Acid Catalysis over Low-Silica Faujasite Zeolites

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

doi:10.1021/jacs.2c01022

Title: Acid Catalysis over Low-Silica Faujasite Zeolites

Journal Article · Tue May 17 00:00:00 EDT 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c01022· OSTI ID:1969740

Li, Xinyu ^[1];

^[2]; Xu, Wenqian ^[3]; Hwang, Son-Jong ^[4]; Shi, Zhichen ^[1]; Lu, Peng ^[5];

^[1];

^[6]

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

We report 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 (H_SUP). 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 (H₃₆₃₀) and site III (H₃₆₅₀) 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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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); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357; SC0001004; FG02-12ER16362; SC00019028; DMR-1420013

OSTI ID:: 1969740

Journal Information:: Journal of the American Chemical Society, Vol. 144, Issue 21; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (31)

Potential and challenges of zeolite chemistry in the catalytic conversion of biomass Ennaert, Thijs; Van Aelst, Joost; Dijkmans, Jan Chemical Society Reviews, Vol. 45, Issue 3 https://doi.org/10.1039/C5CS00859J	journal	January 2016
Organic-Free Synthesis of a Highly Siliceous Faujasite Zeolite with Spatially Biased Q ⁴ ( n Al) Si Speciation Oleksiak, Matthew D.; Muraoka, Koki; Hsieh, Ming-Feng Angewandte Chemie International Edition, Vol. 56, Issue 43 https://doi.org/10.1002/anie.201702672	journal	August 2017
Synthesis, characterisation, and catalytic evaluation of hierarchical faujasite zeolites: milestones, challenges, and future directions Verboekend, D.; Nuttens, N.; Locus, R. Chemical Society Reviews, Vol. 45, Issue 12 https://doi.org/10.1039/C5CS00520E	journal	January 2016
Hierarchical FAU- and LTA-Type Zeolites by Post-Synthetic Design: A New Generation of Highly Efficient Base Catalysts Verboekend, Danny; Keller, Tobias C.; Mitchell, Sharon Advanced Functional Materials, Vol. 23, Issue 15 https://doi.org/10.1002/adfm.201202320	journal	November 2012
Alkylation of Toluene over Basic Catalysts—Key Requirements for Side Chain Alkylation Palomares, A. E.; Eder-Mirth, G.; Rep, M. Journal of Catalysis, Vol. 180, Issue 1 https://doi.org/10.1006/jcat.1998.2253	journal	November 1998
Encapsulation of molecular hydrogen in ion-exchanged a zeolites at 1 atm Efstathiou, A. Journal of Catalysis, Vol. 135, Issue 1 https://doi.org/10.1016/0021-9517(92)90275-M	journal	May 1992
Enhanced Reactivity of Accessible Protons in Sodalite Cages of Faujasite Zeolite Li, Xinyu; Han, He; Xu, Wenqian Angewandte Chemie, Vol. 134, Issue 5 https://doi.org/10.1002/ange.202111180	journal	December 2021
Unlocking the Potential of Hidden Sites in Faujasite: New Insights in a Proton Transfer Mechanism Lakiss, Louwanda; Kouvatas, Cassandre; Gilson, Jean‐Pierre Angewandte Chemie International Edition, Vol. 60, Issue 51 https://doi.org/10.1002/anie.202110107	journal	November 2021
Transformation of Discrete Amorphous Aluminosilicate Nanoparticles into Nanosized Zeolites Guo, Hailing; Zhao, Lei; Martineau‐Corcos, Charlotte Advanced Materials Interfaces, Vol. 8, Issue 4 https://doi.org/10.1002/admi.202000634	journal	May 2020
On the Rotational Intergrowth of Hierarchical FAU/EMT Zeolites Khaleel, Maryam; Wagner, Andrew J.; Mkhoyan, K. Andre Angewandte Chemie International Edition, Vol. 53, Issue 36 https://doi.org/10.1002/anie.201402024	journal	July 2014
Combining Pre- and Post-Nucleation Trajectories for the Synthesis of High FAU-Content Faujasite Nanocrystals from Organic-Free Sols Khaleel, Maryam; Xu, Wenqian; Lesch, David A. Chemistry of Materials, Vol. 28, Issue 12 https://doi.org/10.1021/acs.chemmater.6b00588	journal	June 2016
MAS NMR, TPR, and TEM studies of the interaction of NiMo with alumina and silica–alumina supports Qu, L. Journal of Catalysis, Vol. 215, Issue 1 https://doi.org/10.1016/S0021-9517(02)00181-1	journal	April 2003
One- and two-dimensional high-resolution solid-state NMR studies of zeolite lattice structures Fyfe, C. A.; Feng, Y.; Grondey, H. Chemical Reviews, Vol. 91, Issue 7 https://doi.org/10.1021/cr00007a013	journal	November 1991
Searching for Microporous, Strongly Basic Catalysts: Experimental and Calculated ²⁹ Si NMR Spectra of Heavily Nitrogen-Doped Y Zeolites Dogan, Fulya; Hammond, Karl D.; Tompsett, Geoffrey A. Journal of the American Chemical Society, Vol. 131, Issue 31 https://doi.org/10.1021/ja9031133	journal	July 2009
