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Cited by 121Zeolite Catalysis and SynthesisChemical Synthesis and CharacterizationMetal-Organic Frameworks: Synthesis and Applications

Fast room temperature lability of aluminosilicate zeolites

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Heard, Christopher J., Grajciar, Lukas, Rice, Cameron M., Pugh, Suzi M., Nachtigall, Petr, Ashbrook, Sharon E., Morris, Russell E.·2019·Nature Communications
DOI 10.1038/s41467-019-12752-yPMC PMC6795794
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Abstract

Aluminosilicate zeolites are traditionally used in high-temperature applications at low water vapour pressures where the zeolite framework is generally considered to be stable and static. Increasingly, zeolites are being considered for applications under milder aqueous conditions. However, it has not yet been established how neutral liquid water at mild conditions affects the stability of the zeolite framework. Here, we show that covalent bonds in the zeolite chabazite (CHA) are labile when in contact with neutral liquid water, which leads to partial but fully reversible hydrolysis without framework degradation. We present ab initio calculations that predict novel, energetically viable reaction mechanisms by which Al-O and Si-O bonds rapidly and reversibly break at 300 K. By means of solid-state NMR, we confirm this prediction, demonstrating that isotopic substitution of 17 O in the zeolitic framework occurs at room temperature in less than one hour of contact with enriched water.

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  • Proper mechanistic understanding of BAS-water-zeolite interactions is still lacking, limited to either static calculations at ultra-high vacuum conditions or exploratory (ab initio) dynamical simulations of narrow scope.

    “As a result, the proper mechanistic understanding of BAS-water-zeolite interactions is still lacking, limited to either static calculations at ultra-high vacuum conditions13,14 or exploratory (ab initio) dynamical simulations of narrow scope15–18.”

    From A reactive neural network framework for water-loaded acidic zeolites (2024) · cites this paper as [15]

    The Results (Computational studies) describe biased ab initio molecular dynamics of the initial hydrolysis of water-loaded chabazite, so this paper is an example of a dynamical study with a specific scope. It does not state that mechanistic understanding of Brønsted acid site–water–zeolite interactions is generally lacking or that prior work is limited to the two approaches named in the citing sentence. (LLM, conf=0.84)

    Experimental — accuracy not yet measured

  • A water molecule adsorbs at a surface Si site, which is a standard precursor for Si-O bond hydrolysis.

    “Firstly, a water molecule adsorbs at a surface Si site (Fig. 2b), which is a standard precursor for Si-O bond hydrolysis reported in multiple publications before15,66–68.”

    From A reactive neural network framework for water-loaded acidic zeolites (2024) · cites this paper as [15]

    The Results (Computational studies; page not provided) describe water interacting directly with Si as the first step in Si–O bond hydrolysis. The study concerns Si sites in a zeolite framework, however, and calls its hydrolysis mechanism novel; it does not establish this as a standard precursor at a surface Si site. (LLM, conf=0.86)

    Experimental — accuracy not yet measured

  • This process finally leads to the cleavage of the Si-O(H) bond, creating a silanol defect in an axial position to the previously formed surface silanol, i.e., the same product and mechanism observed previously to take place inside the cage systems of various zeolites (CHA, UTL).

    “This process finally leads to the cleavage of the Si–O(H) bond, creating a silanol defect in an axial position to the previously formed surface silanol, i.e., the same product and mechanism observed previously to take place inside the cage systems of various zeolites (CHA15, UTL18).”

    From A reactive neural network framework for water-loaded acidic zeolites (2024) · cites this paper as [15]

    Split into 2 atoms — 0 confirmed, 2 partially supported, 0 disputed, 0 misattributed, 0 unverifiable. Expand the claim to see per-atom verdicts.

