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Open-Framework Germanates and Nickel Germanates: Synthesis and Characterization
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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 [en]
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: urn:nbn:se:su:diva-75495ISBN: 978-91-7447-489-3 (print)OAI: oai:DiVA.org:su-75495DiVA: diva2:516900
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At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Submitted.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
List of papers
1. Intergrown New Zeolite Beta Polymorphs with Interconnected 12-Ring Channels Solved by Combining Electron Crystallography and Single-Crystal X-ray Diffraction
Open this publication in new window or tab >>Intergrown New Zeolite Beta Polymorphs with Interconnected 12-Ring Channels Solved by Combining Electron Crystallography and Single-Crystal X-ray Diffraction
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2012 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 24, no 19, 3701-3706 p.Article in journal (Refereed) Published
Abstract [en]

Two new polymorphs of zeolite beta, denoted as SU-78A and SU-78B, were synthesized by employing dicyclohexylammonium hydroxides as organic structuredirecting agents. The structure was solved by combining transmission electron microscopy and single-crystal X-ray diffraction. SU-78 is an intergrowth of SU-78A and SU-78B and contains interconnected 12-ring channels in three directions. The two polymorphs are built from the same building layer, similar to that for the zeolite beta family. The layer stacking in SU-78, however, is different from those in zeolite beta polymorph A, B, and C, showing new zeolite framework topologies. SU-78 is thermally stable up to 600°C.

Keyword
porous material, zeolite, zeolite beta, intergrowth, polymorph, crystal structure determination, transmission electron microscopy, electron crystallography
National Category
Inorganic Chemistry Organic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-80854 (URN)10.1021/cm301654d (DOI)000309505100005 ()
Funder
Swedish Research Council
Available from: 2012-10-01 Created: 2012-09-30 Last updated: 2017-12-07Bibliographically approved
2. 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
3. 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
4. Two Open-Framework Germanates with Nickel Complexes Incorporated into the Framework
Open this publication in new window or tab >>Two Open-Framework Germanates with Nickel Complexes Incorporated into the Framework
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2011 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 50, no 20, 9921-9923 p.Article in journal (Refereed) Published
Abstract [en]

Two open-framework germanates, SUT-1 and SUT-2, have been synthesized under hydrothermal conditions using ethylenecliamine (en, H(2)NCH(2)CH(2)NH(2)) as templates and Ni(NO(3))(2)center dot 6H(2)O as the transition-metal source. Their frameworks are built with Gel() clusters and [Ni(en)(2)](2+) complexes. In both structures, Gel clusters form square nets in the a-c plane, while the [Ni(en)2]2+ complexes bridge the square nets via Ni-O-Ge bonds to form 3D networks. They present the first examples to incorporate Ni(2+) complexes into the germanate frameworks. In SUT-2, additional linkages by Ge(2)O(7) clusters between the square nets generate a new type of topology.

National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-69907 (URN)10.1021/ic2013478 (DOI)000295602500019 ()
Funder
Swedish Research Council
Note
7Available from: 2012-01-18 Created: 2012-01-15 Last updated: 2017-12-08Bibliographically approved
5. Synthesis and characterization of two new nickel germanates: SUT-3 and SUT-4
Open this publication in new window or tab >>Synthesis and characterization of two new nickel germanates: SUT-3 and SUT-4
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(English)Manuscript (preprint) (Other academic)
National Category
Inorganic Chemistry
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-75982 (URN)
Available from: 2012-05-08 Created: 2012-05-07 Last updated: 2012-05-08Bibliographically approved

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