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Formation of environmentally-persistent free radicals (EPFR) on α-Al2O3 clusters
Journal article   Open access   Peer reviewed

Formation of environmentally-persistent free radicals (EPFR) on α-Al2O3 clusters

N.W. Assaf, M. Altarawneh, M.W. Radny, J. Al-Nu'airat and B.Z. Dlugogorski
RSC Advances, Vol.7(83), pp.52672-52683
2017
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Abstract

Alumina oxides assume prominent catalytic applications in a wide range of industrial processes. However, alumina surfaces also serve as potent promoters in the heterogeneous formation of the notorious environmentally-persistent free radicals (EPFR). Herein, we theoretically examine dissociative adsorption mechanisms of phenol molecules over Al2O3 and hydrated Al2O3·nH2O clusters that mimic dehydrated and hydrated alumina structures, respectively. We show that fission of the phenol's hydroxyl bond over dehydrated alumina systematically incurs lower energy barriers in reference to the hydrated structures. A 1,2-water elimination step marks the most feasible channel in the interaction of phenol with hydrated clusters. The relevance of the acidity sites to the catalytic activity of alumina is clearly supported by the finding that the catalytic activity of the alumina surface in producing the phenoxy/phenolate species reversibly correlates with the degree of hydroxyl coverage. Desorption of adsorbed phenolates requires sizable desorption energies, and thus is expected to facilitate surface-mediated condensation into dioxin-like moieties.

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Collaboration types
Domestic collaboration
Citation topics
2 Chemistry
2.41 Catalysts
2.41.25 Catalytic Oxidation
Web Of Science research areas
Chemistry, Multidisciplinary
ESI research areas
Chemistry
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