Green synthesis of Ag nanoparticles in large quantity by cryomilling

Most of the synthetic methods for the preparation of Ag nanoparticles (Ag NPs) involve wet chemical synthesis, in which hazardous chemicals are used and the NPs are further stabilized by a surfactant. The presence of a surfactant is detrimental to the purity as well as to the native properties of the Ag NPs. The present study reports a unique technique to prepare ultrapure free-standing Ag NPs in large quantities without the use of any hazardous chemicals. This has been achieved by cryomilling. Note that cryomilling is a cost effective method to prepare metal NPs, involving ball milling below 160 ± 10 °C under a protective Ar atmosphere. The experimental results reveal that it is possible to obtain Ag NPs with a narrow size distribution (4–8 nm). The level of contamination (34 ppb of W) in the nanoparticles was estimated by EPMA, whereas the ultra-high purity of the Ag NPs was confirmed by ICP-OES and XPS. The surfactant-free Ag NPs were also stable at elevated temperatures (400 °C) and exhibited free-standing nature in liquids including ethanol, methanol, and water. The results have been discussed based on the low-temperature deformation behaviour of Ag and the electrostatic stabilization of highly pure Ag NPs in different polar liquids.