Stable Silica-Based Zeolites with Three-Dimensional Systems of Extra-Large Pores.

Zeolites are microporous crystalline materials that find a very wide range of applications, which, however, are limited by the size and dimensionality of their pores. Stable silica zeolites with a three-dimensional (3D) system of extra-large pores (ELP, i.e., pores with minimum windows along the diffusion path consisting of more than 12 SiO4/2 tetrahedra, 12R) are in demand for processing larger molecules than zeolites can currently handle. However, they have challenged worldwide synthetic capabilities for more than eight decades. In this review we first present a brief history of the discovery of ELP zeolites. Next, we show that earlier successes of zeolites with 3D ELP were not actually zeolites, but rather interrupted structures with, in addition, a composition that severely detracted from their stability. Finally, we present three new fully connected stable silica-based 3D ELP zeolites ZEO-1, ZEO-3 and ZEO-5, discuss their preparation methods and stability as well as the clear advantage of their increased porosity in catalysis and adsorption processes involving large molecules. We will discuss peculiar characteristics of their preparation and present two new reaction types giving rise to zeolites (1D-to-3D topotactic condensation and interchain expansion), highlighting how new synthesis methods can provide materials that would otherwise be unfeasible.

Stabilization of Extra-Large-Pore Zeolite by Boron Substitution for the Production of Commercially Applicable Catalysts.

Stable extra-large-pore zeolites are desirable for industrial purposes due to their ability to accommodate bulky reactants and diffusion through channels. Although there are several extra-large pore zeolites reported, stable ones are rare. Thus, their stabilization is a feasible strategy for industrial applications. Here, an extra-large-pore zeolite EWT with boron substitution is presented, and the resulting zeolite B-RZM-3 increased the thermal stability from 600 °C in its silica form to 850 °C. The crystal structure, determined by combining continuous rotation electron diffraction (cRED) and powder X-ray diffraction (PXRD), shows that B atoms preferentially substitute the interrupted (HO)T(OT)3 (Q3 ) sites and are partially converted into 3-coordination to relax framework deformation upon heating. After Al-reinsertion post-treatment, Al-B-RZM-3 shows higher ethylbenzene selectivity and ethylene conversion rate per mol acid site than commercial ZSM-5 and Beta zeolite in benzene alkylation reaction. Synthesizing extra-large-pore zeolite in borosilicate form is a potential approach to stabilize interrupted zeolites for commercial applications.

HPM-14: A New Germanosilicate Zeolite with Interconnected Extra-Large Pores Plus Odd-Membered and Small Pores*.

HPM-14 is a new extra-large pore zeolite synthesized using imidazolium-based organic structure-directing agents (SDAs), fluoride anions, and germanium and silicon as tetrahedral components of the framework. Owing to the presence of stacking disorder, the structure elucidation of HPM-14 was challenging, and different techniques were necessary to clarify the details of the structure and to understand the nature of the disorder. The structure has been solved by three-dimensional electron-diffraction technique (3D ED) and consists of an intergrowth of two polymorphs possessing a three-dimensional channel system, including an extra-large pore opened through windows made up of sixteen tetrahedral atoms (16-membered ring, 16MR) as well as two additional sets of odd-membered (9MR) and small (8MR) pores. The intergrowth has been studied by scanning transmission electron microscopy (Cs -STEM) and powder X-ray diffraction simulations (DIFFaX), which show a large predominance of the monoclinic polymorph A.

Synthesis, Structure and Properties of an Extra-Large-Pore Aluminosilicate Zeolite NUD-6.

Pure silica zeolites possessing uniform micropores, large surface area and high thermal and chemical stability have been widely studied and used in the fields of fine chemicals and oil industry. The incorporation of aluminium into the framework of silica zeolites changes their properties, making them more industrially useful as adsorbents and catalysts. Herein, we report the synthesis and characterization of an extra-large-pore aluminosilicate zeolite NUD-6 with a 16-membered-ring pore channel. Aluminium was directly incorporated into the zeolite NUD-6 framework, as confirmed by 27 Al MAS NMR studies and ammonia temperature-programmed desorption probes. Al-NUD-6 was not stable when heated at 550 °C to remove the organic templates. However, the organic templates in Al-NUD-6 could be removed by oxidation in nitric acid at room temperature. The obtained Al-NUD-6H retained the crystalline structure and possessed both micropores and mesopores despite the occurrence of severe structural distortions due to the presence of the corner-sharing Q3 Si2 O7 units. The incorporation of aluminium resulted in both medium and strong acid sites in Al-NUD-6H, and could facilitate its use in adsorption and catalysis.

IDM-1: A Zeolite with Intersecting Medium and Extra-Large Pores Built as an Expansion of Zeolite MFI.

IDM-1 is a new silica zeolite with an ordered and well-defined framework constructed by alternating pentasil layers and interrupted layers, giving rise to an intersecting system of straight medium pores and undulating extra-large lobed pores. This unique structure was solved by rotation electron diffraction and refined against synchrotron powder X-ray diffraction data. Despite the presence of both Si(OSi)3 (OH) and Si(OSi)2 (OH)2 sites, this new zeolite presents high thermal stability, withstanding calcination even to 1000 °C. The location of defects at specific sites of the structure results in alternating hydrophobic SiO2 and hydrophilic SiO(2-x) (OH)2x intracrystalline regions. This peculiar combination of intersecting medium and extra-large pores and alternating regions of different chemical character may provide this zeolite with unique catalytic properties.

An Extra-Large-Pore Pure Silica Zeolite with 16×8×8-Membered Ring Pore Channels Synthesized using an Aromatic Organic Directing Agent.

Extra-large-pore zeolites for processing large molecules have long been sought after by both the academia and industry. However, the synthesis of these materials, particularly extra-large-pore pure silica zeolites, remains a big challenge. Herein we report the synthesis of a new extra-large-pore silica zeolite, designated NUD-6, by using an easily synthesized aromatic organic cation as structure-directing agent. NUD-6 possesses an intersecting 16×8×8-membered ring pore channel system constructed by four-connected (Q4 ) and unusual three-connected (Q3 ) silicon species. The organic cations in NUD-6 can be removed in nitric acid to yield a porous material with high surface area and pore volume. The synthesis of NUD-6 presents a feasible means to prepare extra-large pore silica zeolites by using assembled aromatic organic cations as structure-directing agents.

An Extra-Large-Pore Zeolite with 24×8×8-Ring Channels Using a Structure-Directing Agent Derived from Traditional Chinese Medicine.

Extra-large-pore zeolites have attracted much interest because of their important applications for processing larger molecules. Although great progress has been made in academic science and industry, it is challenging to synthesize these materials. A new extra-large-pore zeolite SYSU-3 (Sun Yat-sen University no. 3) has been synthesized by using a novel sophoridine derivative as an organic structure-directing agent (OSDA). The framework structure was solved and refined using continuous rotation electron diffraction (cRED) data from nanosized crystals. SYSU-3 exhibits a new zeolite framework topology, which has the first 24×8×8-ring extra-large-pore system and a framework density (FD) as low as 11.4 T/1000 Å3 . The unique skeleton of the OSDA plays an essential role in the formation of the distinctive zeolite structure. This work provides a new perspective for developing new zeolitic materials by using alkaloids as cost-effective OSDAs.