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.     

The leading role of association in framework modification of highly siliceous zeolites with adsorbed methylamine.

Affinity index (AT value), adsorption heat, X-ray diffraction (XRD), and 13C and 29Si magic-angle spinning (MAS) NMR, FTIR, and Raman spectroscopies were used to study the interaction of highly siliceous MFI-, FAU-, and FER-type zeolites with adsorbed methylamine (MA). Compared with the data for methanol, the much higher AT values and adsorption heats, and significant changes in XRD patterns, 29Si MAS NMR spectra, and FTIR spectra for the zeolites after adsorption of MA, revealed a strong hydrogen-bonding interaction between the perfect framework of the zeolites and the adsorbed MAs. This interaction results from the fact that the H atom of the amine group attacks the [Si-O] framework to form a Si-OHN bond, which leads to the appearance of Si-N bonds in the zeolites at 323 K. Therefore, the zeolite framework can be modified with MA under mild conditions. The highly siliceous MFI zeolite and the H-ZSM-5 zeolite with SiO2/Al2O3=31:1 were modified with MA and investigated by temperature-programmed desorption of CO2. The modified zeolites exhibited greatly enhanced basic properties in comparison with those of the raw materials. The influence of defects in the zeolite on the adsorption and the interaction with MA is discussed.     

CXN天然沸石的研究2: 吸附性质

采用N~2,NH~3,CO~2,乙烯,丙烯,水,甲醇,乙醇,丙醇等作为吸附剂,研究了由我国CXN天然沸石改性制得的H-STI和Na-STI沸石的吸附性质,H-STI和Na-STI沸石的BET表面积及微孔孔体积约为420m^2/g和0.20m^3/g。根据NH~3和CO~2在H-STI沸石上的吸附等温线计算得到它们的吸附热分别为44.8和26.5kJ/mol。乙烯,丙烯,甲醇,乙醇,丙醇等在Na-STI沸石上的吸附等温线表明该沸石对有机分子的吸附具有链长选择性。在低分压下水相对于甲醇的吸附量表明沸石具有一定的疏水性质。     

Relationships between basicity and reactivity of zeolite catalysts

A wide variety of characterization methods, including UV-vis spectroscopy of adsorbed I₂, microcalorimetry of CO₂ adsorption, and x-ray absorption spectroscopy at the Cs L_III edge of zeolite cations, was applied to a series of alkali containing zeolites in order to elucidate the nature of the basic sites on these materials. In addition, three catalytic reactions involving basic zeolites were studied. In the first case, alkali-exchanged zeolites (L, Beta, X and Y) were used as catalysts for the side-chain alkylation of toluene with methanol to form styrene and ethylbenzene. Zeolites with low base site densities and appropriate base strengths catalyzed toluene alkylation without decomposing methanol to carbon monoxide. In the second example, ruthenium metal clusters were supported on alkali and alkaline earth exchanged X zeolites and tested as catalysts for ammonia synthesis. Zeolites containing alkaline earth ions exhibited rates greater than those containing alkali ions. Finally, zeolite X loaded with alkali metal was an active catalyst for toluene alkylation with ethylene whereas zeolite X loaded with alkali oxide was inactive for the reaction. These results suggest that exciting opportunities exist for the use of basic zeolites as catalysts and catalyst supports.     

Electron spin resonance analysis of paramagnetic Pd(I) species in Pd(II)-exchanged H-rho zeolite

Zeolite rho was synthesized and Pd(II) exchanged into it. Pd(II) was reduced to paramagnetic Pd(1) by a thermal activation process. The interactions of Pd(I) in zeolite H-rho with oxygen, water, methanol, ammonia, carbon monoxide and ethylene have been studied by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies. The ESR spectrum of an activated sample shows the formation of one Pd(I) species. Pd(I) interacts with water vapor or molecular oxygen to form Pd(II)–O₂, indicating decomposition of water. Equilibration with methanol results in a broad isotropic ESR signal which is attributed to the formation of small palladium clusters. ESEM shows that the Pd clusters coordinate one molecule of methanol. Adsorption of ammonia produces a Pd(I) complex containing four molecules of ammonia based upon resolved nitrogen superhyperfine coupling. Adsorption of carbon monoxide results in a Pd(I) complex containing two molecules of carbon monoxide based upon resolved¹³C superhyperfine coupling. ESR and ESEM results indicate that exposure to ethylene leads to two new Pd(I) species each of which coordinates one molecule of ethylene.     

