Direct Imaging of Atomically Dispersed Molybdenum that Enables Location of Aluminum in the Framework of Zeolite ZSM‐5

Integrated differential phase‐contrast scanning transmission electron microscopy (iDPC‐STEM) is capable of directly probing guest molecules in zeolites, owing to its sufficient and interpretable image contrast for both heavy and light elements under low‐dose conditions. This unique ability is demonstrated by imaging volatile organic compounds adsorbed in zeolite Silicalite‐1; iDPC‐STEM was then used to investigate molybdenum supported on various zeolites including Silicalite‐1, ZSM‐5, and mordenite. Isolated single‐Mo clusters were observed in the micropores of ZSM‐5, demonstrating the crucial role of framework Al in driving Mo atomically dispersed into the micropores. Importantly, the specific one‐to‐one Mo‐Al interaction makes it possible to locate Al atoms, that is, catalytic active sites, in the ZSM‐5 framework from the images, according to the positions of Mo atoms in the micropores.     

MFI沸石上对二甲苯的热脱附

MFI沸石（ZS－5型）的骨架结构内含十氧元环的二维孔道［‘］，孔容积0．18cm‘·g－‘，硅沸石（Silicallte－1）是骨架中不合铝的ZSM－5．’‘StMASNMR话可揭示沸石的结构对称性、硅铝比和局部缺陷［习．Nagy等人间提出St－OH缺陷在含铅量高时形成．Woolery等门则认为出OH完全是由于骨架内包藏的桂的存在而产生，并随铝合量降低而增大．ZSM－5、硅沸石的结构特征和对二甲苯（Px）的性质决定了Px在ZSM－5上的吸附特性·本文用’‘StMASNLDEL表征硅沸石及不同含铅量的H、Na型ZSM－5的结构，并用＊W＊＊G巾TA分析吸附于…     

低硅铝比ZSM-5分子筛的合成及其正庚烷裂化反应性能

以氨水为矿化剂,通过添加NH₄⁺离子水热合成了具有较低骨架硅铝比的ZSM-5分子筛。通过X射线衍射(XRD)、扫描电镜(SEM)、固体核磁共振(MAS-NMR)等表征手段,研究了硅源、铝源、矿化剂、阳离子等对ZSM-5分子筛的结晶度、形貌尺寸和骨架硅铝比等的影响,研究了ZSM-5分子筛的骨架硅铝比对正庚烷催化裂化反应的影响。研究表明,投料硅铝比越低,铝原子越难进入到分子筛骨架中;当氨水为矿化剂、正硅酸四乙酯为硅源时可以合成骨架硅铝比较低的氢型ZSM-5分子筛,添加NH₄⁺离子可以增强骨架铝的嵌入,进一步降低分子筛的骨架硅铝比(24.2)。正庚烷裂化反应结果表明,降低分子筛的骨架硅铝比可以提高正庚烷裂化反应的活性,但会降低低碳烯烃的选择性。     

129Xe NMR study of ZSM-5 type zeolites Effect of cationic sites

A comprehensive ¹²⁹Xe NMR spectroscopy study on H-ZSM-5 zeolites having different aluminum contents and on cation-exchanged ZSM-5 zeolites is reported. The parent H-ZSM-5 zeolites were ion-exchanged with Group I–III metal ions ( K, Ca, Sr, Ba, Al, La) to varying degrees. The chemical shift of adsorbed ¹²⁹Xe is seen to be a function of the pentasil structure of ZSM-5, of the number of free Brønsted acid sites and of the number of metal cations in the framework. Differences in the chemical shift of ¹²⁹Xe are seen between cations due to their different polarizing forces against xenon. The amount of cations has also an effect on the δ_xe-xe term in Fraissard's equation that may be caused by changes in the diffusional characteristics of Xe atoms in the ZSM-5 framework.     

