SUPRABEADS for Catalysis Susanne Wintzheimer 1,3 , Thomas Zimmermann 1 , Nnamdi Madubuko 2 , Philipp Groppe 1 , Theodor Raczka 1 , Marco Haumann 2 1 Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstrasse 1, D91058 Erlangen, Germany. 2 Institute of Chemical Reaction Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 3, D91058 Erlangen, Germany. 3 Fraunhofer-Institute for Silicate Research ISC, Neunerplatz 2, D97082 Würzburg, Germany. In the past decades, tremendous effort has been made in synthesizing catalytically active nanoparticles because of their unique size-related properties like quantum effects and their high surface area per gram of material. In the last 15 years, a step further has been taken considering nanoparticles as building blocks [1] and creating more complex particulate units from them, i.e. supraparticles. Compared to nanoparticles and macroscale materials, supraparticles provide unique features: They firstly, conserve nanoparticulate properties, while lifting the particle sizes to the (lower) microscale range. Secondly, they often provide additional unexpected functionalities exceeding the sum of properties of their constituent building blocks. [2] Concerning supraparticles for catalysis, this for example means providing beneficial coupling between the building blocks of the supraparticles or an emerging inner porosity of the catalyst material. [3] Supraparticles can thus not only provide nanoparticle-based catalytic activity but also serve at the same time as support material. This permits the creation of complex catalytic materials exceeding the limits of current ones in terms of activity, selectivity, or stability. Thus, their high potential for catalytic applications is beyond all doubt. [4,5] However, the applicability of supraparticles is limited in this field because of their too-small microscale sizes. In commonly used fixed bed reactors particle sizes of 0.5 to 2 mm are required to prevent high-pressure drops in the reactor as well as particle losses. This is why we propose to support SUPRAparticles on BEADS lifting their size to the high micron to millimeter range and thus creating SUPRABEADS. Via this method, high flexibility in terms of the selection of supraparticle morphology, size, and material is guaranteed. In the talk, the first successful fabrication of SUPRABEADS and their use for propane dehydrogenation based on Supported Catalytically Active Liquid Metal Solutions (SCALMS[6]) will be presented. For this approach, platinum is dissolved in liquid gallium droplets supported by silica nanoparticle-based supraparticles, which are fixed on alumina beads. The obtained heterogeneous catalyst ensures an excellent dispersion of the liquid catalytically active phase in the pores of the support material, which is the precondition for its enhanced reactivity and stability compared to traditional catalysts. The successful implementation of SUPRABEADS for SCALMS paves the way for the creation of an entirely new class of supraparticle-based catalyst materials in the future. References
1. S. C. Glotzer, M. J. Solomon, Nature Mater 2007, 6, 557. 2. S. Wintzheimer, T. Granath, et al., ACS nano 2018, 12, 5093.
3. S. Wintzheimer, J. Reichstein, et al., Adv. Funct. Mater. 2021, 31, 2011089. 4. D. P. Debecker, S. Le Bras, et al., Chemical Society Reviews 2018, 47, 4112.
5. K. Hou, J. Han, et al., ACS Materials Lett. 2020, 2, 95. 6. N. Raman, M. Wolf, et al., ACS Catalysis 2021, 11, 13423.
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© The Author(s), 2023
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