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Lanthanide Metal-Organic Frameworks and Hierarchical Porous Zeolitic Imidazolate Frameworks: Synthesis, Properties, and Applications
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0002-3106-8302
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis presents the synthesis, properties, and applications of two important classes of metal-organic frameworks (MOFs); lanthanide MOFs and hierarchical porous zeolitic imidazolate frameworks (ZIFs). The materials have been characterized using a wide range of techniques including diffraction, imaging, various spectroscopic techniques, gas sorption, dynamical light scattering (DLS) and thermogravimetric analysis (TGA).

In Chapter 1, the unique features of MOFs and ZIFs as well as their potential applications are summarized. In Chapter 2, different characterization techniques are presented.

Chapter 3 describes a family of new isoreticular lanthanide MOFs synthesized using tri-topic linkers of different sizes, H3L1-H3L4, denoted SUMOF-7I-IV (Ln) (SU; Stockholm University, Ln = La, Ce, Pr, Nd, Sm, Eu and Gd, Paper I). The SUMOF-7I-III (Ln) contain permanent pores and exhibit exceptionally high thermal and chemical stability. The luminescence properties of SUMOF-7IIs are reported (Paper II). The influences of Ln ions and the tri-topic linkers as well as solvent molecules on the luminescence properties are investigated. Furthermore, the potential of SUMOF-7II (La) for selective sensing of Fe (III) ions and the amino acid tryptophan is demonstrated (Paper III). 

Chapter 4 presents a simple, fast and scalable approach for the synthesis of hierarchical porous zeolitic imidazolate framework ZIF-8 and ZIF-67 using triethylamine (TEA)-assisted approach (Paper IV). Organic dye molecules and proteins are encapsulated directly into the ZIFs using the one-pot method. The photophysical properties of the dyes are improved through the encapsulation into ZIF-8 nanoparticles (Paper IV). The porosity and surface area of the ZIF materials can be tuned using the different amounts of dye or TEA. To further simplify the synthesis of hierarchical porous ZIF-8, a template-free approach is presented using sodium hydroxide, which at low concentrations induces the formation of zinc hydroxide nitrate nanosheets that serve as in situ sacrificial templates (Chapter 5, Paper V). A 2D leaf-like ZIF (ZIF-L) is also obtained using the method. The hierarchical porous ZIF-8 and ZIF-L show good performance for CO2 sorption.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University , 2017.
Keywords [en]
Metal-organic frameworks, Zeolitic imidazolate frameworks, Lanthanide MOFs, Hierarchical porous ZIFs
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-146398ISBN: 978-91-7649-972-6 (print)ISBN: 978-91-7649-973-3 (electronic)OAI: oai:DiVA.org:su-146398DiVA, id: diva2:1137293
Public defence
2017-10-12, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (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: 2017-09-18 Created: 2017-08-30 Last updated: 2019-12-09Bibliographically approved
List of papers
1. Series of Highly Stable Isoreticular Lanthanide Metal-Organic Frameworks with Expanding Pore Size and Tunable Luminescent Properties
Open this publication in new window or tab >>Series of Highly Stable Isoreticular Lanthanide Metal-Organic Frameworks with Expanding Pore Size and Tunable Luminescent Properties
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2015 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 27, no 15, p. 5332-5339Article in journal (Refereed) Published
Abstract [en]

A series of highly porous isoreticular lanthanide-based metal organic frameworks (LnMOFs) denoted as SUMOE-7I to SUMOE-7IV (SU = Stockholm University; Ln = La, Ce, Pr, Nd, Sm, Eu, and Gd) have been synthesized using tritopic carboxylates as the organic linkers. The SUMOF-7 materials display one-dimensional pseudohexagonal channels with the pore diameter gradually enlarged from 8.4 to 23.9 angstrom, as a result of increasing sizes of the organic linkers. The structures have been solved by single crystal X-ray diffraction or rotation electron diffraction (RED) combined with powder X-ray diffraction (PXRD). The SUMOF-7 materials exhibit robust architectures with permanent porosity. More importantly, they exhibit exceptionally high thermal and chemical stability. We show that, by inclusion of organic dye molecules, the luminescence properties of the MOFs can be elaborated and modulated, leading to promising applications in sensing and optics.

