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Metal-Organic Frameworks (MOFs) for Heterogeneous Catalysis: 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]

Metal-organic frameworks (MOFs) are crystalline hybrid materials with interesting chemical and physical properties. This thesis is focused on the synthesis and characterization of different MOFs and their use in heterogeneous catalysis.

Zeolitic imidazolate frameworks (ZIFs), including ZIF-4, ZIF -7 and ZIF -62, Ln(btc)(H2O) (Ln: Nd, Sm, Eu, Gd, Tb, Ho, Er and Yb), Ln2(bpydc)3(H2O)3, (Ln: Sm, Gd, Nd, Eu, Tb, Ho and Er), MOF-253-Ru and Zn(Co-salophen) MOFs were synthesized. Various characterization techniques were applied to study the properties of these MOFs. X-ray powder diffraction (XRPD), single crystal X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) were extensively used.

The effect of synthesis parameters, such as batch composition and temperature, on the formation and morphology of ZIF-7 and ZIF-62 was studied. Structural transformation and flexibility of two series of lanthanide-based MOFs, Ln(btc)(H2O) (Ln: Nd, Ho and Er) and Ln2(bpydc)3(H2O)3, (Ln: Sm and Gd) upon drying and heating were characterized. Relations between metal coordination, structure flexibility and thermal stability among the Sm2(bpydc)3(H2O)3, Nd(btc)(H2O) and MOF-253 were investigated.

Salophen- and phenanthroline-based organic linkers were designed, synthesized and characterized. Metal complexes were coordinated to these linkers to be used as catalytic sites within the MOFs.

Catalytic studies using two MOF materials, Ln(btc) and MOF-253-Ru, as heterogeneous catalysts in organic transformation reactions were performed. The heterogeneous nature and recyclability of these MOFs were investigated and described.

Place, publisher, year, edition, pages
Department of Materials and Environmental Chemistry (MMK), Stockholms University , 2012. , 119 p.
Keyword [en]
metal-organic frameworks, zeolitic imidazolate frameworks, functionalized linkers, structural transformation, heterogeneous catalysis
National Category
Chemical Sciences
Research subject
Structural Chemistry
Identifiers
URN: urn:nbn:se:su:diva-74431ISBN: 978-91-7447-451-0 (print)OAI: oai:DiVA.org:su-74431DiVA: diva2:509109
Public defence
2012-04-13, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of doctoral defence the following papers were unpublished and had a status as follows: Paper nr 4: Submitted; Paper nr 5: Submitted

Available from: 2012-03-22 Created: 2012-03-12 Last updated: 2013-08-14Bibliographically approved
List of papers
1. Crystal Formation and Size Control of Zeolitic Imidazolate Frameworks with Mixed Imidazolate Linkers
Open this publication in new window or tab >>Crystal Formation and Size Control of Zeolitic Imidazolate Frameworks with Mixed Imidazolate Linkers
2013 (English)In: Journal of porous materials, ISSN 1380-2224, E-ISSN 1573-4854, Vol. 20, no 1, 55-63 p.Article in journal (Refereed) Published
Abstract [en]

The effect of synthesis parameters, such as batch composition and synthesis temperature, on the formationand crystal size of zeolitic imidazolate frameworks(ZIFs) using mixed linkers, imidazole (Im) and benzimidazole(bIm), were studied by X-ray powder diffraction(XRPD) and scanning electron microscopy (SEM). ZIF-7and ZIF-62 were identified as the main phases and a phasediagram relating the batch composition and the finalproduct was constructed based on XRPD and SEM. Therange of batch composition giving rise to ZIF-7 and ZIF-62was identified from the phase diagram. Changes of crystalsize and morphology of ZIF-7 and ZIF-62 in terms of batchcomposition and synthesis temperature were studied bySEM and different trends were observed for the two ZIFs.Thermogravimetric analysis (TGA) and in situ XRPDshowed that ZIF-62 possesses a similar high thermal stabilityas ZIF-7.

Keyword
Zeolitic imidazolate framework, Metal-organic framework, Crystal engineering, Phase diagram, Crystal size and morphology control
National Category
Chemical Sciences
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-74386 (URN)10.1007/s10934-012-9574-1 (DOI)000312933400007 ()
Available from: 2012-03-09 Created: 2012-03-09 Last updated: 2017-12-07Bibliographically approved
2. A porous chiral lanthanide metal-organic framework with high thermal stability
Open this publication in new window or tab >>A porous chiral lanthanide metal-organic framework with high thermal stability
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2008 (English)In: Zeolites and related materials: Trends, targets and challenges: Proceedings of the 4th International FEZA Conference, Vol. 174, Part A / [ed] Antoine Gédéon, Pascale Massiani and Florence Babonneau, Amsterdam: Elsevier, 2008, 451-454 p.Conference paper, Published paper (Refereed)
Abstract [en]

A metal-organic framework Nd(BTC)(H2O)·DMF (1), which is isostructural with reported Dy(BTC)(H2O)·DMF [1], Tb(BTC)(H2O)1.5·(DMF) (MOF-76) [2] and Eu(BTC)(H2O)·1.5H2O [3], is synthesized. The compound 1 was characterized by SEM/EDS, TGA and in situ PXRD. The structure was determined by single crystal X-ray diffraction. Compound 1 crystallizes in a chiral space group P43, with a = 10.4278(4) and c = 14.2602(12) Å. The structure contains 1D chiral -Nd-O-C-O-Nd- chains linked by the phenyl groups of BTC ligands. The 3D framework contains circular channels along the [001] direction and is stable up to 400°C.

