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Open-framework Structures Built by Inorganic Clusters: Synthesis and Characterization
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). (Junliang Sun)
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 [en]
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: urn:nbn:se:su:diva-106853ISBN: 978-91-7447-962-1 (print)OAI: oai:DiVA.org:su-106853DiVA: diva2:740537
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
List of papers
1. 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
2. Structure Determination for a Seriously Twinned  Open-framework Germanate Constructed from  Co@Ge14 clusters
Open this publication in new window or tab >>Structure Determination for a Seriously Twinned  Open-framework Germanate Constructed from  Co@Ge14 clusters
(English)Manuscript (preprint) (Other (popular science, discussion, etc.))
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-106858 (URN)
Available from: 2014-08-25 Created: 2014-08-25 Last updated: 2014-08-25Bibliographically approved
3. 3D Open-Framework Vanadoborate as a Highly Effective Heterogeneous Pre-catalyst for the Oxidation of Alkylbenzenes
Open this publication in new window or tab >>3D Open-Framework Vanadoborate as a Highly Effective Heterogeneous Pre-catalyst for the Oxidation of Alkylbenzenes
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2013 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 25, no 24, 5031-5036 p.Article in journal (Refereed) Published
Abstract [en]

Three three-dimensional (3D) open-framework vanadoborates, denoted as SUT-6-Zn, SUT-6-Mn, and SUT-6-Ni, were synthesized using diethylenetriamine as a template. SUT-6-Zn, SUT-6-Mn, and SUT-6-Ni are isostructural and built from (VO)(12)O-6 B18O36(OH)(6) clusters bridged by ZnO5, MnO6, and NiO6 polyhedra, respectively, to form the 3D frameworks. SUT-6 is the first vanadoborate with a 3D framework. The framework follows a semiregular hxg net topology with a 2-fold interpenetrated diamond-like channel system. The amount of template used in the synthesis played an important role in the dimensionality of the resulting vanadoborate structures. A small amount of diethylenetriamine led to the formation of this first 3D vanadoborate framework, while an increased amount of diethylenetriamine resulted in vanadoborates with zero-dimensional (0D) and one-dimensional (1D) structures. SUT-6-Zn was proved to be an efficient heterogeneous precatalyst for the oxidation of alkylbenzenes.

Keyword
vanadoborates, open-framework materials, hxg topology, heterogeneous catalysis, oxidation
National Category
Physical Chemistry Materials Chemistry
Identifiers
urn:nbn:se:su:diva-100387 (URN)10.1021/cm401400m (DOI)000329137800024 ()
Funder
Swedish Research CouncilVinnova
Note

AuthorCount:8;

Funding agencies:

Swedish Research Council (VR)   Swedish Governmental Agency for Innovation Systems (VINNOVA) through Berzelii EXSELENT;   National Basic Research Program of China  2013CB933402; Diamond Light Source I19.

Available from: 2014-02-04 Created: 2014-02-03 Last updated: 2017-12-06Bibliographically approved
4. Construction of Mesoporous Frameworks with Vanadoborate Clusters
Open this publication in new window or tab >>Construction of Mesoporous Frameworks with Vanadoborate Clusters
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2014 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 53, no 14, 3608-3611 p.Article in journal (Refereed) Published
Abstract [en]

A new porous vanadoborate was synthesized by employing the scale chemistry theory with the vanadoborate cluster V10B28. The twofold interpenetrated lvt network was assembled with zinc-containing elliptical vanadoborate clusters and Zn polyhedra. The single lvt framework contains a three-dimensional 38x38x20 ring channel system with the pore size (24.7x12.7 angstrom) reaching the mesoscale, thus indicating the possibility of constructing 3D ordered mesopores with vanadoborate clusters. The porosity of the SUT-7 structure was confirmed by CO2 adsorption of the as-synthesized materials.

