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TU Dresden » Fakultät Mathematik und Naturwissenschaften » Fachrichtung Chemie und Lebensmittelchemie » Metal-Organic Frameworks
Overview of granted projects - Part I

Nano-MOFs:

In situ monitoring and control of the crystallite growth of MOFs in colloidal solution and
at surfaces modified with SAMs employing step-by-step dosing of reactants

 

        Consortium:

        Professor Dr. Roland A. Fischer, Bochum
        Ruhr University of Bochum
        Department of Chemistry and Biochemistry
        Chair of Inorganic Chemistry II

        Professor Dr. Klaus Huber, Paderborn
        University of Paderborn
        Department of Natural Sciences
        Institute of Chemistry

        Professor Dr. Christof Wöll, Karlsruhe
        Karlsruhe Institute of Technology
        Institute of Functional Interfaces


        Project:

        Nano-MOFs: In situ monitoring and control of the crystallite growth of MOFs in colloidal solution and at surfaces modified with SAMs employing step-by-step dosing of reactants

        Abstract:

        A number of interesting potential applications of Metal Organic Frameworks (MOFs) including chemical sensing, smart membranes for gas separation and chromatography, drug release, catalysis, electrochemistry (fuel cells), solar energy harvesting etc. require a more detailed understanding and the precise control of the growth of nm-thickness MOF films at surfaces (“SURMOFs”) as well as in colloidal solution (“nano MOFs”). The project will investigate a novel type of MOF synthesis following a 2D layer-by-layer growth scheme at model surfaces which are deliberately modified by organic self assembled monolayers in order to direct the heterogeneous nucleation and the growth. In parallel, the 3D crystallite growth in colloidal solution initiated by homogeneous nucleation will be studied aiming at the control of the size and shape distribution by the effect of certain additives being present in the solvothermal mother solutions. Both areas of research have in common the (automatic, computer controlled) stepwise dosing of reactants and the time resolved in situ spectroscopic monitoring of the development of the MOF crystallites at the nano scale.

        Results:

         

        The project investigates fabrication of MOF thin films and multilayers by a stepwise liquid phase epitaxial 2D layer-by-layer growth scheme at model surfaces which are modified by organic self assembled monolayers in order to direct the growth orientation. In parallel, the 3D crystallite growth in solvothermal mother solutions is studied aiming at the control of the crystallite size and shape by the effect of additives.

         

        The goal of the proposal is the liquid phase epitaxial (LPE) growth of MOFs thin films (SURMOFs) for applications in selective adsorption and chromatography. Suitably chosen side groups at the organic linkers of the framework will affect the adsorption properties for guest molecules or analytes. Various kinds of heterostructures will be fabricated in which the functionality and substitution pattern at the linkers in combination with the LPE deposition sequence and orientation of the MOF crystallites are controlled (multivariate functionalized SURMOFs).

        Publications:

        Osama Shekhah, Hui Wang, Denise Zacher, Roland A. Fischer, and Christof Wöll
        "Growth Mechanism of Metal–Organic Frameworks: Insights into the Nucleation by Employing a Step-by-Step Route"
        Angew. Chem. Int. Ed. 2009, 48, 5038 –5041
         

         

        M. Darbandi, H. Arslan, H. Wang, O. Shekhah, A. Bashir, A. Birkner and C. Wöll
        "Fabrication of free-standing ultrathin films of porous metal-organic frameworks by liquid-phase epitaxy and subsequent delamination "
        As cover page in Physica Status Solidi, 2010, 4, 197-199.
         

         

        O. Zybaylo, O. Shekhah, H. Wang, M. Tafipolsky, R. Schmid, D. Johannsmann, C. Wöll
        "Novel method to measure diffusion coefficients in porous metal-organic frameworks"
        Physical Chemistry Chemical Physics, 2010, 12, 8092-8097
         

         

        O. Shekhah
        "Layer-by-layer method for the synthesis and growth of surface mounted metal organic frame works (SURMOFs)."
        Special Issue "Inorganic-Organic Hybrid Materials", Materials, 2010, 3, 1302-1315.
         

