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Open-Framework Germanate Built from the Hexagonal Packing of Rigid Cylinders
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
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2009 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 48, no 21, 9962-9964 p.Article in journal (Refereed) Published
Abstract [en]

We present a novel open-framework oxide material constructed from Ge10(O,OH)28 (Ge10) oxide clusters prepared via a nonsurfactant route. The material shows two distinct pore windows of 9.43 and 4.65 Å and a low framework density structure of 12.7 Ge atoms per 1000 Å3. The topological study leads to the recognition of a newly observed trinodal 6,7-heterocoordinated net related to the 7-coordinated swh net. The structure displays large rigid cylinders showing features indicating a growth mechanism by hard-sphere packing of the inorganic moiety similar to that observed in mesoporous materials.

Place, publisher, year, edition, pages
2009. Vol. 48, no 21, 9962-9964 p.
Keyword [en]
synchrotron X-ray diffraction, template, crystal growth mechanism, twinning
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
URN: urn:nbn:se:su:diva-36767DOI: 10.1021/ic900940sISI: 000270987400002OAI: oai:DiVA.org:su-36767DiVA: diva2:290093
Available from: 2010-01-26 Created: 2010-01-26 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Open-Framework Germanates: Synthesis, Structure, and Characterization
Open this publication in new window or tab >>Open-Framework Germanates: Synthesis, Structure, and Characterization
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Novel open-framework germanates and open low-dimensional structures were synthesized and characterized. Their crystal structures were solved by single crystal X-ray diffraction or X-ray powder diffraction combined with other techniques. Although related open-framework materials, such as zeolites, are of interest for the ability to selectively accommodate guest species in their rings, pores and channels, germanates are primarily of interest for their unique structural properties. Compared to aluminosilicate-based zeolites, germanium oxides readily form frameworks with extra-large rings and low framework density. The formation of elegant germanate architectures is attributed to the unique Ge-O bond geometries compared to Si-O, and the tendency to form large clusters.

This thesis is to serve as an introduction to germanate synthesis, structures and characterization. Structures are categorized in accordance to their building units; the Ge7X19 (Ge7), Ge9X25-26 (Ge9) and Ge10X28 (Ge10) (X = O, OH, or F) clusters. Structure determination techniques as well as the characterization techniques used to examine the properties of the materials are presented. While most of the discussed techniques have routinely been used to study crystalline open-frameworks, we introduce the use of infrared spectroscopy for the identification of cluster types, valuable for structure determination by X-ray powder diffraction. Structures and properties of the novel materials ASU-21, SU-62, SU-63, SU-64, SU-65, SU-66, SU-71, SU-72, SU-73, SU-74, SU-75 and SU-JU-14 are described and put into context with previously known structures. The novel structures are all built of the Ge7, Ge9 or Ge10 clusters, and vary from a framework with novel topology to the first open zero-dimensional germanate cavities built of such clusters.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2012. 120 p.
Keyword
Open-framework, zeolites, germanates, porous materials, crystallography, hydrothermal synthesis, crystal structure
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75732 (URN)978-91-7447-519-7 (ISBN)
Public defence
2012-06-13, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
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Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Submitted. Paper 3: Manuscript. Paper 4: Submitted. Paper 6: Submitted. Paper 7: Manuscript. Paper 8. Manuscript. Paper 10: Unpublished book chapter.

 

Available from: 2012-05-10 Created: 2012-04-26 Last updated: 2012-10-25Bibliographically approved

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