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References 53 · Cited by 121

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  1. [1]Li Y Li L Yu J Applications of zeolites in sustainable chemistry Chem 2017 3 928 949 10.1016/j.chempr.2017.10.009 · DOI · Paper page
  2. [2]Agostini G In Situ XAS and XRPD parametric rietveld refinement to understand dealumination of Y zeolite catalyst J. Am. Chem. Soc. 2010 132 667 678 10.1021/ja907696h 20000838 · DOI
  3. [3]Kung HH Enhanced hydrocarbon cracking activity of Y zeolites Top. Catal. 2000 10 59 64 10.1023/A:1019155832086 · DOI
  4. [4]Nielsen M Kinetics of zeolite dealumination: insights from H-SSZ-13 ACS Catal. 2015 5 7131 7139 10.1021/acscatal.5b01496 · DOI
  5. [5]Ma D Deng F Fu R Han X Bao X MAS NMR studies on the dealumination of zeolite MCM-22 J. Phys. Chem. B 2001 105 1770 1779 10.1021/jp003575r · DOI
  6. [6]Mizuno N Mori H Mineo K Iwamoto M Isotopic exchange of oxygen between proton-exchanged zeolites and water J. Phys. Chem. B 1999 103 10393 10399 10.1021/jp992258l · DOI
  7. [7]Freude D Loeser T Michel D Pingel U Prochnow D 17O NMR studies of low silicate zeolites Solid State Nucl. Magn. Reson. 2001 20 46 60 10.1006/snmr.2001.0029 11529419 · DOI
  8. [8]Loeser T Freude D Mabande GTP Schwieger W 17O NMR studies of sodalites Chem. Phys. Lett. 2003 370 32 38 10.1016/S0009-2614(03)00066-6 · DOI
  9. [11]Stanciakova K Ensing B Göltl F Bulo RE Weckhuysen BM Cooperative role of water molecules during the initial stage of water-induced zeolite dealumination ACS Catal. 2019 9 5119 5135 10.1021/acscatal.9b00307 · DOI
  10. [13]Ennaert T Conceptual frame rationalizing the self-stabilization of H-USY zeolites in hot liquid water ACS Catal. 2014 5 754 768 10.1021/cs501559s · DOI
  11. [14]Ravenelle RM Stability of zeolites in hot liquid water J. Phys. Chem. C 2010 114 19582 19595 10.1021/jp104639e · DOI
  12. [15]Prodinger S Improving stability of zeolites in aqueous phase via selective removal of structural defects J. Am. Chem. Soc. 2016 138 4408 4415 10.1021/jacs.5b12785 26972547 · DOI
  13. [16]Xiong H Pham HN Datye AK Hydrothermally stable heterogeneous catalysts for conversion of biorenewables Green Chem. 2014 16 4627 4643 10.1039/C4GC01152J · DOI
  14. [17]Vjunov A Impact of aqueous medium on zeolite framework integrity Chem. Mater. 2015 27 3533 3545 10.1021/acs.chemmater.5b01238 · DOI
  15. [18]Roth WJ A family of zeolites with controlled pore size prepared using a top-down method Nat. Chem. 2013 5 628 633 10.1038/nchem.1662 23787755 · DOI
  16. [20]Zhang L Chen K Chen B White JL Resasco DE Factors that determine zeolite stability in hot liquid water J. Am. Chem. Soc. 2015 137 11810 11819 10.1021/jacs.5b07398 26301890 · DOI · Paper page
  17. [21]Mazur M Synthesis of ‘unfeasible’ zeolites Nat. Chem. 2015 8 58 10.1038/nchem.2374 26673264 · DOI
  18. [22]Bignami GPM Synthesis, isotopic enrichment, and solid-state nmr characterization of zeolites derived from the assembly, disassembly, organization, reassembly process J. Am. Chem. Soc. 2017 139 5140 5148 10.1021/jacs.7b00386 28319391 PMC5403117 · DOI
  19. [23]Klemperer WG 17O-NMR spectroscopy as a structural probe Angew. Chem. 1978 17 246 254 10.1002/anie.197802461 · DOI
  20. [24]Borfecchia E Cu-CHA – a model system for applied selective redox catalysis Chem. Soc. Rev. 2018 47 8097 8133 10.1039/C8CS00373D 30083666 · DOI
  21. [25]Groothaert MH Smeets PJ Sels BF Jacobs PA Schoonheydt RA Selective oxidation of methane by the bis(μ-oxo)dicopper core stabilized on ZSM-5 and mordenite zeolites J. Am. Chem. Soc. 2005 127 1394 1395 10.1021/ja047158u 15686370 · DOI
  22. [26]Pappas DK Methane to methanol: structure–activity relationships for Cu-CHA J. Am. Chem. Soc. 2017 139 14961 14975 10.1021/jacs.7b06472 28945372 · DOI
  23. [27]De Wispelaere K Insight into the effect of water on the methanol-to-olefins conversion in H-SAPO-34 from molecular simulations and in situ microspectroscopy ACS Catal. 2016 6 1991 2002 10.1021/acscatal.5b02139 · DOI
  24. [28]De Wispelaere K Ensing B Ghysels A Meijer EJ Van Speybroeck V Complex reaction environments and competing reaction mechanisms in zeolite catalysis: insights from advanced molecular dynamics Chem. A Eur. J. 2015 21 9385 9396 10.1002/chem.201500473 25951509 · DOI
  25. [30]Hühn C Erlebach A Mey D Wondraczek L Sierka M Ab Initio energetics of Si–O bond cleavage J. Comput. Chem. 2017 38 2349 2353 10.1002/jcc.24892 28749567 · DOI
