High-performance Pt/CeO2-ZrO2 catalysts for selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols under mild reaction conditions: “Giant” hydrogen spillover behind the activity enhancement

High-performance Pt/CeO2-ZrO2 catalysts for selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols under mild reaction conditions: “Giant” hydrogen spillover behind the activity enhancement Научная публикация

Журнал

Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694

Вых. Данные

Год: 2024, Том: 429, Номер статьи : 115231, Страниц : DOI: 10.1016/j.jcat.2023.115231

Авторы

Redina Elena A. ^1,2 , Krylov Igor B. ¹ , Novikov Roman A. ¹ , Kapustin Gennady I. ¹ , Tkachenko Olga P. ¹ , Vikanova Ksenia V. ¹ , Ivanova Inna I. ^3,1 , Dmitrenok Andrey S. ¹ , Kustov Leonid M. ^1,2

Организации

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect 119991, Moscow, Russian Federation
2	NUST MISIS, 4 Leninsky Prospect 119049, Moscow, Russian Federation
3	Mendeleev University of Chemical Technology of Russia, 9 Miusskaya sq. 125047, Moscow, Russian Federation

Pt supported on CeO2-ZrO2 mixed oxide showed unusually high activity and regioselectivity compared to common commercial hydrogenation catalysts in hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols. DRIFTS-CO, TEM, XPS, TPR-H2 studies demonstrated that the CeO2-ZrO2 support stabilizes Pt as small clusters, especially for the catalysts with ultra-low Pt loadings < 0.1 % wt. Interaction of Pt clusters with the easily reducible CeO2-ZrO2 mixed oxide leads to intense low-temperature hydrogen spillover effect, which in turn is responsible for active hydrogen species generation on Pt and their transfer to the support leading to reduction of CeO2 with the formation of Ce3+, where the carbonyl bond can be adsorbed and activated. According to the results of EPR studies of hydrogen species generated on the catalyst surface, we assume that hydrogen on a Pt/CeO2-ZrO2 catalyst can undergo heterolytic dissociation with the formation of hydride ions, which provide selective carbonyl bond hydrogenation, but not with the predominant formation of radical type (H●) species that lead to unselective hydrogenation of both C = O and C = C bonds. A careful 1H magic angle spinning solid-state NMR (1H MAS SS NMR) study of hydrogen adsorbed on Pt/CeO2-ZrO2 and Pt supported on non-reducible oxide (SiO2) confirmed the formation of hydride on Pt/CeO2-ZrO2, whilst only molecular hydrogen was detected on the Pt/SiO2 sample.

Redina E.A. , Krylov I.B. , Novikov R.A. , Kapustin G.I. , Tkachenko O.P. , Vikanova K.V. , Ivanova I.I. , Dmitrenok A.S. , Kustov L.M.
High-performance Pt/CeO2-ZrO2 catalysts for selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols under mild reaction conditions: “Giant” hydrogen spillover behind the activity enhancement
Journal of Catalysis. 2024. V.429. 115231 . DOI: 10.1016/j.jcat.2023.115231 WOS Scopus OpenAlex

Web of science:	WOS:001134997800001
Scopus:	2-s2.0-85179477880
OpenAlex:	W4389209371

БД	Цитирований
OpenAlex	17
Scopus	16
Web of science	15