Flexible Cation Exchange Environment via Ligand-Free Metal Chalcogenide Thin Films

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Author(s)Lacey, Hannah R.
Author(s)Dobson, Kevin D.
Author(s)Hernández- Pagán, Emil A.
Date Accessioned2024-11-12T16:32:12Z
Date Available2024-11-12T16:32:12Z
Publication Date2024-11-07
DescriptionThis article was originally published in ACS Nanoscience Au. The version of record is available at: https://doi.org/10.1021/acsnanoscienceau.4c00023. © 2024 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/) .
AbstractCation exchange (CE) has emerged as a premier postsynthetic method to carefully tune the chemical composition and properties of nanocrystals with excellent morphology retention. However, reaction conditions are typically dictated by the ubiquitous ligands bound to their surface, limiting their solubility and influencing the thermodynamics/kinetics of the reaction. To bypass these challenges, we report on CE reactions with Cu+, Ag+, Cu2+, Cd2+, Zn2+, and Mn2+ utilizing ligand-free CdS and CuxSey thin films as host templates. The exchange reactions could be performed sequentially or simultaneously (i.e., two guest cations) to access compositionally diverse products. The incorporation of cations on the host films was confirmed using SEM-EDS, XPS, and ICP-MS analyses, as well as tracking wavelength shifts in the UV–vis absorption spectra. The flexibility of this approach was demonstrated as reactions were carried out using an array of different guest precursor salts and solvents with a range of polarities. Moreover, the reactions were generalizable among selenide and sulfide films and proceeded under milder conditions in comparison with reported nanocrystal reactions. A ligand-free environment with flexible reaction conditions, as the work herein, could aid in deconvoluting the different factors involved in CE reactions and further expand its use for fundamental research and applications like photovoltaics, optoelectronics, and catalysis.
SponsorFunding Financial support was provided by startup funds from the University of Delaware, Department of Chemistry and Biochemistry. Acknowledgments The authors thank Shannon Fields for deposition of CuxSey films and Cameron Armstrong for help with XPS analysis. XPS analysis was performed with the instrument sponsored by the National Science Foundation under grant no. CHE-1428149. AFM and Raman analysis was performed with the instrument sponsored by the National Science Foundation under grant no. CHE-1828325. We thank the reviewers for their comments and suggested experiments.
CitationLacey, Hannah R., Kevin D. Dobson, and Emil A. Hernández- Pagán. “Flexible Cation Exchange Environment via Ligand-Free Metal Chalcogenide Thin Films.” ACS Nanoscience Au, November 7, 2024. https://doi.org/10.1021/acsnanoscienceau.4c00023.
ISSN2694-2496
URLhttps://udspace.udel.edu/handle/19716/35555
Languageen_US
PublisherACS Nanoscience Au
dc.rightsAttribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
Keywordscation exchange
Keywordschalcogenides
Keywordstransition metals
Keywordsthin films
Keywordsligands
KeywordsHSAB
TitleFlexible Cation Exchange Environment via Ligand-Free Metal Chalcogenide Thin Films
TypeArticle
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