0000000001299404
AUTHOR
Fernando Rey
Use of alkylarsonium directing agents for the synthesis and study of zeolites
[EN] Expanding the previously known family of -onium (ammonium, phosphonium, and sulfonium) organic structure-directing agents (OSDAs) for the synthesis of zeolite MFI, a new member, the arsonium cation, is used for the first time. The new group of tetraalkylarsonium cations has allowed the synthesis of the zeolite ZSM-5 with several different chemical compositions, opening a route for the synthesis of zeolites with a new series of OSDA. Moreover, the use of As replacing N in the OSDA allows the introduction of probe atoms that facilitate the study of these molecules by powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (MAS NMR), and X-ray absorption spectroscopy (XAS)…
Cobalt Metal-Organic Framework Based on Layered Double Nanosheets for Enhanced Electrocatalytic Water Oxidation in Neutral Media
A new cobalt metal-organic framework (2D-Co-MOF) based on well-defined layered double cores that are strongly connected by intermolecular bonds has been developed. Its 3D structure is held together by π-π stacking interactions between the labile pyridine ligands of the nanosheets. In aqueous solution, the axial pyridine ligands are exchanged by water molecules, producing a delamination of the material, where the individual double nanosheets preserve their structure. The original 3D layered structure can be restored by a solvothermal process with pyridine, so that the material shows a "memory effect"during the delamination-pillarization process. Electrochemical activation of a 2D-Co-MOF@Nafi…
A highly stable and hierarchical tetrathiafulvalene-based metal organic framework with improved performance as a solid catalyst
[EN] Herein we report the synthesis of a tetrathiafulvalene (TTF)-based MOF, namely MUV-2, which shows a non-interpenetrated hierarchical crystal structure with mesoporous one-dimensional channels of ca. 3 nm and orthogonal microporous channels of ca. 1 nm. This highly stable MOF (aqueous solution with pH values ranging from 2 to 11 and different organic solvents), which possesses the well-known [Fe3(¿3-O)(COO)6] secondary building unit, has proven to be an efficient catalyst for the aerobic oxidation of dibenzothiophenes.
An Ultrahigh CO2-Loaded Silicalite-1 Zeolite: Structural Stability and Physical Properties at High Pressures and Temperatures
[EN] We report the formation of an ultrahigh CO2-loaded pure-SiO2, silicalite-1 structure at high pressure (0.7 GPa) from the interaction of empty zeolite and fluid CO, medium. The CO2-filled structure was characterized in situ by means of synchrotron powder X-ray diffraction. Rietveld refinements and Fourier recycling allowed the location of 16 guest carbon dioxide molecules per unit cell within the straight and sinusoidal channels of the porous framework to be analyzed. The complete filling of pores by CO, molecules favors structural stability under compression, avoiding pressure-induced amorphization below 20 GPa, and significantly reduces the compressibility of the system compared to th…
Isostructural compartmentalized spin-crossover coordination polymers for gas confinement
[EN] Here we present two FeII coordination polymers that possess discrete compartments suitable for CO2 physisorption despite the lack of permanent channels. The two crystalline materials, of general formula [Fe(btzbp)3](X)2 (X = ClO4 or BF4), present voids of ca. 250 Å3, which each can accommodate up to two CO2 molecules. The abrupt spin transition can be modified upon CO2 sorption, and different magnetic behaviour is observed depending on the number of molecules sorbed.
Cobalt Metal-Organic Framework based on two dinuclear secondary building units for electrocatalytic oxygen evolution
[EN] The synthesis of a new microporous metal-organic framework (MOF) based on two secondary building units, with dinuclear cobalt centers, has been developed. The employment of a well-defined cobalt cluster results in an unusual topology of the Co-2-MOF, where one of the cobalt centers has three open coordination positions, which has no precedent in MOF materials based on cobalt. Adsorption isotherms have revealed that Co-2-MOF is in the range of best CO2 adsorbents among the carbon materials, with very high CO2/CH4 selectivity. On the other hand, dispersion of Co-2-MOF in an alcoholic solution of Nafion gives rise to a composite (Co-2-MOF@Nafion) with great resistance to hydrolysis in aqu…
Computational screening of structure directing agents for the synthesis of zeolites. A simplified model
Abstract Zeolite micropores become more energetically stable by the occlusion of organic structure directing agents (templates). This energetic stabilisation, if approximated by van der Waals zeo-template interactions, can be calculated in a fast way by using modern computing techniques incorporating big data handling algorithms for massive screening. A software suite is presented which calculates an arbitrarily large 2-D matrix (template×zeolite) giving the zeo-template van der Waals interaction energy corresponding to the minimum energy conformation assuming one template molecule in a pure silica zeolite unit cell. With the goal of simplicity, the software only needs two coordinate input …
A New Aluminosilicate Molecular Sieve with a System of Pores between Those of ZSM-5 and Beta Zeolite
[EN] A new aluminosilicate zeolite (ITQ-39) has been synthesized. This is an extensively faulted structure with very small domains that makes the structure elucidation very difficult. However, a combination of adsorption spectroscopy and reactivity studies with selected probe molecules suggests that the pore structure of ITQ-39 is related to that of Beta zeolite, with a three-directional channel system with large pores (12-MR), but with an effective pore diameter between those of Beta and ZSM-5, or a three-directional channel system with interconnected large (12-MR) and medium pores (10-MR). The pore topology of ITQ-39 is very attractive for catalysis and shows excellent results for the pre…
Synthesis of a novel zeolite through a pressure-induced reconstructive phase transition process
et al.
