Bifunctional Janus Silica Spheres for Pickering Interfacial Tandem Catalysis

Nature provides much inspiration for the design of multistep conversion processes, with numerous reactions running simultaneously and without interference in cells, for example. A key challenge in mimicking nature's strategies is to compartmentalize incompatible reagents and catalysts, for example, for tandem catalysis. Here, we present a new strategy for antagonistic catalyst compartmentalization. The synthesis of bifunctional Janus catalyst particles carrying acid and base groups on the particle's opposite patches is reported as is their application as acid‐base catalysts in oil/water emulsions. The synthesis strategy involved the use of monodisperse, hydrophobic and amine‐functionalized silica particles (SiO(2)−NH(2)−OSi(CH(3))(3)) to prepare an oil‐in‐water Pickering emulsion (PE) with molten paraffin wax. After solidification, the exposed patch of the silica particles was selectively etched and refunctionalized with acid groups to yield acid‐base Janus particles (Janus A–B). These materials were successfully applied in biphasic Pickering interfacial catalysis for the tandem dehydration‐Knoevenagel condensation of fructose to 5‐(hydroxymethyl)furfural‐2‐diethylmalonate (5‐HMF‐DEM) in a water/4‐propylguaiacol PE. The results demonstrate the advantage of rapid extraction of 5‐hydroxymethylfurfural (5‐HMF), a prominent platform molecule prone to side product formation in acidic media. A simple strategy to tune the acid/base balance using PE with both Janus A–B and monofunctional SiO(2)−NH(2)−OSi(CH(3))(3) base catalysts proved effective for antagonistic tandem catalysis.