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Overview of granted projects - Part I

MOF Based Sorption Sensors by Rare Earth Luminescence



        Professor Dr. Claus Feldmann, Karlsruhe
        Karlsruhe Institute of Technology
        Institute of Inorganic Chemistry

        Dr. Ralf Köhn, Hamburg
        Center for Free-Electron Laser Science

        Prof. Dr. Klaus Müller-Buschbaum, Würzburg
        University of Würzburg
        Institute of Inorganic Chemistry


        MOF Based Sorption Sensors by Rare Earth Luminescence


        The project entitled „MOF Based Sorption Sensors by Rare Earth Luminescence” combines luminescence as an intrinsic property of rare earth elements with sorption abilities of MOFs. The combination of both will be used to develop a new type of sensors for adsorption processes by influencing and quenching of the luminescence. The project consists of two different approaches: In the first instance luminescence as an intrinsic property of the MOF itself by using lanthanide metal centres is used on the base of Ln-NMOFs which are already known for their luminescence. In contrast to carboxylate frameworks amides are much more endurable vs. energy sources and thus also vs. the excitation radiation. The investigation of the framework luminescence depending on different adsorbents like NH3, N2O, NO, NO2, CO2, CO, SO2, SO3, H2, O2 etc and improved MOFs is planned. The second approach of the project is the utilization of known carboxylate MOFs such as IRMOF-8 or MIL-82 and to study luminescent rare earth particles, both in solutions as well as solid particles in dispersions and their interaction with the MOF structures. This expands the project to non-inert conditions and aqueous solutions. Altogether the main goal is an application of suitable sensors that allow determining sorption by changes or quenching of the luminescence, the latter being a luminescence switch. In order to investigate chemically different adsorbents development of suitable surface determination methods is planned. Therefore the project combines expertises of Ln-Amide and MOF chemistry, luminescence as well as sorption and surface determinations.



        Figure 1 and Table 1: The luminescent MOF 38[Sr1-xEux(Im)2] (x = 0.01-1.0) excited by UV and visible light as well as data on the excitation, emission, colour point and quantum efficiency.

        The project takes a successful course regarding the evaluation of luminescence and porosity determinations of Ln-N-MOFs, the syntheses of new and improved MOFs regarding regarding both properties. Promising substances for a sensor effect of the dependence of luminescence and sorption have been found. Two MOFs show luminescence in combination with a selective adsorption of gases. In both cases adsorption of CO2 results in quenching of the luminescence so that the principle goal of a sorption sensor by rare earth luminescence was reached. Moreover the MOF with highest quantum efficiency (almost 90%) of all MOFs known today and dye-modified zirconium phosphates (DMZP’s) as an alternative class of luminescent nano particles for MOF incorporation were synthesized.


        A. Zurawski, M. Mai, D. Baumann, C. Feldmann, K. Müller-Buschbaum
        "Homoleptic Imidazolate Frameworks 3[Sr1-xEux(Im)2] – Hybrid Materials with Efficient Tunable Luminescence"

        Chem. Commun. 2010, DOI: 10.1039/C0CC02093A


        J.-C. Rybak, C. J. Höller, P. R. Matthes, K. Müller-Buschbaum, M. Mai, C. Feldmann, R. Köhn
        "Steps Towards MOF Based Sorption Sensors by Rare Earth Luminescence"

        Z. Anorg. Allg. Chem. 2010, 636, 2099.


        J.-C. Rybak, I. Schellenberg, R. Pöttgen, K. Müller-Buschbaum
        "MOFs by Transformation of 1D-Coordination Polymers II: The Homoleptic Divalent Rare Earth 3D-Benzotriazolate 3[Eu(Btz)2] Initiating from 1[Eu(Btz)2(BtzH)2]"

        Z. Anorg. Allg. Chem. 2010, 636, 1720


        A. Zurawski, F. Hintze, K. Müller-Buschbaum
        "Utilizing Metal Melts of Low-Melting Metals as a Novel Approach for MOF Synthesis: The 3D-Imidazolate 3[Ga2(Im)6ImH] from Gallium and Imidazole"

