Enhanced Reactivity of Accessible Protons in Sodalite Cages of Faujasite Zeolite

Li, Xinyu; Han, He; Xu, Wenqian; Hwang, Son‐Jong; Lu, Peng; Bhan, Aditya; Tsapatsis, Michael

doi:10.1002/anie.202111180

Enhanced Reactivity of Accessible Protons in Sodalite Cages of Faujasite Zeolite

Journal Article · Fri Nov 12 04:00:00 EST 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202111180· OSTI ID:1855604

Li, Xinyu ^[1]; Han, He ^[2]; Xu, Wenqian ^[3]; Hwang, Son‐Jong ^[4]; Lu, Peng ^[5]; ^[1]; ^[6]

Univ. of Minnesota Twin Cities, Minneapolis, MN (United States)
Univ. of Minnesota Twin Cities, Minneapolis, MN (United States); Dalian Univ. of Technology (China)
Argonne National Lab. (ANL), Lemont, IL (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)
Johns Hopkins Univ., Baltimore, MD (United States)
Univ. of Minnesota Twin Cities, Minneapolis, MN (United States); Johns Hopkins Univ., Baltimore, MD (United States)

We report Faujasite (FAU) zeolites (with Si/Al ratio of ca. 1.7) undergo mild dealumination at moderate ion exchange conditions (0.01 to 0.6 M of NH₄NO₃ solutions) resulting in protons circumscribed by sodalite cages becoming accessible for reaction without conspicuous changes to bulk crystallinity. The ratio of protons in sodalite cages (H_SOD) to supercages (H_SUP) can be systematically manipulated from 0 to ca. 1 by adjusting ammonium concentrations used in ion exchange. The fraction of accessible protons in the sodalite cages is assessed by virtue of infrared spectra for H-D exchange of deuterated propane based on the band area ratio of OD₂₆₂₀/OD₂₆₈₀ (OD_SOD/OD_SUP). Protons in sodalite cages (H-_SOD) show higher rate constants of propane dehydrogenation (k_D) and cracking (k_C) than protons in supercages (H_SUP) plausibly due to confinement effects being more prominent in smaller voids. Rate constants of dehydrogenation and cracking including k_D/k_C ratios are also augmented as the fraction of accessible protons in the sodalite cages is enhanced. These effects of accessibility and reactivity of protons in sodalite cages hitherto inconspicuous are revealed herein via methods that systematically increase accessibility of cations located in sodalite cages.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; SC0001004; SC0008688

OSTI ID:: 1855604

Alternate ID(s):: OSTI ID: 1836592
OSTI ID: 2479057

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 5 Vol. 61; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Enhanced Reactivity of Accessible Protons in Sodalite Cages of Faujasite Zeolite

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