Transition metal-modified polyoxometalates supported on carbon as catalyst in 2-(methylthio)-benzothiazole sulfoxidation

Abstract

Polyoxometalates with lacunary Keggin structure modified with transition metal ions [PW₁₁O₃₉ M(H₂O)]⁵⁻, where M= Ni²⁺, Co²⁺,, Cu²⁺, or Zn²⁺,, were synthesized and supported on activated carbon to obtain the PW11MC catalysts. Using FT-IR and DTA-TGA it was concluded that the [PW11O₃₉M(H₂O)]⁵⁻ species are interacting with the functional groups of the support, and that thermal treatment leads to the loss of the coordinatively bonded water molecules without any noticeable anion degradation. The activity and selectivity of the catalysts in the sulfoxidation reaction of 2-(methylthio)-benzothiazole, an emerging environmental pollutant, were evaluated. The reaction was carried out in acetonitrile as solvent using H₂O₂ 35% p/v as a clean oxidant. The conversion values decreased in the following order: PW11NiC > PW11CuC > PW11CoC > PW11ZnC, with selectivity to sulfoxide higher than 69%. The catalyst could be reused without appreciable loss of the catalytic activity at least three times. The materials were found to be efficient and recyclable catalysts for 2-(methylthio)-benzothiazole sulfoxidation in order to obtain a more biodegradable product than the corresponding substrate.