  26. [31]Pelmenschikov A Leszczynski J Pettersson LGM Mechanism of dissolution of neutral silica surfaces: including effect of self-healing J. Phys. Chem. A 2001 105 9528 9532 10.1021/jp011820g · DOI
  27. [32]Tamada O Gibbs GV Boisen MB Jr Rimstidt JD Silica dissolution catalyzed by NaOH: reaction kinetics and energy barriers simulated by quantum mechanical strategies J. Mineral. Petrol. Sci. 2012 107 87 98 10.2465/jmps.110909 · DOI
  28. [33]Heard CJ Grajciar L Nachtigall P The effect of water on the validity of Löwenstein’s rule Chem. Sci. 2019 10.1039/C9SC00725C 31293755 PMC6563785 · DOI
  29. [34]Vener MV Rozanska X Sauer J Protonation of water clusters in the cavities of acidic zeolites: (H2O)n·H-chabazite, n = 1–4 Phys. Chem. Chem. Phys. 2009 11 1702 1712 10.1039/b817905k 19290341 · DOI
  30. [35]Schwarz K Nusterer E Blöchl PE First-principles molecular dynamics study of small molecules in zeolites Catal. Today 1999 50 501 509 10.1016/S0920-5861(98)00484-2 · DOI
  31. [36]Vjunov A Tracking the chemical transformations at the Brønsted acid site upon water-induced deprotonation in a zeolite pore Chem. Mater. 2017 29 9030 9042 10.1021/acs.chemmater.7b02133 · DOI
  32. [37]Silaghi M-C Regioselectivity of Al–O bond hydrolysis during zeolites dealumination unified by Brønsted–evans–polanyi relationship ACS Catal. 2015 5 11 15 10.1021/cs501474u · DOI · Paper page
  33. [38]Xu Z Stebbins JF Oxygen sites in the zeolite stilbite: a comparison of static, MAS, VAS, DAS and triple quantum MAS NMR techniques Solid State Nucl. Magn. Reson. 1998 11 243 251 10.1016/S0926-2040(97)00019-2 9694393 · DOI
  34. [39]Pingel UT High-field 17O NMR studies of the SiOAl bond in solids Chem. Phys. Lett. 1998 294 345 350 10.1016/S0009-2614(98)00847-1 · DOI
  35. [40]Peng L Liu Y Kim N Readman JE Grey CP Detection of Brønsted acid sites in zeolite HY with high-field 17O-MAS-NMR techniques Nat. Mater. 2005 4 216 219 10.1038/nmat1332 15711551 · DOI
  36. [41]Zimmermann NER Jakobtorweihen S Beerdsen E Smit B Keil FJ In-depth study of the influence of host-framework flexibility on the diffusion of small gas molecules in one-dimensional zeolitic pore systems J. Phys. Chem. C 2007 111 17370 17381 10.1021/jp0746446 · DOI
  37. [42]Kapko V Dawson C Treacy MMJ Thorpe MF Flexibility of ideal zeolite frameworks Phys. Chem. Chem. Phys. 2010 12 8531 8541 10.1039/c003977b 20589266 · DOI
  38. [43]Morris RE Brammer L Coordination change, lability and hemilability in metal-organic frameworks Chem. Soc. Rev. 2017 46 5444 5462 10.1039/C7CS00187H 28795752 · DOI
  39. [44]Frydman L Harwood JS Isotropic spectra of half-integer quadrupolar spins from bidimensional magic-angle spinning NMR J. Am. Chem. Soc. 1995 117 5367 5368 10.1021/ja00124a023 · DOI
  40. [45]Amoureux J-P Fernandez C Steuernagel S Z Filtering in MQMAS NMR J. Magn. Reson. Ser. A 1996 123 116 118 10.1006/jmra.1996.0221 8980071 · DOI
  41. [46]Pike KJ Malde RP Ashbrook SE McManus J Wimperis S Multiple-quantum MAS NMR of quadrupolar nuclei. Do five-, seven- and nine-quantum experiments yield higher resolution than the three-quantum experiment? Solid State Nucl. Magn. Reson. 2000 16 203 215 10.1016/S0926-2040(00)00081-3 10868573 · DOI
  42. [47]Pronk S GROMACS 4.5: a high-throughput and highly parallel open source molecular simulation toolkit Bioinformatics 2013 29 845 854 10.1093/bioinformatics/btt055 23407358 PMC3605599 · DOI
  43. [48]Kresse G Hafner J Ab initio molecular dynamics for liquid metals Phys. Rev. B 1993 47 558 561 10.1103/PhysRevB.47.558 10004490 · DOI
  44. [49]Kresse G Hafner J Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Phys. Rev. B 1994 49 14251 14269 10.1103/PhysRevB.49.14251 10010505 · DOI
  45. [50]Kresse G Furthmüller J Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Comput. Mater. Sci. 1996 6 15 50 10.1016/0927-0256(96)00008-0 9984901 · DOI
  46. [51]Kresse G Furthmüller J Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Phys. Rev. B 1996 54 11169 11186 10.1103/PhysRevB.54.11169 9984901 · DOI · Paper page
  47. [52]Perdew JP Burke K Ernzerhof M Generalized gradient approximation made simple Phys. Rev. Lett. 1996 77 3865 3868 10.1103/PhysRevLett.77.3865 10062328 · DOI · Paper page
  48. [53]Grimme S Antony J Ehrlich S Krieg H A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J. Chem. Phys. 2010 132 154104 10.1063/1.3382344 20423165 · DOI · Paper page

