The effect of solvent nature on conversion, product yields and reaction kinetics of selective propylene glycol oxidation with tert-butyl hydroperoxide over porous chromium terephthalate Cr-MIL-101 used as a heterogeneous catalyst is considered. Differences in hydrogen bonding of propylene glycol molecules in different solvents and adsorption of components of the reaction mixture on the active sites of the catalyst are studied by Fourier-transformed infrared spectroscopy. The characteristics of the solvent are shown to play a key role in the process under consideration. In the case of aprotic solvents, the oxidant utilization efficiency, the propylene glycol conversion and the product yields are significantly higher in comparison with those in protic solvents. The protic solvents can adsorb on the active sites of the catalyst which leads to a decrease of their accessibility for the reagents. The initial rate of propylene glycol oxidation decreases linearly with the increasing of the diameter of molecules of the protic solvents. DFT calculations support the competitive adsorption of the molecules of protic solvents on Cr active sites of MIL-101. In the aprotic solvents, the reactivity and distribution of propylene glycol molecules in the solution are determined by the involvement of hydroxyl groups of the substrate into the intermolecular interactions. The ability of the aprotic solvents to break the hydrogen bond network in the associates of propylene glycol is responsible for the concentration of the substrate molecules in the pores of Cr-MIL-101. The highest selectivities towards hydroxyacetone for Cr-MIL-101 catalyst are obtained in solvents, where the initial rates of propylene glycol oxidation are the lowest ones.
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