Micro- and Nanoscale Heterogeneities in Zeolite Beta as Measured by Atom Probe Tomography and Confocal Fluorescence Microscopy. 2023

Sophie H van Vreeswijk, and Luke A Parker, and J J Erik Maris, and Jonathan D Poplawsky, and Bert M Weckhuysen
Inorganic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterial Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.

Micro- and nanoscale information on the activating and deactivating coking behaviour of zeolite catalyst materials increases our current understanding of many industrially applied processes, such as the methanol-to-hydrocarbon (MTH) reaction. Atom probe tomography (APT) was used to reveal the link between framework and coke elemental distributions in 3D with sub-nanometre resolution. APT revealed 10-20 nanometre-sized Al-rich regions and short-range ordering (within nanometres) between Al atoms. With confocal fluorescence microscopy, it was found that the morphology of the zeolite crystal as well as the secondary mesoporous structures have a great effect on the microscale coke distribution throughout individual zeolite crystals over time. Additionally, a nanoscale heterogeneous distribution of carbon as residue from the MTH reaction was determined with carbon-rich areas of tens of nanometres within the zeolite crystals. Lastly, a short length-scale affinity between C and Al atoms, as revealed by APT, indicates the formation of carbon-containing molecules next to the acidic sites in the zeolite.

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