Morphology Control in AgCu Nanoalloy Synthesis by Molecular Cu(I) Precursors

0531514 - ÚFM 2021 RIV US eng J - Journal Article
Vykoukal, V. - Halasta, V. - Babiak, M. - Buršík, Jiří - Pinkas, J.
Morphology Control in AgCu Nanoalloy Synthesis by Molecular Cu(I) Precursors.
Inorganic Chemistry. Roč. 58, č. 22 (2019), s. 15246-15254. ISSN 0020-1669. E-ISSN 1520-510X
R&D Projects: GA ČR(CZ) GA17-15405S
Institutional support: RVO:68081723
Keywords : CARBOXYLATE COMPLEXES * SILVER NANOPARTICLES * CU * OLEYLAMINE * ELECTROCATALYSTS * DECOMPOSITION * NANOCRYSTALS * CRYSTALLINE * COPPER(II)
OECD category: Inorganic and nuclear chemistry
Impact factor: 4.825, year: 2019
Method of publishing: Limited access
https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b02172

As nanoparticle preparation methods employing bottom-up procedures rely on the use of molecular precursors, the chemical composition and bonding of these precursors have a decisive effect on nanoparticle formation and their resulting morphology and properties. We synthesized the Cu(I) complexes [Cu(PPh3)(2) (bea)] (1, bea = benzoate) and [Cu(PPh3)(3) (Hphta)] (2, phta = phthalate) by reducing the corresponding Cu(II) mono- and dicarboxylates with triphenylphosphine. We characterized 1 and 2 by single-crystal X-ray diffraction analysis, elemental analyses, infrared and nuclear magnetic resonance spectroscopy, and mass spectrometry and obtained complete information about their structures in the solid state and in solution. Also, we examined their thermal stability in oleylamine and determined their decomposition temperatures to be used as the minimal reaction temperature in metal nanoparticle synthesis. The complexes 1 and 2 differ in the number of reducing PPh 3 ligands and the strength of carboxylate bonding to the Cu(I) center. Therefore, we employed them in combination with [Ag(NH2C12H25)(2)]NO3 as molecular precursors in the solvothermal hot injection synthesis of AgCu nanoalloys in oleylamine and demonstrated their influence on the elemental distribution, phase composition, particle size distribution, shape, morphology, and optical properties of the resulting nanoparticles. The nanoalloy particles from the benzoate complex 1 were oblate and polydisperse and exhibited two surface plasmons at 393 and 569 nm, which is caused by their Janus-type structure. The nanoparticles prepared from the phthalate complex 2 were round and monodisperse and exhibited one plasmon at 413 nm, as they formed an AgCu solid solution with a random distribution of the elements in a particle.
Permanent Link: http://hdl.handle.net/11104/0310157