Zeolite nanocrystals inside mesoporous TUD-1: a high-performance catalytic composite

A hierarchically structured composite material with interconnecting meso- and micropores has been developed with the aim to optimize zeolite performance. A general synthetic method has been developed that, in a controlled manner, allows for various types of nanosized zeolite to be incorporated into a three-dimensional mesoporous matrix. Nanosized zeolite Beta was used to exemplify this new approach, resulting in a system in which zeolite Beta shows a higher cracking activity per gram of zeolite than pure nanosized zeolite Beta for the model feed n-hexane. Additionally, FTIR studies of CO and NH3 adsorption revealed that the nature of the acid sites in the nanozeolite has been partially modified due to the interactions with the mesoporous matrix, TUD-1.     

键阻断原理构建中孔A型沸石

采用不同类型的有机硅烷化SiO2作为基本合成单元,制备了具有晶内中孔的A型沸石。考察了反应碱度、Si/Al比、晶化时间等合成条件对产品的影响。结果表明,苯胺基丙基三甲氧基硅烷是合成中孔A型沸石的最佳硅烷化试剂;硅烷化试剂的应用,使中孔沸石晶化过程可以通过"键阻断原理"有效控制;沸石的中孔尺寸可以通过不同类型的有机硅烷化试剂进行调控;一定范围内,其外比表面积、中孔体积随SiO2表面硅烷化度的增加而增加。通过沸石晶化过程中的"键阻断",可以制备具有晶内中孔的A型沸石。     

键阻断原理构建中孔A型沸石

采用不同类型的有机硅烷化SiO₂作为基本合成单元, 制备了具有晶内中孔的A型沸石。考察了反应碱度、Si/Al比、晶化时间等合成条件对产品的影响。结果表明, 甲氨基丙基三甲氧基硅烷是合成中孔A型沸石的最佳硅烷化试剂;硅烷化试剂的应用, 使中孔沸石晶化过程可以通过“键阻断原理”有效控制;沸石的中孔尺寸可以通过不同类型的有机硅烷化试剂进行调控; 一定范围内, 其外比表面积、中孔体积随SiO₂表面硅烷化度的增加而增加。通过沸石晶化过程中的“键阻断”, 可以制备具有晶内中孔的A型沸石。     

Encapsulating Palladium Nanoparticles Inside Mesoporous MFI Zeolite Nanocrystals for Shape‐Selective Catalysis

Pd nanoparticles were successfully encapsulated inside mesoporous silicalite‐1 nanocrystals (Pd@mnc‐S1) by a one‐pot method. The as‐synthesized Pd@mnc‐S1 with excellent stability functioned as an active and reusable heterogeneous catalyst. The unique porosity and nanostructure of silicalite‐1 crystals endowed the Pd@mnc‐S1 material general shape‐selectivity for various catalytic reactions, including selective hydrogenation, oxidation, and carbon–carbon coupling reactions.     

Dual‐Mesoporous ZSM‐5 Zeolite with Highly b‐Axis‐Oriented Large Mesopore Channels for the Production of Benzoin Ethyl Ether

Dual‐mesoporous ZSM‐5 zeolite with highly b axis oriented large mesopores was synthesized by using nonionic copolymer F127 and cationic surfactant CTAB as co‐templates. The product contains two types of mesopores—smaller wormlike ones of 3.3 nm in size and highly oriented larger ones of 30–50 nm in diameter along the b axis—and both of them interpenetrate throughout the zeolite crystals and interconnect with zeolite microporosity. The dual‐mesoporous zeolite exhibits excellent catalytic performance in the condensation of benzaldehyde with ethanol and greater than 99 % selectivity for benzoin ethyl ether at room temperature, which can be ascribed to the zeolite lattice structure offering catalytically active sites and the hierarchical and oriented mesoporous structure providing fast access of reactants to these sites in the catalytic reaction. The excellent recyclability and high catalytic stability of the catalyst suggest prospective applications of such unique mesoporous zeolites in the chemical industry.     

High Catalytic Activity of Palladium(II)‐Exchanged Mesoporous Sodalite and NaA Zeolite for Bulky Aryl Coupling Reactions: Reusability under Aerobic Conditions

Exchange for the better : Mesoporous sodalite and NaA zeolite exchanged with Pd²⁺ exhibit remarkably high activity and reusability in C? C coupling reactions under aerobic atmosphere. It is proposed that the catalytic reactions are mediated by a molecular Pd⁰ species generated in situ within the pores (see picture), which is oxidized back to Pd²⁺ by O₂, preventing the formation of catalytically inactive Pd⁰ agglomerates.

     

Well-organized zeolite nanocrystal aggregates with interconnected hierarchically micro-meso-macropore systems showing enhanced catalytic performance

Preparation and characterization of well-organized zeolitic nanocrystal aggregates with an interconnected hierarchically micro-meso-macro porous system are described. Amorphous nanoparticles in bimodal aluminosilicates were directly transformed into highly crystalline nanosized zeolites, as well as acting as scaffold template. All pores on three length scales incorporated in one solid body are interconnected with each other. These zeolitic nanocrystal aggregates with hierarchically micro-meso-macroporous structure were thoroughly characterized. TEM images and (29)Si NMR spectra showed that the amorphous phase of the initial material had been completely replaced by nanocrystals to give a micro-meso-macroporous crystalline zeolitic structure. Catalytic testing demonstrated their superiority due to the highly active sites and the presence of interconnected micro-meso-macroporosity in the cracking of bulky 1,3,5-triisopropylbenzene (TIPB) compared to traditional zeolite catalysts. This synthesis strategy was extended to prepare various zeolitic nanocrystal aggregates (ZSM-5, Beta, TS-1, etc.) with well-organized hierarchical micro-meso-macroporous structures.     

