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Simultaneous determination of structural and kinetic parameters characterizing the interconversion of highly dispersed species: the interaction of NO with Rh-I(CO)(2)/gamma-Al2O3

Simultaneous determination of structural and kinetic parameters characterizing the interconversion of highly dispersed species: the interaction of NO with Rh-I(CO)(2)/gamma-Al2O3
Simultaneous determination of structural and kinetic parameters characterizing the interconversion of highly dispersed species: the interaction of NO with Rh-I(CO)(2)/gamma-Al2O3
Energy-dispersive EXAFS (EDE), combined with mass spectrometry and a flow microreactor system, has been used to investigate the reaction of an Al2O3-supported Rh-I(CO)(2) species with NO. This combined in situ approach uniquely permits a priori analysis of the structures of the species involved (on a time scale of ca. 2 s) and simultaneous determination of reaction mechanism and kinetic parameters. In the current case, it is found that the Al(O)Rh-I(CO)(2)Cl species reacts to form an intermediate Al(O)Rh(NO)(2)Cl Cl species (v approximate to 0.357 +/- 0.125 s(-1), E-act approximate to 11 +/- 1.25 kJ mol(-1)), which subsequently forms an (AlO)(2)Rh(NO)Cl- species and N2O(g) (v approximate to 2 +/- 0.5 x 10(4) s(-1), E-act approximate to 40 +/- 3.5 kJ mol(-1)) showing a bent (134 degrees) RhNO bond. This combination of rapid and complementary techniques should be applicable to a wide range of disciplines where quantitative structural and kinetic determinations are of importance.
x-ray-absorption, in-situ, spectroscopy, catalysts, co, adsorption, chemistry, crystal, oxide
1089-5639
5965-5970
Newton, Mark A.
73aab2af-4641-47f3-89ad-3b7d3026164f
Burnaby, Daryl G.
51acab60-97a6-410e-bec8-86537860d185
Dent, Andrew J.
24c2a218-cb0e-4193-af0b-3ff1dc42b552
Diaz-Moreno, Sofia
4e280df3-7f62-4280-8058-2803c740ae00
Evans, John
05890433-0155-49fe-a65d-38c90ea25c69
Fiddy, Steven G.
f6c255cf-6aa1-4798-85ca-1a2ccdaa1186
Neisius, Thomas
22f85c0b-ae48-41ca-87f0-34ec82d2b496
Pascarelli, Sakura
183a2077-aa7f-4f27-801d-e32a9b650159
Turin, Sandra
6691348e-e3e2-4afb-8384-131a363a07d0
Newton, Mark A.
73aab2af-4641-47f3-89ad-3b7d3026164f
Burnaby, Daryl G.
51acab60-97a6-410e-bec8-86537860d185
Dent, Andrew J.
24c2a218-cb0e-4193-af0b-3ff1dc42b552
Diaz-Moreno, Sofia
4e280df3-7f62-4280-8058-2803c740ae00
Evans, John
05890433-0155-49fe-a65d-38c90ea25c69
Fiddy, Steven G.
f6c255cf-6aa1-4798-85ca-1a2ccdaa1186
Neisius, Thomas
22f85c0b-ae48-41ca-87f0-34ec82d2b496
Pascarelli, Sakura
183a2077-aa7f-4f27-801d-e32a9b650159
Turin, Sandra
6691348e-e3e2-4afb-8384-131a363a07d0

Newton, Mark A., Burnaby, Daryl G., Dent, Andrew J., Diaz-Moreno, Sofia, Evans, John, Fiddy, Steven G., Neisius, Thomas, Pascarelli, Sakura and Turin, Sandra (2001) Simultaneous determination of structural and kinetic parameters characterizing the interconversion of highly dispersed species: the interaction of NO with Rh-I(CO)(2)/gamma-Al2O3. Journal of Physical Chemistry A, 105 (25), 5965-5970. (doi:10.1021/jp011621x).

Record type: Article

Abstract

Energy-dispersive EXAFS (EDE), combined with mass spectrometry and a flow microreactor system, has been used to investigate the reaction of an Al2O3-supported Rh-I(CO)(2) species with NO. This combined in situ approach uniquely permits a priori analysis of the structures of the species involved (on a time scale of ca. 2 s) and simultaneous determination of reaction mechanism and kinetic parameters. In the current case, it is found that the Al(O)Rh-I(CO)(2)Cl species reacts to form an intermediate Al(O)Rh(NO)(2)Cl Cl species (v approximate to 0.357 +/- 0.125 s(-1), E-act approximate to 11 +/- 1.25 kJ mol(-1)), which subsequently forms an (AlO)(2)Rh(NO)Cl- species and N2O(g) (v approximate to 2 +/- 0.5 x 10(4) s(-1), E-act approximate to 40 +/- 3.5 kJ mol(-1)) showing a bent (134 degrees) RhNO bond. This combination of rapid and complementary techniques should be applicable to a wide range of disciplines where quantitative structural and kinetic determinations are of importance.

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Published date: 28 June 2001
Keywords: x-ray-absorption, in-situ, spectroscopy, catalysts, co, adsorption, chemistry, crystal, oxide

Identifiers

Local EPrints ID: 19580
URI: http://eprints.soton.ac.uk/id/eprint/19580
ISSN: 1089-5639
PURE UUID: 207d7af0-cb23-49a9-8993-9d33c494392f

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Date deposited: 14 Feb 2006
Last modified: 17 Jul 2017 16:31

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Contributors

Author: Mark A. Newton
Author: Daryl G. Burnaby
Author: Andrew J. Dent
Author: Sofia Diaz-Moreno
Author: John Evans
Author: Steven G. Fiddy
Author: Thomas Neisius
Author: Sakura Pascarelli
Author: Sandra Turin

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