Boosting the catalysis of cesium phosphomolybdate encapsulated in hierarchical porous UiO-66 by microenvironment modulation for epoxidation of alkenes.

The chemical microenvironment of polyoxometalates (POMs) encapsulated in metal-organic frameworks (MOFs) presents a significant influence on their catalytic performance, which can be easily regulated by the linker functional group alteration or metal substitution in MOFs. Herein, a series of cesium phosphomolybdate (CsPM) encapsulated in hierarchical porous UiO-66-X composites (CsPM@HP-UiO-66-X, X = H, 2CH3, or 2OH, where X represents the alterable group grafted onto the linker benzene ring) were successfully synthesized through a one pot modulated solvothermal method. The catalytic performances of the obtained materials were explored in alkene epoxidation reaction with tert-butyl hydroperoxide (t-BuOOH). CsPM@HP-UiO-66-2CH3 showed relatively high catalytic activity, stability, and epoxidation selectivity in cyclooctene epoxidation among the CsPM@HP-UiO-66-X composites. Moreover, CsPM@HP-UiO-66-2CH3 was effective in the epoxidation of numerous alkenes, especially cyclic alkenes. The superior catalytic activity of CsPM@HP-UiO-66-2CH3 is mainly attributed to the modulation of the microenvironment surrounding CsPM active sites by introducing a hydrophobic methyl group. Meanwhile, the size-matched effect, the introduction of cesium cations, and the strong metal-support interactions (SMSIs) between CsPM and HP-UiO-66-2CH3 play a crucial role in the stability of CsPM@HP-UiO-66-2CH3.