Perret, N., Alexander, A.-M., Hunter, S. M., Chung, P., Hargreaves, J. S.J. , Howe, R. F. and Keane, M. A. (2014) Synthesis, characterisation and hydrogenation performance of ternary nitride catalysts. Applied Catalysis A: General, 488, pp. 128-137. (doi: 10.1016/j.apcata.2014.09.026)
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Publisher's URL: http://dx.doi.org/10.1016/j.apcata.2014.09.026
Abstract
Synthesis of phase pure Co<sub>3</sub>Mo<sub>3</sub>N and Fe<sub>3</sub>Mo<sub>3</sub>N by temperature programmed ammonolysis has been established by XRD and elemental analysis. The ternary nitrides are characterised by a η-6 structure and low surface area (4-9 m<sup>2</sup> g<sup>−1</sup>). Pseudomorphic transformation of cobalt nitrate generated rod-shaped crystals while the use of iron chloride resulted in Fe<sub>3</sub>Mo<sub>3</sub>N aggregates with irregular morphology and wide size distribution. XPS measurements have revealed surface N enrichment relative to the bulk where the passivated samples show a range of oxidation states; Co<sub>3</sub>Mo<sub>3</sub>N exhibited Mo<sup>2+</sup> and Co<sup>n+</sup> (0 ≤ n ≤ 3) whereas Fe<sub>3</sub>Mo<sub>3</sub>N was characterised by higher oxidation states (Fe<sup>3+</sup> and Mo<sup>3+</sup>). Temperature programmed reduction (TPR) to 823 K served to remove the passivation layer where subsequent H<sub>2</sub>chemisorption and temperature programmed desorption (TPD) has demonstrated greater uptake on Fe<sub>3</sub>Mo<sub>3</sub>N relative to Co<sub>3</sub>Mo<sub>3</sub>N, resulting in a higher nitrobenzene hydrogenation rate (to aniline). Fe<sub>3</sub>Mo<sub>3</sub>N promoted selective reduction of–NO<sub>2</sub> in p-chloronitrobenzene to generate p-chloroaniline as sole product whereas Co<sub>3</sub>Mo<sub>3</sub>N favoured C-Cl scission with the formation of nitrobenzene (in addition to p-chloroaniline). Hydrodechlorination properties were further established for Co<sub>3</sub>Mo<sub>3</sub>N in the conversion of chlorobenzene (to benzene) under conditions where Fe<sub>3</sub>Mo<sub>3</sub>N was inactive. A temporal deactivation of both nitrides is associated with Cl poisoning of Co3Mo3N and structural changes to Fe<sub>3</sub>Mo<sub>3</sub>N.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Alexander, Miss Anne-Marie and Hunter, Mr Stuart and Hargreaves, Professor Justin and Chung, Mr Peter |
| Authors: | Perret, N., Alexander, A.-M., Hunter, S. M., Chung, P., Hargreaves, J. S.J., Howe, R. F., and Keane, M. A. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Applied Catalysis A: General |
| Publisher: | Elsevier |
| ISSN: | 0926-860X |
| ISSN (Online): | 1873-3875 |
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