        Z. Anorg. Allg. Chem. 2010, 636, 1333.


        C. J. Höller, K. Müller-Buschbaum
        "Frameworks by Solvent Free Synthesis of Rare Earth Chlorides with Molten 1,3-Benzodintrile and Tailoring of the Particle Size: 3[LnCl3 (1,3-Ph(CN)2)], Ln = Y, Dy, Ho, Er, Yb"

        Eur. J. Inorg. Chem. 2010, 454


        C. J. Höller, M. Mai, C. Feldmann, K. Müller-Buschbaum
        "The Interaction of Rare Earth Chlorides with 4,4'-Bipyridine for the Reversible Formation of Template Based Luminescent Ln-N-MOFs"

        Dalton Trans. 2010, 39, 461


        C. J. Höller, P. Matthes, J. Beckmann, K. Müller-Buschbaum
        "MOF Formation vs. Reversible High Ligand Uptake in Anhydrous Halides: Two Opposing Aspects of 3[La2Cl6(4,4-bipy)5 ]•(4,4-bipy)4"

        Z. Anorg. Allg. Chem. 2010, 636, 395.


        J.-C. Rybak, M. Tegel, D. Johrendt and K. Müller-Buschbaum
        "Polymorphism of Isotypic Series of Homoleptic 1,2,3-Triazolate MOFs [Ln(Tz*)3] Containing the Heavy Lanthanides Gd-Lu: From Open to Dense Frameworks of Varying Dimensionality"

        Z. Kristallogr. 2010, 225, 187.


        A. Zurawski, J. Sieler, K. Müller-Buschbaum
        "A First and Homoleptic Rare Earth 3D-Bipyrazolate MOF: 3[Eu(Me4BpzH)3 (Me4BpzH2)]"

        Z. Anorg. Allg. Chem. 2009, 635, 2034.


        J.-C. Rybak, K. Müller-Buschbaum
        "2∞[Tb(Tz*)3], A Homoleptic 2-Dimensional Framework from a Solvent Free Synthesis of Terbium Metal with 1H-1,2,3-Triazole"

        Z. Anorg. Allg. Chem. 2009, 635, 1124.


        J.-C. Rybak, Y. Mokaddem, K. Müller-Buschbaum
        "Dependencies in Structural Chemistry, Derivations and Topologies in Triazolate Networks of the Rare Earth Elements"

        Z. Kristallogr., Suppl. 2009, 29, 36.


        K. Müller-Buschbaum, Y. Mokaddem
        "MOFs by Transformation of 1D-Coordination Polymers: From 1[Ln(Btz)3BtzH] to the Homoleptic Rare Earth 3D-Benzotriazolate Frameworks 3[Ln(Btz)3], Ln = La, Ce"

        Z. Anorg. Allg. Chem. 2008, 634, 2360


        K. Müller-Buschbaum, Y. Mokaddem
        "MOFs by Solvent Free High Temperature Synthesis Exemplified by 3[Eu3 (Tz*)6(Tz*H)2]"

        Solid State Sci. 2008, 416


        M. Roming, H. Lünsdorf, K. E. J. Dittmar, C. Feldmann
        "ZrO(HPO4)1-x(FMN)x: Schnelle und einfache Synthese eines nanokaligen Lumineszenzbiomarkers"

        Angew. Chem. 2010, 122, 642


        M. Roming, H. Lünsdorf, K. E. J. Dittmar, C. Feldmann
        "ZrO(HPO4)1-x(FMN)x: Quick and Easy Synthesis of a Nanoscale Luminescent Biomarker"

        Angew. Chem. Int. Ed. 2010, 49, 632-637.


        H. Goesmann, C. Feldmann
        "Nanopartikuläre Funktionsmaterialien (Review)"

        Angew. Chem. 2010, 122, 1402-1437


        H. Goesmann, C. Feldmann
        "Nanoparticulate Functional Materials (Review)"

        Angew. Chem. Int. Ed. 2010, 49, 1362-1395


        M. Roming, C. Feldmann
        "Zirconium Umbelliferonephosphate – A Luminescent Organic-Inorganic Hybrid Nanomaterial"

        Solid State Sci. 2011, in press


        M. Roming, C. Feldmann
        "Anorganisch-organischer Kompositleuchtstoff"

        Patent application DE 10 2008 009541.9, US 12 867,348, WO 2009 100800 A1.







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