C2-C2直链烯烃在HY 和H-ZSM-5分子筛上的吸附

采用ONIOM(B3LYP/6-311++G(d,p):UFF)分层计算方法, 研究了C₂-C₅直链烯烃在HY 和H-ZSM-5 分 子筛上的吸附性质. 理论计算结果表明: 烯烃与分子筛的Br?nsted 酸性位相互作用形成π配位超分子复合物; 随着碳链的增长, 烯烃的吸附能增加, 增加量近似为一个常数(HY 分子筛: 约12 kJ·mol^-1; H-ZSM-5 分子筛: 约 25 kJ·mol^-1), 与烷烃在分子筛上的吸附具有相同的规律. 双键位置对烯烃的吸附能影响很大, 2位烯烃的吸附能 要远大于1 位烯烃的吸附能. 不同类型分子筛对烯烃的吸附性能也有很大差别, 由于局域效应的影响, 小孔径 H-ZSM-5分子筛上的吸附能大于大孔径的HY分子筛,而且碳链越长,这种差别越大.从微观结构上看,吸附的烯 烃与H-ZSM-5分子筛酸性位的距离要远大于它们与HY分子筛酸性位的距离, 这是由于不同类型分子筛的微孔 结构产生的范德华作用是不同的,这种作用随着孔径的减小而增强.前线轨道分析表明, 对于小分子烯烃,大孔径 HY分子筛对其催化活性相近,而小孔径H-ZSM-5分子筛随着烯烃碳原子数的增加催化活性有减弱的趋势.     

由新型铜胺络合物模板剂设计合成活性优异的Cu-SSZ-13分子筛

以低廉的铜胺络合物为新型模板剂, 成功地合成了含铜的 SSZ-13 沸石分子筛 (Cu-ZJM-1). 在合成过程中, 铜胺络合物既是模板分子, 又是催化活性组分铜物种的直接来源. 理论计算表明, 该模板分子的构型与尺寸恰好与构成 SSZ-13 分子筛结构的 CHA 笼相匹配, 因而可以成功地导向该沸石分子筛结构. 采用 X 射线衍射、扫描电镜、氮气吸附、红外、紫外-可见吸收光谱、差热-热重分析、氨气程序升温脱附及氢气程序升温还原等手段对样品的性质及模板分子的状态进行了系统表征. 结果表明, 所制 Cu-ZJM-1 样品为结晶度很高的 SSZ-13 沸石结构, 硅铝比和铜负载量可调且铜处于高分散状态, 在 NH3 选择催化还原氮氧化物反应中表现出优异的催化性能.     

Adsorption of methylene blue and orange II onto unmodified and surfactant-modified zeolite

Adsorption of cationic methylene blue and anionic orange II onto unmodified and surfactant-modified zeolites was studied using a batch equilibration method. The effects of equilibrium time, solution pH, and sorption temperature were examined. The results suggested that 2% sodium dodecyl benzenesulfonate (SDBS)- and 3% sodium dodecyl sulfate (SDS)-modified zeolites had higher adsorption capacities for methylene blue than the unmodified zeolite, while 2% cetylpyridinium bromide hexadecyl (CPB)- and 2% hexadecylammonium bromide (HDTMA)-modified zeolites were the best adsorbents for orange II. The adsorption conditions were optimized, and the mechanisms of adsorption are briefly discussed.     

DFT investigation of alkoxide vs alkylammonium formation in amine-substituted zeolites

Density functional theory (DFT) cluster calculations were used to describe bifunctional acid-base properties of amine-substituted zeolites containing a Br?nsted acid site. Preliminary results (J. Am. Chem. Soc. 2004, 126, 9162) indicated that efficient use of both functional groups might lead to a substantial lowering of activation barriers. In this paper, comparison is made between the alkoxide formation in zeolites containing only oxygen bridges and alkylammonium formation on the bridging NH groups in amine-functionalized zeolites for various guest species, such as methanol, ethene, and chloromethane. The amine functionalization only lowers barriers for SN2 type reactions with otherwise highly strained transition states, as is the case for chloromethane. In these new materials more basic sites are introduced into the zeolite framework, enabling optimal linear SN2 type transition states incorporating various T sites.     

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.     

