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Open AccessArticle

Keggin-Type Heteropoly Salts as Bifunctional Catalysts in Aerobic Baeyer-Villiger Oxidation

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, 30-239 Krakow, Poland
Faculty of Chemical Engineering and Technology, Cracow University of Technology, Warszawska 24, 31-155 Krakow, Poland
Author to whom correspondence should be addressed.
Materials 2018, 11(7), 1208;
Received: 31 May 2018 / Revised: 2 July 2018 / Accepted: 9 July 2018 / Published: 13 July 2018
The cobalt, manganese, and iron salts of tungstophosphoric or molybdophosphoric acid with growing content of metals were applied for the first time as catalysts in the Baeyer-Villiger (BV) oxidation of cyclohexanone to ε-caprolactone with molecular oxygen. The catalysts were characterized with Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence (XRF), and ethanol decomposition reaction. Introduction of transition metals into the heteropoly structure increases the activity of resulting heteropoly salts in comparison with parent heteropolyacids. It was shown that the most active catalysts are salts of the heteropoly salts with one metal atom introduced and one proton left (HMPX) type, (where M = Co, Fe, Mn, and X = W, Mo) with the metal to proton ratio equal one. Among all of the studied catalysts, the highest catalytic activity was observed for HCoPW. The effect indicates that both the acidic and redox properties are required to achieve the best performance. The Baeyer-Villiger (BV) oxidation mechanism proposed identifies the participation of heteropoly compounds in three steps of the investigated reaction: oxidation of aldehyde to peracid (redox function), activation of carbonyl group (Lewis acidity), and decomposition of the Criegee adduct to ε-caprolactone (Brønsted acidity). View Full-Text
Keywords: polyoxometalates; Baeyer-Villiger oxidation; ε-caprolactone; molecular oxygen polyoxometalates; Baeyer-Villiger oxidation; ε-caprolactone; molecular oxygen
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Pamin, K.; Połtowicz, J.; Prończuk, M.; Kryściak-Czerwenka, J.; Karcz, R.; M. Serwicka, E. Keggin-Type Heteropoly Salts as Bifunctional Catalysts in Aerobic Baeyer-Villiger Oxidation. Materials 2018, 11, 1208.

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