Catalytic Hydrogenation of p-Chloronitrobenzene to p-Chloroaniline Mediated by γ-Mo2N

Z.N. Jaf; M. Altarawneh; H.A. Miran; M.H. Almatarneh; Z-T Jiang; B.Z. Dlugogorski

doi:10.1021/acsomega.8b01936

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Catalytic Hydrogenation of p-Chloronitrobenzene to p-Chloroaniline Mediated by γ-Mo2N

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Catalytic Hydrogenation of p-Chloronitrobenzene to p-Chloroaniline Mediated by γ-Mo2N

Z.N. Jaf, M. Altarawneh, H.A. Miran, M.H. Almatarneh, Z-T Jiang and B.Z. Dlugogorski

ACS Omega, Vol.3(10), pp.14380-14391

2018

DOI: https://doi.org/10.1021/acsomega.8b01936

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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 Baghdad
M. Altarawneh (Author/Creator) - Al-Hussein Bin Talal University
H.A. Miran (Author/Creator) - University of Baghdad
M.H. Almatarneh (Author/Creator) - University of Jordan
Z-T Jiang (Author/Creator) - Murdoch University
B.Z. Dlugogorski (Author/Creator) - Murdoch University
Publication Details: ACS Omega, Vol.3(10), pp.14380-14391
Publisher: American Chemical Society
Identifiers: 991005542731907891
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