Computational study of the structural and electronic properties of dopant ions in microporous AlPOs. 2. Redox catalytic activity of trivalent transition metal ions

Saadoune, I. and Cora, F. and Alfredsson, M. and Catlow, C.R.A. (2003) Computational study of the structural and electronic properties of dopant ions in microporous AlPOs. 2. Redox catalytic activity of trivalent transition metal ions. Journal of Physical Chemistry B, 107 (13). pp. 3012-3018. ISSN 1520-6106. (The full text of this publication is not available from this repository)

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Abstract

Periodic ab initio QM calculations are employed in order to study the structure and redox properties of Cr, Mn, Fe. and Co trivalent transition metal dopants in AlPO-34. Our results show that the local environment of Mn and Co dopants is a distorted tetrahedron due to Jahn-Teller distortions. The bonding between the Me-III dopants and the neighboring oxygens is ionic in nature, and explains the Lewis acidity of the Me-III ions. The replacement energy DeltaE(III) of the 3+ dopant ions in AlPO-34 increases linearly as a function of the Me-O bond distance. Finally, the calculated redox energies of the Me-II/Me-III couples indicate that, among the transition metal ions investigated, Fe is the most stable in the 3+ oxidation state, whereas Mn is the most stable as 2+ ion. Cr and Co, instead, have intermediate behavior and can switch more easily between the two oxidation states. These results contribute to elucidate the mechanistic details of catalytic processes occurring in MeAlPOs.

Item Type: Article
Additional information: ISI Document Delivery No.: 662AC Times Cited: 5 Cited Reference Count: 42
Uncontrolled keywords: MOLECULAR-SIEVE CATALYSTS X-RAY-ABSORPTION SELECTIVE OXIDATION ALUMINUM PHOSPHATE AQUEOUS-SOLUTIONS WATER CLUSTERS HYDRATION ALUMINOPHOSPHATES SPECTROSCOPY DIFFRACTION
Subjects: Q Science
Divisions: Faculties > Science Technology and Medical Studies > School of Physical Sciences > Functional Materials Group
Depositing User: Maria Alfredsson
Date Deposited: 05 Sep 2008 12:03
Last Modified: 14 Jan 2010 14:17
Resource URI: http://kar.kent.ac.uk/id/eprint/4784 (The current URI for this page, for reference purposes)
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