4.8 Article

One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 8, Issue 37, Pages 24671-24681

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.6b06576

Keywords

zeolite membrane; MET; metal cluster; propane dehydrogenation; membrane reactor

Funding

  1. Dow Chemical Company
  2. U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-98CH10886]
  3. ORNL's ShaRE User Facility

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Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanodusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyt-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal dusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal dusters. To characterize the properties of the hybrid (zeolite/metal)' Membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 degrees C and 1 at-m. The results indicate that Pt metal dusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction-along with H-2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanodusters and reduced catalyst deactivation.

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