Journal article
Catalytic Hydrogenation of p-Chloronitrobenzene to p-Chloroaniline Mediated by γ-Mo2N
ACS Omega, Vol.3(10), pp.14380-14391
2018
Abstract
Promoting the production of industrially important aromatic chloroamines over transition-metal nitrides catalysts has emerged as a prominent theme in catalysis. This contribution provides an insight into the reduction mechanism of p-chloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN) over the γ-Mo2N(111) surface by means of density functional theory calculations. The adsorption energies of various molecularly adsorbed modes of p-CNB were computed. Our findings display that, p-CNB prefers to be adsorbed over two distinct adsorption sites, namely, Mo-hollow face-centered cubic (fcc) and N-hollow hexagonal close-packed (hcp) sites with adsorption energies of −32.1 and −38.5 kcal/mol, respectively. We establish that the activation of nitro group proceeds through direct pathway along with formation of several reaction intermediates. Most of these intermediaries reside in a significant well-depth in reference to the entrance channel. Central to the constructed mechanism is H-transfer steps from fcc and hcp hollow sites to the NO/–NH groups through modest reaction barriers. Our computed rate constant for the conversion of p-CNB correlates very well with the experimental finding (0.018 versus 0.033 s–1 at ∼500 K). Plotted species profiles via a simplified kinetics model confirms the experimentally reported high selectivity toward the formation of p-CAN at relatively low temperatures. It is hoped that thermokinetics parameters and mechanistic pathways provided herein will afford a molecular level understanding for γ-Mo2N-mediated conversion of halogenated nitrobenzenes into their corresponding nitroanilines; a process that entails significant industrial applications.
Details
- Title
- Catalytic Hydrogenation of p-Chloronitrobenzene to p-Chloroaniline Mediated by γ-Mo2N
- Authors/Creators
- Z.N. Jaf (Author/Creator) - University of BaghdadM. Altarawneh (Author/Creator) - Al-Hussein Bin Talal UniversityH.A. Miran (Author/Creator) - University of BaghdadM.H. Almatarneh (Author/Creator) - University of JordanZ-T Jiang (Author/Creator) - Murdoch UniversityB.Z. Dlugogorski (Author/Creator) - Murdoch University
- Publication Details
- ACS Omega, Vol.3(10), pp.14380-14391
- Publisher
- American Chemical Society
- Identifiers
- 991005542731907891
- Copyright
- © 2018 American Chemical Society
- Murdoch Affiliation
- School of Engineering and Information Technology
- Language
- English
- Resource Type
- Journal article
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- Collaboration types
- Domestic collaboration
- International collaboration
- Citation topics
- 2 Chemistry
- 2.41 Catalysts
- 2.41.1843 Nitroarene Hydrogenation
- Web Of Science research areas
- Chemistry, Multidisciplinary
- ESI research areas
- Chemistry