FER型沸石的合成、结构与吸附性质

在TMEDA(四甲基乙基二胺)-Na2O-SiO2-Al2O3-H2O体系(I),Na2O-K2O-Al2O3-SiO2-H2O-HCO3^--CO3^2^-体系(II)及Py(吡啶)-PrNH2(正丙胺)-HF-SiO2-H2O体系(III)中, 分别合成了纯相FER沸石及FER硅沸石。用粉末XRD, FT-IR, 29Si MAS NMR及TG/DTA等表征其结构性质, 并用超微量电子真空吸附天平测定这些沸石样品对正己烷, 甲醇和水的吸附等温线。结果表明: 各体系合成的样品虽然结晶度高, 呈现出FER沸石的典型结构特征, 但由于它们的组成和晶格微结构不同, 热稳定性与吸附性质有明显的差异。在(I)体系中合成的FER沸石层错缺陷少, 晶格完美, 正己烷与甲醇的吸附量可达到理论值, 结构破坏温度为1190℃。红外精细谱及29Si MAS NMR高分辨谱证明FER硅沸石具有十分完美的骨架结构。由于晶胞收缩, 它对正己烷与甲醇吸附量略低于理论值, 并呈现出高度的疏水性。它的结构破坏温度高于1300℃。在(II)体系中合成的FER型沸石结构缺陷多, 沸石孔中的钾离子不易被质子完全交换。它的正己烷与甲醇吸附量均较低, 而水的吸附量相对较高。吸附现象表明, 正己烷和甲醇都被吸附于FER沸石的十元环主孔道中, 分压较高时, 甲醇可通过八元环进入小笼, 而水的吸附性质则主要与各样品的Si-OH缺陷及骨架中的阳离子含量有关。     

Carbonates in zeolites: Formation,properties, reactivity

Two possible schemes of carbonate formation (with and without water participation) in cationic form zeolites are considered. Activation energy for the formation of hydrogen carbonate in NaX zeolite from water and carbon dioxide is calculated at the DFT level with periodic boundary conditions, while the problems of modeling the formation of symmetric carbonate in the same zeolite are discussed. The formation of copper carbonate is studied using binuclear CuOCu clusters from CO₂ where the influence of water on the barrier is discussed. The questions related to DFT application to binuclear copper clusters are also considered by comparison with the data obtained at the MP2 level. The reactivity of copper carbonate is tested in the reaction with methanol. © 2015 Wiley Periodicals, Inc.     

In situ infrared molecular detection using palladium-containing zeolite films

In situ IR detection of carbon monoxide in the presence of hydrocarbons (methanol and pentane) using Pd-containing zeolite thin films is reported. The thin films are prepared by spin coating deposition of nanosized LTL and BEA type zeolites suspensions; the palladium clusters are introduced in the nanosized zeolites by ion exchange followed by γ radiolysis of the coating suspensions. The Pd-containing zeolite films with a thickness of 200 nm are exposed to a single gas (either CO or hydrocarbons) or gas mixtures in the presence of water (100 ppm), and the IR spectra are collected continuously at 25, 75, and 100 °C. The fast recognition of very low concentrations of CO (2-100 ppm) in the presence of highly concentrated vapors of methanol or pentane (400-4000 ppm) with the Pd-containing zeolite films is demonstrated. The detection of CO and hydrocarbons is instant, which is a function of the low thickness of the films, small size of the individual zeolite crystals, and regular size and high stability of the Pd clusters in the zeolite films. The heat of adsorption for all experiments is similar (15 kJ.mol(-1)), which is explained with weak interactions between the carbon monoxide and palladium clusters in the zeolite films at temperatures below 100 °C. The nanosized zeolites with homogeneously distributed Pd clusters deposited in thin films demonstrate high molecular recognition capacity toward low concentrations of carbon monoxide under real environmental conditions, i.e., in the presence of water and hydrocarbons.     

