José L. Jordá

High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10- member rings

Crystalline molecular sieves with large pores and high adsorption capacities have many potential applications. Of these materials, zeolites are of particular interest owing to their stability in a wide range of experimental conditions. An aluminophosphate with very large circular channels5 containing 18 oxygen atoms (18-ring channels) has been synthesized, but in the search for large-pore zeolites, most of the materials which have been synthesized up to now contain only 14-ring channels; the synthesis of zeolites with larger ring structures has been believed to be hindered by the low Si-O-Si bond angles available. A silicogaloaluminate (ECR-34) with unidirectional 18-ring channels was recently reported, but exhibited low micropore volume, thus rendering the material less attractive for catalytic applications. Here we report the structure and catalytic activity of the silicogermanate zeolite ITQ-33; this material exhibits straight large pore channels with circular openings of 18-rings along the c axis interconnected by a bidirectional system of 10-ring channels, yielding a structure with very large micropore volume. The conditions for synthesis are easily accessible, but are not typical, and were identified using high-throughput techniques.

A Miniaturized Linear pH Sensor Based on a Highly Photoluminescent Self-Assembled Europium(III) Metal–Organic Framework†

The field of lanthanide-based metal–organic frameworks (LnMOFs) with twoor three-dimensional structures is rapidly growing because of the discovery of new crystalline structures that exhibit interesting properties and have potential applications in catalysis, sensors, contrast agents, non-linear optics, 22] displays, and electroluminescent devices. For photoluminescence applications, it is necessary to prepare lanthanide-containing materials with high quantum efficiencies, in order to achieve the required miniaturization and reduce energy losses from undesirable quenching processes. Moreover, it is highly desirable to combine the properties of ligands and antennae in one organic moiety. A well-known powerful sensitizing ligand for Eu ions in solution is 1,10-phenanthroline-2,9-dicarboxylic acid (H2PhenDCA), in which both carboxylic and phenanthroline moieties may coordinate to the metal center. 27] The proximity between the coordinative parts means that this chelating agent has the tendency to form zero-dimensional (molecular) complexes that are useful in some solution-based analytical applications, but cannot be applied as solid sensors or light-emitting materials. Thus, it is of interest to obtain the twoor three-dimensional insoluble counterparts of these zero-dimensional water-soluble complexes. To achieve this goal, we have used hydrothermal synthesis, which is a powerful technique for the preparation of metastable compounds that may not be accessible by using conventional methods. 29] Hydrothermal synthesis also allows the use of chelating agents that are sparingly soluble in water at temperatures below 373 K, thus enhancing the lanthanidecoordinating ability of the ligand. Herein, we report the synthesis, structure, and sensing properties of a new Eu metal–organic framework ITQMOF-3-Eu (ITQMOF = Instituto de Tecnologia Quimica Metal Organic Framework) that contains the ligand 1,10-phenanthroline-2,9-dicarboxylic acid. The excellent balance between absorption, energy transfer, and emission rate of the Eu ITQMOF-3 (ITQMOF-3-Eu) allowed the fabrication of a miniaturized pH sensor prototype that functions in the biologically interesting range (5–7.5). By combining this material and an optical fiber, a linear photoluminescence response, which also allows the self-calibration of the emitting signal within this pH range, was achieved. The ITQMOF-3Eu material was obtained by reacting the H2PhenDCA ligand and the Eu salt or oxide under hydrothermal conditions (see the Supporting Information). The crystal has a strong red luminescence under ultraviolet light (see Figure 1 a). Chemical and elemental analyses showed that the formula of the material is [Eu3(C14H6N2O4)4(OH)(H2O)4]·2 H2O.

Synthesis and Structure Determination of the Hierarchical Meso-Microporous Zeolite ITQ-43

A zeolite with microporous channels (6 to 7 angstrom diameter) and mesoporous channels (~2-nanometer diameter) was made. The formation of mesopores in microporous zeolites is generally performed by postsynthesis acid, basic, and steam treatments. The hierarchical pore systems thus formed allow better adsorption, diffusion, and reactivity of these materials. By combining organic and inorganic structure-directing agents and high-throughput methodologies, we were able to synthesize a zeolite with a hierarchical system of micropores and mesopores, with channel openings delimited by 28 tetrahedral atoms. Its complex crystalline structure was solved with the use of automated diffraction tomography.

