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.
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
29 August 2013
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), .
(doi:10.1021/jp405549k).
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.
This record has no associated files available for download.
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
Catalogue record
Date deposited: 18 Nov 2013 13:41
Last modified: 29 Oct 2024 02:32
Export record
Altmetrics
Contributors
Author:
Otello Maria Roscioni
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
