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Series of Highly Stable Isoreticular Lanthanide Metal-Organic Frameworks with Expanding Pore Size and Tunable Luminescent Properties
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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2015 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 27, no 15, 5332-5339 p.Article 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.

Place, publisher, year, edition, pages
2015. Vol. 27, no 15, 5332-5339 p.
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-120686DOI: 10.1021/acs.chemmater.5b01711ISI: 000359499100022OAI: oai:DiVA.org:su-120686DiVA: diva2:855587
Funder
Swedish Research CouncilBerzelii Centre EXSELENTKnut and Alice Wallenberg FoundationVINNOVA
Available from: 2015-09-21 Created: 2015-09-15 Last updated: 2017-08-31Bibliographically approved
In thesis
1. Lanthanide Metal-Organic Frameworks and Hierarchical Porous Zeolitic Imidazolate Frameworks: Synthesis, Properties, and Applications
Open this publication in new window or tab >>Lanthanide Metal-Organic Frameworks and Hierarchical Porous Zeolitic Imidazolate Frameworks: Synthesis, Properties, and Applications
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
Keyword
Metal-organic frameworks, Zeolitic imidazolate frameworks, Lanthanide MOFs, Hierarchical porous ZIFs
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-146398 (URN)978-91-7649-972-6 (ISBN)978-91-7649-973-3 (ISBN)
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: 2017-10-24Bibliographically approved

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