Ligand conversion in nanocrystal synthesis: The oxidation of alkylamines to fatty acids by nitrate
Calcabrini M, Van den Eynden D, Sanchez Ribot S, Pokratath R, Llorca J, De Roo J, Ibáñez M. 2021. Ligand conversion in nanocrystal synthesis: The oxidation of alkylamines to fatty acids by nitrate. JACS Au. 1(11), 1898–1903.
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Calcabrini, MarianoISTA 
;
Van den Eynden, Dietger;
Sanchez Ribot, SergiISTA;
Pokratath, Rohan;
Llorca, Jordi;
De Roo, Jonathan;
Ibáñez , MariaISTA
;
Van den Eynden, Dietger;
Sanchez Ribot, SergiISTA;
Pokratath, Rohan;
Llorca, Jordi;
De Roo, Jonathan;
Ibáñez , MariaISTA Corresponding author has ISTA affiliation
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Abstract
Ligands are a fundamental part of nanocrystals. They control and direct nanocrystal syntheses and provide colloidal stability. Bound ligands also affect the nanocrystals’ chemical reactivity and electronic structure. Surface chemistry is thus crucial to understand nanocrystal properties and functionality. Here, we investigate the synthesis of metal oxide nanocrystals (CeO2-x, ZnO, and NiO) from metal nitrate precursors, in the presence of oleylamine ligands. Surprisingly, the nanocrystals are capped exclusively with a fatty acid instead of oleylamine. Analysis of the reaction mixtures with nuclear magnetic resonance spectroscopy revealed several reaction byproducts and intermediates that are common to the decomposition of Ce, Zn, Ni, and Zr nitrate precursors. Our evidence supports the oxidation of alkylamine and formation of a carboxylic acid, thus unraveling this counterintuitive surface chemistry.
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Publishing Year
Date Published
2021-11-22
Journal Title
JACS Au
Publisher
American Chemical Society
Acknowledgement
This work was financially supported by IST Austria and the Werner Siemens Foundation. M.C. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 665385. The work was also financially supported by University of Basel, SNSF NCCR Molecular Systems Engineering (project number: 182895) and SNSF R’equip (project number: 189622). J.L. is a Serra Húnter Fellow and is grateful to ICREA Academia program and MICINN/FEDER RTI2018-093996-B-C31 and GC 2017 SGR 128 projects.
Volume
1
Issue
11
Page
1898-1903
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IST-REx-ID
Cite this
Calcabrini M, Van den Eynden D, Sanchez Ribot S, et al. Ligand conversion in nanocrystal synthesis: The oxidation of alkylamines to fatty acids by nitrate. JACS Au. 2021;1(11):1898-1903. doi:10.1021/jacsau.1c00349
Calcabrini, M., Van den Eynden, D., Sanchez Ribot, S., Pokratath, R., Llorca, J., De Roo, J., & Ibáñez, M. (2021). Ligand conversion in nanocrystal synthesis: The oxidation of alkylamines to fatty acids by nitrate. JACS Au. American Chemical Society. https://doi.org/10.1021/jacsau.1c00349
Calcabrini, Mariano, Dietger Van den Eynden, Sergi Sanchez Ribot, Rohan Pokratath, Jordi Llorca, Jonathan De Roo, and Maria Ibáñez. “Ligand Conversion in Nanocrystal Synthesis: The Oxidation of Alkylamines to Fatty Acids by Nitrate.” JACS Au. American Chemical Society, 2021. https://doi.org/10.1021/jacsau.1c00349.
M. Calcabrini et al., “Ligand conversion in nanocrystal synthesis: The oxidation of alkylamines to fatty acids by nitrate,” JACS Au, vol. 1, no. 11. American Chemical Society, pp. 1898–1903, 2021.
Calcabrini M, Van den Eynden D, Sanchez Ribot S, Pokratath R, Llorca J, De Roo J, Ibáñez M. 2021. Ligand conversion in nanocrystal synthesis: The oxidation of alkylamines to fatty acids by nitrate. JACS Au. 1(11), 1898–1903.
Calcabrini, Mariano, et al. “Ligand Conversion in Nanocrystal Synthesis: The Oxidation of Alkylamines to Fatty Acids by Nitrate.” JACS Au, vol. 1, no. 11, American Chemical Society, 2021, pp. 1898–903, doi:10.1021/jacsau.1c00349.
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