Tandem hydroformylation/hydrogenation over novel immobilized Rh-containing catalysts based on tertiary amine-functionalized hybrid inorganic-organic materials

Abstract

Non-phosphorous rhodium-containing catalysts for direct conversion of olefins to alcohols via tandem hydroformylation/hydrogenation have been designed and synthesized. Interaction between Rh(acac)(CO)2 and tertiary amino groups on the surface of mesoporous hybrid organic-inorganic supports yielded materials which were successfully used in the tandem process. Data obtained for a selected catalyst KN demonstrate that rhodium is in the Rh+1 state highly dispersed on the surface and is bonded with nitrogen atoms both before and after use. Evaluation of the catalytic performance shows high activity (hydroformylation TOF 312 h−1), chemoselectivity and stable hydroformylation yield at least in the first 5 cycles with a decrease in alcohol selectivity. The influence of temperature, reaction time, total pressure, and molar CO/H2 ratio of syngas on oxygenate yields is described. Type of the hydroformylation active sites and possible pathways for the observed decrease in hydrogenation are discussed.