A high-silica zeolite with a TON structure designated as ZJM-4 was successfully synthesized in the absence of any organic templates and zeolite seeds. Many factors such as the SiO₂/K₂O ratio, Si/Al ratio, SiO₂/H₂O in the starting aluminosilicate gels, crystallization temperature, and crystallization time strongly influence the formation of the ZJM-4 zeolite. Interestingly, this synthesis shows very efficient silica utilization in the starting gels (>80 %). Catalytic tests on the isomerization of m-xylene to p-xylene show that the ZJM-4 catalyst has high selectivity to p-xylene (ca. 80 %), which could be potentially important for industrial applications for the ZJM-4 zeolite as a candidate catalyst in the future.

The rational design of catalytic materials from the reaction characteristics is expected to be a useful strategy to create highly efficient catalysts. Herein, according to a well-established reaction pathway of epoxide hydration catalyzed a dual-molecular system of Co³⁺/salen in which a high concentration of active sites is favorable to enhance the activity, we provide an alternative way to prepare a highly efficient heterogeneous catalyst with a high concentration of Co³⁺/salen from the polymerization of vinyl-functionalized salen monomers followed by the loading of Co³⁺ species (Co³⁺/POL-salen). Co³⁺/POL-salen has a hierarchical porosity and an extraordinary hydrothermal stability. Importantly, catalytic tests in epoxide hydration demonstrate that Co³⁺/POL-salen affords excellent high activities, which are even better than those of the homogeneous version. This phenomenon is related to the very high concentration of Co³⁺/salen in the catalyst. In addition, this catalyst can be recycled readily because of its excellent hydrothermal stability.

Development of sustainable routes for synthesizing aluminophosphate-based zeolites are very important because of their wide applications. As a typical sustainable route, solvent-free synthesis of zeolites not only decreases polluted wastes but also increases product yields. Systematic solvent-free syntheses of hierarchically porous aluminophosphate-based zeolites with AEL and AFI structures is presented. XRD patterns and SEM images show that these samples have high crystallinity. N₂ sorption isotherm tests show that these samples are hierarchically porous, and their surface areas are comparable with those of corresponding zeolites from hydrothermal route. Chosen as an example, catalytic oxidation of ethylbenzene with O₂ shows that cobalt substituted APO-11 from the solvent-free route (S-CoAPO-11) is more active than conventional CoAPO-11 from hydrothermal route owing to the sample hierarchical porosity.

A family of polymer-attached phenanthrolines was prepared from solvothermal copolymerization of divinylbenzene with N-(1,10-phenanthroline-5-yl)acrylamide in different ratios. The polymer-supported copper catalysts were obtained through typical impregnation with copper(II) salts. The polymers and supported copper catalysts have been characterized by N₂ adsortion, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TG); they exhibit a high surface area, hierarchical porosity, large pore volume, and high thermal and chemical stabilities. The copper catalyst has proved to be highly active for Glaser homocoupling of alkynes and Huisgen 1,3-diolar cycloaddition of alkynes with benzyl azide under mild conditions at low catalyst loading. The heterogeneous copper catalyst is more active than commonly used homogeneous and nonporous polystyrene-supported copper catalysts. In particular, the catalyst is easily recovered and can be recycled at least ten times without any obvious loss in catalytic activity. Metal leaching was prevented due to the strong binding ability of phenanthroline and products were not contaminated with copper, as determined by ICP analysis.

ZSM-5 zeolite crystals with controllable b-axis length (sheet-like, S-ZSM-5; chain-like, C-ZSM-5) have been synthesized by using urea and starch as additives in the starting aluminosilicate gels. X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images show that these zeolite samples have good crystallinity. Transmission electron microscopy (TEM) images show that there is a strong chemical interaction between the stacked crystals in C-ZSM-5 samples. N₂ sorption isotherms indicate that C-ZSM-5 crystals are mesoporous. Catalytic tests for the formation of p-xylene from m-xylene isomerization show that, compared with other zeolite catalysts, C-ZSM-5 catalysts give both high conversion and improved p-xylene selectivity, which are attributed to the combination of relatively long b-axis length and the present mesoporosity in the crystals. The improvement of p-xylene selectivity in catalytic m-xylene isomerisation is of great importance for selective industrial production of p-xylene in the future.

Bulky particles of TS-1 zeolite (larger than 20 μm) are successfully collected by simple filtration after crystallization of TS-1 zeolite in the presence of H₂O₂. Bulky TS-1 (B-TS-1) has good stability under both ultrasonic conditions and in recycling of the catalyst. Nitrogen isotherms show that B-TS-1 has a larger mesopore volume (0.55 cm³ g⁻¹) than conventional TS-1 nanocrystals (N-TS-1; less than 300 nm) obtained from high-speed centrifugation (0.28 cm³ g⁻¹). In catalytic hydroxylation of phenol with H₂O₂, both fresh (25 %) and recycled B-TS-1 (24 %) show similar high activities to N-TS-1 (28 %). B-TS-1 was further characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV/Vis spectroscopy, and other techniques. The results suggest that bulky particles of B-TS-1 were formed by strong interactions of the nanocrystals with each other in the synthesis of TS-1 zeolite. Such unique structural features might be responsible for the high stability of the bulky particles, large mesopore volume, and high catalytic activities in phenol hydroxylation, as well as the collection of B-TS-1 from a simple filtration route.