Antioxidation Properties and Surface Interactions of Polyvinylpyrrolidone-Capped Zerovalent Copper Nanoparticles Synthesized in Supercritical Water

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• 作者：Takuya Morioka ; Masafumi Takesue ; Hiromichi Hayashi ; Masaru Watanabe ; Richard L. Smith Jr.
• 刊名：ACS Applied Materials & Interfaces
• 出版年：2016
• 出版时间：January 27, 2016
• 年：2016
• 卷：8
• 期：3
• 页码：1627-1634
• 全文大小：491K
• ISSN：1944-8252

文摘

Zerovalent copper nanoparticles (CuNPs) (diameter, 26.5 ± 9 nm) capped with polyvinylpyrrolidone (PVP) were synthesized in supercritical water at 400 °C and 30 MPa with a continuous flow reactor. The PVP-capped CuNPs were dispersed in distilled water, methanol, ethanol, 1-propanol, 2-propanol, butanol, and their mixed solvents to study their long-term stability. Temporal variation of UV–vis spectra and surface plasmon resonance were measured and showed that ethanol, the propanols, and butanol solvents provided varying degrees of oxidative protection for Cu⁰. Fourier transform infrared spectroscopy showed that PVP adsorbed onto the surface of the CuNPs with a pyrrolidone ring of PVP even if the CuNPs were oxidized. Intrinsic viscosities of PVP were higher for solvents that provided antioxidation protection than those that give oxidized CuNPs. In solvents that provided Cu⁰ with good oxidative protection (ethanol, the propanols, and butanol), PVP polymer chains formed large radii of gyration and coil-like conformations in the solvents so that they were arranged uniformly and orderly on the surface of the CuNPs and could provide protection of the Cu⁰ surface against dissolved oxygen. In solvents that provided poor oxidative protection for Cu⁰ (water, alcohol–water mixed solvents with 30% water), PVP polymer chains had globular-like conformations due to their relatively high hydrogen-bonding interactions and sparse adsorption onto the CuNP surface. Antioxidative properties of PVP-capped CuNPs in a solvent can be ascribed to the conformation of PVP polymer chains on the Cu⁰ particle surface that originates from the interaction between polymer chains and its interaction with the solvent.