From Silver Plates to Spherical Nanoparticles: Snapshots of Microwave-Assisted Polyol Synthesis

The fabrication of silver nanoparticles (Ag NPs) with different sizes by microwave (MW)-assisted synthesis is presented. The fast heating of the MW technique, combined with the possibility to thermally quench the reactions, enabled us to capture snapshots of nucleation and growth processes difficult to accomplish in other techniques. The Ag NPs were synthesized using poly(vinylpyrrolidone) (PVP) through a polyol approach. The effects of the reaction time, the reaction temperatures, and the silver precursor concentration were investigated. The influence of agitation, the PVP concentration, and the initial conditions of the silver precursor was also studied. It is found that at very short reaction times and at low temperatures, polyhedral plates are formed with sizes ca. 300 nm and large polydispersity. However, by increasing the time or the temperature, a size and shape refinement is observed resulting in 10 nm spherical NPs with low polydispersity. Mechanistic insights are provided based on the observations extracted from transmission electron microscopy (TEM) and ultraviolet−visible spectroscopy (UV−vis). A formation mechanism starting from kinetically favored silver polyhedral plates to thermodynamically favored spherical nanoparticles is proposed. Understanding these effects allowed us to control the particle size and the tuning of Ag NPs ondemand. Moreover, the reproducibility and scalability of the process and the long-term stability of the NPs in aqueous solutions are demonstrated. Finally, we provide a recommendation regarding the use of fresh PVP as a capping and stabilizing agent.This research received funding from the Spanish Ministry of Science, Innovation and Universities through the PCIN-2017- 090 and RTI2018-096273-B-I00 projects, the “Severo Ochoa” Programme for Centers of Excellence in R&D grants (SEV2015-0496), and the Generalitat de Catalunya (2017SGR765 grant). The Spanish Ministry of Education funded the FPU Fellow of MT (FPU16/05452). The authors would also like to thank Judith Orófrom the TEM service at ICMAB and Marcos Rosado from the HRTEM service at ICN2 (Catalan Institute of Nanoscience and Nanotechnology).Peer reviewe