Boosting Catalytic Selectivity through a Precise Spatial Control of Catalysts at Pickering Droplet Interfaces

Exploration of new methodologies to tune catalytic selectivity is a long-sought goal in catalytic community. In this work, oil–water interfaces of Pickering emulsions are developed to effectively regulate catalytic selectivity of hydrogenation reactions, which was achieved via a precise control of the spatial distribution of metal nanoparticles at the droplet interfaces. It was found that Pd nanoparticles located in the inner interfacial layer of Pickering droplets exhibited a significantly enhanced selectivity for p-chloroaniline (up to 99.6%) in the hydrogenation of p-chloronitrobenzene in comparison to those in the outer interfacial layer (63.6%) in pure water (68.5%) or in pure organic solvents (46.8%). Experimental and theoretical investigations indicated that such a remarkable interfacial microregion-dependent catalytic selectivity was attributed to the microenvironments of the coexistence of water and organic solvent at the droplet interfaces, which could provide unique interfacial hydrogen-bonding interactions and solvation effects so as to alter the adsorption patterns of p-chloronitrobenzene and p-chloroaniline on the Pd nanoparticles, thereby avoiding the unwanted contact of C–Cl bonds with the metal surfaces. Our strategy of precise spatial control of catalysts at liquid–liquid interfaces and the unprecedented interfacial effect reported here not only provide new insights into the liquid–liquid interfacial reactions but also open an avenue to boost catalytic selectivity.