Stabilization of catalytic sol-gel entrapped perruthenate

A combination of more stable counter-cation (tetraphenylphosphonium in place of tetrapropylammonium), of local basic microenvironment, and of a non-solubilizing reaction medium (supercritical CO2) improves the life-cycle and reusability of catalytic ORMOSILs doped with perruthenate in the oxidation of alcohols with O2. A number of different bases were co-entrapped and their effect on catalysis assessed in the oxidative dehydrogenation of benzyl alcohol in dense phase carbon dioxide at 22 MPa and 75 C. The optimized catalyst retains most of its activity after five consecutive runs when a normal ORMOSIL-entrapped TPAP has become inactive. Deactivation of TPAP could be ascribed by EPR analysis to the formation of catalytically inactive RuO2.