Catalysts based on vanadium-containing heteropoly compounds: influence of the outer-sphere cation on physicochemical and catalytic properties of Si-W-V heteropolyacid

The effect of the introduction of catalytically active vanadium(V) atoms on the physicochemical properties of silicotungstic heteropolyacid has been studied. The insertion of vanadium(V) atoms into the framework of monovacant lacunar W-containing heteropolyanions in the form of a H₆V₁₀O₂₈ solution prepared by an environmentally friendly peroxide method has been shown to ensure the formation of a mixed Si-W-V heteropolyanions while maintaining the integrity of the structure. It has been demonstrated that the partial replacement of protons with large cations, such as Cs⁺ and nBu₄N⁺, leads to the precipitation of insoluble acid salts of the composition A_4,5H_0,5SiW₁₁VO₄₀, the properties of which vary significantly depending on the type of introduced counterion (A⁺). The textural characteristics of the synthesized salts have been compared, the TG/DTG/DSC profiles have been obtained, and a phase composition has been analyzed. Characterization of samples after hydrothermal treatment by IR, XRD, and ICP-AES methods has proved the high stability of the synthesized salts. The samples have demonstrated catalytic activity in the oxidation of 5-hydroxymethylfurfural in an aqueous medium, providing the formation of 2,5-diformylfuran with a yield of up to 89%, and the possibility of reusing.

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