Electro-Catalytic Properties of Palladium and Palladium Alloy Electro-Catalysts Supported on Carbon Nanofibers for Electro-Oxidation of Methanol and Ethanol in Alkaline Medium

Abstract

Carbon nanofibers (CNFs) supported by Pd and Pd-Sn electro-catalysts were prepared by the chemical reduction method using ethylene glycol as the reducing agent. Their physicochemical characteristics were studied using high resolution-transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and Bruanaer-Emmett-Teller (BET) analysis. FTIR revealed that oxygen, hydroxyl, carboxylic and carbonyl functional groups facilitated the dispersion of Pd and Sn nanoparticles. The doping of Pd with Sn to generate PdSn alloy was also confirmed by XPS data. The amorphous nature of CNFs was confirmed by XRD patterns which exhibited the Pd diffraction peaks. When Sn was added to Pd/CNFs, the diffraction peaks moved to lower angles. HRTEM images revealed that the CNFs with cylindrical shape-like morphology and also Pd-Sn nanoparticles dispersed on carbon support. The catalytic activity and stability towards alcohol electro-oxidation in alkaline medium at room temperature was evaluated using cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The obtained Pd-Sn/CNFs electro-catalyst exhibited a better electro-catalytic activity than Pd/CNFs and Pd/C electro-catalysts for both methanol and ethanol oxidation. The improvement of the electrochemical performance was associated with the synergistic effect via the addition of Sn which modified the Pd atom arrangement, thereby promoting oxidation through a dehydrogenation pathway. Furthermore, SnO2 generates abundant OH species which helps with increasing the rate of the oxidative removal of carbon monoxide (CO) intermediates from Pd sites.