Bioinspired Hollow Nanoreactor: Catalysts that Carry Gaseous Hydrogen for Enhanced Gas‐Liquid‐Solid Three‐Phase Hydrogenation Reactions

Abstract For conventional gas‐liquid‐solid three‐phase heterogeneous hydrogenation reactions, hydrogen must be dissolved into the solvent to be a participating reactant, restricting the reaction rates. In this study, we demonstrate that gaseous hydrogen could be directly involved in gas‐liquid‐solid hydrogenation reactions through a bioinspired hollow nanoreactor with superaerophilic surface to enhance the reaction rates. We produce Pd@meso‐SiO 2 hollow nanoreactor, whose external surface is modified with perfluorodecyltriethoxysilane (PFDTS). In aqueous solutions, H 2 gas could be spread quickly on the surface and stored in the cavity of hollow spheres, and participated in hydrogenation reactions, thereby enhancing H 2 concentration around Pd nanoparticles. In hydrogenation of olefin reactions, such three‐phase interface allows rapid and direct transportation of H 2 bubbles to the surface of Pd nanoparticles rather than through diffusion of dissolved H 2 in liquid phase, leading to an enhanced catalytic rate. This strategy is expected to be useful for designing and developing new catalytic systems of gas‐liquid‐solid three‐phase reaction.