Citation: Yuming Li, Haichao Liu. Selective Hydrogenolysis of Glycerol to 1, 3-Propanediol over Supported Platinum-Tungsten Oxide Catalysts[J]. Acta Physico-Chimica Sinica, ;2022, 38(10): 220701. doi: 10.3866/PKU.WHXB202207014 shu

Selective Hydrogenolysis of Glycerol to 1, 3-Propanediol over Supported Platinum-Tungsten Oxide Catalysts

Yuming Li ,
Haichao Liu ^,

Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Corresponding author: Haichao Liu, hcliu@pku.edu.cn
Received Date: 7 July 2022
Revised Date: 29 July 2022
Accepted Date: 29 July 2022
Available Online: 2 August 2022
Fund Project: the National Key Research and Development Program of China 2021YFA1501104Natural Science Foundation of China 22032001Natural Science Foundation of China 21832001Natural Science Foundation of China 21821004Beijing National Laboratory for Molecular Sciences BNLMS-CXXM-201905

Glycerol is a versatile platform compound that is formed in considerable amounts as a by-product of biodiesel production. The catalytic selective hydrogenolysis of glycerol to 1, 3-propanediol (1, 3-PDO) provides a sustainable route for the synthesis of this important diol. In this study, a series of platinum-tungsten oxide (Pt-WO_x) catalysts with different WO_x surface densities dispersed on titanium(Ⅳ) oxide, zirconium(Ⅳ) oxide, and aluminum oxide supports were prepared and evaluated for the glycerol hydrogenolysis to 1, 3-PDO. The highest reaction activity and 1, 3-PDO selectivity were achieved at a WO_x density of approximately 1.5–2.0 W·nm⁻², with all three support materials. Such a strong dependence on the surface density of WO_x revealed the critical role of the dispersed WO_x domains in the hydrogenolysis of glycerol to 1, 3-PDO. The infrared spectra for carbon monoxide adsorption confirmed the electron transfer and strong interaction between the Pt particles and WO_x domains. These phenomena were hypothesized to contribute to the superior selectivity to 1, 3-PDO over 1, 2-PDO of the supported Pt-WO_x catalysts when compared with the corresponding supported Pt catalysts. The realized superior 1, 3-PDO selectivity was consistent with its higher stability on the Pt-WO_x catalysts, as reflected by the lower reaction rate constant of 1, 3-PDO than those of 1, 2-PDO and glycerol obtained in their hydrogenolysis reactions. There existed a volcano-type dependence of the glycerol reaction activity on the hydrogen partial pressure. Such a dependence, together with the measured ratio (1 : 2) of the secondary to the primary C−H bonds in 1, 3-PDO in the presence of deuterium and deuterium oxide (replacing hydrogen and water, respectively), indicated that the glycerol hydrogenolysis proceeds by the kinetically relevant dehydrogenation of glycerol to the glyceraldehyde intermediate, followed by the dehydration and hydrogenation of glyceraldehyde to 1, 3-PDO over the Pt-WO_x catalysts.
- Glycerol,
- 1,3-propandiol,
- Hydrogenolysis,
- Platinum,
- Tungsten oxide,
- Strong interaction
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