Citation: Kang Kong, Difan Li, Wenbao Ma, Qingqing Zhou, Guoping Tang, Zhenshan Hou. Aluminum(III) triflate-catalyzed selective oxidation of glycerol to formic acid with hydrogen peroxide[J]. Chinese Journal of Catalysis, ;2019, 40(4): 534-542. doi: S1872-2067(19)63319-X shu

Aluminum(III) triflate-catalyzed selective oxidation of glycerol to formic acid with hydrogen peroxide

Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Received Date: 10 November 2018
Revised Date: 25 January 2019

Fund Project: The authors are grateful for support from the National Natural Science Foundation of China (21773061, 21373082), and the Innovation Program of Shanghai Municipal Education Commission (15ZZ031).

Glycerol is a by-product of biodiesel production and is an important readily available platform chemical. Valorization of glycerol into value-added chemicals has gained immense attention. Herein, we carried out the conversion of glycerol to formic acid and glycolic acid using H₂O₂ as an oxidant and metal (Ⅲ) triflate-based catalytic systems. Aluminum(Ⅲ) triflate was found to be the most efficient catalyst for the selective oxidation of glycerol to formic acid. A correlation between the catalytic activity of the metal cations and their hydrolysis constants (K_h) and water exchange rate constants was observed. At 70℃, a formic acid yield of up to 72% could be attained within 12 h. The catalyst could be recycled at least five times with a high conversion rate, and hence can also be used for the selective oxidation of other biomass platform molecules. Reaction kinetics and ¹H NMR studies showed that the oxidation of glycerol (to formic acid) involved glycerol hydrolysis pathways with glyceric acid and glycolic acid as the main intermediate products. Both the[Al(OH)_x]ⁿ⁺ Lewis acid species and CF₃SO₃H Brønsted acid, which were generated by the in-situ hydrolysis of Al(OTf)₃, were responsible for glycerol conversion. The easy availability, high efficiency, and good recyclability of Al(OTf)₃ render it suitable for the selective oxidation of glycerol to high value-added products.
- Aluminum(III) triflate,
- Glycerol,
- Hydrogen peroxide,
- Selective oxidation,
- Formic acid
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