Mesoporous zeolites are useful solid catalysts for conversion of bulky molecules because they offer fast mass transfer along with size and shape selectivity. We report here the successful synthesis of mesoporous aluminosilicate zeolite Beta from a commercial cationic polymer that acts as a dual-function template to generate zeolitic micropores and mesopores simultaneously. This is the first demonstration of a single nonsurfactant polymer acting as such a template. Using high-resolution electron microscopy and tomography, we discovered that the resulting material (Beta-MS) has abundant and highly interconnected mesopores. More importantly, we demonstrated using a three-dimensional electron diffraction technique that each Beta-MS particle is a single crystal, whereas most previously reported mesoporous zeolites are comprised of nanosized zeolitic grains with random orientations. The use of nonsurfactant templates is essential to gaining single-crystalline mesoporous zeolites. The single-crystalline nature endows Beta-MS with better hydrothermal stability compared with surfactant-derived mesoporous zeolite Beta. Beta-MS also exhibited remarkably higher catalytic activity than did conventional zeolite Beta in acid-catalyzed reactions involving large molecules.

Microporous crystalline aluminosilicate and silicoaluminophosphate zeolites are currently regarded as the most useful zeolite catalysts for industrial processes. [1] For example, aluminosilicate Y zeolite is efficient for fluid catalytic cracking, [2] and silicoaluminophosphate SAPO-34 zeolite is a selective catalyst for the formation of light olefins from methanol. [3] Notably, the synthesis of these zeolites usually requires the presence of solvents such as water and alcohols under hydrothermal, solvothermal, or ionothermal conditions. [1][2][3][4][5][6][7][8][9][10][11][12] The use of solvents normally results in polluted water, reduced synthesis efficiency owing to autoclave space being used by the solvent, and generates high pressure under hightemperature solvothermal conditions. [4] The ionothermal route, which has been successfully developed for synthesizing aluminophosphate-based zeolites, can effectively eliminate the high pressure problem, because of the low vapor pressure of ionic liquids. [5,6] Recently, Ren et al. reported the solventfree synthesis of aluminosilicate zeolites with the advantage of reducing waste production and increasing zeolite yield, as well as eliminating high pressure. [4b] Morris et al. have also highlighted the importance of solventless synthesis, [7] but this route has still not been successfully applied to the synthesis of aluminophosphate-based zeolites.Herein, we report the solvent-free synthesis of silicoaluminophosphate (SAPO-34, SAPO-11, SAPO-20, and SAPO-43), aluminophosphate (APO-11), and heteroatom-containing aluminophosphate (M-APO-11 and M-SAPO-46; M = Co or Mg) zeolites by mixing, grinding, and heating the raw materials. The solvent-free synthesis of SAPO-34 (S-SAPO-34) is carefully investigated as a model reaction. Importantly, S-SAPO-34 exhibits good catalytic performance in catalytic tests for methanol-to-olefin (MTO) conversion. Figure 1 shows X-ray diffraction (XRD) pattern, N 2 sorption isotherms, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) images of calcined S-SAPO-34. XRD patterns show well-resolved peaks in the range of 4-408 (Figure 1 A), which are in good agreement with that of a CHA zeolite structure. [8] N 2 sorption isotherms of the sample (Figure 1 B) exhibit a steep increase in the curve at a relative pressure of 10 À6 < P/P 0 < 0.01, which is due to the filling of micropores. [4a] Additionally, at a relative pressure of 0.50-0.98, a hysteresis loop can be observed, which suggests that the sample is both meso-and macroporous. [9] Accordingly, the sample Barrett-Joyner-Halenda (BJH) pore-size distribution appears at 11 nm and ca. 100 nm (Figure 1 C). The Brunauer-Emmett-Teller (BET) surface area and pore volume are 459 m 2 g À1 and 0.27 cm 3 g À1 , respectively. Figure 1 D and E show low and high magnification SEM images of the sample. The low magnification image (Figure 1 D) shows that the sample has very uniform cubic morphology, with particle sizes of 10-30 mm. The high magnification image (Figure 1 E) clea...

We reported a universal route for synthesizing porous organic ligands (POLs) via solvothermal polymerization. The POLs were obtained quantitatively, showing high surface area, large pore volume, hierarchical porosity, and superior stability. The POL bearing a triphenylphosphine supported rhodium catalyst (Rh/POL-PPh3) exhibits high activity and excellent recyclability in 1-octene hydroformylation.

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.

No abstract