Mild Homogeneous Synthesis of Gold Nanoparticles through the Epoxide Route: Kinetics, Mechanisms, and Related One-Pot Composites

Chemistry. 2020 Mar 9;26(14):3157-3165. doi: 10.1002/chem.201905335. Epub 2020 Feb 19.

Abstract

A new one-pot homogeneous methodology at room temperature to obtain Au nanoparticles (AuNP) on the basis of the epoxide route is presented. The proposed method takes advantage of the homogenous generation of OH- moieties driven by epoxide ring-opening, mediated by chloride nucleophilic attack. Once reached alkaline conditions, the reducing medium allows the quantitative formation of AuNP under well-defined kinetic control. A stabilizing agent, such as polyvinylpyrrolidone (PVP) or cetyltrimethylammonium chloride (CTAC), is required to maintain the AuNP stable. Meanwhile their presence dramatically affects the reduction kinetics and pathway, as demonstrated by the evolution of the UV/Vis spectra, small-angle X-ray scattering (SAXS) patterns, and pH value along the reaction. In the presence of PVP nanogold spheroids are obtained following a similar reduction mechanism as that observed for control experiments in the absence of PVP. However, if CTAC is employed a stable complex with AuIII is formed, leading to a different reaction pathway and resulting in ellipsoidal-like shaped AuNP. Moreover, the proposed methodology allows stabilize the growing AuNP, by coupling their formation with nonalkoxidic sol-gel reactions, leading to nanocomposite gels with embedded metallic nanoparticles. The epoxide route thus offers a versatile scenario for the one-pot preparation of new metal nanoparticles-inorganic/hybrid matrices nanocomposites with valuable optical properties.

Keywords: epoxides; gold; kinetics; nanoparticles; sol-gel processes.