Addressing Ru Leaching in Reformate Hydrogen PEM Fuel Cells: Development of a Rotating Disk Electrode-Based Accelerated Stress Test
The adoption of PEM fuel cells for heavy-duty applications, such as maritime transport, often necessitates the use of liquid hydrogen carriers like methanol due to storage and handling considerations.[1] Methanol reforming is an efficient method to generate hydrogen and CO₂ on-site; however, trace amounts of CO invariably remain in the reformate gas, despite subsequent purification steps such as water-gas shift and selective oxidation.[2,3] These residual CO levels, typically in the low ppm range, significantly exceed the tolerance threshold of platinum-based catalysts on the anode (<0.2 ppm),[4] resulting in catalyst poisoning and diminished cell performance. To address this, RuPt alloy nanoparticles supported on carbon are frequently employed for their enhanced tolerance to CO under reformate conditions.[3] Nevertheless, operational challenges arise as Ruthenium (Ru) leaches from the anode catalyst during prolonged use. This Ru migrates through the membrane and deposits on the cathode, poisoning the Pt/C catalyst and severely inhibiting oxygen reduction reaction (ORR) activity.[3,5]Efforts to mitigate Ru leaching have focused on modifying catalyst surface composition and structure. However, because Ru leaching is a long-term phenomenon, accelerated stress tests (ASTs) are essential for investigating this behavior in a practical timeframe. Traditional MEA-based ASTs, while effective, are hindered by high material requirements, long preparation times, and elevated costs, making them less suitable for early-stage catalyst screening. Additionally, quantifying the total amount of Ru leached has remained a significant challenge.In this study, we developed a robust, material-efficient AST protocol using the rotating disk electrode (RDE) to quantitatively evaluate Ru leaching. Three commercial RuPt catalysts with Ru:Pt atomic ratios of 1:1, 1.5:1, and 2:1 were examined, along with a heat-treated 2:1 ratio catalyst with larger particle size and reduced electrochemical surface area (ECSA). The RDE-based AST involved cyclic voltammetry to simulate catalyst aging, with key parameters such as cycle number (100–1000), scan rate (10–100 mV s⁻¹), and upper potential limit (0.8–0.9 V_RHE) systematically varied. Ru dissolution was quantified using inductively coupled plasma optical emission spectroscopy (ICP-OES) from collected electrolyte samples (0.1M H₂SO₄), and changes in catalyst surface composition were assessed through shifts in CO-oxidation peaks.MEA-based AST measurements were also performed to evaluate the stability of these commercial catalysts and compare the results with those obtained from the RDE protocol. This study examines the correlations between RDE- and MEA-derived stability rankings and discusses the limitations of RDE-based ASTs when applied to practical fuel cell conditions.The validated RDE protocol was further applied to self-synthesized RuPt/C and Ru_corePt_shell materials, providing a reliable and cost-effective approach for assessing Ru leaching during early-stage catalyst development. These findings highlight the potential of the RDE-based AST for advancing PEM fuel cell anode catalysts tailored for reformate hydrogen applications.
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