期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 3, 页码 1169-1178出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201403835
关键词
copper; nanoparticles; NMR spectroscopy; oxidation; surface chemistry
资金
- ANR Blanc SIMI7 CopperTree [11-BS07-018-02]
- ANRT
- STMicroelectronics SAS Tours
- CNRS
- Paul Sabatier University (Toulouse III)
The hydrogenolysis of [Cu-2{(iPrN)(2)(CCH3)}(2)] in the presence of hexadecylamine (HDA) or tetradecylphosphonic acid (TDPA) in toluene leads to 6-9nm copper nanocrystals. Solution NMR spectroscopy has been used to describe the nanoparticle surface chemistry during the dynamic phenomenon of air oxidation. The ligands are organized as multilayered shells around the nanoparticles. The shell of ligands is controlled by both their intermolecular interactions and their bonding strength on the nanocrystals. Under ambient atmosphere, the oxidation rate of colloidal copper nanocrystals closely relies on the chemical nature of the employed ligands (base or acid). Primary amine molecules behave as soft ligands for Cu atoms, but are even more strongly coordinated on surface Cu-I sites, thus allowing a very efficient corrosion protection of the copper core. On the contrary, the TDPA ligands lead to a rapid oxidation rate of Cu nanoparticles and eventually to the re-dissolution of Cu-II species at the expense of the nanocrystals.
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