Distribution of aluminum and boron in the periodical building units of boron-containing Beta zeolites

Various boron only ([B]-BEA) as well as aluminum- and boron-containing beta zeolites ([Al,B]-BEA) have been prepared and modified by ion exchange of ammonium, sodium, and nickel ions. The zeolite samples have been characterized by 11B, 27Al, and 29Si MAS as well as three of them by 11B and 27Al 3Q-MAS NMR spectroscopy. The quantitative contributions of defect-free Si(nX) (n = 2, 1, 0; X = Al, B) and Si(OH)x (x = 2, 1) sites to the NMR signal intensities were calculated from the various Si/(Al + B) ratios and relative 11B, 27Al, and 29Si NMR signal intensities using the special distribution of aluminum and boron in different periodical building units of the zeolite framework. The boron atoms are sitting exclusively in diagonal positions in the four-membered rings of [B]-BEA zeolites, while the aluminum atoms are situated both in diagonal and lone positions in the four-membered rings of [Al,B]-BEA zeolites. A higher part of boron atoms are positioned in framework-related deformed tetrahedral boron species than in lattice positions in the [B]-BEA than in the [Al,B]-BEA zeolites. All extraframework octahedral aluminum species are transformed back to lattice positions due to ion exchange from the protonated form to ammonium-, sodium-, or nickel-ions containing zeolites. Oppositely, trigonal boron leaves the zeolite structure completely during ion exchange.     

The quantum-chemical estimation of the effect of phosphorus atoms on the electron acceptor properties of aluminum- and boron-containing zeolite clusters

The effect of a phosphorus atom introduced in a zeolite cluster involving ten silicon and aluminum atoms on the state of active catalytic structure sites is estimated. Zeolite clusters modified with boron are also considered. The effect of the electron density redistribution upon zeolite modification with boron and phosphorus, as well as the effect upon the coordination of probe water and ammonia molecules to the clusters, is analyzed. The bond energies of water or ammonia molecules coordinated to acceptor sites of phosphorus-containing zeolites are estimated. Experimentally discovered changes in the acidic properties of zeolites resulting from their modification with boron and phosphorus are interpreted.     

ZSM-5分子筛转化乙醇为乙醚的研究

用原位红外技术、程序升温热脱附和X射线光电子能谱研究了乙醇和乙醚在HZSM-5和PZSM-5上的吸附及表面状态, 并与催化乙醇为乙醚的活性和选择性相关联. 结果表明, 乙醇与质子酸中心作用形成吸附态乙醇, 该吸附态乙醇与气相乙醇反应生成吸附态乙醚, 然后从表面脱附. 磷的掺入能有效抑制积炭发生.     

不同来源的钛硅沸石的孔结构,酸性和催化性能

用气固相类质同晶取代和水热方法合成了Ｔｉ－ＺＳＭ－５和ＴＳ－１沸石，对它们的组成、孔结构、酸性和催化活性进行了比较。以季铵盐为模板剂水热合成的无铝ＴＳ－１沸石骨架Ｔｉ含量高，表面无强酸位，且随骨架Ｔｉ含量增加，沸石晶内由缺陷造成的二次孔数量增多。类质同晶取代的Ｔｉ－ＺＳＭ－５沸石骨架Ｔｉ含量有限，样品内尚保留部分骨架Ａｌ，沸石表面强弱酸位同时存在。增加沸石骨架Ｔｉ含量和晶内二次孔对提高苯酚过氧化氢     

用IR/TPD法测定氢型丝光沸石上氨的脱附活化能

通过IR/TPD的改进方法, 测定了氨在氢型丝光沸石(HM)上的Bronsted酸位上的脱附活化能和相应的集居数。结果表明, 在HM上有三种不同强度的Bronsted酸位, 分别对应脱附活化能为63.6、49.8和35.4kJ/mol。     

The effect of the “Inert” support on relative photocatalytic activity in the oxidative decomposition of alcohols on irradiated titanium dioxide composites

