McAllister, M. I., Boulho, C., Gilpin, L. F., McMillan, L., Brennan, C. and Lennon, D. (2019) Hydrogenation of benzonitrile over supported Pd catalysts: kinetic and mechanistic insight. Organic Process Research and Development, 23(5), pp. 977-989. (doi: 10.1021/acs.oprd.9b00058)
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Abstract
The liquid phase hydrogenation of benzonitrile over a 5wt% Pd/C catalyst using a stirred autoclave is investigated. The reaction conforms to a consecutive reaction sequence: firstly benzonitrile is hydrogenated to produce benzylamine, which subsequently undergoes a hydrogenolysis step to form toluene. Benzonitrile hydrogenation obeys first order kinetics with an activation energy of 27.6 kJ mol−1. In contrast, the benzylamine hydrogenolysis stage obeys zero order kinetics and exhibits an activation energy of 80.1 kJ mol−1. A 1wt% Pd/Al2O3 catalyst is additionally examined, which is also seen to support hydrogenolysis activity alongside the hydrogenation pathway. Gas phase transmission infrared spectroscopic measurements of the hydrogenation of benzonitrile and benzylamine over the 1wt% Pd/Al2O3 catalyst utilising hydrogen and deuterium are undertaken, which enable reaction schemes incorporating adsorption geometries of intermediate adsorption complexes to be proposed.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Boulho, Dr Cedric and McAllister, Mairi and McMillan, Mr Liam and Gilpin, Miss Lauren and Lennon, Professor David |
| Authors: | McAllister, M. I., Boulho, C., Gilpin, L. F., McMillan, L., Brennan, C., and Lennon, D. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Organic Process Research and Development |
| Publisher: | American Chemical Society |
| ISSN: | 1083-6160 |
| ISSN (Online): | 1520-586X |
| Published Online: | 27 March 2019 |
| Copyright Holders: | Copyright © 2019 American Chemical Society |
| First Published: | First published in Organic Process Research and Development 23(5):977-989 |
| Publisher Policy: | Reproduced in accordance with the publisher copyright policy |
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