Evaluation of the Mechanism of Heterogeneous Hydrogenation of alpha,beta-Unsaturated Carbonyl Compounds via Pairwise Hydrogen Addition
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
ACS Catalysis
ISSN: 2155-5435
|
| Вых. Данные |
Год: 2014,
Том: 4,
Номер: 6,
Страницы: 2022-2028
Страниц
: 7
DOI:
10.1021/cs500426a
|
| Ключевые слова |
heterogeneous hydrogenation, pairwise hydrogen addition, parahydrogen-induced polarization (PHIP), reaction mechanism, α,β-unsaturated carbonyl compounds |
| Авторы |
Salnikov Oleg G.
1,2
,
Kovtunov Kirill V.
1,2
,
Barskiy Danila A.
1,2
,
Khudorozhkov Alexander K.
2,3
,
Inozemtseva Elizaveta A.
2,3
,
Prosvirin Igor P.
3
,
Bukhtiyarov Valery I.
2,3
,
Koptyug Igor V.
1,2
|
| Организации |
| 1 |
International Tomography Center, SB RAS, 3A Institutskaya St., Novosibirsk 630090, Russia
|
| 2 |
Novosibirsk State University, 2 Pirogova St., Novosibirsk 630090, Russia
|
| 3 |
Boreskov Institute of Catalysis, SB RAS, 5 Acad. Lavrentiev Pr., Novosibirsk 630090, Russia
|
|
Информация о финансировании (7)
|
1
|
Российский фонд фундаментальных исследований
|
14-03-00374
|
|
2
|
Президиум РАН
|
5.1.1
|
|
3
|
Российский фонд фундаментальных исследований
|
12-03-00403
|
|
4
|
Совет по грантам Президента Российской Федерации
|
МК-4391.2013.3
|
|
5
|
Президиум СО РАН
|
60
|
|
6
|
Президиум СО РАН
|
61
|
|
7
|
Российский фонд фундаментальных исследований
|
14-03-31239 (01201450183)
|
Heterogeneous hydrogenation of α,β-unsaturated carbonyl compounds was addressed using the parahydrogen-induced polarization (PHIP) technique. PHIP effects were observed in hydrogenation of C═C bond of acrolein and crotonaldehyde over different supported metal catalysts, demonstrating the existence of a pairwise route of hydrogen addition to the substrate. Hydrogenation of acrolein over Pd–Sn/Al2O3, Pd–Sn/TiO2, Pd–Zn/TiO2, and Pd/TiO2 catalysts with parahydrogen also led to the polarization of the proton of CHO group of propanal. This was explained by C(O)–H bond dissociation which represents a side process on the catalyst surface. Formation of polarized cis- and trans-2-butenes was detected in hydrogenation of acrolein with parahydrogen over several Rh-based catalysts. This observation is made possible only due to the high NMR signal enhancement provided by PHIP. It was also found that hydrogenation of acetone and propanal with parahydrogen leads to polarized propane formation as a result of C–O bond hydrogenolysis.