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Novel framework materials: organically templated silicogermanates and hybrid fluorotitanates
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Two types of novel framework materials, including six organically templated silicogermanates and five hybrid fluorotitanates, have been synthesized, and their structures have been determined by single crystal X-ray diffraction. Their structures and the interactions between the organic and inorganic species are discussed in some detail.

The frameworks of the six silicogermanates, SU-9, SU-10, SU-11, SU-12, SU-14 and SU-21, are built up from either tetrahedra exclusively, or from mixed polyhedra. SU-9, SU-10 and SU-11 consist only of tetrahedra, and SU-12, SU-14 and SU-21 are built up from mixed polyhedra. In all silicogermanates, Si and Ge share the tetrahedrally coordinated positions, and only Ge occupies the 5- and 6-coordinated positions.

The frameworks of SU-9, SU-10 and SU-11 belong to zeolite frameworks. SU-9 and SU-10 are built up from the same periodic building units (PBUs) that are formed by 4/4-4 units, and they adopt the known zeolite framework types AST and ASV, respectively. SU-11 is built up from 5-1 units and adopts the known zeolite framework type MFI. This is the first time that the frameworks of AST, ASV and MFI have been prepared in silicogermanate form.

The 3-D frameworks of SU-12 and SU-14 contain (Ge,Si)7 composite building units that form one-dimensional 24-ring channels along the c axis. Their structures contain intersecting channels. SU-12 contains 8-, 10- 12- and 24-ring channels; while SU-14 has 9-, 10-, 12- and 24-ring channels. SU-21 is a two-dimensional framework structure containing 10-ring channels. It is the first silicogermanate with the template covalently bonded to Ge.

All silicogermanates were synthesized by using organic amines as templates. The templates play a very important role in directing the structure of the inorganic framework.

The obtained five hybrid fluorotitanates are SUF-1, SUF-2, SUF-3, SUF-4 and SUF-5. Their hybrid frameworks are built up from fluorotitanate anions, N-containing cations and crystal water/oxonium cations. Zero-dimensional fluorotitanate clusters are normally obtained when cyclic organic amines such as 1,4-diazabicyclo[2,2,2]octane (DABCO) and piperazine are used. Increasing the pH value of the starting solutions led to more condensed fluorotitanate anions, from isolated octahedra to pairs and eventually chains of octahedra. The formation of the hybrid frameworks of fluorotitanates is strongly dependent on hydrogen bonds between the fluorotitanate anions, N-containing organic cations and water molecules/oxonium ions.

Place, publisher, year, edition, pages
Stockholm: Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi , 2005. , 88 p.
Keyword [en]
framework materials, silicogermanates, hybrid fluorotitananates
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-440ISBN: 91-7155-048-8 (print)OAI: oai:DiVA.org:su-440DiVA: diva2:193895
Public defence
2005-05-02, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00
Opponent
Supervisors
Available from: 2005-04-05 Created: 2005-04-05Bibliographically approved
List of papers
1. Synthesis and structures of new silicogermanates
Open this publication in new window or tab >>Synthesis and structures of new silicogermanates
2004 (English)In: Studies in Surface Science and Catalysis, ISSN 0167-2991, Vol. 154, no 1, 739-745 p.Article in journal (Refereed) Published
Abstract [en]

Three new micro-porous silicogermanates, (NH4)F[(Ge3.14Si6.86)O20] (SU-9), (NH4F[(Ge6.78Si3.22)O20] (SU-10) and [(Ge2.40Si9.60)O24] (SU-11) were synthesized under hydrothermal conditions with the presence of structure directing agents and the structures were solved by single crystal X-ray diffraction. SU-9 and SU-10 are built up by the double T4-rings (D4Rs) and they have the zeolite structure types of AST and ASV, respectively. SU-11 is built up by the T12-units and has the zeolite structure type of MFI. In three compounds, both silicon and germanium atoms are tetrahedrally coordinated with oxygen atoms and share the same tetrahedral sites.

Place, publisher, year, edition, pages
Elsevier B.V., 2004
Keyword
silicogermanate; AST; ASV; MFI; hydrothermal synthesis
National Category
Environmental Sciences
Identifiers
urn:nbn:se:su:diva-23658 (URN)10.1016/S0167-2991(04)80878-4 (DOI)
Note
Part of urn:nbn:se:su:diva-440Available from: 2005-04-05 Created: 2005-04-05 Last updated: 2011-01-31Bibliographically approved
2. SU-12: a silicon-substituted ASU- 16 with circular 24-rings and templated by a monoamine
Open this publication in new window or tab >>SU-12: a silicon-substituted ASU- 16 with circular 24-rings and templated by a monoamine
2005 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 17, no 10, 2530-2536 p.Article in journal (Refereed) Published
Abstract [en]

