New Alkaline-Earth Polymeric Frameworks as green materials for sorption and heterogeneous catalysis

Metal-Organic Frameworks (or MOFs) are porous organic-inorganic crystalline materials in which the metallic centers are joined through organic ligands via coordination bonds to give frameworks with different dimensionalities. The work presented in this thesis is focused on the obtaining of new MOFs using alkaline-earth elements as metal centers, which could represent a comparatively cheap, nontoxic and green alternative to conventional MOFs based on transition metals or rare-earth elements.The obtained materials have shown interesting properties like heterogeneous catalysis under mild conditions or selective sorption of organic compounds.Peer reviewe

Insight into lewis acid catalysis with alkaline-earth MOFs: The role of polyhedral symmetry distortions

We propose a multidisciplinary approach to face the interpretation of heterogeneous catalysis with alkaline-earth metal-organic frameworks (MOFs). Their oxygen-based polyhedra, which do not exhibit regular geometries, do act as very active Lewis acid sites. Four novel alkaline-earth MOFs that belong to three different structural types - Mg-AEPF-11, Mg-APF-12, Ca-AEPF-13 and Sr-APF-13 - are reported, together with their net topologies, and a study of the symmetry distortions around the alkaline-earth metal polyhedra by using a continuous shape mapping (CShM) description. These MOFs are good catalysts in the selective hydrogenation of styrene. Even more, Sr-AEPF-13 shows the best conversions ever published with alkaline-earth MOFs for the hydrogenation of activated alkenes under mild conditions. A combination of crystallographic and topological analysis and theoretical calculations, together with experimental catalytic results, has been applied to understand the catalytic activity of these four novel alkaline-earth MOFs. This work demonstrates that the presence of symmetry-distorted alkaline-earth polyhedra gives rise to highly catalytic-active MOFs in the hydrogenation of activated alkenes. A matter of shape! There are many aspects that remain poorly understood in catalysis with alkaline-earth metal-organic frameworks (MOFs). Their metal polyhedra, which do not exhibit regular geometries, act as very active Lewis acids. In this work a new multidisciplinary approach is proposed to understand the catalytic activity of four novel alkaline-earth MOFs in the selective hydrogenation of alkenes (see figure). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.This work has been supported by the Spanish MCYT Project Mat 2010-17571, PHAMA S2009/Mat-1756 Comunidad de Madrid, and Consolider-Ingenio CSD2006-2001. A.E.P.P. acknowledges a JAE fellowship from the CSIC and the Fondo Social Europeo from the EU.Peer Reviewe

Unravelling the local structure of catalytic Fe-oxo clusters stabilized on the MOF-808 metal organic-framework

Stabilizing catalytic iron-oxo-clusters within nanoporous metal–organic frameworks (MOFs) is a powerful strategy to prepare new active materials for the degradation of toxic chemicals, such as bisphenol A. Herein, we combine pair distribution function analysis of total X-ray scattering data and X-ray absorption spectroscopy, with computational modelling to understand the local structural nature of added redox-active iron-oxo clusters bridging neighbouring zirconia-nodes within MOF-808

Catalytic Fe-Oxo Clusters Stabilized on the MOF-808 Metal Organicframework for the Degradation of Water Pollutants

Stabilizing catalytic iron-oxo-clusters within nanoporous metal-organic frameworks (MOF) is a powerful strategy to prepare new active materials for the degradation of toxic chemicals, such as bisphenol A. Herein, we combine pair distribution function analysis of total X-ray scattering data and X-ray absorption spectroscopy, with computational modelling to understand the local structural nature of added redox-active iron-oxo clusters bridging neighbouring zirconia-nodes within MOF-808.</p

Material órgano-inorgánico microporoso cristalino basado en cationes alcalinotérreos, procedimiento de preparación y usos

Material órgano-inorgánico microporoso cristalino basado en cationes alcalinotérreos, procedimiento de preparación y usos. La presente invención se refiere a una familia de materiales órgano-inorgánicos microporosos cristalinos conteniendo cationes alcalinotérreos y ácidos dicarboxílicos, su procedimiento de preparación y su uso como catalizadores heterogéneos reutilizables para reacciones en química orgánica, como tamices moleculares y como absorbentes de gases y líquidos.Peer reviewedConsejo Superior de Investigaciones Científicas (España), Instituto Madrileño de Estudios Avanzados en Energía (IMDEA-ENERGÍA)A1 Solicitud de patentes con informe sobre el estado de la técnic

Dynamic calcium metal-organic framework acts as a selective organic solvent sponge

