4.8 Article

Unique Role of GeO2 as a Noninvasive Promoter of Nano-Sized Zeolite Crystals

Journal

ADVANCED MATERIALS
Volume 34, Issue 49, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/adma.202205885

Keywords

catalysts; germanium oxide; nanocrystals; nonclassical crystallization; zeolites

Funding

  1. U.S. Department of Energy Office of Basic Energy Sciences [DE-SC0021384]
  2. Welch Foundation [E-1794]
  3. Swedish research council [VR 2017-04321, VR 2019-00815]
  4. Knut & Alice Wallenberg Foundation [2012.0112, 2018.0237]
  5. U.S. Department of Energy (DOE) [DE-SC0021384] Funding Source: U.S. Department of Energy (DOE)

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Adding germanium oxide to the zeolite growth mixture directs the formation of zeolites with ultrasmall dimensions. This method not only enhances the performance of zeolite catalysts, but also has the potential to reduce mass-transport limitations in various applications.
The synthesis of zeolites with nano-sized dimensions is often limited to a narrow design space that conventionally relies upon the design of organics to direct hierarchical materials. Here, it is demonstrated that the addition of an inorganic modifier, germanium oxide (GeO2), to a zeolite growth mixture directs the formation of crystals with ultrasmall dimensions. This effect is observed for zeolites ZSM-11 and ZSM-5 over a range of synthesis conditions wherein the role of GeO2 in zeolite crystallization deviates from its typical function as a heteroatom. Notably, the final products contain trace amounts of Ge, which indicates the inorganic modifier does not compete for sites in the zeolite framework based on its formation of a discrete phase that enables GeO2 recovery. Catalytic tests using the methanol-to-hydrocarbons reaction reveal significant enhancement in the performance of zeolite catalysts prepared with GeO2 compared to reported examples of nano-sized zeolites. These findings highlight a potentially generalizable and commercially viable synthesis method to reduce mass-transport limitations in zeolites for diverse applications.

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