Reduced quantum efficiencies for the photocatalytic degradation of cyclohexanol, cyclododecanol, 2-hexanol, and benzyl alcohol are observed on TiO₂ particles included within small pore zeolitic supports suspended in acetonitrile. A modest reduction in photocatalytic activity observed with TiO₂ included within large pore zeolites and pillared clays is attributed to reflective and refractive losses of incident light. No appreciable substrate size selectivity could be observed in this series of supported TiO₂ composites. TS-1, a titanium-containing zeolite with Ti in tetrahedral lattice sites, was photoactive, although ETS-10, a titanium-containing zeolite with Ti in octahedral lattice sites, was less so. The low quantum yield residual photoactivity observed with these alcoholic substrates on unmodified zeolites may derive from surface charge transfer complexation, as suggested by diffuse reflectance absorption measurements.     

The influence of acidities of boron- and aluminium-containing MFI zeolites on co-reaction of methanol and ethene

A series of boron- and aluminium-containing MFI zeolites were synthesized and various characterization techniques, such as NMR ((27)Al, (29)Si and (11)B), were employed to study the acidities of zeolites. Moreover, in situ IR was applied to investigate the interaction of methanol and ethene with the acid sites, and those catalytic materials were used for co-reaction of methanol and ethene to produce propene. The production of propene was related to the Al content of the zeolites with Si/Al ratios of higher than 90. It is implied that the presence of boron during the synthesis directed the aluminium to occupy certain tetrahedral sites in the zeolite framework, thus preventing the formation of ethene oligomers, and resulting in increased propene selectivity.     

Characterization and removal of extra lattice species in faujasites

The acidic properties of dealuminated Y-type zeolites were characterized by infrared (IR) spectroscopy, microcalorimetry, ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and temperature-programmed desorption (TPD). Microcalorimetric measurements exhibited a uniform heat of adsorption (140 kJ/mol) of ammonia on the strong Brönsted acid sites. The differences in the acid site concentrations measured by adsorption of ammonia from the gas phase and by decomposition of ammonium-exchanged zeolites are discussed. The results indicate that parts of the extra lattice material consisting of cationic aluminium oxide species or silica alumina species are removed by ion exchange with aqueous solutions of ammonium hydroxide. Based on this, a method for the controlled removal of extra lattice material was developed.     

One-pot fluoro-de-diazoniation of anilines in organic medium

Treatment of anilines with tert-butyl nitrite in the presence of boron trifluoride in ortho-dichlorobenzene leads to in situ fluoro-de-diazoniation and affords the corresponding fluoroaromatics with fair yields. This process, conducted in organic medium without Broensted acids, does not require isolation of hazardous diazonium salts and reduces the amounts of wastes. The results of the first screening are given.     

Effect of interparticle interactions on the rate of injection of charge carriers into electroactive polymer films

A phenomenological approach is used for deriving a difference equation for the density of reduced sites in films of electroactive polymers with conspicuous interparticle interactions. The approach involves simultaneous application of the lattice methods and Broensted’s rule. This leads to generalization of equations for the surface layer that are known in theory of surface tension for nonelectrolytic solutions. Together with the Poisson equation for electric potential, the derived relationships make a complicated system of differential equations. Nevertheless, it can be solved by iterative methods. In the framework of this approach, expressions for the rates of injection of charge carriers into polymer films are obtained. Within a first approximation with regard to allowance for the forces of short-range interactions, their influence on the rates of injection of electrons and protons into a film is discussed.     

On the possibility of the detachment of hydrogen as a result of electron capture by a Broensted center on zeolites

The structure and reactivity of the radical anion center in ZSM-5 zeolite were studied by the density functional theory method. It was shown that the interaction of the hydrogen zeolite form with adsorbed olefins and aromatic hydrocarbons could be accompanied by electron transfer from hydrocarbon molecules to the Broensted acid center with the formation of a radical anion fragment. The radical anion fragment formed is unstable, which contributes to the probability of the exothermic process (ΔE = ?21 kcal/mol) of atomic hydrogen detachment with the activation energy not exceeding 10–12 kcal/mol. The atomic hydrogen split off can initiate hydrocarbon transformations, and such a radical anion center can play the role of a catalytic activity carrier on acid zeolites.     

