Elucidating activating and deactivating effects of carboxylic acids on polyoxometalate-catalysed three-phase liquid–liquid-gas reactions

Poller MJ, Bönisch S, Bertleff B, Raabe JC, Görling A, Albert J (2022)


Publication Type: Journal article

Publication year: 2022

Journal

Book Volume: 264

Article Number: 118143

DOI: 10.1016/j.ces.2022.118143

Abstract

Three-phase liquid–liquid gas reactions are promising strategies to combine highly active and selective homogeneous-catalysed oxidation reactions with in-situ product isolation. Several approaches like the three-phasic oxidation of biomass to formic acid (OxFA process) or the three-phasic extraction-coupled oxidative desulfurization (ECODS process) of fuels have been developed. Hereby, an aqueous polyoxometalate (POM) catalyst solution in combination with molecular oxygen as oxidant is used. However, contrary effects on the oxidation performance of the POM-catalyst were observed for different carboxylic acids as reaction products or intermediates. By using model calculations employing Density-Functional Theory (DFT) in combination with magnetic and optical spectroscopy, we could explain the experimental observations that oxalic acid activates the POM catalyst and therefore promotes its oxidation performance while acetic and especially formic acid form stable complexes with the active centres and therefore inhibit the oxidation activity. These findings greatly improve the understanding of POM-acid complexes and their effect on the catalytic performance.

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APA:

Poller, M.J., Bönisch, S., Bertleff, B., Raabe, J.C., Görling, A., & Albert, J. (2022). Elucidating activating and deactivating effects of carboxylic acids on polyoxometalate-catalysed three-phase liquid–liquid-gas reactions. Chemical Engineering Science, 264. https://doi.org/10.1016/j.ces.2022.118143

MLA:

Poller, Maximilian J., et al. "Elucidating activating and deactivating effects of carboxylic acids on polyoxometalate-catalysed three-phase liquid–liquid-gas reactions." Chemical Engineering Science 264 (2022).

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