The development process of catalytic core/shell microreactors, possessing a poly(ethylene glycol) (PEG) core and a polyurea (PU) shell, by implementing an emulsion-templated non-aqueous encapsulation method, is presented. The microreactors' fabrication process begins with an emulsification process utilizing an oil-in-oil (o/o) emulsion of PEG-in-heptane, stabilized by a polymeric surfactant. Next, a reaction between a poly(ethylene imine) (PEI) and a toluene-2,4-diisocyanate (TDI) takes place at the boundary of the emulsion droplets, resulting in the creation of a PU shell through an interfacial polymerization (IFP) process. The microreactors were loaded with palladium nanoparticles (NPs) and were utilized for the hydrogenation of alkenes and alkynes. Importantly, it was found that PEG has a positive effect on the catalytic performance of the developed microreactors. Interestingly, besides being an efficient green reaction medium, PEG plays two crucial roles: first, it reduces the palladium ions to palladium NPs; thus, it avoids the unnecessary use of additional reducing agents. Second, it stabilizes the palladium NPs and prevents their aggregation, allowing the formation of highly reactive palladium NPs. Strikingly, in one sense, the suggested system affords highly reactive semi-homogeneous catalysis, whereas in another sense, it enables the facile, rapid, and inexpensive recovery of the catalytic microreactor by simple centrifugation. The durable microreactors exhibit excellent activity and were recycled nine times without any loss in their reactivity.
Keywords: hydrogenation; non-aqueous interfacial polymerization; oil-in-oil emulsions; poly(ethylene glycol); polyurea microcapsules.