Catalytic Activity of γ-Al2O3(110) in the NO + H2 Reaction: A DFT Study Full article
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PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084 |
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| Output data | Year: 2023, Volume: 25, Number: 36, Pages: 24686-24695 Pages count : 10 DOI: 10.1039/d3cp02909c | ||
| Tags | GAMMA-ALUMINA, GAMMA-Al2O3 INSIGHTS; SURFACES; DFT; DEHYDRATION; ACIDITY | ||
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| Affiliations |
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Funding (1)
| 1 | Ministry of Science and Higher Education of the Russian Federation | 0239-2021-0002 |
Abstract:
In this work, the interaction of the surface of γ-Al2O3(110) with NO and H2 was studied using density functional theory calculations. Free γ-Al2O3(110) adsorbs NO and binds H atoms, but repels the H2 molecule. A triplet of low-coordinated OII–AlIII–OII atoms provides the catalytic activity of γ-Al2O3(110) along the path: (i) the adsorption of NO/AlIII is followed by the binding of H2 to form a hydroxylamine derivative NHOH through an intermediate NO/AlIII + 2 × H/OII complex; (ii) recombination of NHOH with the release of N2 through an intermediate NHOH/AlIII + NHOH/AlIV or adsorption of NO followed by the release of N2O through the intermediate NHOH/AlIII + NO/AlIV; the pathway ends with the regeneration of γ-Al2O3(110). The calculated adsorption heats ensure the diffusion of H atoms from the deposited Pt to the surface (110), initiating the formation of the NH2/AlIII + H/OII complex, which releases NH3 endothermically and is stable enough to inhibit stage (ii) of the above reaction pathway. An excess of O2 in the NO + H2 mixture excludes H/Pt and eliminates inhibition. The formation of oxynitrides is suppressed, but not excluded by more exothermic surface processes. The N-doped conductivity of bulk and surface oxynitrides Al32O47N and the dependence of the heat of adsorption of H atoms on the band gap width were revealed, which suggests a relationship between the band gap width and catalytic activity.
Cite:
Cholach A.
Catalytic Activity of γ-Al2O3(110) in the NO + H2 Reaction: A DFT Study
PCCP: Physical Chemistry Chemical Physics. 2023. V.25. N36. P.24686-24695. DOI: 10.1039/d3cp02909c WOS Scopus РИНЦ AN PMID OpenAlex
Catalytic Activity of γ-Al2O3(110) in the NO + H2 Reaction: A DFT Study
PCCP: Physical Chemistry Chemical Physics. 2023. V.25. N36. P.24686-24695. DOI: 10.1039/d3cp02909c WOS Scopus РИНЦ AN PMID OpenAlex
Dates:
| Submitted: | Jun 22, 2023 |
| Accepted: | Aug 24, 2023 |
| Published online: | Aug 25, 2023 |
| Published print: | Sep 28, 2023 |
Identifiers:
| Web of science: | WOS:001061581800001 |
| Scopus: | 2-s2.0-85171479279 |
| Elibrary: | 54959377 |
| Chemical Abstracts: | 2023:1832964 |
| PMID: | 37668017 |
| OpenAlex: | W4386177308 |