         

        R. Heck, O. Shekhah, P. Weidler, F. Friedrich, C. Wöll
        "Loading of two related MOFs, Cu(bdc)(dabco)1/2 and Cu(ndc)(dabco)1/2, with Ferrocene"
        Microporous and Mesoporous Materials, 2010, submitted
         

         

        O. Shekhah , J. Liu, R. Fischer C. Wöll
        "MOF thin films: existing and future applications "
        Chemical Society Reviews, 2010, In press, DOI: 10.1039/c0cs00147c
         

         

        O. Shekhah, K. Hirai, H. Wang, H. Uehara, M. Kondo,S. Diring,D. Zacher,R. Fischer,O. Sakata, S. Kitagawa, S. Furukawa, C. Wöll
        "MOF-on-MOF Heteroepitaxy: Highly oriented [Zn2(ndc)2(dabco)]ngrown on [Cu2(ndc)2(dabco)]nthin films"
        Dalton Transcations, 2011, submitted
         

         

        K. Yusenko, M. Meililkhov,D. Zacher,F. Wieland, C. Sternemann, X. Stammer, T. Ladnorg, C. Wöll,R. Fischer
        "Step-by-Step growth of highly oriented and continuous seeding layers of [Cu2(ndc)2(dabco)] on bare oxide and nitride substrate"
        Crystal Engineering Communications, 2010, 12, 2086-2090
         

         

        D. Zacher, O. Shekhah, C. Wöll, R. A. Fischer
        "Thin films of metal-organic frameworks"
        Chem. Soc. Rev. 2009, 38, 1418-1429.
         

         

        R. A. Fischer, C. Wöll
        "Layer-by-Layer Liquid-Phase Epitaxy of Crystalline Coordination Polymers at Surfaces"
        Angew. Chem.-Int. Edit. 2009, 48, 6205-6208
         

         

        J. Cravillon ,S. Münzer, S.-J. Lohmeyer, A. Feldhoff, K. Huber, M. Wiebcke
        "Rapid Room-Temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework"
        Chemistry of Materials (2009) 21, 1410-1412
         

         

        D. Zacher, J. Liu, K. Huber, R. A. Fischer
        "Nanocrystals of [Cu3(btc)2](HKUST-1]: A combined time-resolved light scattering and scanning electron microscopy study"
        Chemical Communications (2009), 1031-1033
         

         

        A. Betard, D. Zacher, R. A. Fischer
        "Dense and homogeneous coatings of porous CO2 adsorbents: the CPO-27-M family"
        Cryst. Eng. Commun. 2010, 12, 3768-3772 (featured as hot article)
         

         

        M. Meilikhov, K. Yusenko, A. Torrisi, B. Jee, C. Mellot-Draznieks, A. Pöppl, R. A. Fischer
        "Reduction of a Metal Organic Framework by an Organometallic Complex: Magnetic Properties and Structure of the Inclusion Compound [(h5-C5H5)2Co]0.5@MIL-47(V)"
        Angew. Chem.-Int. Edit. 2010, 49, 6212-6215
         

         

        O. Shekhah, H. Wang, M. Paradinas, C. Ocal, B. Schupbach, A. Terfort, D. Zacher, R. A. Fischer, C. Wöll
        "Controlling interpenetration in metal-organic frameworks by liquid-phase epitaxy"
        Nature Materials 2009, 8, 481-484.
         

         

        D. Zacher, R. Schmid, C. Wöll, R. A. Fischer
        "Surface Chemistry of Metal-Organic Frameworks at the Liquid/Solid Interface: A Perspective"
        Angew. Chem.-Int. Edit. 2011, 50, 176-199
         

         

        B. Liu, M. Ma, D. Zacher, A. Betard, K. Yusenko, N. Metzler-Nolte, C. Wöll, R. Fischer
        "Chemistry of SURMOFs: Layer selective installation of functional groups and post synthetic covalent modification probed by fluorescence microscopy"
        J. Am. Chem. Soc. 2011, DOI 10.1021/ja1109826
         

         

        B. Liu, M. Ma, D. Zacher, A. Betard, K. Yusenko, N. Metzler-Nolte, C. Wöll, R. Fischer
        "Chemistry of SURMOFs: Layer selective installation of functional groups and post synthetic covalent modification probed by fluorescence microscopy"
        J. Am. Chem. Soc. 2011, DOI 10.1021/ja1109826
         

         

        S. Henke, R. Schmid, J.-D. Grunwaldt, R. A. Fischer
        "Flexibility And Sorption Selectivity In Rigid Metal-Organic Frameworks: The Impact Of Ether-Functionalized Linkers "
        Chem. Eur. J. 2011,DOI: 10.1002/chem.201002341 (featured with a frontispiece)
         

         

        D. Zacher, K. Yusenko, A. Bétard, M. Meilikhov, T. Ladnorg, O. Shekhah, T. de los Arcos, M. Krasnopolski, M. Meilikhov, J. Winter, A. Terfort, C. Wöll, R. A. Fischer
        "Multi-component liquid phase epitaxy of layer-based PCPs: Importance of deposition sequence"
        Chem. Eur. J. 2011, DOI: 10.1002/chem.201002381 (featured with a frontispiece)
         

         

        D. Zacher, R. Schmid, C. Wöll, R. A. Fischer
        "Surface Chemistry of Metal-Organic Frameworks at the Liquid/Solid Interface: A Perspective"
        Angew. Chem.-Int. Edit. 2011, 50, 176-199
 
 

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