Hollow Carbon Sphere Nanoreactors Loaded with PdCu Nanoparticles: Void‐Confinement Effects in Liquid‐Phase Hydrogenations

Nanoreactors with hollow structures have attracted great interest in catalysis research due to their void‐confinement effects. However, the challenge in unambiguously unraveling these confinement effects is to decouple them from other factors affecting catalysis. Here, we synthesize a pair of hollow carbon sphere (HCS) nanoreactors with presynthesized PdCu nanoparticles encapsulated inside of HCS (PdCu@HCS) and supported outside of HCS (PdCu/HCS), respectively, while keeping other structural features the same. Based on the two comparative nanoreactors, void‐confinement effects in liquid‐phase hydrogenation are investigated in a two‐chamber reactor. It is found that hydrogenations over PdCu@HCS are shape‐selective catalysis, can be accelerated (accumulation of reactants), decelerated (mass transfer limitation), and even inhibited (molecular‐sieving effect); conversion of the intermediate in the void space can be further promoted. Using this principle, a specific imine is selectively produced. This work provides a proof of concept for fundamental catalytic action of the hollow nanoreactors.