Polyoxometalate-Embedded Cu-Triazole Cycle: Catalytic Oxidation of Alcohols

Abstract

In the present study, a novel three-dimensional (3D) porous framework, [Cu3ICu4IICl(TRZ)7][GeW12O40]·7H2O, designated as Cu-W-TRZ, was synthesized through a hydrothermal approach by integrating the {GeW12} cluster into a Cu(I/II)-TRZ framework. This material exhibited remarkable catalytic activity in the oxidation of alcohols. Under optimized conditions, it attained high substrate conversion rates (surpassing 99%) and selectivity (surpassing 99%). The excellent catalytic performance of Cu-W-TRZ can be ascribed to the synergistic interaction between the Cu(I/II) sites and the {GeW12} cluster in multifunctional catalysis. The abundant Cu ions act as active sites to activate the O−O bond of TBHP, resulting in the generation of tert-butyl oxygen (t-BuO•) radical species. Moreover, the incorporation of the {GeW12} cluster promotes proton coupling, enhancing the Brønsted basicity of the material and facilitating the smooth progress of the reaction.