NO + H2 Reaction over Pd(110): TPD, TPR and DFT Study Full article
| Journal |
Molecular Catalysis
ISSN: 2468-8231 |
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| Output data | Year: 2018, Volume: 448, Pages: 53-62 Pages count : 10 DOI: 10.1016/j.mcat.2018.01.009 | ||||
| Tags | DFT, NO dissociation, NO reduction, Palladium, Surface chemical reactions | ||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Federal Agency for Scientific Organizations | 0303-2016-0003 |
| 2 | Federal Agency for Scientific Organizations | 0303-2016-0001 |
Abstract:
Temperature-programming desorption (TPD) and temperature-programmed reaction (TPR) have been applied to study the reduction of 15NO by deuterium on a Pd(110) surface. TPR results show that the reaction occurs in the autocatalytic regime of surface explosion with the rate-limiting step of 15NOads dissociation into highly reactive Oads and 15Nads atoms. The steady-state reaction leads to formation of 15N2, D2O, 15ND3 and 15N2O products. The phenomena of a reaction rate hysteresis observed during a heating-cooling cycle can be attributed to accumulation of 15NOads at low temperatures followed by surface explosion at T ∼ 490 K. The binding energies and structural parameters of species involved in the NO + H2 reaction over Pd(110) have been calculated by the DFT technique, and plausible reaction pathways have been considered. NO dissociation from the most stable short bridge site (Eb = −1.94 eV) occurs via the intermediates in on-top and long bridge modes with lower binding energy (Eb = −1.31 to 1.65 eV). The energy of transition states reaches 0.2–0.26 eV over energy of NO in a gas phase, which confirms the rate-limiting role of NO dissociation. It has been demonstrated that OHads-group formation is the rate-limiting step of water molecule generation. Subsequent H2O formation occurs via disproportionation of the OHads intermediates.
Cite:
Bryliakova A.A.
, Matveev A.V.
, Tapilin V.M.
, Gorodetskii V.V.
NO + H2 Reaction over Pd(110): TPD, TPR and DFT Study
Molecular Catalysis. 2018. V.448. P.53-62. DOI: 10.1016/j.mcat.2018.01.009 WOS Scopus РИНЦ ANCAN OpenAlex
NO + H2 Reaction over Pd(110): TPD, TPR and DFT Study
Molecular Catalysis. 2018. V.448. P.53-62. DOI: 10.1016/j.mcat.2018.01.009 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Oct 1, 2017 |
| Accepted: | Jan 10, 2018 |
| Published online: | Feb 21, 2018 |
| Published print: | Apr 1, 2018 |
Identifiers:
| Web of science: | WOS:000428498500007 |
| Scopus: | 2-s2.0-85042407334 |
| Elibrary: | 35531700 |
| Chemical Abstracts: | 2018:1320087 |
| Chemical Abstracts (print): | 169:311734 |
| OpenAlex: | W2792718760 |