Graphene-based “Core-Shell” Hierarchical Nanostructured Low-Pt Electrocatalysts for Proton Exchange Membrane Fuel Cells

The operation of proton exchange fuel cells (PEMFCs) is bottlenecked by the sluggishness of the oxygen reduction reaction (ORR) [1]. Accordingly, the development of advanced electrocatalysts (ECs) capable to promote the ORR kinetics is one of the main goals of the research. It is further highlighted that, as of today, the only ORR ECs capable to provide PEMFCs with a performance level compatible with applications require a high loading of strategic elements such as platinum-group metals (PGMs), raising critical issues associated with supply shortages and high costs [1]. This work addresses the above points by the development of innovative ECs characterized by the following features: (i) a low loading of PGMs; (ii) an improved ORR activity in comparison with conventional state-of-the-art ECs [2]; (iii) a “core-shell” morphology. In the proposed ECs the “core” support exhibits a hierarchical structure including the following constituents: (i) graphene flakes, to exploit the benefits associated with the large specific surface area and high electron mobility of graphene [3-6]; (ii) carbon black nanoparticles, to further promote the mass and charge transfer processes of the ECs; and (iii) copper nanoparticles, which are introduced as a sacrificial component modulating the EC morphology and the chemical composition of ORR active sites. The hierarchical “core” support is covered by a carbon nitride “shell”, providing “coordination nests” that embed the ORR active sites [7]. The latter are based on a very low loading of Pt (ca. 3 wt% of the EC) and also include Ni and Cu as “co-catalysts”. The proposed L-PGM ECs are obtained customizing the synthetic protocol devised in our research group [7]. In this work, the final ECs are obtained after a post-synthesis activation process carried out by electrochemical cycling, that plays a crucial role to modulate the physicochemical properties and the morphology. Preliminary results indicate that the proposed approach is promising, as the proposed L-PGM ECs exhibit an improved specific and mass activity in comparison with the state of the art (see Figure). The assay of the metals in the L-PGM ECs is evaluated by inductively-coupled plasma atomic emission spectroscopy (ICPAES). Vibrational spectroscopies (e.g., confocal micro-Raman) and wide-angle X-ray diffraction (WAXD) are adopted to probe the structure. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM), both conventional and at high resolution, are used to study the morphology. Cyclic voltammetry with the rotating ring-disk electrode method (CV-TFRRDE) investigates the electrochemical performance and ORR reaction mechanism. Finally, the fuel cell performance in operating conditions is tested on PEMFC prototypes including the proposed L-PGM ECs at the cathode. Acknowledgements This work was funded by the Strategic Project of the University of Padova “From Materials for Membrane-Electrode Assemblies to Energy Conversion and Storage Devices – MAESTRA”. The research leading to these results has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement n°696656. REFERENCES [1] I. Katsounaros, S. Cherevko, A. R. Zeradjanin, K. J. J. Mayrhofer, Angew. Chem. Int. Ed., 53, 102 (2014). [2] J. Zhang, Front. Energy, 5, 137 (2011). [3] S. Sharma, B. G. Pollet, J. Power Sources, 208, 96 (2012). [4] M. Liu, R. Zhang, W. Chen, Chem. Rev., 114, 5117 (2014). [5] A. C. Ferrari, F. Bonaccorso, V. Fal’ko et al., Nanoscale, 7, 4587 (2015). [6] J. H. Chen, C. Jang, S. Xiao, M. Ishigami, M. S. Fuhrer, Nature Nanotech., 3, 206 (2008). [7] V. Di Noto, E. Negro, K. Vezzù, F. Bertasi, G. Nawn, The Electrochemical Society Interface, Summer 2015, 59 (2015).