Enhanced oxygen reduction activity with rare earth metal alloy catalysts in proton exchange membrane fuel cells

Alloying platinum is an approach to increase the oxygen reduction reaction (ORR) activity and at the same time reduce the amount of precious platinum catalyst in proton exchange membrane fuel cells (PEMFC). In this work the cathode activity of thin films of rare earth metals (REM) alloys, Pt Y, Pt Gd and Pt Tb, produced by sputter deposition onto gas diffusion layers, are evaluated in a fuel cell by means of polarization curves in O /H , and cyclic- and CO-stripping voltammetry in N /5% H . Prior to evaluation, the model electrodes were acid-treated to obtain a Pt skin covering the PtREM alloy bulk, as was revealed by energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The core shell alloys of Pt Y and Pt Gd catalysts show a specific activity enhancement at 0.9 V of 2.5 times compared to pure Pt. The slightly lower enhancement factor of 2.0 for Pt Tb is concluded to be due to leaching of the REM, that resulted in a thicker, and subsequently less strained, Pt overlayer. The high activity, combined with the minor changes in surface composition, achieved in the fuel cell environment shows that PtREM core shell catalysts are promising for the cathode reaction in PEMFC

Surface Composition of a Highly Active Pt3Y Alloy Catalyst for Application in Low Temperature Fuel Cells

Currently, platinum is the most widely used catalyst for low temperature proton exchange membrane fuel cells (PEMFC). However, the kinetics at the cathode are slow, and the price of platinum is high. To improve oxygen reduction reaction (ORR) kinetics at the cathode, platinum can be alloyed with rare earth elements, such as yttrium. We report that Pt3Y has the potential to be over 2 times more active for the ORR compared with Pt inside a real fuel cell. We present detailed photoemission analysis into the nature of the sputtered catalyst surface, using synchrotron radiation photoelectron spectroscopy (SRPES) to examine if surface adsorbates or impurities are present and can be removed. Pretreatment removes most of the yttrium oxide in the surface leaving behind a Pt overlayer which is only a few monolayers thick. Evidence of a substochiometric oxide peak in the Y 3d core level is presented, this oxide extends into the surface even after Ar+ sputter cleaning in-situ. This information will aid the development of new highly active nanocatalysts for employment in real fuel cell electrodes

Unraveling the Surface Chemistry and Structure in Highly Active Sputtered Pt3Y Catalyst Films for the Oxygen Reduction Reaction

Platinum is the most widely used and best performing sole element for catalyzing the oxygen reduction reaction (ORR) in low-temperature fuel cells. Although recyclable, there is a need to reduce the amount used in current fuel cells for their extensive uptake in society. Alloying platinum with rare-earth elements such as yttrium can provide an increase in activity of more than seven times, reducing the amount of platinum and the total amount of catalyst material required for the ORR. As yttrium is easily oxidized, exposure of the Pt-Y catalyst layer to air causes the formation of an oxide layer that can be removed during acid treatment, leaving behind a highly active pure platinum overlayer. This paper presents an investigation of the overlayer composition and quality of Pt3Y films sputtered from an alloy target. The Pt3Y catalyst surface is investigated using synchrotron radiation X-ray photoelectron spectroscopy before and after acid treatment. A new substoichiometric oxide component is identified. The oxide layer extends into the alloy surface, and although it is not completely removed with acid treatment, the catalyst still achieves the expected high ORR activity. Other surface-sensitive techniques show that the sputtered films are smooth and bulk X-ray diffraction reveals many defects and high microstrain. Nevertheless, sputtered Pt3Y exhibits a very high activity regardless of the film\u27s oxide content and imperfections, highlighting Pt3Y as a promising catalyst. The obtained results will help to support its integration into fuel cell systems