Parvizian, Mahsa;
Duràn Balsa, Alejandra;
Pokratath, Rohan;
Kalha, Curran;
Lee, Seungho;
Van den Eynden, Dietger;
Ibáñez, Maria;
... De Roo, Jonathan; + view all
(2022)
The Chemistry of Cu₃N and Cu₃PdN Nanocrystals.
Angewandte Chemie
, 134
(31)
, Article e202207013. 10.1002/ange.202207013.
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Abstract
The precursor conversion chemistry and surface chemistry of Cu3N and Cu3PdN nanocrystals are unknown or contested. Here, we first obtain phase-pure, colloidally stable nanocubes. Second, we elucidate the pathway by which copper(II) nitrate and oleylamine form Cu3N. We find that oleylamine is both a reductant and a nitrogen source. Oleylamine is oxidized by nitrate to a primary aldimine, which reacts further with excess oleylamine to a secondary aldimine, eliminating ammonia. Ammonia reacts with CuI to form Cu3N. Third, we investigated the surface chemistry and find a mixed ligand shell of aliphatic amines and carboxylates (formed in situ). While the carboxylates appear tightly bound, the amines are easily desorbed from the surface. Finally, we show that doping with palladium decreases the band gap and the material becomes semi-metallic. These results bring insight into the chemistry of metal nitrides and might help the development of other metal nitride nanocrystals.
Type: | Article |
---|---|
Title: | The Chemistry of Cu₃N and Cu₃PdN Nanocrystals |
Open access status: | An open access version is available from UCL Discovery |
DOI: | 10.1002/ange.202207013 |
Publisher version: | https://doi.org/10.1002/ange.202207013 |
Language: | English |
Additional information: | Copyright © 2022 The Authors. Angewandte Chemie published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
Keywords: | Copper Nitride, Ligands, Nitrides, Reaction Mechanisms, Structural Analysis, Surface Chemistry |
UCL classification: | UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry UCL > Provost and Vice Provost Offices > UCL BEAMS UCL |
URI: | https://discovery.ucl.ac.uk/id/eprint/10154028 |
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