Herein, we present a Ca-based metal–organic framework named AEPF-1, which is an active and selective catalyst in olefin hydrogenation reactions. AEPF-1 exhibits a phase transition upon desorption of guest molecules. This structural transformation takes place by a crystal to crystal transformation accompanied by the loss of single-crystal integrity. Powder diffraction methods and computational studies were applied to determine the structure of the guest-free phase. This work also presents data on the exceptional adsorption behavior of this material, which is shown to be capable of separating polar from nonpolar organic solvents, and is a good candidate for selective solvent adsorption under mild conditions.This work has been supported by the Spanish MCYT Project Mat 2007-60822, CTQ 2007-28909-E/BQU, and Consolider-Ingenio CSD2006-2001. A.E.P.P. acknowledges a JAE fellowship from CSIC and Fondo Social Europeo from EU. V.A.P.O. acknowledges financial support from the MCYT in the Ramón y Cajal research program.Peer Reviewe

Towards inorganic porous materials by design: Looking for new architectures

Crystalline porous materials, such as zeolites and metal-organic frameworks (MOFs), possess a regular and well-defined system of pores. While zeolites have been known for a long time and are widely used in industry, MOFs are still a new type of compounds with a huge potential for numerous applications. MOFs and zeolites may feature certain similarities as well as large differences, but concepts such as flexibility of the framework, thermodynamic versus kinetic control of the crystallization or stabilizing effect of guest species are key issues in both fields. This article presents a vision on the state of the art of such materials. Crystalline porous materials, such as zeolites and metal-organic frameworks, present a very large interest for actual and/or potential technological uses. Their syntheses by design for targeted applications critically depend on the ability to shape their structures and functionalities. This requires a deep understanding of structure-direction issues, whose state of the art is briefly reviewed in this article. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.This work has been supported by the Spanish MICINN Projects Mat 2007-60822, MAT2009-09960, CTQ 2007-28909-E/BQU, CAM: S2009/MAT-1756/CAM, and Consolider-Ingenio CSD2006-2001; AEPP and AR acknowledge JAE fellowship from CSIC and Fondo Social Europeo from EU.Peer Reviewe

Towards inorganic porous materials by design: Looking for new architectures

Crystalline porous materials, such as zeolites and metal-organic frameworks (MOFs), possess a regular and well-defined system of pores. While zeolites have been known for a long time and are widely used in industry, MOFs are still a new type of compounds with a huge potential for numerous applications. MOFs and zeolites may feature certain similarities as well as large differences, but concepts such as flexibility of the framework, thermodynamic versus kinetic control of the crystallization or stabilizing effect of guest species are key issues in both fields. This article presents a vision on the state of the art of such materials. Crystalline porous materials, such as zeolites and metal-organic frameworks, present a very large interest for actual and/or potential technological uses. Their syntheses by design for targeted applications critically depend on the ability to shape their structures and functionalities. This requires a deep understanding of structure-direction issues, whose state of the art is briefly reviewed in this article. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.This work has been supported by the Spanish MICINN Projects Mat 2007-60822, MAT2009-09960, CTQ 2007-28909-E/BQU, CAM: S2009/MAT-1756/CAM, and Consolider-Ingenio CSD2006-2001; AEPP and AR acknowledge JAE fellowship from CSIC and Fondo Social Europeo from EU.Peer Reviewe

Material organo-inorgánico microporoso cristalino basdo en cationes alcalinotérreos, procedimiento de preparación y usos

[ES] La presente invención se refiere a una familia de materiales organo-inorgánicos microporosos cristalinos conteniendo cationes alcalinotérreos y ácidos dicarboxílicos, su procedimiento de preparación y su uso como catalizadores heterogéneos reutilizables para reacciones en química orgánica, como tamices moleculares y como absorbentes de gases y líquidos.[EN] The present invention relates to a family of organic/inorganic microporous crystalline materials containing alkaline-earth cations and dicarboxylic acids, the method for preparation thereof and the use thereof as reusable heterogeneous catalysts for reactions in organic chemistry, as molecular sieves and as gas and liquid absorbents.Peer reviewedConsejo Superior de Investigaciones Científicas (CEspaña), Instituto Madrileño de Estudios Avanzados en EnergíaA1 Solicitud de patentes con informe sobre el estado de la técnic

Copper(II) invigorated EHU-30 for continuous electroreduction of CO2CO_2 into value-added chemicals

The doping of zirconium based EHU-30 and EHU-30-NH$_2$ metal–organic frameworks with copper(II) yielded a homogeneous distribution of the dopant with a copper/zirconium ratio of 0.04–0.05. The doping mechanism is analysed by chemical analysis, microstructural analysis and pair distribution function (PDF) analysis of synchrotron total scattering data in order to get deeper insight into the local structure. According to these data, the Cu(II) atoms are assembled within the secondary building unit by a transmetalation reaction, contrarily to UiO-66 series in which the post-synthetic metalation of the MOF takes place through chemical anchorage. The resulting materials doubled the overall performance of the parent compounds for the CO$_2$ electroreduction, while retained stable the performance during continuous transformation reaction