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Selective hydrogenation of chloronitrobenzene to chloroaniline in supercritical carbon dioxide over Ni/TiO2: Significance of molecular interactions
| Title: | Selective hydrogenation of chloronitrobenzene to chloroaniline in supercritical carbon dioxide over Ni/TiO2: Significance of molecular interactions |
| Authors: | Meng, Xiangchun Browse this author | | Cheng, Haiyang Browse this author | | Fujita, Shin-ichiro Browse this author →KAKEN DB | | Hao, Yufen Browse this author | | Shang, Yanjiao Browse this author | | Yu, Yancun Browse this author | | Cai, Shuxia Browse this author | | Zhao, Fengyu Browse this author | | Arai, Masahiko Browse this author →KAKEN DB |
| Keywords: | Chloronitrobenzene | | Chloroaniline | | Hydrogenation | | Carbon dioxide | | Intermolecular interaction |
| Issue Date: | 1-Jan-2010 |
| Publisher: | Elsevier |
| Journal Title: | Journal of Catalysis |
| Volume: | 269 |
| Issue: | 1 |
| Start Page: | 131 |
| End Page: | 139 |
| Publisher DOI: | 10.1016/j.jcat.2009.10.024 |
| Abstract: | The hydrogenation of chloronitrobenzene to chloroaniline was investigated over Ni/TiO2 at 35℃ in supercritical CO2 (scCO2), ethanol, and n-hexane. The reaction rate followed the order of scCO2 > n-hexane > ethanol. In scCO2, the selectivity to chloroaniline and to aniline over Ni/TiO2 were 97-99.5% and < 1%, respectively, in the conversion range of 9-100%. The high chemoselectivity to chloroaniline cannot be achieved over Ni/TiO2 in ethanol and n-hexane. In situ high-pressure Fourier transform infrared measurements were made to study the molecular interactions of CO2 with the following reactant and reaction intermediates: chloronitrobenzene, chloronitrosobenzene, and N-chlorophenylhydroxylamine. The molecular interaction modifies the reactivity of each species and accordingly the reaction rate and the selectivity. The influence of Cl substituent on the interaction modes of CO2 with these reacting species is discussed. Possible reaction pathways for the hydrogenation of chloronitrobenzene in scCO2 over Ni/TiO2 are also proposed. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/42642 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 荒井 正彦
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