表面活性剂改性有机沸石对废水中亚甲基蓝的吸附行为

用表面活性剂十六烷基三甲基溴化铵(CTMAB)和十二烷基硫酸钠(SDS)复合改性沸石,制备了阴阳离子表面活性剂改性沸石,利用X射线衍射和红外吸收光谱表征了改性前后沸石的结构,并研究了改性沸石对亚甲基蓝的吸附行为.结果表明,改性后沸石的吸附性能明显增强;在溶液pH 8、常温,吸附时间100 min、改性沸石用量20 g/...     

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.     

Directing Aluminum Atoms into Energetically Favorable Tetrahedral Sites in a Zeolite Framework by Using Organic Structure‐Directing Agents

The Al location in zeolites can have massive influences on the zeolite properties because it directly correlates with the cationic active sites. Herein, the synthesis of IFR zeolites with controlled Al distribution at different tetrahedral sites (T sites) is reported. The computational calculations suggest that organic structure‐directing agents (OSDAs) used for zeolite synthesis can alter the energetically favorable T sites for Al. Zeolite products synthesized under identical conditions but with different OSDAs are found to have altered fractions of Al at different T sites in accordance with the energies derived from the zeolite–OSDA complexes. Our finding thus provides evidence for the ability of OSDAs to direct Al into more energetically favorable T sites, thereby offering rational synthetic guidelines for the selective placement of Al into specific crystallographic sites.     

Influence of pore dimension and sorption configuration on the heat of sorption of hexane on monodimensional siliceous zeolites

Sorption of n-hexane on monodimensional pure silica SSZ-35, CIT-5, ZSM-12, and ZSM-22 zeolites with different pore dimension and on recently synthesized ITQ-29 was studied by IR spectroscopic and computational chemistry methods. Heats of sorption of n-hexane on these zeolites was determined experimentally from the temperature dependence of the intensity of IR bands of sorbed hexane as well as from theoretical calculations. Calculations have shown the different orientations of sorbed hexane molecules inside zeolite channels, which depend on the type of zeolite and loading. At high loadings, ordering of hexane inside the channels is observed due to optimization of sorbate-sorbate and sorbate-zeolite interaction energies. Such ordering is responsible for the increase of the sorption energy. A decrease of the sorption energy upon increasing the pore dimension of zeolite was observed, in agreement with results previously published in the literature. Effects of pore diameter of zeolites and ordering of molecules inside zeolite channels on the sorption energy of hexane are discussed.     

Diisocyanates as novel molecular binders for monolayer assembly of zeolite crystals on glass

Isocyanate groups readily form urethane linkages with surface hydroxy groups on glass and zeolites and this phenomenon was utilized in the assembly of monolayers of zeolite microcrystals on glass by employing diisocyanates as novel molecular binders.     

Reactivity of isobutane on zeolites: a first principles study

In this work, ab initio and density functional theory methods are used to study isobutane protolytic cracking, primary hydrogen exchange, tertiary hydrogen exchange, and dehydrogenation reactions catalyzed by zeolites. The reactants, products, and transition-state structures are optimized at the B3LYP/6-31G* level, and the final energies are calculated using the CBS-QB3 composite energy method. The computed activation barriers are 52.3 kcal/mol for cracking, 29.4 kcal/mol for primary hydrogen exchange, 29.9 kcal/mol for tertiary hydrogen exchange, and 59.4 kcal/mol for dehydrogenation. The zeolite acidity effects on the reaction barriers are also investigated by changing the cluster terminal Si-H bond lengths. The analytical expressions between activation barriers and zeolite deprotonation energies for each reaction are proposed so that accurate activation barriers can be obtained when using different zeolites as catalysts.     

Detailed process of adsorption of alkanes and alkenes on zeolites

The adsorption of alkanes and alkenes on zeolites is investigated by comparing the adsorption characteristics for three types of zeolite: ferrierite, ZSM-5, and mordenite. The activation energy for the diffusion of propane and n-butane on ferrierite and the heat of adsorption of C(2)-C(4) alkanes and alkenes on zeolites and silica are estimated based on Fourier transform infrared spectroscopy, and the diffusion processes in the micropores are elucidated by comparing the results with previously reported activation energies for n-butene diffusion. The adsorption of 1-butene on mordenite is also examined. The structure and process of experimentally observable adsorption is found to differ depending on the type of zeolite and adsorbing molecule, reflecting differences in the sizes of molecules and pores. This differing behavior is utilized to interpret the elementary adsorption processes of alkanes and alkenes on zeolites.     

