Amphiphilic Covalent Organic Framework Nanoparticles for Pickering Emulsion Catalysis with Size Selectivity.

Exploiting advanced amphiphilic solid catalysts is crucial to the development of Pickering emulsion catalysis. Herein, covalent organic framework (COF) nanoparticles constructed with highly hydrophobic monomers as linkers were found to show superior amphiphilicity and they were then developed as a new class of solid emulsifiers for Pickering emulsion catalysis. Employing amphiphilic COFs as solid emulsifiers, Pickering emulsions with controllable emulsion type and droplet sizes were obtained. COF materials have also been demonstrated to serve as porous surface coatings to replace traditional surface modifications for stabilizing Pickering emulsions. After implanting Pd nanoparticles into amphiphilic COFs, the obtained catalyst displayed a 3.9 times higher catalytic efficiency than traditional amphiphilic solid catalysts with surface modifications in the biphasic oxidation reaction of alcohols. Such an enhanced activity was resulted from the high surface area and regular porous structure of COFs. More importantly, because of their tunable pore diameters, Pickering emulsion catalysis with remarkable size selectivity was achieved. This work is the first example that COFs were applied in Pickering emulsion catalysis, providing a platform for exploring new frontiers of Pickering emulsion catalysis.

Nonsacrificial Self-Template Synthesis of Colloidal Magnetic Yolk-Shell Mesoporous Organosilicas for Efficient Oil/Water Interface Catalysis.

Using interfacial reaction systems for biphasic catalytic reactions is attracting more and more attention due to their simple reaction process and low environmental pollution. Yolk-shell structured materials have broad applications in biomedicine, catalysis, and environmental remediation owing to their open channels and large space for guest molecules. Conventional methods to obtain yolk-shell mesoporous materials rely on costly and complex hard-template strategies. In this study, a mild and convenient nonsacrificial self-template strategy is developed to construct yolk-shell magnetic periodic mesoporous organosilica (YS-mPMO) particles by using the unique swelling-deswelling property of low-crosslinking density resorcinol formaldehyde (RF). The obtained YS-mPMO microspheres possess an amphiphilic outer shell, high surface area (393 m2 g-1 ), uniform mesopores (2.58 nm), a tunable middle hollow space (50-156 nm), and high superparamagnetism (34.4-37.1 emu g-1 ). By tuning the synthesis conditions, heterojunction structured yolk-shell Fe3 O4 @RF@void@PMO particles with different morphologies can be produced. Owing to the amphipathy of PMO framworks, the YS-mPMO particles show great emulsion stabilization ability and recyclability under a magnetic field. YS-mPMO microspheres with immobilized Au nanoparticles (≈3 nm) act as both solid emulsifier for dispersing styrene (St) in water and interface catalysts for selective conversion of St into styrene oxide with a high selectivity of 86%, and yields of over 97%.