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Open-Framework Germanates: Synthesis, Structure, and Characterization
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). (Xiaodong Zou)
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 [en]
Open-framework, zeolites, germanates, porous materials, crystallography, hydrothermal synthesis, crystal structure
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
URN: urn:nbn:se:su:diva-75732ISBN: 978-91-7447-519-7 (print)OAI: oai:DiVA.org:su-75732DiVA: diva2:523727
Public defence
2012-06-13, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
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
List of papers
1. Investigation of the GeO2-1,6-Diaminohexane-Water-Pyridine-HF Phase Diagram Leading to the Discovery of Two Novel Layered Germanates with Extra-Large Rings
Open this publication in new window or tab >>Investigation of the GeO2-1,6-Diaminohexane-Water-Pyridine-HF Phase Diagram Leading to the Discovery of Two Novel Layered Germanates with Extra-Large Rings
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2011 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 50, no 1, 201-207 p.Article in journal (Refereed) Published
Abstract [en]

The systematic exploration of the phase diagram of the GeO2-1,6-diaminohexane-water-pyridine-HF system has allowed the identification of specific roles of the HF, H2O contents, and HF/H2O ratio in the formation of Ge7X19 (Ge7), Ge9X25−26 (Ge9), and Ge10X28 (Ge10) clusters (X = O, OH, F). This work has led to the discovery of two novel structures with extra-large 18-membered rings accommodating 1,6-diaminohexane (DAH): SU-63, |1.5H2DAH|[Ge7O14X3]·2H2O, a layered germanate constructed from Ge7 clusters with the Kagom topology, and SU-64, |11H2DAH|[Ge9O18X4][Ge7O14X3]6·16H2O, a germanate built of two-dimensional slabs containing both Ge7 and Ge9 clusters (X = OH or F). We also put SU-64 in context with previously reported cluster germanate compounds with related topologies by means of a simple crystal deconstruction study.

National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-50704 (URN)10.1021/ic1017505 (DOI)000285559800023 ()
Note
7Available from: 2010-12-30 Created: 2010-12-30 Last updated: 2017-12-11Bibliographically approved
2. Three Low-Dimensional Open-Germanates Derived from the 4^4 Net
Open this publication in new window or tab >>Three Low-Dimensional Open-Germanates Derived from the 4^4 Net
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(English)In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033Article in journal (Refereed) Submitted
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75915 (URN)
Available from: 2012-05-04 Created: 2012-05-03 Last updated: 2017-12-07Bibliographically approved
3. SU-65: The Orientation of Five-connected Ge7X19(X = O, OH, F) Clusters in the fee Net
Open this publication in new window or tab >>SU-65: The Orientation of Five-connected Ge7X19(X = O, OH, F) Clusters in the fee Net
(English)Manuscript (preprint) (Other academic)
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75920 (URN)
Available from: 2012-05-04 Created: 2012-05-03 Last updated: 2012-05-04Bibliographically approved
4. A Stacking Faults-containing Silicogermanate with 24-ring Channels and Unbranched Zweier Silica Double Chains
Open this publication in new window or tab >>A Stacking Faults-containing Silicogermanate with 24-ring Channels and Unbranched Zweier Silica Double Chains
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(English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505Article in journal (Refereed) Submitted
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75942 (URN)
Note
In the first submitted version, the paper was called "A Silicogermanate with 24-Ring Channels, Unbranched Zweirer Silica Double Chains, and Stacking Faults".Available from: 2012-05-04 Created: 2012-05-04 Last updated: 2017-12-07Bibliographically approved
5. SU-62: Synthesis and Structure Investigation of a Germanate with a Novel Three-Dimensional Net and Interconnected 10- and 14-Ring Channels
Open this publication in new window or tab >>SU-62: Synthesis and Structure Investigation of a Germanate with a Novel Three-Dimensional Net and Interconnected 10- and 14-Ring Channels
2012 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 12, no 1, 369-375 p.Article in journal (Refereed) Published
Abstract [en]

A novel 3D open-framework germanate, vertical bar N(2)C(4)H(14)vertical bar(4) [Ge(20)O(41)(OH)(6)]center dot 3H(2)O (SU-62), was prepared from hydrothermal synthesis using 1,4-diaminobutane as the organic structure directing agent (SDA). The crystal structure was solved by single crystal X-ray diffraction. The framework is built from Ge(10)(O,OH)(27) (Ge(10)) secondary building units and exhibits an irregular three-dimensional channel system encircled by 10- and 14-rings. The framework of SU-62 has an underlying topology that follows a novel five-coordinated svh-5-I4(1)/amd net, while the pores follow the tsi net. The thermal behavior of SU-62 was studied by thermogravimetric (TG) analysis and in situ X-ray diffraction (XRPD). Crystallographic data: orthorhombic, space group Fdd2, unit cell parameters a = 15.297(3) angstrom, b = 53.58(1) angstrom, c = 14.422(3) angstrom, V = 11821(4) angstrom(3), Z = 8.