National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-120686 (URN)10.1021/acs.chemmater.5b01711 (DOI)000359499100022 ()
Funder
Swedish Research CouncilBerzelii Centre EXSELENTKnut and Alice Wallenberg FoundationVINNOVA
Available from: 2015-09-21 Created: 2015-09-15 Last updated: 2019-12-12Bibliographically approved
2. Luminescence Properties for a Family of Highly Stable Lanthanide Metal-Organic Frameworks
Open this publication in new window or tab >>Luminescence Properties for a Family of Highly Stable Lanthanide Metal-Organic Frameworks
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(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-146347 (URN)
Available from: 2017-08-29 Created: 2017-08-29 Last updated: 2019-12-12Bibliographically approved
3. A water-stable lanthanide metal-organic framework for fluorimetric detection of ferric ions and tryptophan
Open this publication in new window or tab >>A water-stable lanthanide metal-organic framework for fluorimetric detection of ferric ions and tryptophan
2017 (English)In: Microchimica Acta, ISSN 0026-3672, E-ISSN 1436-5073, Vol. 184, no 9, p. 3363-3371Article in journal (Refereed) Published
Abstract [en]

The preparation of a highly water stable and porous lanthanide metal-organic framework (MOF) nanoparticles (denoted SUMOF-7II; SU refers to Stockholm University) is described. SUMOF-7II was synthesized starting from the tritopic linker of 2,4,6-tri-p-carboxyphenyl pyridine (H3L2) and La(III) as metal clusters. SUMOF-7II forms a stable dispersion and displays high fluorescence emission with small variation over the pH range of 6 to 12. Its fluorescence is selectively quenched by Fe(III) ions compared to other metal ions. The intensity of the fluorescene emission drops drops linearly in 16.6–167 μM Fe(III) concentration range, and Stern-Volmer plots are linear. The limit of detection (LOD) is 16.6 μM (at an S/N ratio of >3). This indicator probe can also be used for selective detection of tryptophan among several amino acids. Compared to the free linker H3L2, SUMOF-7II offers improved sensitivity and selectivity of the investigated species.

Keywords
Lanthanum-organic frameworks, Luminescence, Metal ions detection, Amino acids, Sensing
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-146333 (URN)10.1007/s00604-017-2306-0 (DOI)000407371700036 ()
Available from: 2017-08-29 Created: 2017-08-29 Last updated: 2019-12-12Bibliographically approved
4. A Fast and Scalable Approach for Synthesis of Hierarchical Porous Zeolitic Imidazolate Frameworks and One-Pot Encapsulation of Target Molecules
Open this publication in new window or tab >>A Fast and Scalable Approach for Synthesis of Hierarchical Porous Zeolitic Imidazolate Frameworks and One-Pot Encapsulation of Target Molecules
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2017 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 56, no 15, p. 9139-9146Article in journal (Refereed) Published
Abstract [en]

A trimethylamine (TEA)-assisted synthesis approach that combines the preparation of hierarchical porous zeolitic imidazolate framework ZIF-8 nanoparticles and one-pot encapsulation of target molecules is presented. Two dye molecules, rhodamine B (RhB) and methylene blue (MB), and one protein (bovine serum albumin, BSA) were tested as the target molecules. The addition of TEA into the solution of zinc nitrate promoted the formation of ZnO nanocrystals, which rapidly transformed to ZIF-8 nanoparticles after the addition of the linker 2-methylimidazole (Hmim). Hierarchical porous dye@ZIF-8 nanoparticles with high crystallinity, large BET surface areas (1300–2500 m2/g), and large pore volumes (0.5–1.0 cm3/g) could be synthesized. The synthesis procedure was fast (down to 2 min) and scalable. The Hmim/Zn ratio could be greatly reduced (down to 2:1) compared to previously reported ones. The surface areas, and the mesopore size, structure, and density could be modified by changing the TEA or dye concentrations, or by postsynthetic treatment using reflux in methanol. This synthesis and one-pot encapsulation approach is simple and can be readily scaled up. The photophysical properties such as lifetime and photostability of the dyes could be tuned via encapsulation. The lifetimes of the encapsulated dyes were increased by 3–27-fold for RhB@ZIF-8 and by 20-fold for MB@ZIF-8, compared to those of the corresponding free dyes. The synthesis approach is general, which was successfully applied for encapsulation of protein BSA. It could also be extended for the synthesis of hierarchical porous cobalt-based ZIF (dye@ZIF-67).

National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-146302 (URN)10.1021/acs.inorgchem.7b01191 (DOI)000407405500060 ()
Available from: 2017-08-29 Created: 2017-08-29 Last updated: 2019-12-09Bibliographically approved
5. Template-Free Synthesis of Hierarchical Porous Zeolitic Imidazole Frameworks Nanoparticles and their CO2 Sorption
Open this publication in new window or tab >>Template-Free Synthesis of Hierarchical Porous Zeolitic Imidazole Frameworks Nanoparticles and their CO2 Sorption
(English)Manuscript (preprint) (Other academic)
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-146348 (URN)
Available from: 2017-08-29 Created: 2017-08-29 Last updated: 2019-12-09Bibliographically approved

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