The Concept of Quasimolecular Electrophilic Oxygen in Ethylene Epoxidation over Silver Full article
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Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
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| Output data | Year: 1999, Volume: 40, Number: 5, Pages: 653-672 Pages count : 20 | ||
| Tags | PARTIAL OXIDATION; HIGH-TEMPERATURE; MOLECULAR CALCULATIONS; ATMOSPHERIC-PRESSURE; ELECTRONIC-STRUCTURE; CATALYTIC-OXIDATION; SELECTIVE OXIDATION; Ag(110) SURFACE; METAL-SURFACES; SINGLE-CRYSTAL | ||
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Abstract:
The ethylene-epoxidizing form of oxygen (O-ep) adsorbed on Ag(111) and Ag(110) single crystals and polycrystalline silver foil was examined by X-ray and UV photoelectron spectroscopy (XPS and UPS). It was shown that O-ep has a quasimolecular nature and exhibits high thermal stability (T > 700 K). The quantum-chemical study of associative forms of oxygen on the defects of the silver surface was carried out by the methods of density functional theory (DFT) in a cluster approximation. It was found that the associative (molecular) ozone-like species of oxygen on the surface of silver with cationic vacancies (V) is more stable than atomic oxygen (the energy difference is 44 kcal/mol). The identification of emission bands in UV photoelectron spectra performed on the basis of theoretical calculations of the ozone-like structure supported the quasimolecular nature of O-ep. The mechanisms known for ethylene epoxidation were analyzed. A new mechanism implying the participation of quasimolecular electrophilic oxygen O-ep in epoxidation was proposed. This mechanism describes the major regularities of epoxidation observed in the experiments on a regular basis.
Cite:
Boronin A.I.
, Avdeev V.I.
, Koshcheev S.V.
, Murzakhmetov K.T.
, Ruzankin S.F.
, Zhidomirov G.M.
The Concept of Quasimolecular Electrophilic Oxygen in Ethylene Epoxidation over Silver
Kinetics and Catalysis. 1999. V.40. N5. P.653-672. WOS Scopus РИНЦ ANCAN
The Concept of Quasimolecular Electrophilic Oxygen in Ethylene Epoxidation over Silver
Kinetics and Catalysis. 1999. V.40. N5. P.653-672. WOS Scopus РИНЦ ANCAN
Original:
Боронин А.И.
, Авдеев В.И.
, Кощеев С.В.
, Мурзахметов К.Т.
, Рузанкин С.Ф.
, Жидомиров Г.М.
Развитие представлений о квазимолекулярной природе электрофильного кислорода, участвующего в реакции эпоксидирования этилена на серебре
Кинетика и катализ. 1999. Т.40. №5. С.721-741. РИНЦ
Развитие представлений о квазимолекулярной природе электрофильного кислорода, участвующего в реакции эпоксидирования этилена на серебре
Кинетика и катализ. 1999. Т.40. №5. С.721-741. РИНЦ
Dates:
| Submitted: | Apr 28, 1999 |
Identifiers:
| Web of science: | WOS:000083503200006 |
| Scopus: | 2-s2.0-0033201267 |
| Elibrary: | 13310283 |
| Chemical Abstracts: | 1999:721542 |
| Chemical Abstracts (print): | 132:41048 |