FTIR studies of zeolite matrix effects on the properties of palladium clusters confined in the supercages of NaX and NaY

Palladium clusters have been synthesized by the "ship-in-a-bottle" approach in the supercages of NaX and NaY faujasite zeolites. In comparison with CO adsorbed on a bulk Pd electrode, the same molecule adsorbed on the Pd clusters electrodes evoked an enhanced IR absorption (EIRA). The enhancement factors have been determined to be about 38 and 51 in NaX and NaY, respectively. IR band centers of linear-bonded CO, bridge-bonded CO, and multi-bonded CO in NaX are measured, respectively, 12, 14, and 11 cm(-1) lower than those of the corresponding adsorption modes in NaY. The adsorption of CO and the oxidation of adsorbed CO in NaX matrix are faster than that in NaY matrix. These results suggest that part of the Pd2+ ions in NaX are located in sites III and III' that are near the 12-ring window of the supercage of zeolite, which lead to the formation of small Pd clusters. The present study is of significant importance in exploring the dependence of catalyst properties on structures, as well as in understanding and predicting the locations and properties of metal clusters in zeolites.     

On the nature of acid centers in Mg-containing ZSM-5 zeolites

The catalytic activity of ZSM-5 zeolites containing Mg cations in various concentrations has been studied in the alkylation of toluene by ethylene. The concentration of acid centers of different nature in these zeolites was characterized by IR spectroscopy of OH-groups and adsorbed CO. The state of Mg cations in the samples was studied by¹⁵N NMR of the adsorbed N₂O. The increase of Mg content was shown to decrease both the concentration of non-protic acid sites of medium strength and the activity of samples, which is related to the increase of association degree of Mg cations in the zeolite.     

High Ethylene Selectivity in Methanol‐to‐Olefin (MTO) Reaction over MOR‐Zeolite Nanosheets

Precisely controlled crystal growth endows zeolites with special textural and catalytic properties. A nanosheet mordenite zeolite with a thickness of ca. 11 nm, named as MOR‐NS, has been prepared using a well‐designed gemini‐type amphiphilic surfactant as bifunctional structure‐directing agent (SDA). Its benzyl diquarternary ammonium cations structurally directed the formation of MOR topology, whereas the long and hydrophobic hexadecyl tailing group prevented the extensive crystal growth along b axis. This kind of orientated crystallization took place through the inorganic–organic interaction between silica species and SDA molecules present in the whole process. The thin MOR nanosheets, with highly exposed (010) planes and 8‐membered ring (MR) windows, exhibited a much improved ethylene selectivity (42.1 %) for methanol‐to‐olefin (MTO) reactions when compared with conventional bulk MOR crystals (3.3 %).     

Quantum-mechanical simulation of the interaction of aluminum- and boron-containing zeolite clusters with molecules of water and ammonia

Quantum-mechanical computations of zeolite clusters with molecules of water and ammonia have been carried out. The clusters consisted of ten atoms of silicon and aluminum, where one atom of aluminum was also replaced with an atom of boron. Values of the bond length and bond angles have been obtained; the geometry of adsorption complexes and the bond energy for molecules of water and ammonia with atoms of aluminum and boron of a zeolite fragment have been determined. The computed values of bond energy for molecule probes yield the quantitative strength characteristic of zeolite aprotic acid centers.     

