Zeolites are crystalline microporous materials constructed by corner-sharing tetrahedra (SiO₄ and AlO₄), with many industrial applications as ion exchangers, adsorbents and heterogeneous catalysts^1,2,3,4. However, the presence of micropores impedes the use of zeolites in areas dealing with bulky substrates. Introducing extrinsic mesopores, that is, intercrystal/intracrystal mesopores, in zeolites is a solution to overcome the diffusion barrier^5,6,7,8. Still, those extrinsic mesopores are generally disordered and non-uniform; moreover, acidity and crystallinity are always, to some extent, impaired⁹. Thus, synthesizing thermally stable zeolites with intrinsic mesopores that are of uniform size and crystallographically connected with micropores, denoted here as intrinsic mesoporous zeolite, is highly desired but still not achieved. Here we report ZMQ-1 (Zeolitic Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, no. 1), an aluminosilicate zeolite with an intersecting intrinsic meso-microporous channel system delimited by 28 × 10 × 10-rings, in which the 28-ring has a free diameter of 22.76 Å × 11.83 Å, which reaches the mesopore domain. ZMQ-1 has high thermal and hydrothermal stability with tunable framework Si/Al molar ratios. ZMQ-1 is the first aluminosilicate zeolite with an intrinsic meso-microporous channel system. The Brønsted acidity of ZMQ-1 imparts high activity and unique selectivity in the catalytic cracking of heavy oil. The position of the organic structure-directing agent (OSDA) used for ZMQ-1 synthesis was determined from three-dimensional electron diffraction (3D ED) data, which shows the unique structure-directing role of the OSDA in the formation of the intrinsic meso-microporous zeolite. This provides an incentive for preparing other stable mesopore-containing zeolites.

Synthesis of a pentasil‐type zeolite with ultra‐small few‐unit‐cell crystalline domains, which we call FDP (few‐unit‐cell crystalline domain pentasil), is reported. FDP is made using bis‐1,5(tributyl ammonium) pentamethylene cations as structure directing agent (SDA). This di‐quaternary ammonium SDA combines butyl ammonium, in place of the one commonly used for MFI synthesis, propyl ammonium, and a five‐carbon nitrogen‐connecting chain, in place of the six‐carbon connecting chain SDAs that are known to fit well within the MFI pores. X‐ray diffraction analysis and electron microscopy imaging of FDP indicate ca. 10 nm crystalline domains organized in hierarchical micro‐/meso‐porous aggregates exhibiting mesoscopic order with an aggregate particle size up to ca. 5 μm. Al and Sn can be incorporated into the FDP zeolite framework to produce active and selective methanol‐to‐hydrocarbon and glucose isomerization catalysts, respectively.

Dications consisting of 1,2-dimethylimidazolium units linked by chains of 4, 5 or 6 methylene groups display structure direction towards the chiral zeolite STW as racemic conglomerates with decreasing strength as the length of the linker increases. A phase transformation from the denser and less strained MTW to the less dense and more strained STW reveals significant stabilization in the case of the 4-methylene dication, which is able to produce STW even in the absence of germanium (i.e., for a pure silica composition), and to a lesser extent for the 5-methylene derivative. When Ge is introduced in the synthesis the crystallization is easier and the crystallization field is wider, with Ge preferentially occupying positions at the double four ring units of the STW framework, as revealed by Rietveld refinement from synchrotron data. Quantum mechanics calculations show that the interaction energy diminishes as the length of the linker increases, in agreement with the experimental findings. In addition, calculation of the ¹³C NMR chemical shieldings and comparison with experimental spectra allowed us to identify different conformations and orientations of the imidazolium rings in the asymmetric STW cavities, depending on the spacer length. An exploratory study strongly suggests that an asymmetric derivative with additional methyl groups at both sides of the tetramethylene chain could afford the crystallization of the homochiral zeolite even as a pure silica material.