4.8 Article

Acid Catalysis over Low-Silica Faujasite Zeolites

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 21, 页码 9324-9329

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AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c01022

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资金

  1. Catalysis Center for Energy Innovation - U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences [DE-SC0001004]
  2. U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences [DE-FG02-12ER16362]
  3. U.S. Department of Energy, Office of Basic Energy Science, Catalysis Science Program [DE-SC00019028, DMR-1420013]
  4. DOE Office of Science [DE-AC02-06CH11357]

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Low-silica faujasite zeolites sustain framework integrity and porosity upon moderate ion exchange, introducing two kinds of protons within supercages. Protons on site II exhibit higher reactivity for propane reactions compared to protons on site III. Low-silica proton-form FAU zeolites possess protons on site III and provide high-temperature structural and chemical stability, enabling their application as solid-acid catalysts.
Low-silica faujasite (FAU) zeolites (with Si/Al ratio of ca. 1.2-1.8) sustain framework integrity and porosity upon moderate ion exchange (0.01 M NH4NO3 solution for 1 h at ambient temperature), which introduces two kinds of protons, distinctive in reactivity and coordination to the zeolite framework, within supercages (HSUP). Moderate ion exchange limited within supercages transpires while maintaining full occupancy of Na+ cations within associated sodalite cages; this in turn helps stabilize the framework of low-silica H-FAU zeolites. Protons located on site II (H-3630) and site III (H-3650) within supercages on low-silica FAU zeolites can be classified and enumerated by virtue of infrared spectroscopy, providing an opportunity to compare reactivities of these distinct protons for monomolecular protolytic reactions of propane. Protons on site II exhibit prominently higher reactivity for monomolecular propane dehydrogenation and cracking than protons on site III. Low-silica proton-form FAU zeolites (zeolite X) upon moderate ion exchange possess protons on site III that are unavailable on high-silica FAU zeolites (zeolite Y) and limit ion exchange within supercages, providing unprecedented high-temperature structural and chemical stability (>773 K) and enabling their application as solid-acid catalysts.

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