A new hierarchically porous Pd@HSQ monolithic catalyst for Mizoroki–Heck cross-coupling reactions

Abstract

Pore architecture of catalyst supports is an important factor facilitating accessibility of reactants to catalytic sites. This holds the key to improving catalytic activities. Amongst various catalytic reactions, supported Pd nanoparticles-catalyzed C–C cross-coupling reactions have been attracting a great deal of attention in the last decade. Although various supports have been examined, applications of hierarchically porous monolithic materials have never been reported, mainly because of difficulties in multistep synthesis of catalysts. We herein report a novel on-site reduction-based methodology using hierarchically porous hydrogen silsesquioxane (HSQ) monoliths for one-step synthesis of Pd nanoparticles-embedded monoliths (Pd@HSQ). Characterization of these monoliths evidences the on-site reduction, i.e. formation of Pd nanoparticles and conversion of Si–H present in the monolith to Si–O . Fast, quantitative reduction of Pd[2+] to Pd(0) to form supported Pd nanoparticles is achieved with preservation of the porous structure of the original monolith, which makes this material attractive as a catalyst for C–C cross-coupling reactions. The obtained Pd@HSQ catalyst has been employed in the Mizoroki–Heck cross-coupling reaction. High accessibility of reactant molecules, undetectable leaching of Pd nanoparticles and easy separation of the monolith from liquid media provide high catalytic activity, reusability and easy handling.