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/ange.202111180

Enhanced Reactivity of Accessible Protons in Sodalite Cages of Faujasite Zeolite

Journal Article · Fri Dec 17 23:00:00 EST 2021 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202111180· OSTI ID:1836621

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

Department of Chemical Engineering and Materials Science University of Minnesota Twin Cities 421 Washington Avenue SE Minneapolis MN 55455 USA
Department of Chemical Engineering and Materials Science University of Minnesota Twin Cities 421 Washington Avenue SE Minneapolis MN 55455 USA, State Key Laboratory of Fine Chemicals PSU-DUT Joint Center for Energy Research School of Chemical Engineering Dalian University of Technology Dalian 116024 Liaoning Province China
X-ray Science Division Advanced Photon Source Argonne National Laboratory Lemont IL 60439 USA
Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena CA 91125 USA
Department of Chemical and Biomolecular Engineering &, Institute for NanoBioTechnology Johns Hopkins University 3400 North Charles Street Baltimore MD 21218 USA
Department of Chemical Engineering and Materials Science University of Minnesota Twin Cities 421 Washington Avenue SE Minneapolis MN 55455 USA, Department of Chemical and Biomolecular Engineering &, Institute for NanoBioTechnology Johns Hopkins University 3400 North Charles Street Baltimore MD 21218 USA, Applied Physics Laboratory Johns Hopkins University 11100 Johns Hopkins Road Laurel MD 20723 USA

Abstract

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 NH ₄ NO ₃ 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 OD ₂₆₂₀ /OD ₂₆₈₀ (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 (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0008688; SC0001004; AC02-06CH11357

OSTI ID:: 1836621

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 5 Vol. 134; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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