Reactivity of alkanes on zeolites: a computational study of propane conversion reactions

In this work, quantum chemical methods were used to study propane conversion reactions on zeolites; these reactions included protolytic cracking, primary hydrogen exchange, secondary hydrogen exchange, and dehydrogenation reactions. The reactants, products, and transition-state structures were optimized at the B3LYP/6-31G level and the energies were calculated with CBS-QB3, a complete basis set composite energy method. The computed activation barriers were 62.1 and 62.6 kcal/mol for protolytic cracking through two different transition states, 30.4 kcal/mol for primary hydrogen exchange, 29.8 kcal/mol for secondary hydrogen exchange, and 76.7 kcal/mol for dehydrogenation reactions. The effects of basis set for the geometry optimization and zeolite acidity on the reaction barriers were also investigated. Adding extra polarization and diffuse functions for the geometry optimization did not affect the activation barriers obtained with the composite energy method. The largest difference in calculated activation barriers is within 1 kcal/mol. Reaction activation barriers do change as zeolite acidity changes, however. Linear relationships were found between activation barriers and zeolite deprotonation energies. Analytical expressions for each reaction were proposed so that accurate activation barriers can be obtained when using different zeolites as catalysts, as long as the deprotonation energies are first acquired.     

Mercaptoamine-assisted Post-encapsulation of Metal Nanoparticles within Preformed Zeolites and their Analogues for Hydroisomerization and Methane Decomposition

We report a general synthetic strategy for post-encapsulation of metal nanoparticles within preformed zeolites using post-synthetic modification. Both anionic and cationic precursors to metal nanoparticle are supported on 8- and 10-membered ring zeolites and analogues during wet impregnation using 2-aminoethanethiol (AET) as a bi-grafting agent. Thiol groups are coordinated to metal centers, whereas amine moieties are dynamically attached to micropore walls via acid-base interactions. The dynamic acid-base interactions cause the even distribution of the metal-AET complex throughout the zeolite matrix. These processes encapsulate Au, Rh, and Ni precursors within the CHA, *MRE, MFI zeolite, and SAPO-34 zeolite analogues, for which small channel apertures preclude the post-synthesis impregnation of metal precursors. Sequential activation forms small and uniform nanoparticles (1–2.5 nm in diameter), as confirmed through electron microscopy and X-ray absorption spectroscopy. Containment within the small micropores protected the nanoparticles against harsh thermal sintering conditions and prevented the fouling of the metal surface by coke, thus resulting in a high catalytic performance in n-dodecane hydroisomerization and methane decomposition. The remarkable specificity of the thiol to metal precursors and the dynamic acid-base interaction make these protocols extendable to various metal-zeolite systems, suitable for shape-selective catalysts in challenging chemical environments.     

Theoretical study of the adsorption of ethylene on alkali‐exchanged zeolites

The structures of alkali‐exchanged faujasite (X–FAU, X = Li⁺ or Na⁺ ion) and ZSM‐5 (Li–ZSM‐5) zeolites and their interactions with ethylene have been investigated by means of quantum cluster and embedded cluster approaches at the B3LYP/6‐31G(d, p) level of theory. Inclusion of the Madelung potential from the zeolite framework has a significant effect on the structure and interaction energies of the adsorption complexes and leads to differentiation of different types of zeolites (ZSM‐5 and FAU) that cannot be drawn from a typical quantum cluster model, H₃SiO(X)Al(OH)₂OSiH₃. The Li–ZSM‐5 zeolite is predicted to have a higher Lewis acidity and thus higher ethylene adsorption energy than the Li–FAU zeolites (16.4 vs. 14.4 kcal/mol), in good agreement with the known acidity trend of these two zeolites. On the other hand, the cluster models give virtually the same adsorption energies for both zeolite complexes (8.9 vs. 9.1 kcal/mol). For the larger cation‐exchanged Na–FAU complex, the adsorption energy (11.6 kcal/mol) is predicted to be lower than that of Li–FAU zeolites, which compares well with the experimental estimate of about 9.6 kcal/mol for ethylene adsorption on a less acidic Na–X zeolite. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 333–340, 2003     

