Catalytic Properties of Heteropoly Complexes Containing Fe(III) Ions in Benzene Oxidation by Hydrogen Peroxide Научная публикация
Журнал |
Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169 |
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Вых. Данные | Год: 1996, Том: 111, Номер: 1-2, Страницы: 81-90 Страниц : 10 DOI: 10.1016/1381-1169(96)00207-5 | ||
Ключевые слова | Benzene oxidation, Fe(III)-containing heteropoly complexes, Hydrogen peroxide decomposition, IR, NMR spectroscopy, Peroxo complexes, UV-VIS | ||
Авторы |
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Организации |
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Информация о финансировании (1)
1 | International Science Foundation | RP-5300 |
Реферат:
Elemental analysis, magnetic measurements, IR, 31P NMR, and UV-VIS spectroscopy were used to study heteropoly complexes (HPC), containing Fe(III) ions and heteropoly anion [PW11O39]7−, isolated from aqueous solutions as tetrabutylammonium (TBA) salts and dissolved in acetonitrile. The complexes identified are: Fe(III)-substituted complexes [PW11O39Fe(H2O)]4− (1) and [PW11O39Fe(SO4)]6− (1′); Fe(III)-substituted hydroxo complex [PW11O39Fe(OH)]5− (2′) formed during the precipitation of binuclear μ-oxo complex [(PW11O39Fe)2O]10− (2) from aqueous solutions (pH = 3 ÷ 5) by TBA cations; polynuclear Fe(III)- hydroxo complexes [PW11O39FenOxHy]m− (3) (n ∼ 8). The catalytic activity of complexes both in the hydrogen peroxide decomposition and benzene oxidation in a one-phase system HPC + CH3CN + H2O2(aq) + C6H6, with [HPC] = 6 · 10−3, [H2O2] = 0.175 ÷ 1.6, and [C6H6] = 1.4 ÷ 5.6 M at 70°C have been studied. In the presence of 1 or 1′, the molar ratio between phenol formed and H2O2 decomposed equals 10–20%. HPC containing SO2−4 ions shows a far lower activity in both reactions. The kinetics of PhOH accumulation conforms to the chain mechanism of H2O2 decomposition. Benzene is oxidized by OH radicals coordinated to HPC. In the presence of complex 2′ the rate of H2O2 decomposition is considerably lower. Thus the molar ratio of phenol formed and H2O2 decomposed is almost 60%. The mechanism of H2O2 activation by 2′ includes most likely the initial formation of a peroxo complex which was observed in absorption spectra. The state of HPC affected by the reaction mixture components was studied by UV-VIS spectra. The products of one-electron phenol (or pyrocatechol) oxidation inhibit the catalytic activity due to the complex formation with Fe(III) ions in HPC.
Библиографическая ссылка:
Kuznetsova L.I.
, Detusheva L.G.
, Fedotov M.A.
, Likholobov V.A.
Catalytic Properties of Heteropoly Complexes Containing Fe(III) Ions in Benzene Oxidation by Hydrogen Peroxide
Journal of Molecular Catalysis A: Chemical. 1996. V.111. N1-2. P.81-90. DOI: 10.1016/1381-1169(96)00207-5 WOS Scopus РИНЦ
Catalytic Properties of Heteropoly Complexes Containing Fe(III) Ions in Benzene Oxidation by Hydrogen Peroxide
Journal of Molecular Catalysis A: Chemical. 1996. V.111. N1-2. P.81-90. DOI: 10.1016/1381-1169(96)00207-5 WOS Scopus РИНЦ
Даты:
Поступила в редакцию: | 5 янв. 1996 г. |
Принята к публикации: | 30 апр. 1996 г. |
Опубликована в печати: | 10 сент. 1996 г. |
Опубликована online: | 31 авг. 1998 г. |
Идентификаторы БД:
Web of science | WOS:A1996VH42700012 |
Scopus | 2-s2.0-0030578881 |
РИНЦ | 13244229 |
Chemical Abstracts | 1996:544575 |
Chemical Abstracts (print) | 125:275077 |
OpenAlex | W1980027619 |