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The Structure of a Complex Open-framework Germanate Obtained by Combining Powder Charge-Flipping and Simulated Annealing
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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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.

Place, publisher, year, edition, pages
2012. Vol. 12, no 10, 4853-4860 p.
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
URN: urn:nbn:se:su:diva-75921DOI: 10.1021/cg300647sISI: 000309493300025OAI: oai:DiVA.org:su-75921DiVA: diva2:524772
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2012-05-04 Created: 2012-05-03 Last updated: 2017-12-07Bibliographically 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)
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
2. Open-Framework Germanates and Nickel Germanates: Synthesis and Characterization
Open this publication in new window or tab >>Open-Framework Germanates and Nickel Germanates: Synthesis and Characterization
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Microporous materials have a wide range of important applications in separation, gas adsorption, ion-exchange and catalysis. Open-framework germanates are a family of microporous compounds and are of particular interest. This thesis focuses on the synthesis and characterization of new open-framework germanates as well as introducing the transition-metal nickel into germanate structures.

One new microporous germanosilicate, SU-78 and four new open-framework germanates, SU-74, SU-75, SU-69 and SU-76 have been obtained by using organic molecules as structure directing agents (SDAs). The incorporation of nickel and organic SDAs in the synthesis resulted in five novel nickel germanates, SUT-1, SUT-2, SUT-3, SUT-4 and SUT-5, in which nickel complexes act either as framework-forming components or as structure directing agents.

The general synthesis route is described and the variables that affect the synthesis products are summarized. Different techniques applied on the characterization of chemical and physical properties of the products are also introduced.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2012. 81 p.
Keyword
open-framework, zeolites, germanates, nickel germanates, structure directing agent, nickel complexes, crystal structure determination, hydrothermal synthesis
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75495 (URN)978-91-7447-489-3 (ISBN)
Public defence
2012-05-30, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Submitted. Paper 2: Submitted. Paper 3: Submitted. Paper 5: Manuscript.

Available from: 2012-05-08 Created: 2012-04-20 Last updated: 2012-10-25Bibliographically approved
3. Open-framework Structures Built by Inorganic Clusters: Synthesis and Characterization
Open this publication in new window or tab >>Open-framework Structures Built by Inorganic Clusters: Synthesis and Characterization
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Novel open-framework germanates and vanadoborates, which are constructed from typical types of clusters, have been synthesized based on different strategies. The crystal structures are solved by using single crystal X-ray diffraction (SXRD) technique or by combined techniques. Additionally, the structures of two open-framework materials, PKU-3 and PKU-16, are determined from nano-sized crystals by rotation electron diffraction (RED) combined with powder X-ray diffraction (PXRD).

This thesis serves as an introduction to synthesis of open-framework germanates and vanadoborates based on different design strategies. Two germanates are obtained; SU-74 is achieved by employing a novel structure directing agent (SDA), SUT-8 is achieved by assembling the novel structure building units (SBUs) of Co@Ge14 with the introduction of cobalt ions in the synthesis. Four strategies are successfully used in construction of open-framework vanadoborates: using metal-oxo polyhedra as the linkages in SUT-6; applying the scale chemistry approach in SUT-7; employing metal-organic complexes as the linkages in SUT-12, SUT-13, SUT-14; and introducing covalent bond organic linkages into SUT-10 and SUT-11. Single crystal X-ray diffraction is used to conduct the structure determination in combination with other techniques.

Furthermore, the structures of two open-framework materials, an aluminoborate PKU-3 and a germanosilicate PKU-16, are solved from nano-sized crystals using RED data. The structures are further confirmed by Rietveld refinement against PXRD data. The advantages of the RED techniques are demonstrated in two aspects. In PKU-3, the presence of seriously preferred orientation and light elements in the structure makes it difficult for structure determination by PXRD, but it is easier by RED. In PKU-16, the RED technique is used to determine its structure from the as-synthesized multi-phasic sample containing nano-sized crystals. After the structure of PKU-16 has been solved, the synthesis of this interesting phase can be optimized and pure PKU-16 can be obtained.

Keywords: Open-framework, germanates, vanadoborates, aluminoborates, germanosilicates, crystal structure, hydrothermal synthesis, single crystal X-ray diffraction, rotation electron diffraction, powder X-ray diffraction

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm Univeristy, 2014. 87 p.
Keyword
Open-framework, germanates, vanadoborates, aluminoborates, germanosilicates, crystal structure, hydrothermal synthesis, crystal X-ray diffraction, rotation electron diffraction, powder X-ray diffraction
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-106853 (URN)978-91-7447-962-1 (ISBN)
Public defence
2014-09-29, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2014-09-07 Created: 2014-08-25 Last updated: 2014-09-15Bibliographically approved

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