Amine‐Appended Hierarchical Ca‐A Zeolite for Enhancing CO2/CH4 Selectivity of Mixed‐Matrix Membranes

An amine‐appended hierarchical Ca‐A zeolite that can selectively capture CO₂ was synthesized and incorporated into inexpensive membrane polymers, in particular polyethylene oxide and Matrimid, to design mixed‐matrix membranes with high CO₂/CH₄ selectivities. Binary mixture permeation testing reveals that amine‐appended mesoporous Ca‐A is highly effective in improving CO₂/CH₄ selectivity of polymeric membranes. In particular, the CO₂/CH₄ selectivity of the polyethylene oxide membrane increases from 15 to 23 by incorporating 20 wt % amine‐appended Ca‐A zeolite. Furthermore, the formation of filler/polymer interfacial defects, which is typically found in glassy polymer‐zeolite pairs, is inhibited owing to the interaction between the amine groups on the external surface of zeolites and polymer chains. Our results suggest that the amine‐appended hierarchial Ca‐A, which was utilized in membrane fabrication for the first time, is a good filler material for fabricating a CO₂‐selective mixed‐matrix membrane with defect‐free morphology.     

Theoretical studies of alkyl radicals in the NaY and HY zeolites

Interplay of quantum mechanical calculations and experimental data on hyperfine coupling constants of ethyl radical in zeolites at several temperatures was engaged to study the geometries and binding energies and to predict the temperature dependence of hyperfine splitting of a series of alkyl radicals in zeolites for the first time. The main focus is on the hyperfine interaction of alkyl radicals in the NaY and HY zeolites. The hyperfine splitting for neutral free radicals and free radical cations is predicted for different zeolite environments. This information can be used to establish the nature of the muoniated alkyl radicals in the NaY and HY zeolites via muSR experiments. The muon hyperfine coupling constants of the ethane radical cation in these zeolites are very large with relatively little dependence on temperature. It was found that the intramolecular dynamics of alkyl free radicals are only weakly affected by their strong binding to zeolites. In contrast, the substrate binding has a significant effect on their intermolecular dynamics.     

Nanoscale Control of Homoepitaxial Growth on a Two‐Dimensional Zeolite

Nanoscale crystal growth control is crucial for tailoring two‐dimensional (2D) zeolites (crystallites with thickness less than two unit cells) and thicker zeolite nanosheets for applications in separation membranes and as hierarchical catalysts. However, methods to control zeolite crystal growth with nanometer precision are still in their infancy. Herein, we report solution‐based growth conditions leading to anisotropic epitaxial growth of 2D zeolites with rates as low as few nanometers per day. Contributions from misoriented surface nucleation and rotational intergrowths are eliminated. Growth monitoring at the single‐unit‐cell level reveals novel nanoscale crystal‐growth phenomena associated with the lateral size and surface curvature of 2D zeolites.     

Confined space synthesis. A novel route to nanosized zeolites

Confined space synthesis is a novel method in zeolite synthesis. It involves crystallization of the zeolite inside the pore system of an inert mesoporous matrix. In this way it is possible to prepare nanosized zeolites with a controlled size distribution by proper choice of the inert matrix. Here, confined space synthesis was adopted to prepare nanosized ZSM-5, zeolite Beta, zeolite X, and zeolite A with tailored crystal size distributions using mesoporous carbon blacks as inert matrices. All zeolites were characterized by X-ray powder diffraction, transmission electron microscopy, and nitrogen adsorption/desorption prior to and after removal of the carbon matrix. ZSM-5 with Si/Al ratios of 50, 100, and infinity (silicalite-1) were synthesized with controlled average crystal sizes in the range 20-75 nm. Nanosized zeolite Beta (7-30 nm), zeolite X (22-60 nm), and zeolite A (25-37 nm) were prepared similarly. Removal of the carbon matrix by controlled combustion allows a convenient method for isolation of the pure and highly crystalline zeolites. Therefore, confined space synthesis appears to be an attractive method for preparation of zeolites with a controlled size distribution.