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A RAIRS, TPD and femtosecond laser-induced desorption study of CO, NO and coadsorbed CO + NO on Pd(111)

A RAIRS, TPD and femtosecond laser-induced desorption study of CO, NO and coadsorbed CO + NO on Pd(111)
A RAIRS, TPD and femtosecond laser-induced desorption study of CO, NO and coadsorbed CO + NO on Pd(111)
Here we present a systematic study of the adsorption and laser induced desorption of CO, NO and CO + NO from a Pd(111) surface at a number of different coverages. We begin by characterising the surfaces using reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). Experiments show that NO displaces pre-adsorbed CO considerably, but that CO has a much smaller effect on pre-adsorbed NO. In both cases, the preferred binding sites of CO are occupied by NO, displacing it to less favourable adsorption sites. Femtosecond laser induced desorption (fs-LID) shows that desorption of CO on Pd(111) follows a power law and is fairly independent of CO coverage, but for NO on Pd(111) we observe a clear deviation from a power law curve at higher coverages, with saturation being observed. This suggests that the cross-section for LID of NO is much larger than that for CO and that NO on Pd(111) is more photoactive than CO on Pd(111). Interestingly, for CO + NO on Pd(111) we find that coadsorption has a strong influence on the photodesorption process and that the structure of the overlayer is also important in controlling the photodesorption products, regardless of the order in which the two molecules are dosed
2046-2069
66346-66359
Butorac, J.
d6863d0d-5a86-4ed0-bd89-1d610404a16f
Wilson, E.L.
ec1e7619-eb7e-4818-89d7-968990e8638a
Fielding, H.H.
02d57d59-c588-4c85-98de-cc74e7325649
Brown, W.A.
35598e98-6b3f-47c2-953b-1087c7ee55f1
Minns, R.
85280db4-c5a6-4a4c-82fe-75693c6a6045
Butorac, J.
d6863d0d-5a86-4ed0-bd89-1d610404a16f
Wilson, E.L.
ec1e7619-eb7e-4818-89d7-968990e8638a
Fielding, H.H.
02d57d59-c588-4c85-98de-cc74e7325649
Brown, W.A.
35598e98-6b3f-47c2-953b-1087c7ee55f1
Minns, R.
85280db4-c5a6-4a4c-82fe-75693c6a6045

Butorac, J., Wilson, E.L., Fielding, H.H., Brown, W.A. and Minns, R. (2016) A RAIRS, TPD and femtosecond laser-induced desorption study of CO, NO and coadsorbed CO + NO on Pd(111). RSC Advances, 6 (70), 66346-66359. (doi:10.1039/C6RA13722A).

Record type: Article

Abstract

Here we present a systematic study of the adsorption and laser induced desorption of CO, NO and CO + NO from a Pd(111) surface at a number of different coverages. We begin by characterising the surfaces using reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). Experiments show that NO displaces pre-adsorbed CO considerably, but that CO has a much smaller effect on pre-adsorbed NO. In both cases, the preferred binding sites of CO are occupied by NO, displacing it to less favourable adsorption sites. Femtosecond laser induced desorption (fs-LID) shows that desorption of CO on Pd(111) follows a power law and is fairly independent of CO coverage, but for NO on Pd(111) we observe a clear deviation from a power law curve at higher coverages, with saturation being observed. This suggests that the cross-section for LID of NO is much larger than that for CO and that NO on Pd(111) is more photoactive than CO on Pd(111). Interestingly, for CO + NO on Pd(111) we find that coadsorption has a strong influence on the photodesorption process and that the structure of the overlayer is also important in controlling the photodesorption products, regardless of the order in which the two molecules are dosed

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Accepted/In Press date: 5 July 2016
e-pub ahead of print date: 5 July 2016
Published date: 5 July 2016
Additional Information: Funded by Royal Society: Royal Society Fellowship (UF100047)
Organisations: Computational Systems Chemistry

Identifiers

Local EPrints ID: 397836
URI: https://eprints.soton.ac.uk/id/eprint/397836
ISSN: 2046-2069
PURE UUID: b26d5dbd-2d03-4cc6-9cac-ae5f644eee3c
ORCID for R. Minns: ORCID iD orcid.org/0000-0001-6775-2977

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Date deposited: 07 Jul 2016 12:53
Last modified: 14 Jul 2018 00:31

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Contributors

Author: J. Butorac
Author: E.L. Wilson
Author: H.H. Fielding
Author: W.A. Brown
Author: R. Minns ORCID iD

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