PdAg Nanoparticles with Different Sizes: Facile One‐Step Synthesis and High Electrocatalytic Activity for Formic Acid Oxidation

Recently, direct formic acid fuel cells (DFAFCs) which possess superior advantages such as a low operating temperature, light environmental pollution and high energy density, have been considered as one of the power generation technologies with a bright prospect. Herein, bimetallic PdAg nanoparticles (NPs) with different particle sizes were successfully produced via an easy one‐pot solvothermal co‐reduction synthetic route and their electrocatalytic performance for formic acid oxidation (FAO) were further investigated. In our strategy, the size of PdAg NPs can be easily controlled by only varying the concentration of precursors. The larger sized PdAg alloy (9.5 nm, noted as PdAg−L) was obtained at a low concentration of precursors, while the smaller PdAg alloy (3.7 nm, named as PdAg−S) was separated from the reaction system with higher solubility by centrifugation. The electrocatalytic activity and stability of the obtained PdAg NPs could be well optimized when incorporated with carbon (C), which is owing to a synergetic effect. The PdAg−S/C exhibits the highest mass activity with around 1.6 times that of PdAg−L/C and 2 times that of commercial Pd/C, which can be attributed to its larger ECSA and lower adsorption energy of the intermediate to facilitate the direct oxidation of HCOOH molecule. A one‐pot solvothermal co‐reduction method without organic protectants was reported to prepare PdAg bimetallic nanoparticles, which is simple, low‐cost and low‐toxicity. The particle size of PdAg can be easily controlled by modifying the concentration of precursor and the smaller PdAg nanoparticles with a size of 3.7 nm show much higher electrocatalytic activity (606 mA mgPd−1) than larger PdAg nanoparticles (380 mA mgPd−1) and Pd/C (310 mA mgPd−1).