The Synthesis of an Extra-Large-Pore Zeolite with Double Three-Ring Building Units and a Low Framework Density†

Zeolites are crystalline inorganic solids formed by TO4 tetrahedra (T=Si, P, Al, Ge, etc.) with a well-defined system of regular pores having diameters up to about 2 nm. The possibility of tuning pore dimensions and framework compositions have made zeolites the most successful materials for applications in gas adsorption and separation and for catalysis. Their uses have been further expanded to microelectronics for preparing materials with low values of the high-frequency dielectric constant or manufacturing encapsulated light-emitting devices (LEDs), to medicine for diagnostic treatments and controlled drug delivery, or for release of semiotics for controlling insect populations in agricultural uses. Those applications often require structures with low framework densities, large internal volumes, and preferentially, extra-large pores. However, up to now, the number of known zeolites with a low framework density (FD 12) is almost negligible, and the number with extra-large pores ( 18-R) is also extremely small. Computational methods can predict a large number of thermodynamically feasible new structures, and they can stimulate and inspire the discovery of new structures. For example, Foster and Treacy have used a symmetry-constrained intersite bond searching method and have generated more than two million structures. With that methodology, the authors predicted a series of thermodynamically feasible extra-large-pore zeolites. Deem et al. have also modeled relatively large number of low density zeolites and were able to show that the low-energy and low-density materials also tend to have desirably large rings. Among the zeolite structures with extra large pores predicted by Foster and Treacy, there is one with 18 10 10-R pore topology that could be of particular interest for catalysis, as it combines an extra-large pore (18-R) for molecular accessibility with connected 10-R pores that can introduce shape-selectivity effects. Recently, the predicted zeolite was synthesized and named ITQ-33. This zeolite has 3-R and D4R units in the structure, and was at the time the silicate-based zeolite with the lowest framework density (12.3.T/1000 ). The pore topology of this extra-large-pore zeolite presented quite unique and interesting catalytic properties: The pore accessibility to large molecules through the 18-R was combined with shape selectivity in the 10-R pores for the primary products formed. In the same data base, Foster and Treacy also predicted an extra-large-pore zeolite that was closely related to ITQ-33 (Zeolite reference 191_4_1985). In that new structure, the 10-R pores of ITQ-33 were expanded to 12-R pores connecting the larger perpendicular 18-R channels. The result was a zeolite with 18 12 12 pore topology instead of the 18 10 10 for ITQ-33. In particular, along with D4R units, the new zeolite contains D3R units that have never been seen in synthesized zeolites, which could be related to geometric strains introduced in the framework owing to the formation of D3R based on silicon. In any case, the pore expansion with the 18 12 12-R pore system in the new zeolite should result in a decrease of the framework density from 12.3 in the case of ITQ-33 to 10.9 T atoms/1000 . Herein, we show that the zeolite containing D3R that was predicted above can be successfully synthesized (ITQ-44) as a silicogermanate by combining a relatively inexpensive, rigid and bulky organic structure-directing agent (SDA) with the directing effect of germanium. Furthermore, we show that in ITQ-44, germanium locates preferentially in D3R (with 50% Ge occupancy), followed by D4R (with 37% Ge occupancy). ITQ-44 was synthesized using (2’-(R),6’-(S))-2’,6’-dimethylspiro[isoindole-2,1’-piperidin-1’-ium] as the SDA (Supporting Information, Figure S1). The synthesis of ITQ-44 was carried out in fluoride media using high-throughput (HT) synthesis techniques, which involve the use of a 15-well multiautoclave. The XRD pattern of a calcined ITQ-44 sample (Figure 1) was collected (as described in the Supporting Information), and the crystal structure was solved using the program FOCUS. The agreement between the observed and calculated XRD patterns are shown in Figure 1; it certainly confirms that this structure corresponds to that of the pure silica polymorph of this material predicted by Foster and Treacy (reference number 191_4_19854). The structure of ITQ-44 is closely related to the previously described zeolite ITQ-33 (Figure 2). It also comprises a building unit formed by a [346] cage with two additional [*] J. Jiang, Dr. J. L. Jorda, Dr. M. J. Diaz-Cabanas, Prof. A. Corma Instituto de Tecnologia Quimica (UPV-CSIC) Universidad Politecnica de Valencia Consejo Superior de Investigaciones Cientificas Av. de los Naranjos s/n, 46022 Valencia (Spain) Fax: (+34)96-387-7809 E-mail: acorma@itq.upv.es

A zeolitic structure (ITQ-34) with connected 9- and 10-ring channels obtained with phosphonium cations as structure directing agents.

Zeolites are materials with a large applied interest. Here we present ITQ-34 a new zeolitic material, obtained combining the use of the highly stable tetraalkylphosphonium cations as structure directing agents with the incorporation of Ge atoms in the structure.

