One-Pot Synthesis of Penta-twinned Palladium Nanowires and Their Enhanced Electrocatalytic Properties

This article reports the design and successful implementation of a one-pot, polyol method for the synthesis of penta-twinned Pd nanowires with diameters below 8 nm and aspect ratios up to 100. The key to the success of this protocol is the controlled reduction of Na₂PdCl₄ by diethylene glycol and ascorbic acid through the introduction of NaI and HCl. The I^- and H⁺ ions can slow the reduction kinetics by forming PdI₄^2- and inhibiting the dissociation of ascorbic acid, respectively. When the initial reduction rate is tuned into the proper regime, Pd decahedral seeds with a penta-twinned structure appear during nucleation. In the presence of I^- ions as a selective capping agent toward the Pd(100) surface, the decahedral seeds can be directed to grow axially into penta-twinned nanorods and then nanowires. The Pd nanowires are found to evolve into multiply twinned particles if the reaction time is extended beyond 1.5 h, owing to the involvement of oxidative etching. When supported on carbon, the Pd nanowires show greatly enhanced specific electrocatalytic activities, more than five times the value for commercial Pd/C toward formic acid oxidation and three times the value for Pt/C toward oxygen reduction under an alkaline condition. In addition, the carbon-supported Pd nanowires exhibit greatly enhanced electrocatalytic durability toward both reactions. Furthermore, we demonstrate that the Pd nanowires can serve as sacrificial templates for the conformal deposition of Pt atoms to generate Pd@Pt core-sheath nanowires and then Pd-Pt nanotubes with a well-defined surface structure.