Molecular Precursor Routes for Ag-Based Metallic, Intermetallic, and Metal Sulfide Nanoparticles: Their Comparative ORR Activity Trend at Solid|Liquid and Liquid|Liquid Interfaces.

The electrochemical conversion of oxygen to water is a crucial process required for renewable energy production, whereas its first two-electron step produces a versatile chemical and oxidant─hydrogen peroxide. Improving performance and widening the limited selection of the potential catalysts for this reaction is a step toward the implementation of clean-energy technologies. As silver is known as one of the most effective catalysts of oxygen reduction reaction (ORR), we have designed a suitable molecular precursor pathway for the selective synthesis of metallic (Ag), intermetallic (Ag 3 Sb), and binary or ternary metal sulfide (Ag 2 S and AgSbS 2 ) nanomaterials by judicious control of reaction conditions. The decomposition of xanthate precursors under different reaction conditions in colloidal synthesis indicates that carbon-sulfur bond cleavage yields the respective metal sulfide nanomaterials. This is not the case in the presence of trioctylphosphine when the metal-sulfur bond is broken. The synthesized nanomaterials were applied as catalysts of oxygen reduction at the liquid-liquid and solid-liquid interfaces. Ag exhibits the best performance for electrochemical oxygen reduction, whereas the electrocatalytic performance of Ag and Ag 3 Sb is comparable for peroxide reduction in an alkaline medium. Scanning electrochemical microscopy (SECM) analysis indicates that a flexible 2-electron to 4-electron ORR pathway has been achieved by transforming metallic Ag into intermetallic Ag 3 Sb.