Carboxylic‐Acid‐Passivated Metal Oxide Nanocrystals: Ligand Exchange Characteristics of a New Binding Motif |
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| Authors: | Jonathan De?Roo Dr Yolanda Justo Katrien De?Keukeleere Freya Van?den?Broeck Prof?Dr José C Martins Prof?Dr Isabel Van?Driessche Prof?Dr Zeger Hens |
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| Affiliation: | 1. Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281‐S3, 9000 Gent (Belgium);2. Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281‐S4, 9000 Gent (Belgium) |
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| Abstract: | Ligand exchange is central in the processing of inorganic nanocrystals (NCs) and requires understanding of surface chemistry. Studying sterically stabilized HfO2 and ZrO2 NCs using 1H solution NMR and IR spectroscopy as well as elemental analysis, this paper demonstrates the reversible exchange of initial oleic acid ligands for octylamine and self‐adsorption of oleic acid at NC surfaces. Both processes are incompatible with an X‐type binding motif of carboxylic acids as reported for sulfide and selenide NCs. We argue that this behavior stems from the dissociative adsorption of carboxylic acids at the oxide surface. Both proton and carboxylate moieties must be regarded as X‐type ligands yielding a combined X2 binding motif that allows for self‐adsorption and exchange for L‐type ligands. |
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| Keywords: | CdSe ligand exchange nanoparticles NMR spectroscopy surface chemistry |
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