Authors
Heard, C. J., Grajciar, L., Rice, C. M., Pugh, S. M., Nachtigall, P., Ashbrook, S. E., & Morris, R. E.
Affiliations
  • Charles University (CZ)
  • University of St Andrews (GB)
Corresponding author
  • Nachtigall, Petr
  • Ashbrook, Sharon E.
  • Morris, Russell E.
ORCID
Venue
Nature Communications
Publisher
Springer Science and Business Media LLC
Published
2019-10-16
Volume
10
Issue
1
Pages
4690-4690
ISSN
2041-1723 (ISSN-L)
DOI
10.1038/s41467-019-12752-y
PMC
PMC6795794
OpenAlex
W2980709935
Cited by
121
References
53
Citations by year
2026: 18 · 2025: 12 · 2024: 16 · 2023: 22 · 2022: 14 · 2021: 17 · 2020: 20 · 2019: 1
FWCI
4.87
Type
journal article
Language
en
Open access
Licence
Locations
  • Nature Communications (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • RePEc: Research Papers in Economics (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion)
  • St Andrews Research Repository (St Andrews Research Repository) (submittedVersion, cc-by)
Funders
  • Univerzita Karlova v Praze (CZ.02.1.01/0.0/0.0/15 003/0000417))
  • Engineering and Physical Sciences Research Council (1949783)
Topics
  • Physical Sciences › Chemistry › Inorganic Chemistry › Zeolite Catalysis and Synthesis
  • Physical Sciences › Environmental Science › Waste Management and Disposal › Chemical Synthesis and Characterization
  • Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Organic Frameworks: Synthesis and Applications
Keywords
aluminosilicate zeolites, chabazite, zeolite framework stability, reaction mechanism, solid-state NMR, first-principles calculations

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