A new silicogermanate, SU-12, |(CH3CH2CH2NH3)3(H2O)2.5|[(Ge6.44Si0.56)O14.5F2], with 24-ring channel systems was synthesized under hydro/solvothermal conditions, and its structure was determined by single-crystal X-ray diffraction. It is the first silicogermanate with extra-large 24-rings templated by a primary monoamine. Crystallographic data: tetragonal, space group I2m, unit cell parameters a = 27.6460(22) Å and c = 17.0885(14) Å, V = 13060.8(17) Å3, Z = 16, ρcalcd = 1.797 g/cm3, R1 = 0.0512 [5471 observed reflections with I > 2σ(I)], wR2 = 0.1487, S (goodness-of-fit on F2) = 1.08. SU-12 has a structure topology similar to that of the pure germanate ASU-16. However, the symmetry of SU-12 is higher than that of ASU-16, and the 24-rings become more circular than those in ASU-16. The interaction between the templates and framework is compared for ASU-16 and SU-12, and their thermal stabilities are studied. The orthorhombic ASU-16 is thermally less stable than the tetragonal SU-12 and transformed to SU-12 by heating. The ion-exchange property of SU-12 is also studied.

Place, publisher, year, edition, pages
American Chemical Society, 2005
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-23659 (URN)10.1021/cm049373f (DOI)
Note
Part of urn:nbn:se:su:diva-440Available from: 2005-04-05 Created: 2005-04-05 Last updated: 2011-01-31Bibliographically approved
3. SU-14, a novel silicogermanate with 24-ring channels
Open this publication in new window or tab >>SU-14, a novel silicogermanate with 24-ring channels
Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-23660 (URN)
Note
Part of urn:nbn:se:su:diva-440Available from: 2005-04-05 Created: 2005-04-05 Last updated: 2010-01-13Bibliographically approved
4. SU-21, a novel open-framework silicogermanate with covalently coordinated organic amines
Open this publication in new window or tab >>SU-21, a novel open-framework silicogermanate with covalently coordinated organic amines
Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-23661 (URN)
Note
Part of urn:nbn:se:su:diva-440Available from: 2005-04-05 Created: 2005-04-05 Last updated: 2010-01-13Bibliographically approved
5. Crystal structure of 1,4-diazabicyclo[2,2,2]octane hexafluorotitanium hydrate, (C6H14N2)[TiF6]·H2O
Open this publication in new window or tab >>Crystal structure of 1,4-diazabicyclo[2,2,2]octane hexafluorotitanium hydrate, (C6H14N2)[TiF6]·H2O
2000 In: Z. Kristallogr, Vol. NCS215, 607-608 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23662 (URN)
Note
Part of urn:nbn:se:su:diva-440Available from: 2005-04-05 Created: 2005-04-05Bibliographically approved
6. Crystal structure of piperazine bis(aquapentafluorotitanate), (C4H12N2)[TiF5(H2O)]2
Open this publication in new window or tab >>Crystal structure of piperazine bis(aquapentafluorotitanate), (C4H12N2)[TiF5(H2O)]2
2001 In: Z. Kristallogr, Vol. NCS 216, 259-260 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23663 (URN)
Note
Part of urn:nbn:se:su:diva-440Available from: 2005-04-05 Created: 2005-04-05Bibliographically approved
7. Crystal structure of dipiperazine decafluorooxodititanate dihydrate, (C4H12N2)2[Ti2F10O)]·2H2O
Open this publication in new window or tab >>Crystal structure of dipiperazine decafluorooxodititanate dihydrate, (C4H12N2)2[Ti2F10O)]·2H2O
2001 In: Z. Kristallogr, Vol. NCS216, 141-142 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23664 (URN)
Note
Part of urn:nbn:se:su:diva-440Available from: 2005-04-05 Created: 2005-04-05Bibliographically approved
8. Crystal structure of dipiperazine decafluorodititanate dihydrate, (C4H11N2)2[Ti2F10]·2H2O
Open this publication in new window or tab >>Crystal structure of dipiperazine decafluorodititanate dihydrate, (C4H11N2)2[Ti2F10]·2H2O
2000 In: Z. Kristallogr, Vol. NCS215, 605-606 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23665 (URN)
Note
Part of urn:nbn:se:su:diva-440Available from: 2005-04-05 Created: 2005-04-05Bibliographically approved
9. Crystal structure of 1,4-diaminobutane tetrafluorooxotitanate, (C4H14N2)[TiF4O]
Open this publication in new window or tab >>Crystal structure of 1,4-diaminobutane tetrafluorooxotitanate, (C4H14N2)[TiF4O]
2001 In: Z. Kristallogr, Vol. NCS216, 257-258 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23666 (URN)
Note
Part of urn:nbn:se:su:diva-440Available from: 2005-04-05 Created: 2005-04-05Bibliographically approved

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