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

doi:10.1016/S1872-2067(19)63319-X

Abstract

Abstract:

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.

Key words: Aluminum(III) triflate, Glycerol, Hydrogen peroxide, Selective oxidation, Formic acid

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.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(19)63319-X

https://www.cjcatal.com/EN/Y2019/V40/I4/534

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