Microwave absorption and structure of zeolite water in heulandite and clinoptilolite by <Superscript>1</Superscript>H NMR

The structure of zeolite water in single crystals of natural zeolites represented by clinoptilolite Na₂K₂Ca[Al₆Si₃₀O₇₂]·22H₂O and heulandite Ca₃Mg[Al₈Si₂₈O₇₂]·24H₂O is studied with ¹H NMR. Below 170 K the distribution of H₂O over the structural positions is shown to be fixed but different for the two minerals. Above 290 K translational and orientational diffusion of zeolite water molecules is observed and the structure of water is almost identical in both heulandite and clinoptilolite. Diffusion mechanism may be associated with the interaction between librational modes of H₂O and high-frequency oscillations of aluminosilicate framework. The microwave absorption is shown to be caused in certain conditions by this type of interaction.     

氢在沸石上的吸附行为

应用基于Ono-Kondo格子理论得到的通用吸附等温方程, 通过分析氢在不同温度下, 在沸石NaX、CaA、NaA和ZSM-5上的吸附数据, 确定了氢的最大单层吸附容量. 并引入维里吸附方程, 由第二维里吸附系数和圆柱孔的Lennard-Jones(12-6)势模型计算了氢与沸石微孔壁面的作用势. 结果表明, 通用吸附等温方程可较好地描述氢在沸石上的超临界吸附行为, 拟合所得的氢在沸石上的最大单层吸附容量与吸附剂相关, 而与吸附温度无关. 圆柱孔作用势模型计算所得的氢分子在沸石上的吸附作用势与吸附热相近. 氢分子间的作用力表现为吸引力.     

Influence of the crystallinity of pentasil-type zeolites on their acidity

The acid properties of intermediate products in crystallization of pentasil-type zeolites have been investigated using programmed thermal desorption of ammonia and adsorption of pyridine. It was found that acidity increases with increasing crystallinity due to proton-donor centers. A correlation was established between this change in acidity and methanol TPSR data.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 31, No. 1, pp. 48–51, January–February, 1995.     

IR Spectroscopic Study of Ethylene Adsorption and Oligomerization on the Hydrogen Form of Mordenite

Diffuse-reflectance IR spectroscopy is used to study adsorption and oligomerization of ethylene on the hydrogen form of mordenite at room temperature. Ethylene adsorbs on bridging acid hydroxyl groups of the zeolite and forms -complexes with a firm hydrogen bond. The interaction with hydroxyl groups most strongly excites composite vibrations in adsorbed molecules. These vibrations are a combination of the stretching vibration of a double bond and the deformational vibrations of the CH₂ group. A conjecture is drawn that these composite vibrations correspond to the reaction coordinate of ethylene transformation to the ethoxy groups. Their further reactions with weakly adsorbed molecules result in ethylene oligomerization. A linear oligomer is formed, grafted on the zeolite surface and filling the pores of zeolites.     

Enthalpies of solvation of ethylene oxide oligomers CH3O(CH2CH2O)nCH3 (n = 1 to 4) in different H-bonding solvents: Methanol,chloroform, and water. Group contribution method as applied to the polar oligomers

The enthalpies of solution and solvation of ethylene oxide oligomers CH₃O(CH₂CH₂O)_nCH₃ (n = 1 to 4) in methanol and chloroform have been determined from calorimetric measurements at T = 298.15 K. The enthalpic coefficients of pairwise solute–solute interaction for methanol solutions have been calculated. The enthalpic characteristics of the oligomers in methanol, chloroform, water and tetrachloromethane have been compared. The hydrogen bonding of the oligomers with chloroform and water molecules is exhibited in the values of solvation enthalpy and coefficient of solute–solute interaction. This effect is not observed for methanol solvent. The thermochemical data evidence an existence of multi-centred hydrogen bonds in associates of polyethers with the solvent molecules. Enthalpies of hydrogen bonding of the oligomers with chloroform and water have been estimated. The additivity scheme has been developed to describe the enthalpies of solvation of ethylene oxide oligomers, unbranched monoethers and n-alkanes in chloroform, methanol, water, and tetrachloromethane. The correction parameters for contribution of repeated polar groups and correction term for methoxy-compounds have been introduced. The obtained group contributions permit to describe the enthalpies of solvation of unbranched monoethers and ethylene oxide oligomers in the solvents with standard deviation up to 0.6 kJ · mol⁻¹. The values of group contributions and corrections are strongly influenced by solvent properties.     

