Ni-Pt-Pd ternary alloy nanoparticles supported on carboxyl-modified carbon nanotubes as highly efficient catalyst for methanol and ethanol electrooxidation

Abstract

Pt-based catalysts are currently the most efficient anode catalysts in alcohol fuel cells. However, their widespread commercialization is hindered by their high cost. In this study, a straightforward method was employed to deposit Ni-Pt-Pd ternary alloy nanoparticles onto carboxyl-modified multi-walled carbon nanotubes (CNTs) and subsequently annealed the synthesized catalysts at different temperatures to adjust the surface composition and alloying degree. The Ni-Pt-Pd alloy exhibits a synergistic effect between Pt and Ni. The presence of Ni effectively modulates the d-band center of Pt, thereby enhancing the electrochemical performance of for alcohol oxidation. The synergistic effect of Pt-Pd alloy is harnessed to enhance both catalytic activity and stability of the catalyst for oxidation of methanol or ethanol. Density functional theory (DFT) calculations demonstrated that alloying Pt with Pd and Ni effectively reduced the Gibbs free energy during EOR and MOR reactions. The resulting catalysts, denoted as Ni6Pt6Pd6 NPs/CNTs-M2, exhibited exceptional catalytic oxidation performance for both ethanol and methanol. Specifically, their electrochemical mass activity for ethanol oxidation reaction (EOR) reached 2345 mA mg-1Pt+Pd, which was 15.5-fold and 2.56-fold higher than that of commercial Pt/C and Pd/C catalysts respectively. Moreover, their mass activity for methanol oxidation reaction (MOR) was measured at 2995 mA mg-1Pt+Pd, which was 8.2-fold and 5.3-fold higher than that of Pt/C and Pd/C catalysts respectively.