(63m) Copper-Phyllosilicate Core-Shell Nanocatalysts with Balanced Active Sites for Carbon-Oxygen Hydrogenolysis Reactions

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

Email: hryue@scu.edu.cn


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


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,

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.