Unexpected Negative Performance of PdRhNi Electrocatalysts toward Ethanol Oxidation Reaction

Abstract

Direct ethanol fuel cells (DEFCs) need newly designed novel affordable catalysts for commercialization. Additionally, unlike bimetallic systems, trimetallic catalytic systems are not extensively investigated in terms of their catalytic potential toward redox reactions in fuel cells. Furthermore, the Rh potential to break the ethanol rigid C-C bond at low applied potentials, and therefore enhance the DEFC efficiency and CO2 yield, is controversial amongst researchers. In this work, two PdRhNi/C, Pd/C, Rh/C and Ni/C electrocatalysts are synthesized via a one-step impregnation process at ambient pressure and temperature. The catalysts are then applied for ethanol electrooxidation reaction (EOR). Electrochemical evaluation is performed using cyclic voltammetry (CV) and chronoamperometry (CA). Physiochemical characterization is pursued using X-ray diffraction (XRD), transmission electron microscope (TEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). Unlike Pd/C, the prepared Rh/C and Ni/C do not show any activity for (EOR). The followed protocol produces alloyed dispersed PdRhNi nanoparticles of 3 nm in size. However, the PdRhNi/C samples underperform the monometallic Pd/C, even though the Ni or Rh individual addition to it enhances its activity, as reported in the literature herein. The exact reasons for the low PdRhNi performance are not fully understood. However, a reasonable reference can be given about the lower Pd surface coverage on both PdRhNi samples according to the XPS and EDX results. Furthermore, adding both Rh and Ni to Pd exercises compressive strain on the Pd lattice, noted by the PdRhNi XRD peak shift to higher angles.

Keywords

• ethanol oxidation reaction
• trimetallic nanoparticles
• Rh effect
• surface metal segregation