An Amorphous Phase Precedes Crystallization: Unraveling the Colloidal Synthesis of Zirconium Oxide Nanocrystals
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One can nowadays readily generate monodisperse colloidal nanocrystals, but the underlying mechanism of nucleation and growth is still a matter of intense debate. Here, we combine X-ray pair distribution function (PDF) analysis, small-angle X-ray scattering (SAXS), nuclear magnetic resonance (NMR), and transmission electron microscopy (TEM) to investigate the nucleation and growth of zirconia nanocrystals from zirconium chloride and zirconium isopropoxide at 340 °C, in the presence of surfactant (tri-n-octylphosphine oxide). Through E1 elimination, precursor conversion leads to the formation of small amorphous particles (less than 2 nm in diameter). Over the course of the reaction, the total particle concentration decreases while the concentration of nanocrystals stays constant after a sudden increase (nucleation). Kinetic modeling suggests that amorphous particles nucleate into nanocrystals through a second order process and they are also the source of nanocrystal growth. There is no evidence for a soluble monomer. The nonclassical nucleation is related to a precursor decomposition rate that is an order of magnitude higher than the observed crystallization rate. Using different zirconium precursors (e.g., ZrBr4 or Zr(OtBu)4), we can tune the precursor decomposition rate and thus control the nanocrystal size. We expect these findings to help researchers in the further development of colloidal syntheses.
| Originalsprog | Engelsk |
|---|---|
| Tidsskrift | ACS Nano |
| Sider (fra-til) | 8796−8806 |
| Antal sider | 11 |
| ISSN | 1936-0851 |
| DOI | |
| Status | Udgivet - 2023 |
Bibliografisk note
Funding Information:
J.D.R., R.P., and J.P.M. thank the University of Basel and the SNF Eccellenza funding scheme (Project Number: 194172). S.J.L.B. was supported by the U.S. National Science Foundation through Grant DMREF-1922234. K.M.Ø.J., J.K.M., and S.R.C. are grateful to the Villum Foundation for financial support through a Villum Young Investigator Grant (VKR00015416). Funding from the Danish Ministry of Higher Education and Science through the SMART Lighthouse is gratefully acknowledged. We thank DANSCATT (supported by the Danish Agency for Science and Higher Education) for support for beamtime travel. S.R.C. received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie Grant Agreement No. 841903. The authors acknowledge Prof. Catherine Housecroft for fruitful discussions. We acknowledge the European Synchrotron Radiation Facility (ESRF) for the provision of beamtime for the total scattering experiments (Proposal CH-5674). We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and we would like to thank Dr. Ann-Christin Dippel for assistance in using beamline P21.1. Beamtime was allocated for Proposal I20200150. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement 865995 - SENECA). We acknowledge SOLEIL for provision of synchrotron radiation facilities and we would like to thank Thomas Bizien for assistance in using beamline SWING. Authors acknowledge Ajmal Roshan Unniram Parambil for the TOC.
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
ID: 347294023