From Zn-N-C to Fe-N-C: Active-Site Imprinting As a New Method for the Synthesis of Highly Active PGM-Free Catalysts for PEMFC

The high cost and the restricted availability of Platinum-Group-Metals (PGM) used in current catalysts is one of the major hurdles for the large-scale commercialization of Proton Exchange Membrane Fuel Cells (PEMFCs). In the last decade, great efforts have been made to develop efficient PGM-free catalysts for the oxygen reduction reaction (ORR), especially metal-nitrogen-doped carbons (M-N-Cs, with M = Fe, Co). The activity gap towards Pt has successfully been narrowed, now reaching the activity requirements for practical applications. 1-3 For this class of catalysts, the active site is a MN 4 moiety, as known from molecules such as phthalocyanines and porphyrins. 4 Due to the metastability of the MN 4 sites at the temperature of their pyrolytic formation, the final transition metal loading is currently limited and significant amounts of inorganic byproducts are formed. Although synthesis protocols have been successfully optimized, multiple processing steps are required, making the preparation time-consuming. In this contribution we will show that Zn 2+ ions can be utilized in our novel concept of active-site imprinting, where Zn is used as template-ion in a pyrolytic process to form Zn-N-C precursor materials. 5 The Zn-N-C materials presented in this work are nitrogen-doped carbons comprising ZnN 4 sites, obtained with high yield and from inexpensive precursors. The active-site imprinted carbon supports possess high surface area and hierarchical porosity, which makes them structurally advantageous for catalytic applications in terms of mass transport and high accessibility of the active sites. Through a zinc-to-iron ion exchange reaction, Fe-N-C catalysts with high Fe loading are obtained at only 170 °C. Since the active-site formation by the Zn-to-Fe exchange reaction can be conducted at low temperatures, the structural properties of the Zn-N-C precursor material are retained. 6 Moreover, this synthetic procedure assures the absence of the otherwise obtained harmful side-phases (e.g., iron carbide). Cryo-Mössbauer and X-ray adsorption spectroscopy, supported by calculations of the extended X-ray absorption fine structure, reveal an exclusive presence of Fe as single atoms coordinated to four nitrogen atoms, i.e., in form of the desired FeN 4 moieties. Identical-location scanning transmission electron microscopy with atomic resolution is further employed to visualize the trans-metalation event. The herein obtained catalysts match the state-of-the-art electrocatalytic activity for Fe-N-C catalyts, both in a rotating disk electrode and in single cell PEMFC measurements. The novel synthesis method will be discussed regarding its advantages and disadvantages compared to the conventional pyrolytic M-N-C catalyst syntheses, with a focus on the potential to surpass the current limitations of restricted active-site density and catalyst stability. ACKNOWLEDGEMENTS: The German Federal Ministry of Economic Affairs and Energy (BMWi) is acknowledged for funding within the Verbundproject innoKA (Project No.: 03ET6096A) REFERENCES: M. Lefèvre, E. Proietti, F. Jaouen and J.-P. Dodelet, Science , 2009, 324 , 71-74. R. Bashyam and P. Zelenay, Nature , 2006, 443 , 63-66. H. A. Gasteiger, S. S. Kocha, B. Sompalli and F. T. Wagner, Applied Catalysis B , 2005, 56 , 9-35. Q. Jia, N. Ramaswamy, U. Tylus, K. Strickland, J. Li, A. Serov, K. Artyushkova, P. Atanassov, J. Anibal, C. Gumeci, S. C. Barton, M.-T. Sougrati, F. Jaouen, B. Halevi and S. Mukerjee, Nano Energy , 2016, 29 , 65-82. A. Mehmood, J. Pampel, G. Ali, H. Y. Ha, F. Ruiz-Zepeda and T.-P. Fellinger, Advanced Energy Materials , 2018, 8 . D. Menga, F. Ruiz-Zepeda, L. Moriau, M. Šala, F. Wagner, B. Koyutürk, M. Bele, U. Petek, N. Hodnik, M. Gaberšček and T.-P. Fellinger, Advanced Energy Materials , 2019, 9 , 1902412. Figure 1