Plasmas with dense concentrations of reactive species such as hydrated electrons and hydroxyl radicals are generated from focusing intense femtosecond laser pulses into aqueous media. These radical species can reduce metal ions such as Au³⁺ to form metal nanoparticles (NPs). However, the formation of H₂O₂ by the recombination of hydroxyl radicals inhibits the reduction of Ag⁺ through back-oxidation. This work has explored the control of hydroxyl radical chemistry in a femtosecond laser-generated plasma through the addition of liquid ammonia. The irradiation of liquid ammonia solutions resulted in a reaction between NH₃ and OH·, forming peroxynitrite and ONOO⁻, and significantly reducing the amount of H₂O₂ generated. Varying the liquid ammonia concentration controlled the Ag⁺ reduction rate, forming 12.7 ± 4.9 nm silver nanoparticles at the optimal ammonia concentration. The photochemical mechanisms underlying peroxynitrite formation and Ag⁺ reduction are discussed.

Laser-assisted metallic nanoparticle synthesis is a versatile “green” method that has become a topic of active research. This chapter discusses the photochemical reaction mechanisms driving AuCl4− reduction using femtosecond-laser irradiation, and reviews recent advances in Au nanoparticle size-control. We begin by describing the physical processes underlying the interactions between laser pulses and the condensed media, including optical breakdown and supercontinuum emission. These processes produce a highly reactive plasma containing free electrons, which reduce AuCl4−, and radical species producing H2O2 that cause autocatalytic growth of Au nanoparticles. Then, we discuss the reduction kinetics of AuCl4−, which follow an autocatalytic rate law in which the first- and second-order rate constants depend on free electrons and H2O2 availability. Finally, we explain strategies to control the size of gold nanoparticles as they are synthesized; including modifications of laser parameters and solution compositions.