Hydroxyl-group-modified polymeric carbon nitride with the highly selective hydrogenation of nitrobenzene toN-phenylhydroxylamine under visible light

Pei, Linjuan; Tan, Hao; Liu, Meixian; Wang, Ruiyi; Gu, Xianmo; Ke, Xuebin; Jia, Jianfeng; Zheng, Zhanfeng

Abstract

Regulating the surface properties of catalysts to control the selectivity of a reaction is a fascinating approach. Bulk polymeric carbon nitride exhibits a poorN-phenylhydroxylamine yield in nitrobenzene reduction reaction mainly due to the uncontrollable condensation side reactions. Thus, adjusting the structure of the catalyst was key to solving the above issue. Herein, -OH groups-modified polymeric carbon nitride was preparedviaa simple hydrothermal treatment. With the introduced -OH groups replacing the terminal amino groups (-NH2) at the surface of the polymeric carbon nitride, a 3-fold increase in reaction rate was achieved, along with a high selectivity towardN-phenylhydroxylamine (ca.80%). The introduced -OH group was found to be beneficial to the adsorption of the nitrobenzene, based on the density functional theory (DFT) calculation. It could also lower the recombination rate of photoinduced electron-hole pairs, which would accelerate the photocatalytic oxidation of isopropanol and supply more protons to participate in the hydrogen-transfer process. Moreover, the elevated conduction band position after -OH modification would provide high energetic photogenerated electrons to promote the reduction of nitrobenzene. These are all important to guarantee the highly selective production ofN-phenylhydroxylamine. This paper not only provides a simple and green approach for the modification of polymeric carbon nitride toward an efficient photocatalyst, but also sheds light on the further study of the selective hydrogenation.

Citation

Pei, L., Tan, H., Liu, M., Wang, R., Gu, X., Ke, X., …Zheng, Z. (2021). Hydroxyl-group-modified polymeric carbon nitride with the highly selective hydrogenation of nitrobenzene toN-phenylhydroxylamine under visible light. Green chemistry : an international journal and green chemistry resource : GC, 23(10), 3612-3622. https://doi.org/10.1039/d1gc00325a

• Journal Article Type: Article
• Acceptance Date: Apr 12, 2021
• Online Publication Date: Apr 12, 2021
• Publication Date: May 21, 2021
• Deposit Date: May 27, 2021
• Publicly Available Date: May 28, 2021
• Journal: Green Chemistry
• Print ISSN: 1463-9262
• Electronic ISSN: 1463-9270
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 23
• Issue: 10
• Pages: 3612-3622
• DOI: https://doi.org/10.1039/d1gc00325a
• Keywords: Pollution; Environmental Chemistry
• Public URL: https://hull-repository.worktribe.com/output/3761771