Contraction and Expansion of Nanocomposites during Ion Exchange Reactions

The next generation of advanced functional materials can greatly benefit from methods for realizing the right chemical composition at the right place. Nanocomposites of amorphous silica and metal carbonate nanocrystals (BaCO₃/SiO₂) form an attractive starting point as they can straightforwardly be assembled in different controllable three-dimensional (3D) shapes, while the chemical composition of the nanocrystals can be completely converted via ion exchange. Nevertheless, it is still unknown-let alone predictable-how nanoscopic changes in the lattice volume of the nanocrystals translate to changes in the microscopic dimensions of 3D BaCO₃/SiO₂ structures during ion exchange. Here, we demonstrate that the microscopic shape adapts to contraction and expansion of the atomic spacing of nanocrystals. Starting from BaCO₃/SiO₂, we systematically decrease and increase lattice volumes by converting the BaCO₃ nanocrystals into a range of chalcogenides and perovskites. Based on geometrical analysis, we obtain a precise prediction for how the microscopic nanocomposite volume follows the change in nanoscopic crystal volume. The silica matrix facilitates mechanical flexibility to adapt to nanoscopic volume changes, while preserving the 3D morphology and fine details of the original composite with high fidelity. The versatility and predictability of shape-preserving conversion reactions open up exciting opportunities for using nanocomposites as functional components.