Reduction of Aqueous Ag+ Steered by Electrochemical Plasma: Connecting the Bulk pH Variation with the Reaction Pathways for Hydrated Electrons

<div><p>Reduction of silver cations followed by nanoparticle (Ag-NPs) synthesis is a model process to understand the reduction mechanism induced by a discharge over an aqueous surface, termed electrochemical plasma. This work aims at studying the silver reduction reaction steered by electrochemical plasma in the presence of other chemically active plasma-related interfaces, namely the plasma-gas and the liquid-gas interfaces. As no other plasma-induced species are able to reduce silver cations, the reduction of silver cations is employed as strategy to selectively detect the presence of hydrated electrons (e-h). The results demonstrate that the global rise of pH (increase in the content of OH-), observed for discharge in the helium gas phase, occurs in connection with the silver reduction, which is interpreted as a vivid experimental evidence of the second-order recombination reaction of the e h − 2 e aq − + 2 H 2 O → H 2 + 2 OH −. On the other hand, the global decrease of pH (increase in the content of H+) observed for discharge in mixed oxygen and nitrogen gas phase, is an event primarily driven by the Birkeland-Eyde process, and it is concomitant but spatially distinct from the electron injection. The acidification interferes in the NP formation, as NPs promptly dissolve in presence of HNO3. Only in complete suppression of the acidification, an experimental evidence of the reaction pathways for hydrated electron could be captured: e-h is competitively consumed through a scavenger-like reaction (reduction of silver cations in this work) and through the second-order recombination reactions of the e-h. The kinetic model proposed in this work further corroborates this interpretation.</p></div>