氢气在A和X型沸石上超临界吸附的格子密度函数模型

采用基于三维Ono-Kondo方程的格子密度函数理论(LDFT)模型模拟了氢气在A和X型微孔沸石上的超临界吸附等温线. 根据沸石孔的尺寸和形状, LDFT模型将氢分子在孔中的吸附位分布近似为简单立方、面心立方和体心立方的团簇结构. 模拟结果表明, LDFT模型可有效地用于描述氢气在A和X型沸石上的单层或多层超临界吸附行为. 模拟所得的吸附等温线与实验测定结果吻合. 特别是, LDFT模型中的氢-沸石作用势能参数的准确性得到了Lennard-Jones(12-6)势能方法的有效验证. 因此, LDFT模型被用于预测了更宽温度和压力范围内氢气在X沸石上的超临界吸附.     

Properties and Characterization of Modified HZSM—5 Zeolites

Physicochemical and catalytic properties of phosphorus and boron modified HZSM-5 zeolites treated with 100% steam at 673K were investigated.The acidity and distribution of acidic sites were studied by infrared spectroscopy using pyridine as probe molecule and temperature programmed desortion (TPD) of ammonia.The structure of the samples was characterized by XRD,and the textural properties of the catalysts were determined by nitrogen isothermal adsorption-desorption measurements and scanning electron microscopy(SEM).The XRD results show that the modified samples have no novel crystalline phase,indicating a high dispersion of phosphorus and boron species.After treatment,the microporous volume and surface area of the samples markedly decrease,implying the bolockage of the channel.The nitrogen adsorption-desorption measurements suggest that the isothermal type of all samples is a combination of isothermal type Ⅰ and Ⅳ，and all hysteresis loops resemble the H4-type in the IUPAC classification.The total acidity of the modified samples,determined by pyrldine adsorption IR and TPD of ammonia,decreases in contrast to that of the parent HZSM-5.The conversion of n-heptane over P and B steammodified HZSM-5 is higher than that of P and B-modified HZSM-5 zeolites but lower than that of the parent HZSM-5.     

Optimization for catalytic performances of Hβ zeolite in the acylation of 2-methylfuran by surface modification and solvents effect

The liquid phase acylation of 2-methylfuran with acetic anhydride over modified Hβ zeolite was first conducted in a continuous flow reactor. The deactivation of Hβ zeolites was attributed to strong adsorption of reactants or products and was verified by GC–MS and ¹³C MAS NMR. Deactivated zeolites can be regenerated to their original state by calcination. The acidic properties was adjusted by surface modification on Hβ, the maximum yield of 89.5 mol% and selectivity of 100 % were obtained over tartaric acid modified by Hβ. The deposition of tetraethoxysilane to silica on Hβ contributed to enhancing the catalytic stability. Combined with the results of NH₃-TPD and Py-FTIR, the amount of Broensted acids played a major role on catalytic activity. A close relationship between the catalytic stability and the ratio of the amount of strong to weak acids at 1:1 was highlighted here. The solvents' effect on the catalytic performances was examined, and 1,2-dichloroethane with moderate polarity exerted a positive effect on catalytic stability.     

Acidity adjustment of HZSM-5 zeolites by dealumination and realumination with steaming and citric acid treatments

This article describes a novel method for acidity adjustment of HZSM-5 zeolites with steaming and citric acid treatments and demonstrates the realumination effect of citric acid on HZSM-5 zeolites dealuminated by steaming. A series of modified HZSM-5 zeolites were prepared by streaming and/or acid treatments and characterized by means of X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), (27)Al MAS NMR spectroscopy, hydroxyl infrared spectroscopy (OH-IR), pyridine-adsorbed infrared spectroscopy, and N(2) adsorption in the present investigation. The results showed that compared with single HCl or citric acid treatment, steaming treatment, and steaming/HCl treatments, citric acid treatment after steaming exclusively increased the amount of framework Al due to reinsertion of extraframework Al into the defective sites of the steamed HZSM-5 framework. This realumination effect of the citric acid treatment on the steamed HZSM-5 zeolite, which is reported here for the first time to the best of our knowledge, could nearly recover the pore structure of the steamed zeolite to that of the parent HZSM-5 zeolite and appropriately tailor the amount and strength of different acid sites, which sheds light on optimizing the physicochemical properties of HZSM-5 zeolites. It was also found that the steaming treatment prior to the citric acid treatment was the precondition of the realumination of HZSM-5 zeolites, suggesting that the lattice defect sites generated during steaming were necessary for citric acid to work.     

