Selective Aerobic Oxidation of Cumene to Cumene Hydroperoxide over Mono- and Bimetallic Trimesate Metal-Organic Frameworks Prepared by a Facile "green" Aqueous Synthesis

Abstract : Co–Ni and Mn–Ni bimetallic trimesate MOFs prepared by a fast aqueous synthesis method are excellent and reusable catalysts for the selective aerobic oxidation of cumene to cumene hydroperoxide (CHP). Isolation of Co2+ (or Mn2+) in an inert Ni-BTC framework is a good strategy to optimize CHP selectivity above 90%: since only Co2+ sites catalyze CHP decomposition, a drop of the CHP selectivity is observed as the cobalt content in the bimetallic MOF increases. The statistical probability of having isolated Co2+ sites is calculated as a function of the total cobalt content of the bimetallic compound, assuming homogeneous distribution of Co2+ ions in the Ni-BTC framework and preferential occupation of terminal sites. Thus, in our best sample, with a Co:Ni ratio of 5:95, 73% of the total Co2+ ions are isolated so that CHP decomposition/overoxidation processes at the surface of the catalyst are not likely to occur before CHP desorption. This can explain the excellent CHP selectivity (91%) attained over this material. This “site isolation” effect is further supported by similar findings on Mn–Ni bimetallic compounds.
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A. Nowacka, P. Briantais, C. Prestipino, F. X. Llabrés I Xamena. Selective Aerobic Oxidation of Cumene to Cumene Hydroperoxide over Mono- and Bimetallic Trimesate Metal-Organic Frameworks Prepared by a Facile "green" Aqueous Synthesis. ACS Sustainable Chemistry & Engineering, American Chemical Society, 2019, 7 (8), pp.7708-7715. ⟨10.1021/acssuschemeng.8b06472⟩. ⟨hal-02122175⟩

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