A Multiunit Catalyst with Synergistic Stability and Reactivity: A Polyoxometalate–Metal Organic Framework for Aerobic Decontamination

A combination of polyanion size and charge allows the Keggin-type polyoxometalate (POM), [CuPW(11)O(39)](5-), a catalyst for some air-based organic oxidations, to fit snuggly in the pores of MOF-199 (HKUST-1), a metal-organic framework (MOF) with the POM countercations residing in alternative pores. This close matching of POM diameter and MOF pore size in this POM-MOF material, [Cu(3)(C(9)H(3)O(6))(2)](4)[{(CH(3))(4)N}(4)CuPW(11)O(39)H] (1), results in a substantial synergistic stabilization of both the MOF and the POM. In addition, this heretofore undocumented POM-MOF interaction results in a dramatic increase in the catalytic turnover rate of the POM for air-based oxidations. While 1 catalyzes the rapid chemo- and shape-selective oxidation of thiols to disulfides and, more significantly, the rapid and sustained removal of toxic H(2)S via H(2)S + 1/2 O(2) → 1/8 S(8) + H(2)O (4000 turnovers in <20 h), the POM or the MOF alone is catalytically slow or inactive. Three arguments are consistent with the catalytic reactions taking place inside the pores. POM activation by encapsulation in the MOF likely involves electrostatic interactions between the two components resulting in a higher reduction potential of the POM.