Although the ICP is not by itself an academic institution, it undertakes educational actions not only with the realization of PhD theses and end-of-career projects, many of them in connection with the Universidad Autónoma de Madrid with which it shares the UAM-CSIC Campus of Excellence, but also by means of master and specialization courses addressed to graduates or to laboratory or industry technicians. The diffusion and coordination of these actions is carried out jointly with CSIC?s Department of Postgraduate Studies and Specialization.
  • Courses

    Postgraduate
    • INTRODUCCIÓN A LOS ORÍGENES DE LA QUÍMICA
      30 horas20/02/2012[+ information]
    CSIC Training Plan
    Other Courses
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  • Master's Degree

    Masters
    • Máster Universitario en Química Aplicada
      0 horas30/09/2013[+ information]
  • PhD

    Funcionalización de soportes de carbón e inmovilización de complejos catalíticos para reacciones de hidrogenación selectivas en química fina.
    Ana Belén Dongil
    Fecha de lectura:10 de February de 2011
    Directores:María Belén Bachiller Baeza, Inmaculada Rodríguez Ramos
    The interest to immobilise homogeneous complexes has extensively been reported
    as it joins the advantages of homogeneous and heterogeneous catalysis, such as the ease
    of separation from reaction media, and reuseability. Several approaches have been
    investigated for the heterogenization of transition metal complexes on solid supports,
    being the covalent attachment on micro and mesoporous inorganic materials the most
    successful. Covalent approach requires the development of grafting and tethering
    methodologies of which the use of silylating agents to react with the surface of different
    silica based materials has been the most studied. Additional advantages derived from
    site isolation and shape selectivity may justify the difficulty on the preparation. In this
    sense, several publications have appeared were, besides mesoporous materials (MCM-41,
    SBA-15...), layered compounds such as clay minerals, are an interesting approach to
    improve selectivity due to molecular sieving effects. In this context, the use of carbon
    materials as a support to immobilize catalytic homogeneous complexes, due to their high
    thermal, mechanical and chemical resistance together with a competitive cost, make
    them ideal candidates to its use as a support in catalysis. However, despite the effort
    devoted to silica, little attention has been paid to the use of carbon materials which has
    been mainly used as a support for metal nanoparticles. The reason can be found on its
    high inertness, hydrophobicity and difficulty to characterize by common spectroscopic
    techniques have hindered its study. Besides, most of the literature concerning the use of
    carbon to immobilise homogeneous complexes is based on active carbon whose textural
    properties may be non suitable for liquid phase reactions.
    To overcome these drawbacks a common procedure is surface oxidation which
    can be performed at the edges and/or the basal planes of graphene layers. In this sense a wide variety of oxidizing treatment techniques have been used to functionalize the
    carbon surface: gaseous (O2, O3, CO2) or liquid (HNO3, H2SO4, H2O2), plasma treatment,
    etc. being wet oxidation with nitric acid the most applied. The proportion of the common
    oxygen functionalities (carboxyl, carbonyl, phenol, quinone, and lactone groups) created
    depends on the oxidation method. When oxidation of graphite is performed by fumic
    acids the obtained material is known as graphite oxide. This material holds hydrophilic
    character due to the epoxy and hydroxyl functionalities placed in the interlayers and
    carboxylic groups on the edges. Its rich chemistry allows intercalation by ionic exchange
    and covalent bonding through the acidic hydroxyl groups on its layers while increasing
    the interlayer space.
    Immobilisation of homogeneous complex it is commonly performed by using
    spacers between the support and the complex. Taking into account that nitrogen is a
    common chelating element for transition metals, a simple route to attach the complex
    would be the formation of surface amide bonds by means of molecules with three amine
    groups. If two of these groups remain free they can be used as building blocks to bridge
    the metal complex to the support. Besides, the use of graphite oxide as support can offer
    further aid to the catalytic selectivity, both owing to the chemical functions on its
    surface and due to confinement effects. In some cases additional steps to include a halide
    pending group to which further attach the chelating molecule are required. In the present
    work isocyanate and organosilane molecules have been used to create covalent bonds
    between the surface and the ligand. While isocyanate may form carbamate and amide
    bonds with hydroxyl/phenol and carboxylic groups respectively, organosilane molecules
    may react with hydroxyl/phenol as it is commonly done for silica materials.
    In order to study the effect of carbon morphology over oxidation treatment, a
    High surface Area Graphite and two carbon nanofibers of the stacked-cup type were
    submitted to wet and plasma oxidation. Those materials and a lab-prepared graphite
    oxide were further treated with appropriate ligands to immobilize the homogeneous
    complex. The optimized functionalized supports were chosen to immobilize RuCl2PPh3
    and Ru-BINAP complexes and tested in the chemoselective hydrogenation of
    cinnamandehyde and in the enantioselective hydrogenation of methyl acetoacetate
    respectively. Based on the characterization and reaction performance, several
    conclusions were found concerning the influence of the textural properties, ligand
    structure and the interactions between the support and the complexes on catalytic
    performance.
    Palabras clave:
    fine chemistry, immobilized homogeneous complexes, enantiselective hydrogenation
  • Projects F.C.

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