Shaping Tin Nanocomposites through Transient Local Conversion Reactions

Shape-preserving conversion offers a promising strategy to transform self-assembled structures into advanced functional components with customizable composition and shape. Specifically, the assembly of barium carbonate nanocrystals and amorphous silica nanocomposites (BaCO₃/SiO₂) offers a plethora of programmable three-dimensional (3D) microscopic geometries, and the nanocrystals can subsequently be converted into functional chemical compositions, while preserving the original 3D geometry. Despite this progress, the scope of these conversion reactions has been limited by the requirement to form carbonate salts. Here, we overcome this limitation using a single-step cation/anion exchange that is driven by the temporal pH change at the converting nanocomposite. We demonstrate the proof of principle by converting BaCO₃/SiO₂ nanocomposites into tin-containing nanocomposites, a metal without a stable carbonate. We find that BaCO₃/SiO₂ nanocomposites convert in a single step into hydroromarchite nanocomposites (Sn₃(OH)₂O₂/SiO₂) with excellent preservation of the 3D geometry and fine features. We explore the versatility and tunability of these Sn₃(OH)₂O₂/SiO₂ nanocomposites as a precursor for functional compositions by developing shape-preserving conversion routes to two desirable compositions: tin perovskites (CH₃NH₃SnX₃, with X = I or Br) with tunable photoluminescence (PL) and cassiterite (SnO₂)-a widely used transparent conductor. Ultimately, these findings may enable integration of functional chemical compositions into advanced morphologies for next-generation optoelectronic devices.