直接法合成ZSM—5型分子筛的物理化学表征

用高分辨~(29)Si、~(27)Al和~(23)Na NMR对直接法合成的不同硅铝比ZSM-5型分子筛局域结构作了表征,用~(29)Si和~(27)Al魔角旋转核磁共振研究了经不同温度水蒸气处理ZSM-5型分子筛的骨架脱铝,对不同条件下ZSM-5型分子筛中发生的正交-单斜晶型变化进行了系统的X射线衍射实验研究。     

Zeolite synthesis using degradable structure-directing agents and pore-filling agents

Zeolites and molecular sieves are synthesized using organic structure-directing agents (SDAs) that have the potential to be degraded into fragments within the pore space so that they can be readily extracted at mild conditions. The zeolites and molecular sieves, VPI-8, ZSM-12, and ZSM-5, are synthesized using the ketal-containing SDA, 8,8-dimethyl-1,4-dioxa-8-azoniaspiro[4,5]decane (SDA-1). As expected, solids with unidimensional pore systems (VPI-8, ZSM-12) are much more difficult to process by this methodology than solids containing multidimensional pore systems (ZSM-5). Pore-filling agents (PFAs) such as isobutylamine and cyclopentylamine are used together with the ketal-containing SDA-1 to prepare ZSM-5. Extraction of the PFA is shown to be feasible, and its removal provides space for components to enter the zeolite micropores where they react with and cleave SDA-1. Removal of the cleavage fragments from SDA-1 gives ZSM-5 that has the appropriate pore volume, framework aluminum (measured by 27Al NMR), and catalytic behavior. Reasons for desiring this new type of zeolite synthesis method are enumerated.     

An in situ Al K-edge XAS investigation of the local environment of H+- and Cu+-exchanged USY and ZSM-5 zeolites

Aluminum coordination in the framework of USY and ZSM-5 zeolites containing charge-compensating cations (NH4+, H+, or Cu+) was investigated by Al K-edge EXAFS and XANES. This work was performed using a newly developed in-situ cell designed especially for acquiring soft X-ray absorption data. Both tetrahedrally and octahedrally coordinated Al were observed for hydrated H-USY and H-ZSM-5, in good agreement with 27Al NMR analyses. Upon dehydration, water desorbed from the zeolite, and octahedrally coordinated Al was converted progressively to tetrahedrally coordinated Al. These observations confirmed the hypothesis that the interaction of water with Br?nsted acid protons can lead to octahedral coordination of Al without loss of Al from the zeolite lattice. When H+ is replaced with NH4+ or Cu+, charge compensating species that absorb less water, less octahedrally coordinated Al was observed. Analysis of Al K-edge EXAFS data indicates that the Al-O bond distance for tetrahedrally coordinated Al in dehydrated USY and ZSM-5 is 1.67 angstroms. Simulation of k3chi(k) for Cu+ exchanged ZSM-5 leads to an estimated distance between Cu+ and framework Al atoms of 2.79 angstroms.     

高硅ZSM-5分子筛和二次合成Ti-ZSM-5分子筛的结构

运用度角旋转（MAS）和交叉极化（CP）等核磁共振波谱和红外光谱技术，分别对采用不同模板剂制备的高硅ZSM－5分子筛和以此为母体，经气固同晶取代法得到Ti－ZSM－5分子筛的结构特性进行了研究．结果表明：在水热法合成高硅ZSM-5分子筛过程中，模板剂明显制约着所制得的分子筛的结构特性．通过选用合适的模板剂，可直接获得具有正交晶系结构的高硅ZSM－5分子筛．在随后的气固相同晶取代过程中，钛原子通过占据分子筛骨架中的缺陷位进入骨架，形成具有一定Ti／Si比例的钛硅分子筛（Ti－ZSM－5）。骨架结构中缺陷位的含量直接影响分子筛的载钛量。     

Quantitative measurement of the Brönsted acid sites in solid acids: toward a single-site design of Mo-modified ZSM-5 zeolite

On the basis of our previous H/D exchange studies devoted to the quantification of the number of Br?nsted acid sites in solid acids, we report here an innovative approach to determine both the amount and the localization of Mo atoms inside the Mo/ZSM-5 catalyst, commonly used for the methane dehydroaromatization reaction. The influence of Mo introduction in the MFI framework was studied by means of BET, X-ray diffraction, 27Al magic angle spinning NMR, NH3 temperature-programmed desorption, and H/D isotopic exchange techniques. A dependence was found between the decrease of acidic OH groups and the Mo content. Depending on the Si/Al ratio of the zeolite, i.e., the proximity of two Br?nsted acid sites, the Mo atoms substitute a different number of OH groups. Consequently, a chemical structure was proposed to describe the geometry of the Mo complex in the channels of the ZSM-5 zeolite.     

