Hollow ZSM‐5 with Silicon‐Rich Surface, Double Shells, and Functionalized Interior with Metallic Nanoparticles and Carbon Nanotubes

Hollow ZSM‐5 single crystals with silicon‐rich exterior surface are prepared by a “dissolution–recrystallization” strategy in tetrapropylammonium hydroxide solution. Selective dissolution and exterior recrystallization cause the silicon components to migrate from the inside to outside, resulting in a regular void in the interior of the crystal, increased Brönsted acid sites and a silicon‐rich external surface. The as‐prepared hollow ZSM‐5 exhibits excellent acid catalysis with enhanced shape selectivity, as shown in biphenyl methylation as a probe reaction, which is attributed to the silicon‐rich external surface and thus the inhibition of isomerization on external surface. More interestingly, hollow ZSM‐5 single crystals with double shells are successfully prepared by layer‐by‐layer technique followed with dissolution–recrystallization strategy. Furthermore, hollow ZSM‐5 encapsulating iron and carbon nanotubes are successfully synthesized. Furthermore, hollow ZSM‐5 nanosized crystals with the interior functionalized as bimetallic (oxide) nanoparticles such as CuO‐Pd are also successfully synthesized.