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Citation: Yuqing Ji, Haichao Liu. Selective hydrogenolysis of sorbitol to ethylene glycol and propylene glycol on ZrO₂-supported bimetallic Pd-Cu catalysts[J]. Chinese Journal of Catalysis, ;2015, 36(9): 1552-1559. doi: 10.1016/S1872-2067(15)60892-0 shu

Selective hydrogenolysis of sorbitol to ethylene glycol and propylene glycol on ZrO₂-supported bimetallic Pd-Cu catalysts

Yuqing Ji ,
Haichao Liu ^,

1.
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Stable and Unstable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Corresponding author: Haichao Liu,
Received Date: 3 May 2015
Available Online: 19 May 2015
Fund Project: 国家重点基础研究发展计划(973计划, 2011CB201400) (973计划, 2011CB201400) 国家自然科学基金(21173008, 21373019, 21433001). (21173008, 21373019, 21433001)

Sorbitol is one of the key building blocks in catalytic conversion of biomass, and its selective hydrogenolysis to ethylene glycol and propylene glycol provides a viable and sustainable route towards the synthesis of the two glycols. Herein, the hydrogenolysis of biomass-derived sorbitol was studied on Pd-modified Cu/monoclinic zirconia (Pd-Cu/ZrO₂) catalysts with a wide range of Cu/Pd atomic ratios in the presence of La(OH)₃. The bimetallic Pd-Cu/ZrO₂ catalysts showed superior activities and selectivities to the two target glycols, compared with the monometallic Cu/ZrO₂ and Pd/ZrO₂ catalysts under identical conditions. At nearly 100% sorbitol conversion, a combined selectivity of 61.7% to ethylene glycol, propylene glycol, and glycerol was obtained on Pd-Cu/ZrO₂ (Cu/Pd=5) at 493 K under 5.0 MPa H₂. Pd-Cu/ZrO₂ was also stable and recyclable, in contrast to Cu/ZrO₂, which suffered severe deactivation because of agglomeration of Cu particles during sorbitol hydrogenolysis. Clearly, the presence of Pd improved not only the activity and selectivity of the Cu catalyst, but also the hydrothermal stability. Characterization of these catalysts by X-ray diffraction, diffuse-reflectance infrared Fourier transform spectroscopy of CO adsorption, and H₂ temperature-programmed reduction suggests that the Cu particles deposited on the Pd surfaces with close contact and strong interaction between the two metals, most likely involving electron transfer from Pd to Cu. Such structural and electronic effects are proposed as the critical contributors to the significant promoting effect of Pd on the activity and stability of Pd-Cu catalysts in sorbitol hydrogenolysis. These findings provide useful information for design of new Cu-based catalysts with higher efficiency and stability for selective hydrogenolysis of polyols and other biomass-derived reactants under hydrothermal conditions.
- Selective hydrogenolysis,
- Sorbitol,
- Ethylene glycol,
- Propylene glycol,
- Bimetallic palladium-copper catalyst
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Selective hydrogenolysis of sorbitol to ethylene glycol and propylene glycol on ZrO2-supported bimetallic Pd-Cu catalysts

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Selective hydrogenolysis of sorbitol to ethylene glycol and propylene glycol on ZrO₂-supported bimetallic Pd-Cu catalysts