New Reaction of Anion Radicals O− with Water on the Surface of FeZSM-5 Full article
| Journal |
Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694 |
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| Output data | Year: 2008, Volume: 254, Number: 1, Pages: 110-120 Pages count : 11 DOI: 10.1016/j.jcat.2007.12.001 | ||
| Tags | α-Oxygen, Anion radical O-, DRIFT spectroscopy, FeZSM-5, N2O, Photocatalytic oxidation | ||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Russian Foundation for Basic Research | 06-03-72551 |
| 2 | Russian Foundation for Basic Research | 06-03-33087 |
Abstract:
Complexes of bivalent iron stabilized in the FeZSM-5 zeolite matrix (α-sites) are known to be able to decompose nitrous oxide stoichiometrically to form oxygen anion radicals, O−, bound to iron (α-oxygen),
(FeII)α + N2O → (FeIIIsingle bondO−)α + N2.
Similar to O− radicals on V and Mo oxides, α-oxygen is highly reactive in respect to CO, H2, methane and other hydrocarbons. It participates in catalytic oxidation of benzene to phenol by nitrous oxide, providing selectivity close to 100%. In this work, adsorption measurements, IR spectroscopy, TPD, and isotope methods were used to describe an earlier unknown reaction of O− species with water, which proceeds at 5–200 °C via the hydrogen abstraction mechanism according to the equation 2(FeIIIsingle bondO−)α + H2O → 2(FeIIIsingle bondOH−)α + (1/2)O2.
The reaction leads to the hydroxyl groups formed on α-sites, and equivalent amount of O2 evolves into the gas phase from water. Desorption of the hydroxyl groups occurs at above 400 °C via their recombination into water and dioxygen, resulting in the reactivation of α-sites, 2(FeIIIsingle bondOH−)α → 2(FeII)α + H2O + (1/2)O2.
High sensitivity of α-oxygen to water admixtures may be an important factor explaining some contradictory results reported in the literature on the behavior of α-oxygen. Because α-oxygen is a typical representative of anion radicals O−, this reaction may be relevant not only to the conventional oxidation catalysis over zeolites and metal oxides, but also to photocatalytic processes, where formation of O− is well documented.
Cite:
Panov G.I.
, Starokon E.V.
, Pirutko L.V.
, Paukshtis E.A.
, Parmon V.N.
New Reaction of Anion Radicals O− with Water on the Surface of FeZSM-5
Journal of Catalysis. 2008. V.254. N1. P.110-120. DOI: 10.1016/j.jcat.2007.12.001 WOS Scopus РИНЦ ANCAN OpenAlex
New Reaction of Anion Radicals O− with Water on the Surface of FeZSM-5
Journal of Catalysis. 2008. V.254. N1. P.110-120. DOI: 10.1016/j.jcat.2007.12.001 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Sep 17, 2007 |
| Accepted: | Dec 5, 2007 |
| Published online: | Jan 8, 2008 |
| Published print: | Feb 15, 2008 |
Identifiers:
| Web of science: | WOS:000253646100012 |
| Scopus: | 2-s2.0-38649087046 |
| Elibrary: | 13582348 |
| Chemical Abstracts: | 2008:152527 |
| Chemical Abstracts (print): | 148:411737 |
| OpenAlex: | W2046380189 |