Highly Efficient Supported Catalysts Based on Zr-Containing Polyoxometalates and Multiwalled Carbon Nanotubes for Selective Oxidation of Thioethers with H2O2 Научная публикация
| Журнал |
Catalysis Science and Technology
ISSN: 2044-4753 , E-ISSN: 2044-4761 |
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| Вых. Данные | Год: 2025, Том: 15, Номер: 6, Страницы: 1825 - 1838 Страниц : 14 DOI: 10.1039/D4CY01526F | ||
| Ключевые слова | Activation analysis; Atomic emission spectroscopy; Catalyst activity; Catalyst selectivity; Catalyst supports; Catalytic oxidation; Chelation; Chlorination; Crystallites; Electron spin resonance spectroscopy; Ligands; Multiwalled carbon nanotubes (MWCN); Nanocatalysts; Near infrared spectroscopy; Photodegradation; Photoelectron spectroscopy; Spectroscopic analysis; Thermogravimetric analysis | ||
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Информация о финансировании (1)
| 1 | Российский научный фонд | 23-13-00156 |
Реферат:
Zirconium-containing polyoxometalates (Zr–POM) with Lindqvist, Keggin, and Wells–Dawson structures have been irreversibly attached to the surface of nitrogen-free and nitrogen-doped multi-walled carbon nanotubes (CNT and N-CNT) using H+ or Zn2+ ions as immobilization agents. The supported catalysts were characterized using low temperature N2 adsorption, thermogravimetric analysis, FT-IR spectroscopy, XPS, HRTEM and HAADF-STEM. Catalytic activity was assessed for the selective oxidation of thioethers to sulfoxides using methyl phenyl sulfide as model substrate and aqueous 30% H2O2 as green oxidant, and the relationships between the catalyst composition and its activity and selectivity have been established. Among the catalysts tested, Zr–POM of the Keggin structure [{PW11O39Zr(μ-OH)}2]8− (PW11Zr) immobilized on N-CNT (1.8 at% N) using Zn2+ (18 wt% PW11Zr/Zn–N-CNT) exhibited superior performance in terms of turnover frequency (TOF 10 200 h−1 in acetonitrile at room temperature) and H2O2 utilization efficiency (90%). Sulfoxide selectivity depends on the solvent nature and varies from 88% (acetonitrile) to 98% (ethanol) at 80–83% substrate conversion attained with only one equiv. of H2O2 and 0.1 mol% of PW11Zr. The reaction can proceed successfully even with 0.01 mol% of the catalyst, achieving turnover number of 9360 with retention of the Zr–POM structure. Hot filtration tests confirmed the heterogeneous nature of the catalysis. The catalyst showed excellent reusability over, at least, five cycles without degradation and was resistant to Zr–POM and Zn leaching, even when using the highly polar protic solvent ethanol. The catalyst 18 wt% PW11Zr/Zn–N-CNT was able to accomplish sulfoxidation of the practically important omeprazole sulfide with 98% selectivity at 95% conversion.
Библиографическая ссылка:
Lopatkin V.A.
, Evtushok V.Y.
, Stonkus O.A.
, Kibis L.S.
, Podyacheva O.Y.
, Kholdeeva O.A.
Highly Efficient Supported Catalysts Based on Zr-Containing Polyoxometalates and Multiwalled Carbon Nanotubes for Selective Oxidation of Thioethers with H2O2
Catalysis Science and Technology. 2025. V.15. N6. P.1825 - 1838. DOI: 10.1039/D4CY01526F WOS Scopus CAPlus OpenAlex
Highly Efficient Supported Catalysts Based on Zr-Containing Polyoxometalates and Multiwalled Carbon Nanotubes for Selective Oxidation of Thioethers with H2O2
Catalysis Science and Technology. 2025. V.15. N6. P.1825 - 1838. DOI: 10.1039/D4CY01526F WOS Scopus CAPlus OpenAlex
Даты:
| Поступила в редакцию: | 20 дек. 2024 г. |
| Принята к публикации: | 4 февр. 2025 г. |
| Опубликована online: | 7 февр. 2025 г. |
| Опубликована в печати: | 21 мар. 2025 г. |
Идентификаторы БД:
| Web of science: | WOS:001418083800001 |
| Scopus: | 2-s2.0-85217892635 |
| Chemical Abstracts: | 2025:360030 |
| OpenAlex: | W4407213193 |
Цитирование в БД:
Пока нет цитирований