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Ruthenium Complexation in an Aluminium Metal-Organic Framework and its Application in Alcohol Oxidation Catalysis
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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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.

Place, publisher, year, edition, pages
2012. Vol. 18, no 48, 15337-15344 p.
Keyword [en]
alcohol oxidation, heterogeneous catalysis, immobilization, metal-organic frameworks, ruthenium
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-84779DOI: 10.1002/chem.201200885ISI: 000311306700019OAI: oai:DiVA.org:su-84779DiVA: diva2:581977
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
In thesis
1. Metal-Organic Frameworks (MOFs) for Heterogeneous Catalysis: Synthesis and Characterization
Open this publication in new window or tab >>Metal-Organic Frameworks (MOFs) for Heterogeneous Catalysis: Synthesis and Characterization
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
metal-organic frameworks, zeolitic imidazolate frameworks, functionalized linkers, structural transformation, heterogeneous catalysis
National Category
Chemical Sciences
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-74431 (URN)978-91-7447-451-0 (ISBN)
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
2. Development of Metal–Organic Frameworks for Catalysis: Designing Functional and Porous Crystals
Open this publication in new window or tab >>Development of Metal–Organic Frameworks for Catalysis: Designing Functional and Porous Crystals
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Metal–organic frameworks, or MOFs, have emerged as a new class of porous materials made by linking metal and organic units. The easy preparation, structural and functional tunability, ultrahigh porosity, and enormous surface areas of MOFs have led to them becoming one of the fastest growing fields in chemistry. MOFs have potential applications in numerous areas such as clean energy, adsorption and separation processes, biomedicine, and sensing. One of the most promising areas of research with MOFs is heterogeneous catalysis.

This thesis describes the design and synthesis of new, carboxylate-based MOFs for use as catalysts. These materials have been characterized using diffraction, spectroscopy, adsorption, and imaging techniques. The thesis has focused on preparing highly-stable MOFs for catalysis, using post-synthetic methods to modify the properties of these crystals, and applying a combination of characterization techniques to probe these complex materials.

In the first part of this thesis, several new vanadium MOFs have been presented. The synthesis of MIL-88B(V), MIL-101(V), and MIL-47 were studied using ex situ techniques to gain insight into the synthesis–structure relationships. The properties of these materials have also been studied.

In the second part, the use of MOFs as supports for metallic nanoparticles has been investigated. These materials, Pd@MIL-101–NH2(Cr) and Pd@MIL-88B–NH2(Cr), were used as catalysts for Suzuki–Miyaura and oxidation reactions, respectively. The effect of the base on the catalytic activity, crystallinity, porosity, and palladium distribution of Pd@MIL-101–NH2(Cr) was studied.

In the final part, the introduction of transition-metal complexes into MOFs through different synthesis routes has been described. A ruthenium complex was grafted onto an aluminium MOF, MOF-253, and an iridium metallolinker was introduced into a zirconium MOF, UiO-68–2CH3. These materials were used as catalysts for alcohol oxidation and allylic alcohol isomerization, respectively.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockkholm University, 2015. 144 p.
Keyword
Metal–organic frameworks, heterogeneous catalysis, nanoparticles, metallolinkers, postsynthetic modification, postsynthetic exchange
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-115819 (URN)978-91-7649-166-9 (ISBN)
External cooperation:
Public defence
2015-06-05, 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 2: Manuscript. Paper 5: Manuscript.

Available from: 2015-05-13 Created: 2015-04-01 Last updated: 2016-08-26Bibliographically approved

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