Modular Organic Structure-Directing Agents for the Synthesis of Zeolites

Routes to Rare Zeolites Zeolites are microporous crystalline solids with well-defined structures. Although many naturally occurring ones have been obtained in laboratory synthesis, some have remained elusive. One of these, boggsite, is of interest for catalytic reactions because it has large channels defined by rings of 10 or 12 atoms that intersect within its crystalline lattice. Simancas et al. (p. 1219) report the synthesis of boggsite by using phosphazenes as the organic groups that directed the formation of rings during synthesis. These reagents can be readily modified—a feature that should allow greater flexibility in synthesis routes. Phosphazene molecules enable the synthesis of a rare naturally occurring zeolite. Organic structure-directing agents (OSDAs) are used to guide the formation of particular types of pores and channels during the synthesis of zeolites. We report that the use of highly versatile OSDAs based on phosphazenes has been successfully introduced for the synthesis of zeolites. This approach has made possible the synthesis of the elusive boggsite zeolite, which is formed by 10- and 12-ring intersecting channels. This topology and these pore dimensions present interesting opportunities for catalysis in reactions of industrial relevance.

Synthesis design and structure of a multipore zeolite with interconnected 12- and 10-MR channels.

A new molecular sieve, ITQ-38, containing interconnected large and medium pores in its structure has been synthesized. The rational combination of dicationic piperidine-derivative molecules as organic structure directing agents (OSDAs) with germanium and boron atoms in alkaline media has allowed the synthesis of ITQ-38 zeolite. High-resolution transmission electron microscopy (HRTEM) has been used to elucidate the framework topology of ITQ-38, revealing the presence of domains of perfect ITQ-38 crystals as well as very small areas containing nanosized ITQ-38/ITQ-22 intergrowths. The structure of ITQ-38 is highly related to ITQ-22 and the recently described polymorph C of ITQ-39 zeolite. It shares a common building layer with ITQ-22 and contains the same building unit as the polymorph C of ITQ-39. All three structures present similar framework density, 16.1 T atoms/1000 Å(3).

Methane hydrate formation in confined nanospace can surpass nature

Natural methane hydrates are believed to be the largest source of hydrocarbons on Earth. These structures are formed in specific locations such as deep-sea sediments and the permafrost based on demanding conditions of high pressure and low temperature. Here we report that, by taking advantage of the confinement effects on nanopore space, synthetic methane hydrates grow under mild conditions (3.5 MPa and 2 °C), with faster kinetics (within minutes) than nature, fully reversibly and with a nominal stoichiometry that mimics nature. The formation of the hydrate structures in nanospace and their similarity to natural hydrates is confirmed using inelastic neutron scattering experiments and synchrotron X-ray powder diffraction. These findings may be a step towards the application of a smart synthesis of methane hydrates in energy-demanding applications (for example, transportation).

A New Microporous Zeolitic Silicoborate (ITQ-52) with Interconnected Small and Medium Pores

A new zeolite (named as ITQ-52) having large cavities and small and medium channels has been synthesized. This was achieved by using a new family of amino-phosphonium cations as organic structure directing agents (OSDA). These cations contain P-C and P-N bonds, and therefore they lie between previously reported P-containing OSDA, such as tetraalkylphosphonium and phosphazenes. In this study, it has been found that 1,4-butanediylbis[tris(dimethylamino)]phosphonium dication is a very efficient OSDA for crystallization of several zeolites, and in some particular conditions, the new zeolite ITQ-52 was synthesized as a pure phase. The structure of ITQ-52 has been solved using high-resolution synchrotron X-ray powder diffraction data of the calcined solid. This new zeolite crystallizes in the space group I2/m, with cell parameters a = 17.511 Å, b = 17.907 Å, c = 12.367 Å, and β = 90.22°. The topology of ITQ-52 can be described as a replication of a composite building unit with ring notation [4(3)5(4)6(1)] that gives rise to the formation of an interconnected 8R and 10R channel system.

Synthesis and Structure Determination of a New Microporous Zeolite with Large Cavities Connected by Small Pores

A new small-pore germanosilicate zeolite, named as ITQ-49, has been synthesized using a new ditetraalkylphosphonium dication as an organic structure-directing agent, and its structure has been solved by direct methods applied to the powder X-ray diffraction pattern of the calcined solid. This new zeolite crystallizes in the space group Immm with cell parameters a = 19.6007(8) Å, b = 18.3274(7) Å, and c = 16.5335(6) Å. The pore topology of ITQ-49 consists of large, nonspherical cavities that are connected to each other through small eight-membered-ring windows, resulting in a unidirectional small-pore zeolite that has a relatively large adsorption capacity. Also, ITQ-49 contains double four-membered-ring units where Ge is preferentially located, and fluoride anions are placed inside these units.