Jump to main content
Jump to site search


Successive C1-C2 Bond Cleavage: Mechanism of Vanadium(V)-Catalyzed Aerobic Oxidation of D-Glucose to Formic Acid in Aqueous Solution

Abstract

Vanadium(V)-catalyzed aerobic oxidation in aqueous solution shows high selectivity in the field of C-C bond cleavage of carbohydrates for chemicals with less carbon atoms. However, the pathway of C-C bond cleavage from carbohydrates and the conversion mechanism are unclear. In this work, we studied the pathway and the mechanism of D-glucose oxidation to formic acid (FA) in NaVO3-H2SO4 aqueous solution using isotope-labeled glucoses as substrates. D-Glucose is first transformed to FA and D-arabinose via C1-C2 bond cleavage. The D-arabinose undergoes a similar C1-C2 bond cleavage to form FA and corresponding D-erythrose, which can be further degraded by C1-C2 bond cleavage. Dimerization and aldol condensation between carbohydrates can also proceed to make the reaction a much more complicated mixture. However, the fundamental reaction, C1-C2 bond cleavage, can drive all the intermediates to form the common product FA. Based on the detected intermediates, isotope-labeled experiments, kinetic isotope effect study and kinetic analysis, the mechanism is proposed. D-Glucose first reacts with vanadium(V) species to form a five-membered-ring complex. Then, the electron transfer occurs and C1-C2 bond weakens, followed by C1-C2 bond cleavage (with no C-H bond cleavage), to generate H3COO•-vanadium(IV) complex and D-arabinose. FA is generated from H3COO• that is oxidized by another vanadium(V) species. The reduced vanadium species is oxidized by O2 to regenerate to its oxidation state. This finding will gain a deeper insight into the process of C-C bond cleavage of carbohydrates for chemicals and provide guidance for screening and synthesizing new highly-efficient catalyst systems for FA production.

Back to tab navigation

Supplementary files

Publication details

The article was received on 13 Apr 2018, accepted on 01 Jun 2018 and first published on 01 Jun 2018


Article type: Paper
DOI: 10.1039/C8CP02352B
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
  •   Request permissions

    Successive C1-C2 Bond Cleavage: Mechanism of Vanadium(V)-Catalyzed Aerobic Oxidation of D-Glucose to Formic Acid in Aqueous Solution

    M. Niu, Y. Hou, W. Wu, S. Ren and R. Yang, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP02352B

Search articles by author

Spotlight

Advertisements