| Institution: | 1. Department of Chemistry, Tsinghua University, Beijing, 100084 China
These authors contributed equally to this work.;2. Department of Chemistry, Tsinghua University, Beijing, 100084 China;3. Center for Reliability Science and Technologies, Chang Gung University, Taoyuan, 33302 Taiwan Kidney Research Center, Department of Nephrology, Chang Gung Memorial Hospital, Linkou, Taoyuan, 33305 Taiwan;4. State Key Laboratory of Particle Detection and Electronics, University of Science and Technology of China, Hefei, 230026 China;5. Key Laboratory of Functional Molecular Solids, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, 241002 China |
| Abstract: | Photocatalytic organic functionalization reactions represent a green, cost-effective, and sustainable synthesis route for value-added chemicals. However, heterogeneous photocatalysis is inefficient in directly activating ammonia molecules for the production of high-value-added nitrogenous organic products when compared with oxygen activation in the formation of related oxygenated compounds. In this study, we report the heterogeneous photosynthesis of benzonitriles by the ammoxidation of benzyl alcohols (99 % conversion, 93 % selectivity) promoted using BiOBr nanosheets with surface vacancy associates. In contrast, the main reaction of catalysts with other types of vacancy sites is the oxidation of benzyl alcohol to benzaldehyde or benzoic acid. Experimental measurements and theoretical calculations have demonstrated a specificity of vacancy type with respect to product selectivity, which arises from the adsorption and activation of NH3 and O2 that is required to promote subsequent C−N coupling and oxidation to nitrile. This study provides a better understanding of the role of vacancies as catalytic sites in heterogeneous photocatalysis. |
| Keywords: | Ammoxidation Benzonitriles Nanostructure Photocatalysts Vacancy Associates |