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

Liquid phase epitaxy (LPE) of functionalized SURMOFs
for application in Gas Chromatography

 

        Consortium:

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

        Professor Dr. Florian Mertens, Freiberg
        Freiberg University of Mining and Technology
        Department of Chemistry and Physics
        Institute of Physical Chemistry

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


        Project:

        Liquid phase epitaxy (LPE) of functionalized SURMOFs for application in Gas Chromatography

        Abstract:

        SURMOFs are crystalline, oriented thin films of Metal Organic Frameworks (MOFs) which are deposited at the surface of given substrates (e.g. modified by Self-assembled organic Monolayers, SAMs) by employing a step by step liquid phase epitaxial growth scheme (i.e. layer by layer growth, lbl). The lbl deposition involves the Controlled SBU Approach (CSA; SBU = Secondary Building Unit). The goal of the project outlined in this proposal is the transfer of the basic results achieved in the first funding period to functionalized MOF thin films for applications in selective adsorption and chromatography. Such fu-SURMOFs (fu = functionalized) may contain suitably chosen side groups at the organic linkers of the framework in order to tailor 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 deposition sequence and orientation of the MOF layers are varied (multivariate fu-SURMOFs). The structural and adsorption properties of the SURMOFs will be investigated (i.e. adsorption isotherms, diffusion constants of guest molecules). Optimized SAMs and lbl growth conditions, which are particularly suited for the fabrication of SURMOFs on oxide surfaces (e.g. SiO2), will be developed.

        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"
        Polymers 2011, 3, 1565-1574.
         

         

        O. Shekhah , J. Liu, R. Fischer C. Wöll
        "MOF thin films: existing and future applications "
        Chem. Soc. Rev., 2011, 40, 1081-1106.
         

         

        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, *40*, 4954-4958.
         

         

        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, 133, 1734-1737.
         

         

        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., 2010, 16, 14296-14306.
         

         

        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, 17, 1448- 1455.
         

         

        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.
         

         

        O. Shekhah, H.K. Arslan, K. Chen, M. Schmittel, R. Maul, W. Wenzel, C. Wöll
        "Post-synthetic modification of epitaxially grown, highly oriented functionalized MOF thin films"
        Chem. Commun., 2011, *47*, 11210-11212.
         

         

        H.K. Arslan, O. Shekhah, J. Wohlgemuth, M. Franzreb, R.A. Fischer, C. Wöll
        "High-Throughput Fabrication of Uniform and Homogenous MOF Coatings"
        Adv. Funct. Mater., 2011, 21, 4228-4231.
         

         

        A. Dragässer, O. Shekhah, O. Zybaylo, C. Shen, M. Buck, C. Wöll, D. Schlettwein
        "Redox mediation enabled by immobilised centres in the pores of a metal-organic framework grown by liquid phase epitaxy"
        Chem. Commun., 2012, 48, 663-665.
         

         

        B. Liu, O. Shekhah, H.K. Arslan, J. Liu, C. Wöll, R.A. Fischer
        "Enantiopure Metal--Organic Framework Thin Films: Oriented SURMOF Growth and Enantioselective Adsorption"
        Angew. Chem. Int. Ed. 2012, 51, 807-810.
         

         

        H. Arslan, O. Shekhah, F. Wieland, M. Paulus, C. Sternemann, M. Schrör, S. Tiemeyer, M. Tolan, R.A. Fischer, C. Wöll
        "Intercalation in Layered Metal-Organic Frameworks: Reversible Inclusion of an Extended p-System"
        J. Am. Soc. 133 (2011), 8158-8161.
         
 
 

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