Two-Step Reduction Pathway of Copper(II) by Oleylamine for the Nucleation of Cu(0) Nanoparticles: A Joint Modelling and Experimental Study.

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL
Maya Guillaumont, Stéphanie Halbert, Alexy P Freitas, Valérie Briois, Sophie Carenco, Hélène Gérard
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引用次数: 0

Abstract

Oleylamine is widely used in the synthesis of colloidal nanoparticles, as a solvent, as a stabilizing agent, and sometimes as a reducing agent. For example, metallic nanoparticles are obtained through reduction when Ni(II) and Pd(II) precursors are used or through disproportionation in the case of Ni(I) or Co(I). A similar dichotomy is observed for Cu precursors, with an additional complexity due to the nature of the precursor salt. In the present article, we report a combined DFT evaluation of possible reduction paths for Cu(II) and Cu(I) reduction by oleylamine, including the competition with Cu(I) disproportionation, and X-ray Absorption Spectroscopy monitoring of the oxidation state of copper(II) acetylacetonate in oleylamine. We show that the reduction of copper(II) acetylacetonate goes through a two-steps process, with the intermediate formation of Cu(I) complexes. The role of phosphine ligands is demonstrated as well as the relevance of these findings in case alternative copper sources such as copper halogen salts.

油胺广泛用于合成胶体纳米粒子,可用作溶剂、稳定剂,有时也用作还原剂。例如,在使用 Ni(II) 和 Pd(II) 前体时,通过还原作用获得金属纳米粒子;在使用 Ni(I) 或 Co(I) 前体时,通过歧化作用获得金属纳米粒子。在铜前驱体中也观察到了类似的二分法,由于前驱体盐的性质而增加了复杂性。在本文中,我们报告了对油胺还原铜(II)和铜(I)的可能还原路径的 DFT 评估(包括与铜(I)歧化的竞争),以及对油胺中乙酰丙酮酸铜(II)氧化态的 X 射线吸收光谱监测。我们发现乙酰丙酮酸铜(II)的还原过程分为两步,中间形成 Cu(I) 复合物。我们证明了膦配体的作用,以及这些发现与铜卤素盐等替代铜源的相关性。
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来源期刊
Chemphyschem
Chemphyschem 化学-物理:原子、分子和化学物理
CiteScore
4.60
自引率
3.40%
发文量
425
审稿时长
1.1 months
期刊介绍: ChemPhysChem is one of the leading chemistry/physics interdisciplinary journals (ISI Impact Factor 2018: 3.077) for physical chemistry and chemical physics. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. ChemPhysChem is an international source for important primary and critical secondary information across the whole field of physical chemistry and chemical physics. It integrates this wide and flourishing field ranging from Solid State and Soft-Matter Research, Electro- and Photochemistry, Femtochemistry and Nanotechnology, Complex Systems, Single-Molecule Research, Clusters and Colloids, Catalysis and Surface Science, Biophysics and Physical Biochemistry, Atmospheric and Environmental Chemistry, and many more topics. ChemPhysChem is peer-reviewed.
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