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Development of Metal–Organic Frameworks for Catalysis: Designing Functional and Porous Crystals
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). (Xiaodong Zou)
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 [en]
Metal–organic frameworks, heterogeneous catalysis, nanoparticles, metallolinkers, postsynthetic modification, postsynthetic exchange
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-115819ISBN: 978-91-7649-166-9 (print)OAI: oai:DiVA.org:su-115819DiVA: diva2:800156
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
List of papers
1. Framework Isomerism in Vanadium Metal-Organic Frameworks: MIL-88B(V) and MIL-101(V)
Open this publication in new window or tab >>Framework Isomerism in Vanadium Metal-Organic Frameworks: MIL-88B(V) and MIL-101(V)
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2013 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 13, no 11, 5036-5044 p.Article in journal (Refereed) Published
Abstract [en]

Two families of metal organic frameworks (MOFs), MIL-88 and MIL-101 built by trinuclear transition metal (TM) clusters (TM = Cr, Fe, or Sc), have been known for several years, but their syntheses are often reported separately. In fact, these MOFs are polymorphs, or framework isomers: they are assembled from the same metal secondary building units and organic linkers, but the connectivity of these components differs. Here we report for the first time the synthesis of the vanadium MOF MIL-88B(V) and compare its synthesis parameters to those of MIL-47(V) and the recently reported MIL-101(V). The properties of MIL-88B(V) and MIL-101(V) are remarkably different. MIL-88B(V) can breathe and is responsive to different solvents, while MIL-101(V) is rigid and contains mesoporous cages. MIL-101(V) exhibits the highest specific surface area among vanadium MOFs discovered so far. In addition, both MIL-88B(V) and MIL-101(V) transform to MIL-47 at higher temperatures. We have also identified the key synthesis parameters that control the formation of MIL-88B(V), MIL-101(V), and MIL-47: temperature, time, and pH. This relates to the rate of reaction between the metal and linkers, which has been monitored by ex situ X-ray powder diffraction and V K-edge X-ray absorption spectroscopy during MOF synthesis. It is therefore important to fully study the synthesis conditions to improve our understanding of framework isomerism in MOFs.

National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-97390 (URN)10.1021/cg4012058 (DOI)000326775000050 ()
Funder
Swedish Research CouncilVINNOVAKnut and Alice Wallenberg Foundation
Note

AuthorCount:7;

Available from: 2013-12-11 Created: 2013-12-09 Last updated: 2017-12-06Bibliographically approved
2. Influence of the Base on Pd@MIL-101-NH2(Cr) as Catalyst for the Suzuki-Miyaura Cross-Coupling Reaction
Open this publication in new window or tab >>Influence of the Base on Pd@MIL-101-NH2(Cr) as Catalyst for the Suzuki-Miyaura Cross-Coupling Reaction
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2015 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 21, no 30, 10896-10902 p.Article in journal (Refereed) Published
Abstract [en]

The chemical stability of metal-organic frameworks (MOFs) is a major factor preventing their use in industrial processes. Herein, it is shown that judicious choice of the base for the Suzuki-Miyaura cross-coupling reaction can avoid decomposition of the MOF catalyst Pd@MIL-101-NH2(Cr). Four bases were compared for the reaction: K2CO3, KF, Cs2CO3 and CsF. The carbonates were the most active and achieved excellent yields in shorter reaction times than the fluorides. However, powder XRD and N-2 sorption measurements showed that the MOF catalyst was degraded when carbonates were used but remained crystalline and porous with the fluorides. XANES measurements revealed that the trimeric chromium cluster of Pd@MIL-101-NH2(Cr) is still present in the degraded MOF. In addition, the different countercations of the base significantly affected the catalytic activity of the material. TEM revealed that after several catalytic runs many of the Pd nanoparticles (NPs) had migrated to the external surface of the MOF particles and formed larger aggregates. The Pd NPs were larger after catalysis with caesium bases compared to potassium bases.

Keyword
cross-coupling, heterogeneous catalysis, metal-organic frameworks, nanoparticles, palladium
National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-119544 (URN)10.1002/chem.201500843 (DOI)000357984900039 ()
Funder
Swedish Research CouncilVINNOVAKnut and Alice Wallenberg Foundation
Available from: 2015-08-20 Created: 2015-08-17 Last updated: 2017-12-04Bibliographically approved
3. Double-Supported Silica-Metal-Organic Framework Palladium Nanocatalyst for the Aerobic Oxidation of Alcohols under Batch and Continuous Flow Regimes
Open this publication in new window or tab >>Double-Supported Silica-Metal-Organic Framework Palladium Nanocatalyst for the Aerobic Oxidation of Alcohols under Batch and Continuous Flow Regimes
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2015 (English)In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 5, no 2, 472-479 p.Article in journal (Refereed) Published
Abstract [en]

Stable and easily synthesized metal-organic framework MIL-88B-NH2 represents an attractive support for catalysts employed in oxidation reactions, which are typically performed under relatively harsh conditions. However, MIL-88B-NH2, the thermodynamic polymorph of the more popular MIL-101-NH2, has been rarely employed in catalytic applications because of a difficult impregnation process caused by the flexible nature of the framework. We report herein a new catalyst denoted Pd@MIL-88B-NH2 (8 wt % Pd), the first example of metallic nanoparticles successfully impregnated in the pores of MIL-88B-NH2. Furthermore, by enclosing the MOF crystals in a tailored protective coating of SiO2 nanoparticles, an even more enduring material was developed and applied to the aerobic oxidation of benzylic alcohols. This doubly supported catalyst Pd@MIL-88B-NH2@nano-SiO2 displayed high activity and excellent performance in terms of endurance and leaching control. Under batch conditions, a very convenient and efficient recycling protocol is illustrated, using a teabag approach. Under continuous flow, the catalyst was capable of withstanding 7 days of continuous operation at 110 degrees C without deactivation. During this time, no leaching of metallic species was observed, and the material maintained its structural integrity.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015
Keyword
palladium nanoparticles, MIL-88B-NH2, aerobic oxidation, teabag catalysis, flow chemistry
National Category
Chemical Sciences
Research subject
Inorganic Chemistry; Organic Chemistry
Identifiers
urn:nbn:se:su:diva-115697 (URN)10.1021/cs501573c (DOI)000349275300001 ()
Funder
VINNOVASwedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:10;

Available from: 2015-03-30 Created: 2015-03-27 Last updated: 2017-08-23Bibliographically approved
4. 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
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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.

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
5. Introduction of an N-heterocyclic Carbene Iridium Complex into a Zirconium Metal–Organic Framework for Catalysis
Open this publication in new window or tab >>Introduction of an N-heterocyclic Carbene Iridium Complex into a Zirconium Metal–Organic Framework for Catalysis
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(English)Manuscript (preprint) (Other academic)
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-115907 (URN)
Available from: 2015-04-08 Created: 2015-04-08 Last updated: 2016-01-29Bibliographically approved

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