Effective Combination of the Metal Centers in MOF-Based Materials toward Sustainable Oxidation Catalysts

A successful encapsulation of Keggin-type polyoxomolybdate (H₃[PMo₁₂O₄₀], PMo₁₂) into metal-organic framework (MOF) materials with an identical framework but distinct metal centers (ZIF-8 with Zn²⁺ and ZIF-67 with Co²⁺) was accomplished by a straightforward room-temperature procedure. The presence of Zn²⁺ in the composite material PMo₁₂@ZIF-8 instead of Co²⁺ in PMo₁₂@ZIF-67 caused a remarkable increase in the catalytic activity that achieved a total oxidative desulfurization of a multicomponent model diesel under moderate and friendly conditions (oxidant: H₂O₂ and solvent: ionic liquid, IL). Interestingly, the parent ZIF-8-based composite with the Keggin-type polyoxotungstate (H₃[PW₁₂O₄₀], PW₁₂), PW₁₂@ZIF-8, did not show the relevant catalytic activity. The ZIF-type supports present an appropriate framework to accommodate active polyoxometalates (POMs) into their cavities without leaching, but the nature of the metallic center from the POM and the metal present in the ZIF framework were vital for the catalytic performance of the composite materials.