High pressure induced atomic and mesoscale phase behaviors of one-dimensional TiO 2 anatase nanocrystals

Here, we report the high pressure phase and morphology behavior of ordered anatase titanium dioxide (TiO 2 ) nanocrystal arrays. One-dimensional TiO 2 nanorods and nanorices were synthesized and self-assembled into ordered mesostructures. Their phase and morphological transitions at both atomic scale and mesoscale under pressure were studied using in situ synchrotron wide- and small-angle x-ray scattering (WAXS and SAXS) techniques. At the atomic scale, synchrotron WAXS reveals a pressure-induced irreversible amorphization up to 35 GPa in both samples but with different onset pressures. On the mesoscale, no clear phase transformations were observed up to 20 GPa by synchrotron SAXS. Intriguingly, sintering of TiO 2 nanorods at mesoscale into nano-squares or nano-rectangles, as well as nanorices into nanowires, were observed for the first time by transmission electron microscopy. Such pressure-induced nanoparticle phase-amorphization and morphological changes provide valuable insights for design and engineering structurally stable nanomaterials. Impact statement The high pressure behavior of nanocrystals (NCs) continues to be of interest, as previous studies have demonstrated that an externally applied pressure can serve as an efficient tool to induce structural phase transitions of NC assemblies at both the atomic scale and mesoscale without altering any chemistry by manipulating NC interatomic and interparticle distances. In addition, the high pressure generated deviatoric stress has been proven to be able to force adjacent NCs to connect and fuse into new crystalline nanostructures. Although the atomic structural evolution of TiO 2 NCs under pressure has been widely investigated in the past decades, open questions remain regarding the mesoscale phase transition and morphology of TiO 2 NC assemblies as a function of pressure. Therefore, in this work, systemic high pressure experiments on ordered arrays of TiO 2 nanorods and nanorices were conducted by employing wide/small angle x-ray scattering techniques. The sintering of TiO 2 assemblies at mesoscale into various nanostructures under pressure were revealed by transmission electron microscopy. Overall, this high pressure work fills the current gap in research on the mesoscale phase behavior of TiO 2 assemblies. The observed morphology tunability attained by applying pressure opens new pathways for engineering nanomaterials and optimizing their collective properties through mechanical compression stresses. Graphical abstract