The University of Southampton
University of Southampton Institutional Repository

Structural characterisation of supported Rh(CO)2/gam-Al2O3 catalysts by periodic DFT calculations

Structural characterisation of supported Rh(CO)2/gam-Al2O3 catalysts by periodic DFT calculations
Structural characterisation of supported Rh(CO)2/gam-Al2O3 catalysts by periodic DFT calculations
Microscopic structures of monodispersed rhodium dicarbonyl species chemisorbed on a ceramic metal-oxide support (?-alumina) have been obtained by density functional theory (DFT) calculations with periodic boundary conditions applied. Several minimum energy structures of species were obtained and their relative energies indicate that, in the most energetically stable geometry, the rhodium atom is coordinated in a square-planar environment and forms a four-membered Rh–O–Al–O ring, with one Al atom octahedrally coordinated. Another docking geometry, close lying in energy, also has a square-planar coordination for the rhodium atom and involves a six-membered Rh–O–Al–O–Al–O ring with one Al octahedrally coordinated and one Al tetrahedrally coordinated. Computed bond lengths were found to be in reasonable agreement with experimental bond lengths as determined by EXAFS spectroscopy. Theoretical Rh K-edge XANES spectra suggest that the pre-edge region probes electronic states localized on the RhI(CO)2 unit, while postedge features probe the electronic states arising from the RhI(CO)2 interaction with the support, which partly depends on the docking geometry of the RhI(CO)2 units.
1932-7447
19464-19470
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Roscioni, Otello Maria
1e75cd73-a2ed-4e6a-9f8f-25c9ffe1e271
Evans, John
05890433-0155-49fe-a65d-38c90ea25c69
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Roscioni, Otello Maria
1e75cd73-a2ed-4e6a-9f8f-25c9ffe1e271
Evans, John
05890433-0155-49fe-a65d-38c90ea25c69

Dyke, John M., Roscioni, Otello Maria and Evans, John (2013) Structural characterisation of supported Rh(CO)2/gam-Al2O3 catalysts by periodic DFT calculations The Journal of Physical Chemistry C, 117, (38), pp. 19464-19470. (doi:10.1021/jp405549k).

Record type: Article

Abstract

Microscopic structures of monodispersed rhodium dicarbonyl species chemisorbed on a ceramic metal-oxide support (?-alumina) have been obtained by density functional theory (DFT) calculations with periodic boundary conditions applied. Several minimum energy structures of species were obtained and their relative energies indicate that, in the most energetically stable geometry, the rhodium atom is coordinated in a square-planar environment and forms a four-membered Rh–O–Al–O ring, with one Al atom octahedrally coordinated. Another docking geometry, close lying in energy, also has a square-planar coordination for the rhodium atom and involves a six-membered Rh–O–Al–O–Al–O ring with one Al octahedrally coordinated and one Al tetrahedrally coordinated. Computed bond lengths were found to be in reasonable agreement with experimental bond lengths as determined by EXAFS spectroscopy. Theoretical Rh K-edge XANES spectra suggest that the pre-edge region probes electronic states localized on the RhI(CO)2 unit, while postedge features probe the electronic states arising from the RhI(CO)2 interaction with the support, which partly depends on the docking geometry of the RhI(CO)2 units.

Full text not available from this repository.

More information

Published date: 29 August 2013
Organisations: Computational Systems Chemistry

Identifiers

Local EPrints ID: 359940
URI: http://eprints.soton.ac.uk/id/eprint/359940
ISSN: 1932-7447
PURE UUID: 636f0def-47b0-4932-8af0-13fbf8a70b07
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

Catalogue record

Date deposited: 18 Nov 2013 13:41
Last modified: 18 Jul 2017 03:16

Export record

Altmetrics

Contributors

Author: John M. Dyke ORCID iD
Author: Otello Maria Roscioni
Author: John Evans

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×