National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75668 (URN)10.1021/cg201482n (DOI)000298726300050 ()
Available from: 2012-05-04 Created: 2012-04-24 Last updated: 2017-12-07Bibliographically approved
6. SU-75: a disordered Ge-10 germanate with pcu topology
Open this publication in new window or tab >>SU-75: a disordered Ge-10 germanate with pcu topology
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2012 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 41, no 40, 12358-12364 p.Article in journal (Refereed) Published
Abstract [en]

A disordered open-framework germanate, denoted as SU-75, was synthesized under hydrothermal conditions using diethylenetriamine (dien) or alternatively 1,4-diaminobutane (dab) as the structure directing agent (SDA). SU-75 crystallizes in a tetragonal space group I-42d(No. 122) with a= 18.145(3) Å and c= 41.701(9) Å. The three-dimensional (3D) framework is built from Ge10(O,OH)28(Ge10) clusters that are connected following the pcu ( primitive cubic) net topology. SU-75 has 10-, 11- and 12-ring channels along the a- and b-axes and channels with alternating 8-, 10-, 12-, 10-ring openings along the c-axis. The framework exhibits a serious disorder, resulted from two possible connectivities between the units of four Ge 10clusters (4Ge10 unit). The chemical formula of SU-75 is |(H2SDA)2(H2O)n|[Ge10O21(OH)2] (SDA = dien or dab,n= 5–6), determined by combining single crystalsynchrotron X-ray diffraction, thermogravimetric analysis (TGA) and CHN elemental analysis. A superoctahedron is introduced to simplify the description of the connectivity of the Ge10 clusters and to illustrate the disorder. This is also used to compare the structure of SU-75 with those of related Ge10 germanates.

Keyword
Germanate, Ge10, pcu topology
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-80852 (URN)10.1039/c2dt30767g (DOI)000309141500005 ()
Available from: 2012-10-25 Created: 2012-09-30 Last updated: 2017-12-07Bibliographically approved
7. The Structure of a Complex Open-framework Germanate Obtained by Combining Powder Charge-Flipping and Simulated Annealing
Open this publication in new window or tab >>The Structure of a Complex Open-framework Germanate Obtained by Combining Powder Charge-Flipping and Simulated Annealing
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2012 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 12, no 10, 4853-4860 p.Article in journal (Refereed) Published
Abstract [en]

A novel open-framework germanate SU-74 containing intersecting 10- and 12-ring channels was prepared by hydrothermal synthesis using 2-methylpentamethylenediamine (MPMD) or 1-(2-aminoethyl)piperazine (AEP) as the organic structure directing agent (SDA). The framework structure of SU-74-MPMD was solved from X-ray powder diffraction (XRPD) data using powder charge-flipping (pCF). The guest species H2MPMD2+, NH4+ cations and water molecules were located in the voids using real-space simulated annealing. SU-74-MPMD contains 51 non-hydrogen atoms in its asymmetric unit and is one of the most complex framework structures solved by XRPD. The structure of SU-74-AEP was solved by single crystal synchrotron X-ray diffraction. SU-74-MPMD and SU-74-AEP have the same framework structure. The location of the NH4+ cations in both structures is similar, while the positions of the SDAs in the pores are different. SU-74 follows the fcu-11-P21/c net. The underlying topology of SU-74 is compared to those of other Ge10 structures containing additional GeO4 tetrahedra. The presence of additional tetrahedra can significantly affect the framework topology through the addition of edges between the Ge10 nodes.

National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75921 (URN)10.1021/cg300647s (DOI)000309493300025 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2012-05-04 Created: 2012-05-03 Last updated: 2017-12-07Bibliographically approved
8. SU-66: An Open-framework Gallogermanate with 26-ringchannels Solved by Combining Infrared Spectroscopy, ElectronDiffraction and X-ray Powder Diffraction
Open this publication in new window or tab >>SU-66: An Open-framework Gallogermanate with 26-ringchannels Solved by Combining Infrared Spectroscopy, ElectronDiffraction and X-ray Powder Diffraction
(English)Manuscript (preprint) (Other academic)
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75922 (URN)
Available from: 2012-05-04 Created: 2012-05-03 Last updated: 2012-05-04Bibliographically approved
9. Open-Framework Germanate Built from the Hexagonal Packing of Rigid Cylinders
Open this publication in new window or tab >>Open-Framework Germanate Built from the Hexagonal Packing of Rigid Cylinders
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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.

Keyword
synchrotron X-ray diffraction, template, crystal growth mechanism, twinning
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-36767 (URN)10.1021/ic900940s (DOI)000270987400002 ()
Available from: 2010-01-26 Created: 2010-01-26 Last updated: 2017-12-12Bibliographically approved
10. Open-Framework Germanates and Related Materials
Open this publication in new window or tab >>Open-Framework Germanates and Related Materials
2013 (English)In: Nanoporous Materials: Synthesis and Applications, London: Taylor & Francis Group, 2013Chapter in book (Other academic)
Place, publisher, year, edition, pages
London: Taylor & Francis Group, 2013
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75919 (URN)
Note
The book chapter is not yet published.Available from: 2012-05-04 Created: 2012-05-03 Last updated: 2012-05-04Bibliographically approved

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