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Deciphering Ligands’ Interaction with Cu and Cu 2 O Nanocrystal Surfaces by NMR Solution Tools
Author(s) -
Glaria Arnaud,
Cure Jérémy,
Piettre Kilian,
Coppel Yannick,
Turrin CédricOlivier,
Chaudret Bruno,
Fau Pierre
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201403835
Subject(s) - nanocrystal , copper , dissolution , nanoparticle , chemistry , colloid , chemical engineering , inorganic chemistry , crystallography , nanotechnology , materials science , organic chemistry , engineering
The hydrogenolysis of [Cu 2 {( i PrN) 2 (CCH 3 )} 2 ] in the presence of hexadecylamine (HDA) or tetradecylphosphonic acid (TDPA) in toluene leads to 6–9 nm 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.