Cyclohexene Oxidation with H2O2 over Metal-Organic Framework MIL-125(Ti): The Effect of Protons on Reactivity
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Catalysts
ISSN: 2073-4344
|
| Вых. Данные |
Год: 2019,
Том: 9,
Номер: 4,
Номер статьи
: 324,
Страниц
: 14
DOI:
10.3390/catal9040324
|
| Ключевые слова |
alkene; epoxidation; heterogeneous catalysis; hydrogen peroxide; metal-organic framework; MIL-125; titanium |
| Авторы |
Maksimchuk Nataliya
1,2
,
Lee Ji Sun
3
,
Ayupov Artem
1
,
Chang Jong-San
3,4
,
Kholdeeva Oxana
1,2
|
| Организации |
| 1 |
Boreskov Institute of Catalysis, Lavrentieva Ave. 5, Novosibirsk 630090, Russia
|
| 2 |
Department of Natural Sciences, Novosibirsk State University, Pirogova Str. 2, Novosibirsk 630090, Russia
|
| 3 |
Research group for nanocatalyst, Korea Research Institute of Chemical Technology, Daejeon 34114, Korea
|
| 4 |
Department of Chemistry, Sungkyunkwan University, Suwon 16419, Korea
|
|
Информация о финансировании (3)
|
1
|
Федеральное агентство научных организаций России
|
0303-2016-0005
|
|
2
|
Korea Research Institute of Chemical Technology
|
SK-1301
|
|
3
|
Российский фонд фундаментальных исследований
|
18-29-04022
|
The catalytic performance of the titanium-based metal–organic framework MIL-125 was evaluated in the selective oxidation of cyclohexene (CyH) with environmentally friendly oxidants, H2O2 and tBuOOH. The catalytic activity of MIL-125 as well as the oxidant utilization efficiency and selectivity toward epoxide and epoxide-derived products can be greatly improved by acid additives (HClO4 or CF3SO3H). In the presence of 1 molar equivalent (relative to Ti) of a proton source, the total selectivity toward CyH epoxide and trans-cyclohexane-1,2-diol reached 75–80% at 38–43% alkene conversion after 45 min of reaction with 1 equivalent of 30% H2O2 at 50 °C. With 50% H2O2 as the oxidant, the total selectivity toward heterolytic oxidation products increased up to 92% at the same level of alkene conversion. N2 adsorption, powder X-ray diffraction (PXRD), and infrared (IR) spectroscopy studies before and after the catalytic oxidations confirmed the absence of structural changes in the Metal–organic framework (MOF) structure. MIL-125 was stable toward titanium leaching, behaved as a truly heterogeneous catalyst, and could easily be recovered and reused several times without any loss of the catalytic properties.