Hierarchically Macroporous Zeolite ZSM-5 Microspheres for Efficient Catalysis

Hollow zeolite microspheres have recently attracted much attention for their applications in catalysis,microreactors and biomedicine.Herein,we present hierarchically structured zeolite ZSM-5 microspheres with unique,abundant macropores that allow more efficient use for catalysis.The hierarchically macroporous zeolite ZSM-5 microspheres are synthesized under the assistance of water/oil emulsions and using polystyrene nanospheres as templates.The zeolite microsphere is assembled by uniform hollow zeolite nanospheres.Their large inner cavities and thin zeolite shells lead to smaller diffusion channel and higher improved accessibility to active sites,contributing to high catalytic performance in the catalytic conversion of benzyl alcohol in mesitylene.Such novel zeolite microspheres with impressive performance will be applied to numerous other industrial catalytic reactions.

Synthesis of ZSM-5 monoliths with hierarchical porosity through a steam-assisted crystallization method using sponges as scaffolds

Self‐supporting ZSM‐5crystals with hierarchical porosity were prepared through a steam‐assisted crystallization method using sponges as rigid scaffolds.The synthesized materials were characterized by X‐ray diffraction,nitrogen sorption,scanning electron microscopy,transmission electron microscopy,solid‐state nuclear magnetic resonance spectroscopy and ammonia temperature‐programmed desorption.The ZSM‐5monoliths exhibited high crystallinities,hierarchical porous structures and strong acidities.They showed superior catalytic performance in the liquid‐phase esterification reaction between benzyl alcohol and hexanoic acid.

Acylation of Anisole Catalyzed by Hierarchical Porous Hβ Zeolite Modified with Cr

Modified hierarchical porous Hβ zeolite was obtained by metal modification of Hβ zeolite, which was treated with alkaline solution, and the catalysts before and after modification were characterized by means of X-ray diffraction（XRD）, nitrogen adsorption-desorption~ scanning electron microscopy（SEM）, X-ray fluorescence（XRF）, NH3 temperature-programmed desorption and Fourier-transform infrared spectroscopy（FTIR）. The activities of acy- lation of anisole with acetic anhydride were also investigated. The results show that the Hp zeolite, which was treated with alkaline solution has microporous and mesoporous structures that could improve the diffusion performance of chemical reaction. The amount of acid was modulated with metal modification. The Hβ zeolite modified by 5%（mass fraction） metal chromium had the best catalytic performance. The conversion of acetic anhydride acylation was 93.01% under the optimal conditions, which was higher than that of other catalysts. The catalyst not only showed good activity, but also exhibited a stable performance in regeneration tests.

Rapid room-temperature synthesis of hierarchical porous zeolitic imidazolate frameworks with high space-time yield

Hierarchical porous zeolitic imidazolate frameworks （ZIFs） have potential for adsorption, catalysis and chemical sensing applications. Ultrafast synthesis of ZIFs at room temperature and pressure is particularly desirable for large-scale industrial production. Here, we developed a green and versatile method using organic amines as supramolecular templates （organic amine-template） to rapidly synthesize hierarchical porous ZIFs （ZIF-8, ZIF-61 and ZIF-90） at room temperature and pressure. The synthesis time was reduced dramatically to within 1 min, and the resulting ZIFs had multimodal hierarchical porous structures with mesopores/ macropores interconnected with micropores. Notably, the space-time yield （STY） of hierarchical porous ZIF-8 was up to 1.29×10^4 kg m^-3 d^-1, which is more than three times higher than that reported using other methods. Furthermore, the morphologies and porosities of the produced ZIFs could be readily tuned by controlling the synthesis time or type of organic amine. The organic amine played two roles in the synthesis： （1） a protonation agent to deprotonate organic ligands, facilitating the formation of ZIF crystals, and （2） an structure directing agent to direct mesopore/macropore formation. The resulting hierarchical porous ZIF-8 exhibited enhanced uptake capacities and diffusion rates for guest molecules relative to its microporous counterpart. This work provides a new direction for the green and efficient synthesis of various hierarchical porous ZIFs with high STYs for a wide range of applications.

Facile fabrication of nanoscale hierarchical porous zeolitic imidazolate frameworks for enhanced toluene adsorption capacity

The development of a simple and facile synthesis route is a highly desirable but challenging process in the fabrication of nanoscale hierarchical porous zeolitic imidazolate frameworks(ZIFs).Herein we describe a facile method for rapidly synthesizing hierarchically porous ZIF-90 nanocrystals(particle sizes of~300 nm)using hydroxyl double salts as intermediates at room temperature.The as-synthesized ZIF-90 contained hierarchical porous structures developed using a crystalline interior and a random stack of multiple nanoparticles.Both the morphology and particle size of ZIF-90 nanocrystals could be tuned by controlling the molar ratio of ICA/Zn^(2+).Note that the as-synthesized hierarchically porous ZIF-90 nanocrystals exhibited higher thermal stability compared with the conventional ZIF-90.Because of the introduction of hierarchical porous structures,the resultant hierarchically porous ZIF-90 nanocrystals showed enhanced toluene adsorption capacity than those of conventional metal organic frameworks and zeolites.

碱酸联合处理H-ZSM-5沸石多级孔改性

采用水热合成和离子交换法制备H-ZSM-5沸石。以硅铝比为47的H-ZSM-5沸石为介孔改性原料,用水热碱预刻蚀—碱溶滤—酸洗处理法制备微孔-介孔材料。采用XRD、N2吸附-脱附、FTIR、SEM、TEM等技术,考察逐级碱酸处理过程和水热碱预刻蚀温度对改性沸石介孔形成、介孔尺度分布和织构性质的影响。实验结果表明,碱酸改性沸石具有较高的比表面积、介孔率和微孔-介孔结构性质,同时较好地保留了H-ZSM-5沸石的骨架结构。升高水热碱预刻蚀温度导致改性沸石的微孔体积、比表面积、相对结晶度和收率逐渐下降,总比表面积增幅由38%降至34%,附加介孔体积与总孔体积的比保持在70%以上。水热碱预刻蚀温度为358 K的HZ-2试样的介孔比表面积和介孔体积最大,分别为209.8 m2/g和0.295 cm3/g,微孔与介孔的体积之和可达0.364 cm3/g。

Trimodel hierarchical yolk-shell porous materials TS-1@mesocarbon:Synthesis and catalytic application

Trimodal hierarchical yolk-shell materials consisting of TS-1 core and mesoporous carbon shell （YS-TS- I@MC） was successfully synthesized by using TS-l@mesosilica as hard template, sucrose as carbon source and organic base tetrapropylammonium hydroxide （TPAOH） as silica etching agent. The resultant YS-TS-I@MC contains the micropores （0.51 nm） in TS-1 core, the mesopores （2.9 rim） in carbon shell as well as a void or a stack pore between TS-1 fragements （TS-1 intercrystal mesopores, -18.4 nm）. Under the rigorous etching conditions, the crystalline structure of TS-1 core was well retained. The YS-TS- I@MC served as a good support for palladium nano-particles （Pd NPs） or Rh（OH）x species, giving rise to efficient bifunctional catalysts for the tandem reactions including one-pot synthesis of propylene oxide or amides.