Variation of Aluminium Distribution in Small-Sized ZSM-5 Crystals during Desilication

Hollow ZSM-5 zeolites of size below one micrometer can be produced by desilication of crystals with aluminium zoning. The parent crystals have a core–shell structure: the core part has nearly no aluminium, whereas the aluminium content in the shell increases when extending to exterior surface. Transmission electron microscopy confirmed the preservation of the crystalline shell after base leaching, but could not identify its subtle change. An increase of the Si/Al ratio of the surface was detected upon leaching the parent material to form the hollow zeolite by using ambient pressure X-ray photoelectron spectroscopy and infrared spectroscopy of substituted alkylpyridines. ²⁷Al MAS NMR showed that base leaching results in a reduced percentage of distorted tetrahedrally coordinated aluminium. The reprecipitation of dissolved species occurs and tetrahedrally coordinated tin atoms can thus be introduced to the shell framework. Overall, the formation of hollow ZSM-5 zeolites by desilication involves not only the removal of silicon-rich core, but also a reduced percentage of exterior aluminium-related acid sites, which should be considered while using hollow zeolites in acid-catalyzed reactions.     

MoCI_5在HZSM-5和APO-5上的负载及调变作用

MoCl_5在HZSM-5和APO-5上没有发生“双聚”,沸石的酸性对MoCl_5负载量的影响大于孔结构。APO-5负载MoCl_5后,仅生成数量和强度都很小的B酸中心。Mo-ZSM-5沸石在MTG反应中有Mo和Al的表面迁移,负载的MoCl_5通过氧化-还原及水解等过程产生羟基,增加了ZSM-5沸石的B酸量,通过B酸-L酸中心的电子协同效应增加载体的B酸强度,调变了催化剂的酸性分布。     

Dealuminated ZSM-5 Zeolite Catalyst for Ethylene Oligomerization to Liquid Fuels

Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Bronsted acid sites in the formation of higher hydrocarbons. The oligomerization of olefins, dependent on the acidity of ZSM-5 zeolite, is an important step in the conversion of natural gas to liquid fuels. The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst. ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios. The FT-IR analysis revealed that the integrated framework aluminum band, non-framework aluminum band, and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated. The performance of the dealuminated zeolite was tested for ethylene oligomerization. The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion, but the gasoline selectivity was reduced compared to the performance     

Synthesis of mesoporous zeolite single crystals with cheap porogens

Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, ²⁷Al magic angle spinning nuclear magnetic resonance (²⁷Al MAS NMR), temperature-programmed desorption of ammonia (NH₃-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystal pores are randomly distributed in the whole crystal. ²⁷Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites.     

Influence of the ZSM-5 Support Acidity on the Catalytic Performance of Pd/ZSM-5 in Lean Methane Oxidation

Although zeolites are characterized by their special acidic properties, there is still no clear consensus on the effect of zeolite support acidity on the catalytic activity of supported Pd catalyst in methane oxidation. Herein, a series of Pd/H-ZSM-5 and Pd/Silicalite-1 catalysts was prepared by the deposition-precipitation method and used in lean methane oxidation. The effect of ZSM-5 support acidity on the catalytic performance of Pd/ZSM-5 was investigated. The results indicate that with the decrease of Si/Al ratio(x), viz., the increase of acid sites in H-ZSM-5(x), the catalytic activity of Pd/H-ZSM-5(x) increases substantially; the activity of various catalysts in the lean methane oxidation decreases in the order of Pd/H-ZSM-5(28)>Pd/H-ZSM-5(48)>Pd/H-ZSM-5(88)>Pd/H-ZSM-5(204)>Pd/Silicalite-1. Furthermore, various characterization measures reveal that the catalytic activity of Pd/H-ZSM-5(x) in lean methane oxidation is mainly related to the Lewis acid sites in the H-ZSM-5 support, whereas less relevant to the Brønsted acid sites. The abundant Lewis acid sites in H-ZSM-5 are capable to enhance the interaction between the Pd species and H-ZSM-5 support, which can inhibit the agglomeration of Pd particles and improve the dispersion of Pd species, and thus boost the catalytic activity of Pd/H-ZSM-5 in methane oxidation.     

