Scalable Synthesis of Stable Electrocatalyst for Oxygen Reduction Reaction

Abstract

Carbon-based materials have been widely recognized as support material of choice for the oxygen reduction reaction due to their intriguing properties, such as high electrical conductivity, structural flexibility, and low cost. Platinum and its alloys supported on carbon are currently considered the benchmark catalysts for the oxygen reduction reaction (ORR) in Proton Exchange Membrane Fuel Cells (PEMFCs). Confining platinum within the pore system of mesoporous carbon prepared by hard-templating has proven to be an effective way to mitigate catalyst degradation in PEMFCs.[1] However, the challenge of template removal and the limited yield have hindered its practical application in industry. As a remedy, we establish a simple synthesis of carbon gels through sol-gel polymerization of resorcinol (R) and formaldehyde (F), ultimately resulting in graphitic mesoporous carbons.The synthesis process involves mixing resorcinol and formaldehyde in the presence of a basic catalyst, followed by heating for a certain period of time to obtain crosslinked gels.[2] Specific metal salts can be incorporated into the reaction to synthesize mesoporous and highly graphitic carbon spheres (GRF-Sphere) in a straightforward manner, without the need for hydrothermal steps, solvent exchanges, supercritical drying, or post-activation techniques. While conventional carbonized RF spheres are typically non-graphitic and microporous (Fig. 1.), modification of the synthesis route allows for the production of mesoporous, highly graphitic carbon spheres (GRF-Sphere) by taking advantage of the porogenic and graphitization effect of Fe(acac)2. Platinum nanoparticles with an average size of ca. 3 nm were deposited into the pores of GRF-spheres by incipient wetness impregnation followed by annealing at 750 °C. The specific activity of the Pt/GRF-Sphere catalyst for the ORR was found to be greater than 0.45 mA cm-2 Pt at 0.9 V vs. RHE, which in comparison with the literature indicates high catalytic activity.[3] The confinement of the active phase within the pores of the GRF-Spheres contributed to enhancing the stability of the catalyst, as confirmed by an accelerated stress test performed within the typical operating range of a PEMFC (0.6 - 1.0 VRHE). The Pt/GRF-Sphere was found to retain a significantly higher proportion of active surface area when compared to a reference Pt/Vulcan catalyst with similar platinum particle size (Fig. 1.).Furthermore, increasing the concentrations of resorcinol and formaldehyde by 25-fold resulted in the synthesis of a mesoporous and highly graphitic gel, namely GRF-Gel, at a substantial volume yield of70 g L-1, which underlines the potential for this process to be scaled up for industrial application. The ORR activity and stability of GRF-Gel in RDE are currently being investigated. Moreover, the electrochemical performance of this material will be evaluated in a single-cell PEMFC in collaboration with the group of Prof. Hubert Gasteiger (TU Munich).Overall, this research provides a promising and straightforward approach to synthesize highly graphitic mesoporous carbon materials using iron acetylacetonate as a porogen and graphitization catalyst. The method is based on the established preparation of RF-gels but includes iron salts. We have demonstrated that Pt/GRF-Sphere, which is produced by depositing Pt nanoparticles into the pore system of the GRF-Sphere, exhibits high activity and stability for the ORR. Given the simplicity and scalability of our synthesis procedure and the tailored morphology of these carbon materials, we believe that Pt/GRF-Sphere and Pt/GRF-Gel have great potential for industrial applications. Acknowledgement: We acknowledge the financial support from the German Federal Ministry for Economic Affairs and Energy (BMWi) in the framework of POREForm (project number 03ETB027F).