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Invited researcher Martin Schröder
Contract number
14.Z50.31.0006
Time span of the project
2014-2016
Head of the laboratory

As of 30.01.2020

27
Number of staff members
27
scientific publications
2
Objects of intellectual property
General information

Name of the project: Porous metal-organic coordination polymers: from fundamental science to new functional materials

Strategy for Scientific and Technological Development Priority Level: б


Goals and objectives

Research directions: Chemistry of porous materials, metal-organic frameworks, coordination polymers, gas adsorption, storage and division of compounds, heterogeneous catalysis, luminescence and sensor qualities, materials for ion transport

Project objective: Synthesis and research of qualities of porous metal-organic coordination polymers to reach scientific breakthrough in porous sorbents, membranes, catalysts, sensors and many other materials


The practical value of the study

  • We have conducted experiments in targeted functionalization of organic ligands of mesoporous MIL framework to produce chemically stable catalytic systems. We have studied aspects of replacement of organic ligand in porous coordination polymers using the solid-state Nuclear magnetic resonance method. The research has shown unusually low activation energy in the process of replacement, suggestions concerning its mechanisms have been made.
  • Our researchers have studied sorption qualities of porous coordination polymers. Quantitative characteristics have been obtained concerning specific surface, volume of pores, absorption heat. We have found lateral solute-solute interactions during sorption of hydrogen into a MIL framework. For the microporous coordination framework [Zn2(tdc)2(dabco)]. we have found unusually high adsorption of CO2 which is twice as high as sorption of the analogous [Zn2(bdc)2(dabco)] compound. Quantum chemical modeling and X-ray structure data have shown that additional binding centers are localized on heteroatoms of sulfur of organic ligand which is quiet a surprising fact as before that it has been considered that only coordination-saturated cations of metals can act as strong sorption centers. Obtained information allows not only for targeted creation of new porous materials with high sorption characteristics but also to enhance qualities of existing sorbent.
  • Our researchers have synthesized a new porous coordination polymer ZFU. The polymer implements anion cavities and has internal dimensions sufficient for inclusion of cations of alkali metals. We have conducted replacement reactions and found inclusion of cations into these cavities with formation of complexes of the cryptand type. Our researchers have found that inclusion of alkali metals leads to significant decrease of intensity of photoluminescence of the framework of the coordination polymer.
  • We have studied characteristics of composite materials with record high proton conductivity based on micro- and mesoporous coordination polymers with inclusion acid or acid salt phases in their cavities. Using X-ray phase analysis and electron microscopy we have shown that inclusion of acid phases generally does not lead to destruction of porous structure of matrices, but hydrolytic stability significantly depends on quality of production of the coordination material. Analysis of experimental correlations between proton conductivity and atmospheric temperature and humidity allowed to come to a conclusion concerning the mechanism of proton transfer in samples. Obtained data demonstrates high potential of the approach used in this research.
  • We have produced coordination polymers with catalytic centers of base nature, studied the Henry reaction and came to conclusions concerning factors affecting output and selectivity of catalytic processes. The Laboratory has developed original methods to synthesize Au and Pd nanoparticles in microcavities of MIL and HKUST coordination frameworks with various concentration of platinum metals.

Education and career development:

  • 1 doctoral dissertations, 6 candidate dissertations, more than 10 bachelor dissertations have been defended.
  • We have organized 3 new education courses for students of the Novosibirsk state University and the Nikolaev Institute of Inorganic Chemistry of the Siberian Department of the Russian Academy of Sciences: «Materials and their qualities» (2014), «Modern aspects of chemistry of metal-organic coordination materials» (2015), «Modern aspects if chemistry of cluster compounds and materials» (2016).
  • Every year about 10 students of the Novosibirsk State University complete internships within their term project.
  • Employees of the Laboratory have participated in organizing lectures for scientific schools on the grounds of the Nikolaev Institute of Inorganic Chemistry of the Siberian Department of the Russian Academy of Sciences, Novosibirsk State University and Buryat State University

Collaborations:

  • University of Nottingham (United Kingdom), Tohoku University (Japan), Kurchatov Institute (Russia), Tomsk State University (Russia), Institute of General and Inorganic Chemistry of the Russian Academy of Sciences (Russia): joint research
  • University of Manchester (United Kingdom), Tomsk State University (Russia): internships of employees

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Sapchenko S.A., Dybtsev D.N., Samsonenko D.G., Belosludov R.V., Belosludov V.R., Kawazoe Y., Schröder M., Fedin V.P.
Selective Gas Adsorption in Microporous Metal-Organic Frameworks Incorporating Urotropine Basic Sites: an Experimental and Theoretical Study. Chemical Communications 51(73): 13918–13921 (2015).
Sapchenko S.A., Demakov P.A., Samsonenko D.G., Dybtsev D.N., Schröder M., Fedin V.P.
A Cryptand Metal-Organic Framework as a Platform for the Selective Uptake and Detection of Group I Metal Cations. Chemistry – A European Journal 23(10): 2286–2289 (2017).
Zavakhina M.S., Yushina I.V., Samsonenko D.G., Dybtsev D.N., Fedin V.P., Argent S.P., Blake A.J., Schröder M.
Halochromic Coordination Polymers Based on a Triarylmethane Dye for Reversible Detection of Acids. Dalton Transactions 46(2): 465–470 (2017).
Bolotov V.A., Kovalenko K.A., Samsonenko D.G., Han X., Zhang X., … Fedin V.P., Dybtsev D.N., Schröder M.
Enhancement of CO2 Uptake and Selectivity in a Metal-Organic Framework by the Incorporation of Thiophene Functionality. Inorganic Chemistry 57(9): 5074–5082 (2018).
Easun T.L., Moreau F., Yan Y., Yang S., Schröder M.
Structural and dynamic studies of substrate binding in porous metal–organic frameworks. Chemical Society Reviews 46(1): 239–274 (2017).
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