Silver Nanoparticle Synthesis in Glycerol by Low-Pressure Plasma-Driven Electrolysis: The Roles of Free Electrons and Photons

Low-temperature plasmas in and in contact with liquids have emerged as a catalyst-free approach for the selective, electrode-free, and green synthesis of novel materials. For the synthesis of nanomaterials, short-lived solvated electrons have been proposed to be the critical reducing species, while the role of ultraviolet (UV) photons from plasma is less explored. Here, we demonstrate that UV radiation contributes ∼70% of the integral plasma effect in synthesizing silver (Ag) nanoparticles within a glycerol solution. We suggest that the UV radiation causes C-H bond cleavage of the glycerol molecules, with an experimentally and theoretically determined threshold photon energy of only 5 eV. The photon-induced dissociation leads to the formation of glycerol fragmentation radicals, causing the reduction of Ag⁺ ions to Ag neutrals, enabling nanoparticle formation in the liquid phase.