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A titanosilicate molecular sieve with adjustable pores for size-selective adsorption of molecules
Abstract
Zeolites and related crystalline microporous oxides-tetrahedrally coordinated atoms covalently linked into a porous framework-are of interest for applications ranging from catalysis to adsorption and ion-exchange. In some of these materials (such as zeolite rho) adsorbates, ion-exchange, and dehydration and cation relocation can induce strong framework deformations. Similar framework flexibility has to date not been seen in mixed octahedral/tetrahedral microporous framework materials, a newer and rapidly expanding class of molecular sieves. Here we show that the framework of the titanium silicate ETS-4, the first member of this class of materials, can be systematically contracted through dehydration at elevated temperatures to 'tune' the effective size of the pores giving access to the interior of the crystal. We show that this so-called 'molecular gate' effect can be used to tailor the adsorption properties of the materials to give size-selective adsorbents suitable for commercially important separations of gas mixtures of molecules with similar size in the 4.0 to 3.0 A range, such as that of N2/CH4, Ar/O2 and N2/O2.
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“Some years later, another zeolite-related material, i.e., contracted Engelhard titanosilicate CTS-1 (Na,Sr-ETS-4 treated at 300–340 °C), was patented to carry out the separation of oxygen from air based on the molecular sieving of oxygen at room temperature,447,448 thus recovering Milton’s original idea.17”
From Zeolites in Adsorption Processes: State of the Art and Future Prospects (2022) · cites this paper as [448]
In the citing paper
“Titanosilicate materials developed by Engelhard Corporation (now BASF), such as ETS-4, CTS-1, Ba-ETS-4, and Sr-ETS-4, have been demonstrated to be excellent adsorbents for this application at a small scale.448,451,457−459”
From Zeolites in Adsorption Processes: State of the Art and Future Prospects (2022) · cites this paper as [448]
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Metadata
- Authors
- Kuznicki, S. M., Bell, V. A., Nair, S., Hillhouse, H. W., Jacubinas, R. M., Braunbarth, C. M., Toby, B. H., & Tsapatsis, M.
- Affiliations
- University of Massachusetts Amherst (US)
- National Institute of Standards and Technology (US)
- Corresponding author
- Kuznicki, Steven M.
- Venue
- Nature
- Published
- 2001-08-16
- Volume
- 412
- Issue
- 6848
- Pages
- 720-724
- ISSN
- 0028-0836 (ISSN-L)
- 1476-4687
- OpenAlex
- W2062719158
- Cited by
- 616
- References
- 29
- Citations by year
- 2026: 17 · 2025: 35 · 2024: 22 · 2023: 20 · 2022: 26 · 2021: 28 · 2020: 21 · 2019: 27 · 2018: 21 · 2017: 20 · 2016: 18 · 2015: 16 · 2014: 29 · 2013: 16 · 2012: 35
- FWCI
- 11.53
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Nature (publishedVersion)
- PubMed (publishedVersion)
- RePEc: Research Papers in Economics (submittedVersion)
- Funders
- Deutsche Forschungsgemeinschaft
- Topics
- Physical Sciences › Chemistry › Inorganic Chemistry › Zeolite Catalysis and Synthesis
- Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Organic Frameworks: Synthesis and Applications
- Physical Sciences › Chemical Engineering › Filtration and Separation › Membrane Separation and Gas Transport
- Keywords
- ETS-4, framework flexibility, size-selective adsorption, gas separation, zeolite-like materials, CH4/N2 separation
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