Organic-Free Synthesis of Zeolite Y with High Si/Al Ratios: Combined Strategy of In Situ Hydroxyl Radical Assistance and Post-Synthesis Treatment

Zeolite Y, with a high SiO₂/Al₂O₃ ratio (SAR), plays an important role in fluidized catalytic cracking processes. However, in situ synthesis of zeolite Y with high SARs remains a challenge because of kinetic limitations. Here, zeolite Y with an SAR of 6.35 is synthesized by a hydroxyl radical assisted route. Density-functional theory (DFT) calculations suggest that hydroxyl radicals preferentially enhanced the formation of Si-O-Si bonds, thus leading to an increased SAR. To further increase the SAR, a dealumination process was carried out using citric acid, with a subsequent second-step hydrothermal crystallization, giving an SAR of up to 7.5 while maintaining good crystallinity and high product yield. The resultant zeolite Y shows good performance in cumene cracking. Introduced here is a new strategy for synthesizing high SAR zeolite Y, which is widely used in commercial applications.     

Zr–Zeolite Beta: A New Heterogeneous Catalyst System for the Highly Selective Cascade Transformation of Citral to (±)‐Menthol

Minty green : Zr–zeolite beta (Zr‐beta) directs the one‐pot catalytic cascade transformation of citral to menthols with high diastereoselectivity. The solid catalyst, a bifunctional Ni/Zr‐beta or a composite Zr‐beta–Ni/MCM‐41 system, is easily recovered and reused in this green synthetic method (see figure).

     

Facile Synthesis,Characterization, and Catalytic Behavior of a Large‐Pore Zeolite with the IWV Framework

Large‐pore microporous materials are of great interest to process bulky hydrocarbon and biomass‐derived molecules. ITQ‐27 (IWV) has a two‐dimensional pore system bounded by 12‐membered rings (MRs) that lead to internal cross‐sections containing 14 MRs. Investigations into the catalytic behavior of aluminosilicate (zeolite) materials with this framework structure have been limited until now due to barriers in synthesis. The facile synthesis of aluminosilicate IWV in both hydroxide and fluoride media is reported herein using simple, diquaternary organic structure‐directing agents (OSDAs) that are based on tetramethylimidazole. In hydroxide media, a zeolite product with Si/Al=14.8–23.2 is obtained, while in fluoride media an aluminosilicate product with Si/Al up to 82 is synthesized. The material produced in hydroxide media is tested for the hydroisomerization of n‐hexane, and results from this test reaction suggest that the effective pore size of zeolites with the IWV framework structure is similar to but slightly larger than that of ZSM‐12 (MTW), in fairly good agreement with crystallographic data.     

A Stable Silanol Triad in the Zeolite Catalyst SSZ‐70

Nests of three silanol groups are located on the internal pore surface of calcined zeolite SSZ‐70. 2D ¹H double/triple‐quantum single‐quantum correlation NMR experiments enable a rigorous identification of these silanol triad nests. They reveal a close proximity to the structure directing agent (SDA), that is, N,N′‐diisobutyl imidazolium cations, in the as‐synthesized material, in which the defects are negatively charged (silanol dyad plus one charged SiO^? siloxy group) for charge balance. It is inferred that ring strain prevents the condensation of silanol groups upon calcination and removal of the SDA to avoid energetically unfavorable three‐rings. In contrast, tetrad nests, created by boron extraction from B‐SSZ‐70 at various other locations, are not stable and silanol condensation occurs. Infrared spectroscopic investigations of adsorbed pyridine indicate an enhanced acidity of the silanol triads, suggesting important implications in catalysis.     

Organic‐Free Synthesis of Zeolite Y with High Si/Al Ratios: Combined Strategy of In Situ Hydroxyl Radical Assistance and Post‐Synthesis Treatment

Zeolite Y, with a high SiO₂/Al₂O₃ ratio (SAR), plays an important role in fluidized catalytic cracking processes. However, in situ synthesis of zeolite Y with high SARs remains a challenge because of kinetic limitations. Here, zeolite Y with an SAR of 6.35 is synthesized by a hydroxyl radical assisted route. Density‐functional theory (DFT) calculations suggest that hydroxyl radicals preferentially enhanced the formation of Si‐O‐Si bonds, thus leading to an increased SAR. To further increase the SAR, a dealumination process was carried out using citric acid, with a subsequent second‐step hydrothermal crystallization, giving an SAR of up to 7.5 while maintaining good crystallinity and high product yield. The resultant zeolite Y shows good performance in cumene cracking. Introduced here is a new strategy for synthesizing high SAR zeolite Y, which is widely used in commercial applications.