Efficient Co/NSPC catalyst for selective hydrogenation of halonitrobenzenes and mechanistic insight

• Published in: Catalysis science & technology Vol. 14; no. 5; pp. 1167 - 118
• Main Authors: Xu, Jiahui, Chen, Xianlang, Bai, Jia-qi, Miao, Zhengan, Tan, Yuan, Zhan, Nannan, Liu, Huangfei, Ma, Mei, Cai, Mengdie, Cheng, Qin, Sun, Song
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 05.03.2024
• Subjects: Catalysts; Fine chemicals; Hydrogenation; Noble metals; Reaction mechanisms; Selectivity; Substrates
• ISSN: 2044-4753; 2044-4761
• DOI: 10.1039/d3cy01767b

The selective hydrogenation of halonitrobenzenes (HNBs) to haloanilines (HANs) is an efficient method to prepare key intermediates in the fine chemical industry. It is still a challenge to develop non-noble metal-based heterogeneous hydrogenation catalysts to achieve high activity and selectivity for this reaction. Herein, we reported a N, S co-doped mesoporous carbon supported Co catalyst for hydrogenation of HNBs, the prepared 5%Co/NSPC-800 catalyst showed superior catalytic performance with a TOF s of 203 h −1 and >99.9% selectivity to p -chloroaniline ( p -CAN), and it also exhibited wide substrate applicability and can be reused at least 4 times. Furthermore, the reaction mechanism of p -CNB hydrogenation over 5%Co/NSPC-800 was proposed on the basis of kinetic studies, spectroscopic studies, and DFT calculations. The hydrogenation of p -CNB over 5%Co/NSPC-800 followed the condensation route, and Co 0 and Co-N x were the main active sites for this reaction. 5%Co/NSPC-800 acted as an effective and robust heterogeneous catalyst for hydrogenation of halonitrobenzenes, and the superior catalytic performance can be ascribed to the synergistic effect of Co-N x and Co 0 .