H(M)ZSM-5杂原子分子筛的表面酸性和裂解催化行为

用IR和ITPD技术研究了H(Al)ZSM-5、H(Ga)ZSM-5和H(Fe)ZSM-5杂原子分子筛的表面酸性。结果表明,这些分子筛表面既存在B酸中心,也存在L酸中心,但是就两种酸的表面浓度比值C_L/C_B而言,H(Ga)ZSM-5和H(Fe)ZSM-5要比H(Al)ZSM-5高得多。在十五烷裂解时,L酸中心起的作用可能更大。     

Dealuminated ZSM—5 Zeolite Catalyst for Ethylene Oligomerization to Liquid Fuels

Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Broensted acid sites in the formation of higher hydrocarbons,The oligomeriztion of olefins,dependent on the acidity of ZSM-5 zeolite ,is an important step in the conversion of natural gas to liquied fuels,The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst,ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios,The FT-IR analysis revealed that the integrated framework aluminum band,non-framework aluminum band,and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated,The performanc of the dealuminated zeolite was tested for ethylene oligomerization.The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion,but the gasoline selectivity was reduced compared to the performance of a ZSM-5 zeolite ,The characterization results revealed the amount of aluminum in the zeolitic framework,the crystallinity of the ZSM-5 zeolite,and the Si/Al ration affected the formation of Broensted acid sites,The number of the Broensted acid sites on the catalyst active sites is important in the olefin conversion to liquied hydrocarbons.     

A theoretical study of hydrothermal stability of P-modified ZSM-5 zeolites

Density functional theory was employed to study the hydrothermal stability of P-modified ZSM-5 zeolites using cluster models. The calculations of hydrolysis energies indicated that the introduction of phos-phorus increases the hydrothermal stability of ZSM-5 zeolites. The initial paths of dealumination were studied with explicit water molecules. It was found that the framework Al—O coordination bond can be replaced by coodination bonds between water molecules and the aluminium. One to three water molecules ...     

ZSM-5分子筛骨架铝落位对甲醇转化制芳烃催化性能影响

采用水热合成法,在合成过程中通过添加矿化剂、尿素和改变硅源,制备了不同骨架铝落位的ZSM-5分子筛。通过SEM、XRD、BET、XRF、MAS NMR、NH_3-TPD和Py-FTIR等表征手段对分子筛的形貌、织构、骨架铝落位和酸性进行了系统研究,同时考察了不同ZSM-5分子筛催化剂甲醇制芳烃的催化性能。研究结果表明,制备的ZSM-5分子筛均具有结晶度高和形貌均一等特点,但在骨架铝落位和酸性方面存在显著差异。椭球状ZSM-5分子筛的骨架铝主要分布于直通孔道或正弦孔道中,并表现出较多的酸性位。块状分子筛中骨架铝主要落位在孔道交叉处,且具有较低的强酸量。在甲醇制芳烃反应中,骨架铝主要位于直通或正弦孔道并表现出较多酸性位的椭球状ZSM-5分子筛催化剂具有较高的活性稳定性和芳烃选择性。     

The appearance of adsorption ability of modified zeolites for sodium dodecylsulfate from its aqueous solution

Hydrophobic faujasite-type zeolites were prepared by the treatment of hydrophilic Na-Y_4.6 with silicon tetrachloride (SiCl₄) by way of dealumination-silicon exchange reaction. Hydrophilic-hydrophobic characters of these zeolite surfaces were evaluated by measurements of immersional heats into water orn-hexane. Adsorption rates of sodium dodecylsulfate (SDoS) on these zeolites from its aqueous solution and their adsorption characteristics were investigated, and compared with those on ZSM-5 with various Si/Al ratios.The adsorption ability of SDoS into zeolite micropores developed on the zeolite only when it was modified to some extent. The adsorption rates of SDoS were very slow and proved to be affected by molecular diffusion in zeolite pores. They depended on hydrophilic-hydrophobic character of zeolites as well as on pore structures. Adsorption isotherms of SDoS were of Langmuir type, which indicates that the adsorption occurred typically into zeolite pores. Adsorbed amount of SDoS depended on the balance of hydrophilic-hydrophobic character and number of cation site of zeolite surfaces, and had a maximum in case of ZSM-5 zeolites.     

以纯硅silicalite-1为晶种制备空心结构ZSM-5沸石分子筛

微孔分子筛在实际应用过程中常常受到扩散限制的影响,分子筛内部的利用率不高.制备空心结构分子筛对于改善分子筛扩散传质、提高分子筛利用率具有重要意义.以纯硅silicalite-1为晶种,以四丙基氢氧化铵(TPAOH)为结构导向剂制备ZSM-5分子筛,无定型硅铝物种首先在晶种表面晶化生长,同时碱性合成体系的碱度则可以溶解不...