Mechanistic Insight into the Precursor Chemistry of ZrO₂ and HfO₂ Nanocrystals; towards Size-Tunable Syntheses

Pokratath, Rohan and Van den Eynden, Dietger and Cooper, Susan Rudd and Mathiesen, Jette Katja and Waser, Valérie and Devereux, Mike and Billinge, Simon J. L. and Meuwly, Markus and Jensen, Kirsten M. Ø. and De Roo, Jonathan. (2022) Mechanistic Insight into the Precursor Chemistry of ZrO₂ and HfO₂ Nanocrystals; towards Size-Tunable Syntheses. JACS Au, 2 (4). pp. 827-838.

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Official URL: https://edoc.unibas.ch/90221/

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ne can nowadays readily generate monodisperse colloidal nanocrystals, but a retrosynthetic analysis is still not possible since the underlying chemistry is often poorly understood. Here, we provide insight into the reaction mechanism of colloidal zirconia and hafnia nanocrystals synthesized from metal chloride and metal isopropoxide. We identify the active precursor species in the reaction mixture through a combination of nuclear magnetic resonance spectroscopy (NMR), density functional theory (DFT) calculations, and pair distribution function (PDF) analysis. We gain insight into the interaction of the surfactant, tri-n-octylphosphine oxide (TOPO), and the different precursors. Interestingly, we identify a peculiar X-type ligand redistribution mechanism that can be steered by the relative amount of Lewis base (L-type). We further monitor how the reaction mixture decomposes using solution NMR and gas chromatography, and we find that ZrCl4 is formed as a by-product of the reaction, limiting the reaction yield. The reaction proceeds via two competing mechanisms: E1 elimination (dominating) and SN1 substitution (minor). Using this new mechanistic insight, we adapted the synthesis to optimize the yield and gain control over nanocrystal size. These insights will allow the rational design and synthesis of complex oxide nanocrystals.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie
UniBasel Contributors:Devereux, Michael and De Roo, Jonathan and Meuwly, Markus and Pokratath, Rohan and Van den Eynden, Dietger
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:16 Nov 2022 06:54
Deposited On:16 Nov 2022 06:54

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