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H5PV2Mo10O40 Polyoxometalate Encapsulated in NU-1000 Metal–Organic Framework for Aerobic Oxidation of a Mustard Gas Simulant

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journal contribution
posted on 21.12.2019 by Cassandra T. Buru, Megan C. Wasson, Omar K. Farha
The immobilization of H5PV2Mo10O40 polyoxometalates (POMs) in the in the mesoporous channel-type metal–organic framework (MOF), NU-1000, via simple impregnation method is reported here. Characterization of the composite PV2Mo10@NU-1000 activated by supercritical CO2 revealed that the POMs occupy the mesopore. Upon heating as low as 40 °C in the absence of bulk solvent, the POMs migrate to the micropore. However, the presence of solvent, such as cyclohexane, impedes this transformation. The material was active for the aerobic oxidation of the mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES), in cyclohexane using isobutyraldehyde a sacrificial reductant and O2 as the oxidant. The activity of the POM allowed for efficient oxidation of CEES in the dark and in air. Immobilization of the POM in the MOF was found to improve the initial turnover frequency compared to the POM itself. Further, the POM catalyst was found to be unstable under the chosen reaction conditions and no activity was found upon washing and reusing the POM. As a composite PV2Mo10@NU-1000, the POMs retained their catalytic activity and allowed for recycling of the catalytic material.

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