scholarly journals Fine cubic Cu2O nanocrystals as highly selective catalyst for propylene epoxidation with molecular oxygen

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Wei Xiong ◽  
Xiang-Kui Gu ◽  
Zhenhua Zhang ◽  
Peng Chai ◽  
Yijing Zang ◽  
...  

AbstractPropylene epoxidation with O2 to propylene oxide is a very valuable reaction but remains as a long-standing challenge due to unavailable efficient catalysts with high selectivity. Herein, we successfully explore 27 nm-sized cubic Cu2O nanocrystals enclosed with {100} faces and {110} edges as a highly selective catalyst for propylene epoxidation with O2, which acquires propylene oxide selectivity of more than 80% at 90–110 °C. Propylene epoxidation with weakly-adsorbed O2 species at the {110} edge sites exhibits a low barrier and is the dominant reaction occurring at low reaction temperatures, leading to the high propylene oxide selectivity. Such a weakly-adsorbed O2 species is not stable at high reaction temperatures, and the surface lattice oxygen species becomes the active oxygen species to participate in propylene epoxidation to propylene oxide and propylene partial oxidation to acrolein at the {110} edge sites and propylene combustion to CO2 at the {100} face sites, which all exhibit high barriers and result in decreased propylene oxide selectivity.

Synlett ◽  
2020 ◽  
Vol 31 (14) ◽  
pp. 1372-1377
Author(s):  
Shinji Harada ◽  
Daiki Matsuda ◽  
Takahiro Morikawa ◽  
Atsushi Nishida

A one-step synthesis of enones from olefins is described. The reaction was performed under visible-light irradiation in the presence of molecular oxygen and a photocatalyst. The reaction proceeded with various types of trisubstituted olefins to give enones in good yields with high regioselectivity. In particular, oxygen- and nitrogen-containing functional groups, heteroaromatic rings, and cyclopropanes were tolerated. Mechanistic studies and previous reports indicated that the active oxygen species generated in the reaction system is singlet oxygen.


1991 ◽  
Vol 57 (9) ◽  
pp. 1711-1715 ◽  
Author(s):  
Nobutaka Suzuki ◽  
Kazue Ogawa ◽  
Binkoh Yoda ◽  
Tateo Nomoto ◽  
Humio Inaba ◽  
...  

Catalysts ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 559
Author(s):  
Shigeru Sugiyama ◽  
Yasunori Hayashi ◽  
Ikumi Okitsu ◽  
Naohiro Shimoda ◽  
Masahiro Katoh ◽  
...  

There are active oxygen species that contribute to oxidative coupling or the partial oxidation during the oxidative dehydrogenation of methane when using solid oxide catalysts, and those species have not been definitively identified. In the present study, we clarify which of the active oxygen species affect the oxidative dehydrogenation of methane by employing photo-catalysts such as TiO2 or WO3, which generate active oxygen from UV-LED irradiation conditions under an oxygen flow. These photo-catalysts were studied in combination with Sm2O3, which is a methane oxidation coupling catalyst. For this purpose, we constructed a reaction system that could directly irradiate UV-LED to a solid catalyst via a normal fixed-bed continuous-flow reactor operated at atmospheric pressure. Binary catalysts prepared from TiO2 or WO3 were either supported on or kneaded with Sm2O3 in the present study. UV-LED irradiation clearly improved the partial oxidation from methane to CO and/or slightly improved the oxidative coupling route from methane to ethylene when binary catalysts consisting of Sm2O3 and TiO2 are used, while negligible UV-LED effects were detected when using Sm2O3 and WO3. These results indicate that with UV-LED irradiation the active oxygen of O2− from TiO2 certainly contributes to the activation of methane during the oxidative dehydrogenation of methane when using Sm2O3, while the active oxygen of H2O2 from WO3 under the same conditions afforded only negligible effects on the activation of methane.


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