article published yes Mariano Calcabrini author 45D7531A-F248-11E8-B48F-1D18A9856A870000-0003-4566-5877 Dietger Van den Eynden author Sergi Sanchez Ribot author ddae5a59-f6e0-11ea-865d-d9dc61e77a2a Rohan Pokratath author Jordi Llorca author Jonathan De Roo author Maria Ibáñez author 43C61214-F248-11E8-B48F-1D18A9856A870000-0001-5013-2843 MaIb department International IST Doctoral Program project HighTE: The Werner Siemens Laboratory for the High Throughput Discovery of Semiconductors for Waste Heat Recovery project IST Austria Open Access Fund project 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. https://research-explorer.ista.ac.at/download/10806/10807/2021_JACSAu_Calcabrini.pdf application/pdfno https://creativecommons.org/licenses/by/4.0/ American Chemical Society2021 eng general medicine 2691-3704 2691-370410.1021/jacsau.1c00349 1111898-1903 https://research-explorer.ista.ac.at/record/12885 https://doi.org/10.26434/chemrxiv-2021-cn2fr M. Calcabrini <i>et al.</i>, “Ligand conversion in nanocrystal synthesis: The oxidation of alkylamines to fatty acids by nitrate,” <i>JACS Au</i>, vol. 1, no. 11. American Chemical Society, pp. 1898–1903, 2021. M. Calcabrini, D. Van den Eynden, S. Sanchez Ribot, R. Pokratath, J. Llorca, J. De Roo, M. Ibáñez, JACS Au 1 (2021) 1898–1903. Calcabrini, M., Van den Eynden, D., Sanchez Ribot, S., Pokratath, R., Llorca, J., De Roo, J., &#38; Ibáñez, M. (2021). Ligand conversion in nanocrystal synthesis: The oxidation of alkylamines to fatty acids by nitrate. <i>JACS Au</i>. American Chemical Society. <a href="https://doi.org/10.1021/jacsau.1c00349">https://doi.org/10.1021/jacsau.1c00349</a> 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.” <i>JACS Au</i>, vol. 1, no. 11, American Chemical Society, 2021, pp. 1898–903, doi:<a href="https://doi.org/10.1021/jacsau.1c00349">10.1021/jacsau.1c00349</a>. 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. <i>JACS Au</i>. 2021;1(11):1898-1903. doi:<a href="https://doi.org/10.1021/jacsau.1c00349">10.1021/jacsau.1c00349</a> 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.” <i>JACS Au</i>. American Chemical Society, 2021. <a href="https://doi.org/10.1021/jacsau.1c00349">https://doi.org/10.1021/jacsau.1c00349</a>. 108062022-03-02T15:24:16Z2026-04-07T13:26:13Z