Topological Transformations of Core-Shell Precursors to Hierarchically Hollow Assemblages of Copper Silicate Nanotubes.

Functional hollow materials have attracted extensive research attention due to their promising prospects for catalysis. Herein, we report an alternative synthesis of hierarchically hollow structured materials directly from core-shell structured templates, based on confined chemical reactions between the solid matter of a core and shell under hydrothermal conditions. More specifically, we have developed a novel and facile strategy to transform core-shell structured Cu2O@mSiO2 (m = mesoporous) to tubular copper silicate assemblages (TCSA). Depending on the original shapes of Cu2O, TCSA can be tailored as spherical or cubic assemblages with stacking copper silicate nanotubes (inner diameter: 4.5 nm, thickness: 0.8 nm, length: ca. 96 nm) in the shell. Moreover, by utilizing the residual reductive Cu(I) (ca. 10 at% of total surface copper) on TCSA support, in situ generations of Pd nanoparticles (∼4.5 nm) and Au nanoparticles (∼5.8 nm) were successfully achieved based on the spontaneous galvanic replacement reactions. Two integrated nanocatalysts (viz., Pd/TCSA and Au/TCSA) have been prepared with this approach. As an example, Pd/TCSA exhibits excellent activity and recyclability for Suzuki-Miyaura cross-coupling reactions.