A Link between Reactivity and Local Structure in Acid Catalysis on Zeolites Bhan, Aditya; Iglesia, Enrique Accounts of Chemical Research, Vol. 41, Issue 4 https://doi.org/10.1021/ar700181t	journal	April 2008
Entropy considerations in monomolecular cracking of alkanes on acidic zeolites Bhan, A.; Gounder, R.; Macht, J. Journal of Catalysis, Vol. 253, Issue 1 https://doi.org/10.1016/j.jcat.2007.11.003	journal	January 2008
Solvation and acid strength effects on catalysis by faujasite zeolites Gounder, Rajamani; Jones, Andrew J.; Carr, Robert T. Journal of Catalysis, Vol. 286 https://doi.org/10.1016/j.jcat.2011.11.002	journal	February 2012
Opening the Cages of Faujasite-Type Zeolite Qin, Zhengxing; Cychosz, Katie A.; Melinte, Georgian Journal of the American Chemical Society, Vol. 139, Issue 48 https://doi.org/10.1021/jacs.7b10316	journal	November 2017
Catalytic Consequences of Spatial Constraints and Acid Site Location for Monomolecular Alkane Activation on Zeolites Gounder, Rajamani; Iglesia, Enrique Journal of the American Chemical Society, Vol. 131, Issue 5 https://doi.org/10.1021/ja808292c	journal	February 2009
The crystal structure of dehydrated NaX Olson, David H. Zeolites, Vol. 15, Issue 5 https://doi.org/10.1016/0144-2449(95)00029-6	journal	June 1995
Ni2+ ion sites in hydrated and dehydrated forms of Ni-exchanged zeolite ferrierite Dalconi, M. C.; Cruciani, G.; Alberti, A. Microporous and Mesoporous Materials, Vol. 39, Issue 3 https://doi.org/10.1016/S1387-1811(00)00216-X	journal	October 2000
Understanding the Role of Sodium during Adsorption: A Force Field for Alkanes in Sodium-Exchanged Faujasites Calero, Sofía; Dubbeldam, David; Krishna, Rajamani Journal of the American Chemical Society, Vol. 126, Issue 36 https://doi.org/10.1021/ja0476056	journal	September 2004
Elementary Steps of Faujasite Formation Followed by in Situ Spectroscopy Prodinger, Sebastian; Vjunov, Aleksei; Hu, Jian Zhi Chemistry of Materials, Vol. 30, Issue 3 https://doi.org/10.1021/acs.chemmater.7b04554	journal	January 2018
Structure of Na43+ in Sodium Zeolite Y Armstrong, A. R.; Anderson, P. A.; Woodall, L. J. Journal of the American Chemical Society, Vol. 117, Issue 35 https://doi.org/10.1021/ja00140a034	journal	September 1995
Origin of the bright photoluminescence of few-atom silver clusters confined in LTA zeolites Grandjean, Didier; Coutiño-Gonzalez, Eduardo; Cuong, Ngo Tuan Science, Vol. 361, Issue 6403 https://doi.org/10.1126/science.aaq1308	journal	August 2018
Nature and Location of Cationic Lanthanum Species in High Alumina Containing Faujasite Type Zeolites Schüßler, Florian; Pidko, Evgeny A.; Kolvenbach, Robin The Journal of Physical Chemistry C, Vol. 115, Issue 44 https://doi.org/10.1021/jp205771e	journal	October 2011
Parallel Alkane Dehydrogenation Routes on Brønsted Acid and Reaction-Derived Carbonaceous Active Sites in Zeolites Kester, Philip M.; Iglesia, Enrique; Gounder, Rajamani The Journal of Physical Chemistry C, Vol. 124, Issue 29 https://doi.org/10.1021/acs.jpcc.0c01808	journal	June 2020
Nature and Catalytic Role of Extraframework Aluminum in Faujasite Zeolite: A Theoretical Perspective Liu, Chong; Li, Guanna; Hensen, Emiel J. M. ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b02268	journal	October 2015
Scaling Relations for Acidity and Reactivity of Zeolites Liu, Chong; Tranca, Ionut; van Santen, Rutger A. The Journal of Physical Chemistry C, Vol. 121, Issue 42 https://doi.org/10.1021/acs.jpcc.7b08176	journal	October 2017
Computational Study of Brønsted Acidity of Faujasite. Effect of the Al Content on the Infrared OH Stretching Frequencies Sastre, German; Katada, Naonobu; Suzuki, Katsuki The Journal of Physical Chemistry C, Vol. 112, Issue 49 https://doi.org/10.1021/jp807623m	journal	November 2008
Combined study of IRMS-TPD measurement and DFT calculation on Brønsted acidity and catalytic cracking activity of cation-exchanged Y zeolites Noda, Takayuki; Suzuki, Katsuki; Katada, Naonobu Journal of Catalysis, Vol. 259, Issue 2 https://doi.org/10.1016/j.jcat.2008.08.004	journal	October 2008

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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deformation
ion exchange
organic reactions
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