A5015139489- Metal-Organic Frameworks: Synthesis and Applications
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Covalent Organic Framework Applications
- Catalytic Processes in Materials Science
- Machine Learning in Materials Science
- Magnetism in coordination complexes
- Advanced Photocatalysis Techniques
- Crystallography and molecular interactions
- Magnesium Oxide Properties and Applications
- Catalysis and Oxidation Reactions
- Nanocluster Synthesis and Applications
- Polyoxometalates: Synthesis and Applications
- Luminescence and Fluorescent Materials
- Zeolite Catalysis and Synthesis
- Nanomaterials for catalytic reactions
- Chemical Synthesis and Reactions
- Chemical Synthesis and Characterization
- Metal complexes synthesis and properties
- Carbon dioxide utilization in catalysis
- Asymmetric Hydrogenation and Catalysis
- Advanced Nanomaterials in Catalysis
- Chemical Synthesis and Analysis
- Ga2O3 and related materials
- Lanthanide and Transition Metal Complexes
Universidad Autónoma de Madrid
2018-2024
Argonne National Laboratory
2015-2021
Institute for Condensed Matter Physics of the National Academy of Sciences of Ukraine
2020
Advanced Photon Source
2017-2018
Advanced Photonix (United States)
2017-2018
Stockholm University
2012-2016
Instituto de Ciencia de Materiales de Madrid
2009-2013
Consejo Superior de Investigaciones Científicas
2011-2012
Centre National de la Recherche Scientifique
2012
Pacific Northwest National Laboratory
2011
A new set of covalent atomic radii has been deduced from crystallographic data for most the elements with numbers up to 96. The proposed show a well behaved periodic dependence that allows us interpolate few which structural is lacking, notably noble gases. therefore fills gaps and solves some inconsistencies in currently used radii. transition metal lanthanide contractions as differences between low spin high configurations metals are illustrated by set.
A series of zirconium-based, metal-organic frameworks (MOFs) were tested for their ability to adsorb and remove selenate selenite anions from aqueous solutions. MOFs adsorption capacity uptake time at different concentrations. NU-1000 was shown have the highest capacity, fastest rates both selenite, all zirconium-based studied here. Herein, mechanism on is explored determine important features that make a superior adsorbent this application.
Zr-based metal–organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due their exceptional stability. Additionally, crystalline nature affords the opportunity for molecular level characterization of both support and catalytically active site, facilitating mechanistic investigations catalytic process. We describe herein installation Co(II) ions Zr6 nodes mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition a MOF...
Schiff-condensation reactions carried out between 1,6-diaminopyrene (DAP) and the tritopical 1,3,5 benzenetricarbaldehyde (BTCA) or 2,4,6-triformylphloroglucinol (TP) ligands give rise to formation of two-dimensional imine-based covalent-organic frameworks (COFs), named IMDEA-COF-1 -2, respectively. These materials show dramatic layer-packing-driven fluorescence in solid state arising from three-dimensional arrangement pyrene units among layers. Layer stacking within these 2D-COF either...
Abstract Nanoparticles of mesoporous MIL‐100(Al, Cr or Fe) metal–organic frameworks were synthesized by a microwave‐assisted solvothermal route with green solvents. The optimization yield, crystallinity, and particle size was achieved through the control synthetic parameters such as temperature, heating rate, dwelling time. strongly depends on metallic cation metal linker precursors; nanoparticles smaller than 100 nm obtained for iron chromium based MIL‐100. Finally, stable colloidal...
A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting the hybrid material, PW12@NU-1000. The POM@MOF composite characterized by suite of physical methods, indicating retention crystallinity and high porosity parent MOF. material also stable to leaching media at varying pH. Finally, tested as heterogeneous catalyst for oxidation 2-chloroethyl ethyl sulfide using hydrogen peroxide oxidant....
Tandem catalytic systems, often inspired by biological offer many advantages in the formation of highly functionalized small molecules. Herein, a new metal–organic framework (MOF) with porphyrinic struts and Hf6 nodes is reported. This MOF demonstrates efficacy tandem oxidation functionalization styrene utilizing molecular oxygen as terminal oxidant. The product, protected 1,2-aminoalcohol, formed selectively high efficiency using this recyclable heterogeneous catalyst. Significantly,...
In situ pair distribution function (PDF) analyses and density functional theory (DFT) computations are used to probe local structural transitions of M6O8 nodes found in two metal organic frameworks (MOFs), NU-1000 UiO-66, for M = Zr, Hf. Such occur without change the global framework symmetry at temperatures within a range relevant many potential MOF applications. For particular M6(O)8 studied here, observed distortions can be mapped polymorphic forms known bulk ZrO2. framework, however,...
Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation new atoms on a crystallographically precise framework. Leveraging broad palette known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. We here demonstrate saturating reaction trimethylindium (InMe3) with node hydroxyls and ligated water NU-1000, which takes place without...
Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal-organic framework (MOF) NU-1000, have been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (<230 °C), affording selective and stable propene production catalyst. In our current work, series promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) Mo(VI), are anchored as metal-oxide,hydroxide clusters NU-1000 followed by Co(II) ion deposition, yielding...
