Highly active carbon supported palladium-rhodium PdXRh/C catalysts for methanol electrooxidation in alkaline media and their performance in anion exchange direct methanol fuel cells (AEM-DMFCs)

In this study carbon supported PdXRh electrocatalysts synthesized by wet chemical reduction process were tested for the potential use in anion-exchange membrane direct methanol fuel cells (AEM-DMFC) and compared to Pd/C and commercially available Pt/C. A metal loading of 20wt% on carbon was confirmed by thermogravimetric analysis (TGA) and catalyst compositions of PdRh3/C, PdRh/C and Pd3Rh/C were found via inductively coupled plasma optical emission spectroscopy (ICP-OES). Transmission electron microscopy (TEM) and x-ray diffraction (XRD) studies showed that the average particle and crystallite sizes of the PdXRh/C catalysts are in the range of 3.1 to 4.3 nm. It was also found that these catalysts are not alloyed. Cyclic voltammetry (CV) data reveals a 85-140 mV lower CH3OH oxidation onset potential and higher mass current densities for PdXRh/C catalysts compared with Pd/C. Steady-state measurements via chronoamperometry (CA) showed a good stability against poisoning during methanol oxidation and higher mass activities for PdRh/C and Pd3Rh/C compared to Pt/C. By using differential electrochemical mass spectrometry (DEMS) it was successfully shown that adding Rh to Pd results in an enhanced CO2 current efficiency (CCE) compared to Pd/C or Pt/C. AEM-DMFCs free from platinum were fabricated and single cell tests at 60 degrees C showed a significant increase of power density at 0.5 V cell potential from 4.8 mW cm(-2) for Pd/C to 16.5 mW cm(-2) for PdRh/C with the anode and cathode fed with 1 M methanol + 2 M KOH and synthetic air, respectively. Peak power density of 104.9 mW cm(-2) was reached for PdRh/C anode catalyst at 80 degrees C using higher KOH and methanol concentrations in anodic fuel and oxygen as cathodic oxidizer.