Place, publisher, year, edition, pages
Amsterdam: Elsevier, 2008
Series
Studies in surface science and catalysis, ISSN 0167-2991
Keyword
lanthanide metal-organic framework, chiral structure, porous material
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-15433 (URN)10.1016/S0167-2991(08)80238-8 (DOI)978-0-444-53297-8 (ISBN)
Conference
Paris, France, 2-6 September 2008
Available from: 2008-12-02 Created: 2008-12-02 Last updated: 2012-03-12Bibliographically approved
3. A family of highly stable lanthanide metal-organic frameworks: structural evolution and catalytic activity
Open this publication in new window or tab >>A family of highly stable lanthanide metal-organic frameworks: structural evolution and catalytic activity
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2010 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 22, no 11, 3316-3322 p.Article in journal (Refereed) Published
Abstract [en]

A family of homeotypic porous lanthanide metal−organic frameworks (MOFs), [Ln(btc)(H2O)]·guest (Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Ho (6), Er (7), and Yb (8); guest: DMF or H2O) was synthesized. The structures of the as-synthesized compounds are tetragonal and contain 1D channels with accessible lanthanide ions. In situ single crystal X-ray diffraction shows that 1 undergoes a single-crystal to polycrystalline to single-crystal transformation from room temperature to 180 °C. During the release of DMF and water molecules from the channels by evacuation and subsequent heating, the structures of 1 and 7 transformed from tetragonal to monoclinic, and then to tetragonal, while the structure of 8 remained tetragonal. The transformation between the monoclinic and the low temperature tetragonal phases is reversible. The Ln(btc) MOFs are stable to at least 480 °C and are among the most thermally stable MOFs. The Ln(btc) MOFs act as efficient Lewis acid catalysts for the cyanosilylation of aldehydes yielding cyanohydrins in high yields within short reaction times. 1 also catalyzes the cyanosilylation of less reactive substrates, such as ketones at room temperature. The Ln(btc) MOFs could be recycled and reused without loss of their crystallinity and activity.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-42172 (URN)10.1021/cm100503q (DOI)000278149300004 ()
Available from: 2010-08-18 Created: 2010-08-18 Last updated: 2017-12-12Bibliographically approved
4. A Family of Flexible Lanthanide Bipyridinedicarboxylate Metal-Organic Frameworks Showing Reversible Single-Crystal to Single-Crystal Transformations
Open this publication in new window or tab >>A Family of Flexible Lanthanide Bipyridinedicarboxylate Metal-Organic Frameworks Showing Reversible Single-Crystal to Single-Crystal Transformations
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2012 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 12, no 6, 3243-3249 p.Article in journal (Refereed) Published
Abstract [en]

A family of flexible lanthanide metal-organic frameworks, [Ln(2)(bpydc)(3)(H2O)(3)]center dot nDMF (denoted as SUMOF-6-Ln; Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er, H(2)bpydc =2,2'-bipyridine-5,5'-dicarboxylic acid), was synthesized and characterized. SUMOF-6-Ln has a monoclinic space group P2(1)/c. The three-dimensional framework contains chains of LnO(n) (n = 7-8) polyhedra connected through the bpydc linkers forming 1D rhombic channels along the c-axis. SUMOF-6-Ln showed reversible breathing phenomenon upon desorption/adsorption of the solvent, with up to 27% changes of the unit cell dimensions and 23% changes of the unit cell volume. Single crystal X-ray diffraction (XRD) revealed that the desolvation and resolvation of SUMOF-6-Ln occurred via single-crystal to single-crystal transformations. The thermal behavior of SUMOF-6-Sm was also examined. SUMOF-6-Eu and SUMOF-6-Tb showed solid-state luminescent properties.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-79892 (URN)10.1021/cg300379u (DOI)000304838000066 ()
Note

AuthorCount:5;

Available from: 2012-09-12 Created: 2012-09-11 Last updated: 2017-12-07Bibliographically approved
5. Ruthenium Complexation in an Aluminium Metal-Organic Framework and its Application in Alcohol Oxidation Catalysis
Open this publication in new window or tab >>Ruthenium Complexation in an Aluminium Metal-Organic Framework and its Application in Alcohol Oxidation Catalysis
Show others...
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 48, 15337-15344 p.Article, review/survey (Refereed) Published
Abstract [en]

A ruthenium trichloride complex has been loaded into an aluminium metalorganic framework (MOF), MOF-253, by post-synthetic modification to give MOF-253-Ru. MOF-253 contains open bipyridine sites that are available to bind with the ruthenium complex. MOF-253-Ru was characterised by elemental analysis, N2 sorption and X-ray powder diffraction. This is the first time that a Ru complex has been coordinated to a MOF through post-synthetic modification and used as a heterogeneous catalyst. MOF-253-Ru catalysed the oxidation of primary and secondary alcohols, including allylic alcohols, with PhI(OAc)2 as the oxidant under very mild reaction conditions (ambient temperature to 40 degrees C). High conversions (up to >99%) were achieved in short reaction times (13 h) by using low catalyst loadings (0.5 mol% Ru). In addition, high selectivities (>90%) for aldehydes were obtained at room temperature. MOF-253-Ru can be recycled up to six times with only a moderate decrease in substrate conversion.

Keyword
alcohol oxidation, heterogeneous catalysis, immobilization, metal-organic frameworks, ruthenium
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-84779 (URN)10.1002/chem.201200885 (DOI)000311306700019 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:7;

Available from: 2013-01-03 Created: 2013-01-02 Last updated: 2017-12-06Bibliographically approved

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