Keyword
3D frameworks, cluster compounds, CO2 adsorption, mesoporous materials, vanadoborates
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-105231 (URN)10.1002/anie.201311122 (DOI)000333447500004 ()
Funder
Swedish Research CouncilVinnova
Note

AuthorCount:6;

Available from: 2014-07-02 Created: 2014-06-24 Last updated: 2017-12-05Bibliographically approved
5. Layered V-B-O Polyoxometalate Nets Linked by Diethylenetriamine Complexes with Dangling Amine Groups
Open this publication in new window or tab >>Layered V-B-O Polyoxometalate Nets Linked by Diethylenetriamine Complexes with Dangling Amine Groups
2014 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 43, no 41, 15283-15286 p.Article in journal (Refereed) Published
Abstract [en]

Two layered V-B-O contained polyoxometalate (POM) net structures, denoted as SUT-12 and SUT-13, are reported here. SUT-12 was synthesized by the boric acid flux method, and it represents the first 2D structure constructed from the V6B20 vanadoborate cluster. SUT-13 was synthesized through the hydrothermal method and constructed from V12B6P12 vanadium borophosphate clusters. In both structures, the vanadoborate or vanadium borophosphate clusters were linked through in-situ formed Zn(DETA)2 or Cu(DETA)2 complexes. Surprisingly, for all DETA molecules in the two metal complexes, there is one dangling amine group when it coordinated to the metal. The phenomena of the dangling amine group feature is abnormal and the Cu(DETA)2 complexes in SUT-13 was taken as an example and studied by density function theory (DFT) calculation in order to understand this unusual feature.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-106861 (URN)10.1039/C4DT01533A (DOI)000342757600003 ()
Available from: 2014-08-25 Created: 2014-08-25 Last updated: 2017-12-05Bibliographically approved
6. Construction of 3D Porous Polyoxometalate Frameworks Through Covalently Bonded Linkages
Open this publication in new window or tab >>Construction of 3D Porous Polyoxometalate Frameworks Through Covalently Bonded Linkages
(English)Manuscript (preprint) (Other (popular science, discussion, etc.))
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-106860 (URN)
Available from: 2014-08-25 Created: 2014-08-25 Last updated: 2014-08-25Bibliographically approved
7. PKU-3: An Effective Heterogeneous Catalyst for Strecker Reaction
Open this publication in new window or tab >>PKU-3: An Effective Heterogeneous Catalyst for Strecker Reaction
(English)Manuscript (preprint) (Other (popular science, discussion, etc.))
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-106859 (URN)
Available from: 2014-08-25 Created: 2014-08-25 Last updated: 2014-08-25Bibliographically approved
8. A Germanosilicate Structure with 11 x 11 x 12-Ring Channels Solved by Electron Crystallography
Open this publication in new window or tab >>A Germanosilicate Structure with 11 x 11 x 12-Ring Channels Solved by Electron Crystallography
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2014 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 53, no 23, 5868-5871 p.Article in journal (Refereed) Published
Abstract [en]

Zeolites have been widely used in industry owing to their ordered micropores and stable frameworks. The pore sizes and shapes are the key parameters that affect the selectivity and efficiency in their applications in catalysis, sorption, and separation. Zeolites with pores defined by 10 and 12 TO4 tetrahedra are often used for various catalytic processes. To optimize the performance of zeolites, it is extremely desirable to fine-tune the pore sizes/shapes. The first germanosilicate zeolite with a three-dimensional 11 x 11 x 12-ring channel system, PKU-16 (PKU, Peking University) is presented. Nanosized PKU-16 was structurally characterized by the new three-dimensional rotation electron diffraction (RED) technique. PKU-16 is structurally related to the zeolite beta polymorph C (BEC, 12 x 12 x 12-ring channels) by rotating half of the four-rings in double mtw units.

Keyword
electron microscopy, porous materials, powder X-ray diffraction, structure elucidation, zeolites
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-106085 (URN)10.1002/anie.201309766 (DOI)000337094200022 ()
Note

AuthorCount:6;

Available from: 2014-07-28 Created: 2014-07-21 Last updated: 2017-12-05Bibliographically approved

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