Surfactant-Free Monodispersed Pd Nanoparticles Template for Core-Shell Pd@PdPt Nanoparticles as Electrocatalyst towards Methanol Oxidation Reaction (MOR)

An eco-friendly two-step synthetic method for synthesizing Pd@PdPt/CNTs nanoparticles was introduced and studied for the methanol oxidation reaction. The Pd@PdPt alloy core-shell structure was synthesized by preparing a surfactant-free monodispersed Pd/CNTs precursor through the hydrolysis of tetrachloropalladate (II) ion ([PdCl4]2−) in the presence of carbon nanotubes (CNTs) and the subsequent hydrogen reduction and followed by a galvanic replacement reaction. This method opens up an eco-friendly, practical, and straightforward route for synthesizing monometallic or bimetallic nanoparticles with a clean surfactant-free electrocatalytic surface. It is quite promising for large-scale preparation. The Pd@PdPt/CNTs electrocatalyst demonstrated a high specific mass activity for methanol oxidation (400.2 mAmgPt−1) and excellent stability towards direct methanol oxidation compared to its monometallic counterparts.

PdAg/C Electrocatalysts Synthesized by Thermal Decomposition of Polymeric Precursors Improve Catalytic Activity for Ethanol Oxidation Reaction

An efficient ethanol oxidation reaction (EOR) is required to enhance energy production in alcohol-based fuel cells. The use of bimetallic catalysts promises decreasing reliance on platinum group metal (PGM) electrocatalysts by minimizing the use of these expensive materials in the overall electrocatalyst composition. In this article, an alternative method of bimetallic electrocatalyst synthesis based on the use of polymeric precursors is explored. PdAg/C electrocatalysts were synthesized by thermal decomposition of polymeric precursors and used as the anode electrocatalyst for EOR. Different compositions, including pristine Pd/C and Ag/C, as well as bimetallic Pd80Ag20/C, and Pd60Ag40/C electrocatalysts, were evaluated. Synthesized catalysts were characterized, and electrochemical activity evaluated. X-ray diffraction showed a notable change at diffraction peak values for Pd80Ag20/C and Pd60Ag40/C electrocatalysts, suggesting alloying (solid solution) and smaller crystallite sizes for Pd60Ag40/C. In a thermogravimetric analysis, the electrocatalyst Pd60Ag40/C presented changes in the profile of the curves compared to the other electrocatalysts. In the cyclic voltammetry results for EOR in alkaline medium, Pd60Ag40/C presented a more negative onset potential, a higher current density at the oxidation peak, and a larger electrically active area. Chronoamperometry tests indicated a lower poisoning rate for Pd60Ag40/C, a fact also observed in the CO-stripping voltammetry analysis due to its low onset potential. As the best performing electrocatalyst, Pd60Ag40/C has a lower mass of Pd (a noble and expensive metal) in its composition. It can be inferred that this bimetallic composition can contribute to decreasing the amount of Pd required while increasing the fuel cell performance and expected life. PdAg-type electrocatalysts can provide an economically feasible alternative to pure PGM-electrocatalysts for use as the anode in EOR in fuel cells.