444280 Copper-Phyllosilicate Core-Shell Nanocatalysts with Balanced Active Sites for Carbon-Oxygen Hydrogenolysis Reactions

Monday, April 11, 2016
Exhibit Hall E (George R. Brown )
Jiankang Ying Sr., College of Chemical Engineering, Sichuan University, chengdu, China, Weimao Fang Sr., Sichuan University, chengdu, China and Hairong Yue, College of Chemical Engineering, Sichuan University, Chengdu, China

Copper-Phyllosilicate Core-shell Nanocatalysts with Balanced Active Sites for Carbon-Oxygen Hydrogenolysis Reactions

Hairong Yue, Weimao Fang, Changmin Liu, Jiankang Ying

College of Chemical Engineering, Sichuan University, Chengdu, China

Abstract

Hydrogenolysis of carbon-oxygen (C¨CO) bonds (e.g., esters, ethers, furfural, and CO2) has emerged as a versatile synthetic tool in organic methodology, as it could produce a variety of products (e.g., chemicals, fuels, and polymers). Copper-based catalysts have been intensively explored for hydrogenation reactions as the copper sites account for the selective hydrogenation of carbon-oxygen bonds and relatively inactive for the hydrogenolysis of carbon-carbon bonds. Work on understanding the active sites of copper catalysts for hydrogenation reactions indicted that both Cu0 and Cu+ species were crucial to the activity of Cu-based catalysts. However, researchers were not able to establish a relationship between activity and Cu0/Cu+ active species since the conventional Cu-based catalysts is the deactivation by metal particle growth and unstable surface Cu0 and Cu+ active species in the strong reductive H2 and oxidizing carbon-oxygen atmosphere.

We renctly present on efficient approaches for fabrication of a series of copper-phyllosilicate core-shell nanocatalysts and nanoreactors with balanced and stable Cu0 and Cu+ active species. We chose the hydrogenation of dimethyl oxalate, ethylene cyclicarbonate and as probe reactions for a better understanding of properties of active sites and the structure-activity relationship. The results indicated a synergy between copper and the oxide components and the balanced surface Cu0 and Cu+ species can greatly improve the catalytic C-O hydrogenolysis performance of the catalysts. These nanocatalysts with balanced and stable Cu0 and Cu+ active species, confinement effect, intrinsic high surface of Cu0 and Cu+ and unique tunable tubular morphology, has potential applications in the high-temperature hydrogenation reactions.

Keywords: core-shell nanocatalysts, Hydrogenation reaction; copper catalyst

References

1. Yue, H.; Zhao, Y.; Ma, X.; Gong, J.: Ethylene glycol: properties, synthesis, and applications. Chem Soc Rev 2012, 41, 4218-4244.

2. Gong, J.; Yue, H.; Zhao, Y.; Zhao, S.; Zhao, L.; Lv, J.; Wang, S.; Ma, X.: Synthesis of Ethanol via Syngas on Cu/SiO2 Catalysts with Balanced Cu0-Cu+ Sites. J Am Chem Soc 2012, 134, 13922-13925.

3. Zhao, S.; Yue, H.; Zhao, Y.; Wang, B.; Geng, Y.; Lv, J.; Wang, S.; Gong, J.; Ma, X.: Chemoselective synthesis of ethanol via hydrogenation of dimethyl oxalate on Cu/SiO2: Enhanced stability with boron dopant. J Catal 2013, 297, 142-150.

4. Yue, H.; Ma, X.; Gong, J.: An Alternative Synthetic Approach for Efficient Catalytic Conversion of Syngas to Ethanol. Acc Chem Res 2014, 47(5):1483-1492

5. Yue, H.; Zhao, Y.; Zhao, L.; Lv, J.; Wang, S.; Gong, J.; Ma, X.: Hydrogenation of dimethyl oxalate to ethylene glycol on a Cu/SiO2/cordierite monolithic catalyst: Enhanced internal mass transfer and stability. AIChE J 2012, 58, 2798-2809.

6. Yue, H.; Zhao, Y.; Zhao, S.; Wang, B.; Ma, X.; Gong, J.: A copper-phyllosilicate core-sheath nanoreactor for carbon¨Coxygen hydrogenolysis reactions. Nat Commun 2013, 4, 2339.


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