Synthesis and Structure of a 22 × 12 × 12 Extra-Large Pore Zeolite ITQ-56 Determined by 3D Electron Diffraction.

A multidimensional extra-large pore germanosilicate, denoted ITQ-56, has been synthesized by using modified memantine as an organic structure-directing agent. ITQ-56 crystallizes as plate-like nanocrystals. Its structure was determined by 3D electron diffraction/MicroED. The structure of ITQ-56 contains extra-large 22-ring channels intersecting with straight 12-ring channels. ITQ-56 is the first zeolite with 22-ring pores, which is a result of ordered vacancies of double 4-ring (d4r) units in a fully connected zeolite framework. The framework density is as low as 12.4 T atoms/1000 Å3. The discovery of the ITQ-56 structure not only fills the missing member of extra-large pore zeolite with 22-ring channels but also creates a new approach of making extra-large pore zeolites by introducing ordered vacancies in zeolite frameworks.

Synthesis and structure determination of the hierarchical meso-microporous zeolite ITQ-43.

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 ITQ-37 mesoporous chiral zeolite.

The synthesis of crystalline molecular sieves with pore dimensions that fill the gap between microporous and mesoporous materials is a matter of fundamental and industrial interest. The preparation of zeolitic materials with extralarge pores and chiral frameworks would permit many new applications. Two important steps in this direction include the synthesis of ITQ-33, a stable zeolite with 18 x 10 x 10 ring windows, and the synthesis of SU-32, which has an intrinsically chiral zeolite structure and where each crystal exhibits only one handedness. Here we present a germanosilicate zeolite (ITQ-37) with extralarge 30-ring windows. Its structure was determined by combining selected area electron diffraction (SAED) and powder X-ray diffraction (PXRD) in a charge-flipping algorithm. The framework follows the SrSi(2) (srs) minimal net and forms two unique cavities, each of which is connected to three other cavities to form a gyroidal channel system. These cavities comprise the enantiomorphous srs net of the framework. ITQ-37 is the first chiral zeolite with one single gyroidal channel. It has the lowest framework density (10.3 T atoms per 1,000 A(3)) of all existing 4-coordinated crystalline oxide frameworks, and the pore volume of the corresponding silica polymorph would be 0.38 cm(3) g(-1).

Monomers that form conducting polymers as structure-directing agents: synthesis of microporous molecular sieves encapsulating poly-para-phenylenevinylene.

We have developed a novel concept that uses monomers required for making conducting polymers as organic structure-directing agents, for the synthesis of microporous molecular sieves. We show that these monomers facilitate the formation of crystalline and amorphous molecular sieves depending on the synthesis procedure. The monomers filling the pores of the silicates can be polymerized under certain conditions, resulting in a polymer immobilized and protected inside the matrix. The concept was exemplified with para-phenylenemethylene-bis(1-tetrahydrothiophenium) and para-phenylenemethylene-bis(trimethylammonium) that were used to template microporous molecular sieves and subsequently to obtain poly-para-phenylenevinylene (PPV) inside the matrix. The organic self-assembled organic-inorganic material was extensively characterized and the implication on electrical conductivity is presented.

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 channels(5) 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.

Synthesis of micro- and mesoporous molecular sieves at room temperature and neutral pH catalyzed by functional analogues of silicatein.

By using functional mimics of the protein silicatein alpha together with organic structure directing agents, it was possible to produce different mesoporous and microporous molecular sieves at room temperature and neutral pH.

P-derived organic cations as structure-directing agents: synthesis of a high-silica zeolite (ITQ-27) with a two-dimensional 12-ring channel system.

Recently, efforts have been made to synthesize large-pore, multidimensional zeolite frameworks as a basis for new catalysts to improve various hydrocarbon conversions. A new aluminosilicate zeolite, ITQ-27, has been prepared using the phosphorus-containing structure-directing agent, dimethyldiphenylphosphonium. Its crystal structure was determined in its calcined form by direct methods (FOCUS) on synchrotron powder diffraction data (lambda = 0.8702 A) after the unit cell and space group were determined from tilt electron diffraction experiments on individual microcrystals. The material crystallizes in space group Fmmm, where a = 27.7508(5) A, b = 25.2969(7) A, and c = 13.7923(4) A. The final model, refined by Rietveld methods, comprises seven unique T-sites forming a framework with straight 12-MR channels that are connected by 14-MR openings between them. (Corresponding 12-ring pore dimension is 6.94 A x 6.20 A.) Since access from one 14-MR opening to the next is through the 12-MR channel, the structure is best described as a two-dimensional, 12-MR framework.

Rational design and HT techniques allow the synthesis of new IWR zeolite polymorphs.

By combining a rational design of structure directing agents and high throughput and data mining techniques, it has been possible to obtain Ge-free ITQ-24 as pure silica as well as borosilicate polymorphs up to a Si/TIII ratio of 10. Al can be exchanged by B giving strong acid materials. Also, the availability of the pure silica material allows one to determine more precisely the crystal symmetry. This work opens the possibility to synthesize the Ge-free polymorphs of a large number of new germanosilicate structures reported in the last five years. This certainly will increase their possibilities for industrial application.

A large-cavity zeolite with wide pore windows and potential as an oil refining catalyst.

Crude oil is an important feedstock for the petrochemical industry and the dominant energy source driving the world economy, but known oil reserves will cover demand for no more than 50 years at the current rate of consumption. This situation calls for more efficient strategies for converting crude oil into fuel and petrochemical products. At present, more than 40% of oil conversion is achieved using catalysts based on faujasite; this zeolite requires extensive post-synthesis treatment to produce an ultrastable form, and has a large cavity accessible through four 0.74-nm-wide windows and thus limits the access of oil molecules to the catalytically active sites. The use of zeolites with better accessibility to their active sites should result in improved catalyst efficiency. To date, two zeolites with effective pore diameters exceeding that of faujasite have been reported, but their one-dimensional pore topology excludes use in oil refining. Similarly, zeolites with large pores and a three-dimensional pore topology have been reported, but in all these materials the pore openings are smaller than in faujasite. Here we report the synthesis of ITQ-21, a zeolite with a three-dimensional pore network containing 1.18-nm-wide cavities, each of which is accessible through six circular and 0.74-nm-wide windows. As expected for a zeolite with this structure, ITQ-21 exhibits high catalytic activity and selectivity for valuable products in preliminary oil refining tests.