The ever-emerging demands on miniaturization of electronic devices have pushed the development innovative materials with desired properties. One major endeavor is organic- or organic-inorganic hybrid-based electronics as alternatives supplements to silicon-based devices. Herein we report first observation coexistence resistance switching and ferroelectricity in a metal-organic framework (MOF) material, [InC16H11N2O8]·1.5H2O, denoted RSMOF-1. electrical RSMOF-1 can be turned off repeatedly...
Two families of metal–organic frameworks (MOFs), MIL-88 and MIL-101 built by trinuclear transition metal (TM) clusters (TM = Cr, Fe, or Sc), have been known for several years, but their syntheses are often reported separately. In fact, these MOFs polymorphs, framework isomers: they assembled from the same secondary building units organic linkers, connectivity components differs. Here we report first time synthesis vanadium MOF MIL-88B(V) compare its parameters to those MIL-47(V) recently...
Promoters are ubiquitous in industrial heterogeneous catalysts. The wider roles of promoters accelerating catalysis and/or controlling selectivity are, however, not well understood. A model system has been developed where a heterobimetallic active site comprising an metal (Rh) and promoter ion (Ga) is preassembled delivered onto metal-organic framework (MOF) support, NU-1000. Rh-Ga sites NU-1000 selectively catalyze the hydrogenation acyclic alkynes to E-alkenes. overall stereoselectivity...
Abstract A diverse set of more than 40 highly functionalized biaryls was synthesized successfully through the Suzuki–Miyaura cross‐coupling reaction catalyzed by Pd nanoparticles supported in a mesoporous MOF (8 wt % Pd@MIL‐101(Cr)‐NH 2 ). This could be achieved under some mildest conditions reported to date and strong control over leaching metallic species maintained, despite presence functional groups and/or several heteroatoms. Some targeted molecules are important intermediates synthesis...
Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, shown to exhibit high activity for ethylene hydrogenation while exhibiting resistance sintering up 200 °C. In situ IR spectroscopy reveals presence both single that depend upon synthesis conditions. Operando X-ray absorption pair distribution analyses reveal unique...
Metal–organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration these nodes, so that the single-site character and activity are lost. In this work, we present a simple nanocasting approach to thermally stable secondary scaffold MOF-based sites, preventing their aggregation even after exposure air at 600 °C. We describe NU-1000, MOF with...
Covalent organic frameworks (COFs) are commonly synthesized under harsh conditions yielding unprocessable powders. Control in their crystallization process and growth has been limited to studies conducted hazardous solvents. Herein, we report a one-pot synthetic method that yields stable aqueous colloidal solutions of sub-20 nm crystalline imine-based COF particles at room temperature ambient pressure. Additionally, through the combination experimental computational studies, investigated...
Metal–organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged approach to functionalize MOF surfaces wide variety of catalytic metal-oxo species. Understanding the structure newly deposited species how they are tethered within is critical understanding...
A two-dimensional imine-linked covalent organic framework bearing pyrene has been prepared and exfoliated in water as nanosheets to produce a stable colloid. As proof-of-concept, this COF colloid used detect the presence of several dyes polynitro-aromatic derivatives. These results show high potential these nanomaterials for applications chemical sensing pollutants directly water.
Layered covalent organic frameworks (2D-COFs), composed of reversible imine linkages and accessible pores, offer versatility for chemical modifications towards the development catalytic materials. Nitrogen-enriched COFs are good candidates binding Pd species. Understanding local structure reacting sites bonded to COF pores is key rationalize interactions between active porous surfaces. By combining advanced synchrotron characterization methods with periodic computational DFT modeling,...
Encapsulating ultrasmall Cu nanoparticles inside Zr-MOFs to form core-shell architecture is very challenging but of interest for CO2 reduction. We report the first time incorporation NCs into a series benchmark Zr-MOFs, without aggregation, via scalable room temperature fabrication approach. The NCs@MOFs composites show much enhanced reactivity in comparison confined pore MOFs, regardless their similar intrinsic properties at atomic level. Moreover, introducing polar groups on MOF structure...
Abstract Metal–organic frameworks (MOFs) are a rapidly growing class of materials that offer great promise in various applications. However, the synthesis remains challenging: for example, range crystal structures can often be accessed from same building blocks, which complicates phase selectivity. Likewise, high sensitivity to slight changes conditions may cause reproducibility issues. This is crucial, as it hampers research and commercialization affected MOFs. Here, presents first‐ever...
First direct images of cobalt nanoparticles covered by a few atomic layers thick TiOx moieties after reduction treatment Co/TiO2 system with the simultaneous formation Co–O–Ti bonds confirm development SMSI decoration effect.
The application of atomic layer deposition (ALD) to metal-organic frameworks (MOFs) offers a promising new approach synthesize designer functional materials with precision. While ALD on flat substrates is well established, the complexity pore architecture and surface chemistry in MOFs present challenges. Through situ synchrotron X-ray powder diffraction, we visualize how deposited atoms are localized redistribute within MOF during ALD. We demonstrate that regioselective, preferential...