NH4BF4改性Y沸石的结构和性质

用NH₄BF₄溶液处理普通的Y沸石后,得到了一系列不含B的脱铝Y沸石。本文运用多种实验手段对它们进行了表征,并与其它改性方法得到的脱铝Y沸石进行比较,发现这类Y沸石脱铝羟基空穴较少,晶格热稳定性较高,且具有特殊的表面酸性分布,因而NH₄BF₄处理亦是一种有特色的Y沸石改性方法。     

高硅沸石骨架结构及其稳定性的模拟计算(I)*

The lattice energy of a series of high-silica zeolites was determined using the lattice energy minimization method. The results were compared to the lattice energy of dense polymorphs of SiO2. All high-silica zeolites frameworks are only 30～67kJ•mol-1 less stable than α-quartz This may imply that there is little energy barrier to the formation of high-silica zeolites frame-works and explain the structural diversity observed for high-silica zeolites. The relationships of calculated lattice energies and framework Structures was disscussed. The results revealed a good linear relationship between framework density of these molecular sieves and all-silica framework lattice energies.     

Electronic structure of octagonal boron nitride nanotubes

The effect of an octagonal lattice configuration on a boron nitride nanotube is explored using first principle calculations. Calculations show that the formational energy of an octagonal boron nitride nanotube (o‐BNNT) is an exothermic reaction. Boron and nitrogen atoms within an o‐BNNT have an average of 2.88 electrons and 9.09 electrons, respectively, indicating ionic‐like bonding. In addition, the electronic structure of the octagonal boron nitride nanotube shows semiconductive properties, while h‐BNNT is reported to be an insulator. Additional o‐BNNTs with varying diameters are calculated where the results suggest that the diameter has an effect on the binding energy and bandgap of the o‐BNNT. The defect sites of the o‐BNNT are reactive against hydrogen where a boron defect is particularly reactive. Thus, this work suggests that physical and chemical properties of a boron nitride nanotube can be tailored and tuned by controlling the lattice configuration of the nanotube.     

改性对β沸石表面酸性及丙烯水合醚化反应性能的影响

采用浸渍法和离子交换法，制备出一系列改性β沸石催化剂，考察了改性剂对β沸石表面酸性及丙烯水合醚化反应性能的影响。结果表明：硼、锌、铝改性可以提高β沸石的L酸中心，磷、镧、铈改性后β沸石的B酸中心增加。催化剂的B酸和L酸中心与丙烯转化率和异丙醚选择性之间存在着一定的对应关系：B酸量增加有利于提高丙烯转化率，L酸量增加有利于提高异丙醚的选择性。合适的B／L酸比例是催化剂同时具有高活性和高异丙醚选择性的关键。     

Stabilization of Extra-Large-Pore Zeolite by Boron Substitution for the Production of Commercially Applicable Catalysts

Stable extra-large-pore zeolites are desirable for industrial purposes due to their ability to accommodate bulky reactants and diffusion through channels. Although there are several extra-large pore zeolites reported, stable ones are rare. Thus, their stabilization is a feasible strategy for industrial applications. Here, an extra-large-pore zeolite EWT with boron substitution is presented, and the resulting zeolite B-RZM-3 increased the thermal stability from 600 °C in its silica form to 850 °C. The crystal structure, determined by combining continuous rotation electron diffraction (cRED) and powder X-ray diffraction (PXRD), shows that B atoms preferentially substitute the interrupted (HO)T(OT)₃ (Q³) sites and are partially converted into 3-coordination to relax framework deformation upon heating. After Al-reinsertion post-treatment, Al-B-RZM-3 shows higher ethylbenzene selectivity and ethylene conversion rate per mol acid site than commercial ZSM-5 and Beta zeolite in benzene alkylation reaction. Synthesizing extra-large-pore zeolite in borosilicate form is a potential approach to stabilize interrupted zeolites for commercial applications.