Gibbs ensemble Monte Carlo simulation of supercritical CO2 adsorption on NaA and NaX zeolites

Adsorption of supercritical carbon dioxide on two kinds of zeolites with identical chemical composition but different pore structure (NaA and NaX) was studied using the Gibbs ensemble Monte Carlo simulation. The model frameworks for the two zeolites with SiAl ratio being unity have been chosen as the solid structures in the simulation. The adsorption behaviors of supercritical CO2 on the NaA and NaX zeolites, based on the adsorption isotherms and isosteric heats of adsorption, were discussed in detail and were compared with the available experimental results. A good agreement between the simulated and experimental results is obtained for both the adsorbed amount and the bulk phase density. The intermediate configurational snapshots and the radial distribution functions between zeolite and adsorbed CO2 molecules were collected in order to investigate the preferable adsorption locations and the confined structure behavior of CO2. The structure behaviors of the adsorbed CO2 molecules show various performances, as compared with the bulk phase, due to the confined effect in the zeolite pores.     

CuHY分子筛中铜离子的分布与吸附脱硫性能

采用等体积浸渍法制备具有不同Cu担载量的CuHY 分子筛吸附剂. 用X射线衍射(XRD)、比表面积(BET)和氨程序升温脱附(NH3-TPD)技术对分子筛吸附剂进行了表征, 并测定了CuHY 分子筛吸附剂在含二苯并噻吩(DBT)模拟柴油中的吸附脱硫性能; 通过多晶XRD确定了Cu2+在Cu8HY 分子筛笼内的结构与分布. 实验结果表明, 分子筛的骨架结构没有发生改变, 部分Cu2+进入Y型分子筛笼内, 分子筛样品强酸中心有所减少, 中强酸中心有所增加; 进入Y型分子筛笼内的Cu2+, 一部分处于β 笼的SI' 位, 另一部分位于分子筛超笼中的SIII位上, 并与笼内的水分子配位. 处于超笼中的SⅢ位Cu2+对模拟柴油中的DBT分子具有吸附作用, 是吸附脱硫的中心. 而当模拟柴油中存在萘时, 与DBT分子会产生竞争吸附.     

镧改性的CuHY分子筛中铜离子的分布及其对吸附脱硫性能的影响

在氮气气氛下采用等体积浸渍法制备了载Cu的HY和LaHY分子筛.用x射线衍射(XRD)、N2吸附、氨程序升温脱附和X射线光电子能谱对分子筛进行了表征.通过多晶XRD确定了Cu2+离子在Y型分子筛笼内的结构与分布,并测定了分子筛在含二苯并噻吩(DBT)的模拟柴油中的吸附脱硫性能.结果表明,前驱体CuCl2中的大部分Cu物种与HY和LaHY分子筛进行了离子交换.对于La3+改性的CuHY分子筛(CuLaHY),进入分子筛超笼中的Cu2+离子与骨架氧和水分子配位,牢固地定位于Y型分子筛超笼的SⅡ及SⅢ位;对于CuHY分子筛,超笼中的Cu2+离子只接近于SⅡ及SⅢ位.极少部分CuCl分子高度分散在分子筛笼内,没有定位.处于超笼中SⅡ及SⅢ位的Cu2+离子对模拟柴油中的DBT分子具有吸附作用,是吸附脱硫的活性中心.CuLaHY分子筛的吸附脱硫性能优于CuHY分子筛.当模拟柴油中含有萘时,萘与DBT分子会产生竞争吸附.