V-containing MCM-41 and MCM-48 catalysts for the selective oxidation of propane in gas phase
Well-organised V-containing MCM-41 and -48 (0.3‐1 wt.% of V content) have been synthesised by one-pot synthesis or by grafting using VOSO4 or VOCl3 as V sources, respectively. The samples before and after the calcination step have been characterised by several physicochemical techniques (Ar and N2 adsorption, XRD, diffuse reflectance-UV‐VIS (DR-UV‐VIS) spectroscopy, temperature-programmed reduction). It was found that V species in the as-prepared catalysts were mainly as vanadyl ions (VO 2C ), while highly dispersed V 5C species with tetrahedral coordination were observed in the calcined materials. The catalytic behaviour of the calcined materials for the gas phase oxidation of propane has …
Structural evolution of CO2 filled pure silica LTA zeolite under high-pressure high-temperature conditions
[EN] The crystal structure of CO2-filled pure-SiO2 LTA zeolite has been studied at high pressures and temperatures using synchrotron-based X-ray powder diffraction. Its structure consists of 13 CO2 guest molecules, 12 of them accommodated in the large alpha-cages and one in the beta-cages, giving a SiO2/CO2 stoichiometric ratio smaller than 2. The structure remains stable under pressure up to 20 GPa with a slight pressure-dependent rhombohedral distortion, indicating that pressure-induced amorphization is prevented by the insertion of guest species in this open framework. The ambient temperature lattice compressibility has been determined. In situ high-pressure resistive-heating experiments…
Correspondence: Strongly-driven Re+CO2 redox reaction at high-pressure and high-temperature.
Correspondence: Strongly-driven Re+CO 2 redox reaction at high-pressure and high-temperature
Identification of New Templates for the Synthesis of BEA, BEC, and ISV Zeolites Using Molecular Topology and Monte Carlo Techniques
The presence of organic structure directing agents (templates) in the synthesis of zeolites allows the synthesis to be directed, in many cases, toward structures in which there is a large stabilization between the template and the zeolite micropore due to dispersion interactions. Although other factors are also important (temperature, pH, Si/Al ratio, etc.), systems with strong zeolite-template interactions are good candidates for an application of new computational algorithms, for instance those based in molecular topology (MT), that can be used in combination with large databases of organic molecules. Computational design of new templates allows the synthesis of existing and new zeolites …
Solvent-free synthesis of ZIFs: a route toward the elusive Fe(II) analogue of ZIF-8
Herein we report the synthesis of an elusive metal-organic framework, the iron(II) analogue of ZIF-8 with the formula Fe(2-methylimidazolate) , here denoted as MUV-3. The preparation of this highly interesting porous material, inaccessible by common synthetic procedures, occurs in a solvent-free reaction upon addition of an easily detachable template molecule, yielding single crystals of MUV-3. This methodology can be extended to other metals and imidazolate derivatives, allowing the preparation of ZIF-8, ZIF-67, and the unprecedented iron(II) ZIFs Fe(2-ethylimidazolate) and Fe(2-methylbenzimidazolate) . The different performance of MUV-3 toward NO sorption, in comparison to ZIF-8, results …
Gas confinement in compartmentalized coordination polymers for highly selective sorption
Discrimination between different gases is an essential aspect for industrial and environmental applications involving sensing and separation. Several classes of porous materials have been used in this context, including zeolites and more recently MOFs. However, to reach high selectivities for the separation of gas mixtures is a challenging task that often requires the understanding of the specific interactions established between the porous framework and the gases. Here we propose an approach to obtain an enhanced selectivity based on the use of compartmentalized coordination polymers, named CCP-1 and CCP-2, which are crystalline materials comprising isolated discrete cavities. These compar…
Spin-Crossover Modification through Selective CO2 Sorption
[EN] We present a spin-crossover Fe-II coordination polymer with no permanent channels that selectively sorbs CO2 over N-2. The one-dimensional chains display internal voids of similar to 9 angstrom diameter, each being capable to accept one molecule of CO2 at 1 bar and 273 K. X-ray diffraction provides direct structural evidence of the location of the gas molecules and reveals the formation of O=C=O(delta(-))center dot center dot center dot pi interactions. This physisorption modifies the spin transition, producing a 9 K increase in T-1/2.
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CCDC 1910863: Experimental Crystal Structure Determination
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CCDC 910547: Experimental Crystal Structure Determination
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CCDC 1473650: Experimental Crystal Structure Determination
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CCDC 1440481: Experimental Crystal Structure Determination
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CCDC 1579606: Experimental Crystal Structure Determination
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CCDC 1825894: Experimental Crystal Structure Determination
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CCDC 1899778: Experimental Crystal Structure Determination
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CCDC 921439: Experimental Crystal Structure Determination
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