Novel phthalocyanine-based stopcock for zeolite L

We report the first phthalocyanine-based stopcock for selective adsorption to the channel entrances of zeolite L and realisation of a new electronic dipole moment coupling situation.     

Dye-modified nanochannel materials for photoelectronic and optical devices

Artificial photonic antenna systems have been realised by incorporating organic dyes into zeolite L. The size and aspect ratio of the cylindrically shaped zeolite crystals can be tuned over a wide range, adding to the versatility of this host material. A 600 nm sized crystal, for example, consists of about 96 000 one-dimensional channels oriented parallel to the cylinder axis. Geometrical constraints imposed by the host structure lead to supramolecular organisation of the guests, allowing high concentrations of non- or only very weakly interacting dye molecules. A special twist is added to these systems by plugging the channel openings with a second type of fluorescent dye, a so-called stopcock molecule. The two types of molecules are precisely tuned to each other; the stopcocks are able to accept excitation energy from the dyes in the channels, but cannot pass it back. The supramolecular organisation of dyes in the zeolite channels corresponds to a first stage of organisation, allowing light-harvesting within the volume of a cylindrical crystal and radiationless energy transport to either the cylinder ends or centre. The second stage of organisation represents the coupling to an external acceptor or donor stopcock fluorophore at the channel entrances, which can then trap or inject electronic excitation energy. The third stage of organisation is realised by interfacing the material to an external device through a stopcock intermediate. We observed that electronic-excitation-energy transfer in dye-zeolite L materials occurs mainly along the channel axis and we have shown that macroscopically organised materials can be prepared. The new materials offer unique possibilities as building blocks for optical, electro-optical and sensing devices.     

Injecting electronic excitation energy into an artificial antenna system through an Ru2+ complex

The Ru2+ complex [Ru(bpy)2(bpy-ph4-Si(CH3)3)]2+ can be electrostatically bound to the negatively charged channel entrances of dye-loaded zeolite L crystals where it acts as a functional stopcock molecule. Impressive electronic triplet-singlet excitation energy transfer from the Ru2+ complex to the acceptor dye oxazine 1 (Ox1) located inside the channels can be observed when the donor molecule is selectively excited. Time-resolved luminescence experiments have been performed on the separate components and on the assembled donor-acceptor material. The luminescence lifetime of the Ru2+ complex attached to the zeolite is reduced by a factor of 30 when Ox1 acceptor molecules are present. The fluorescence decay of Ox1 incorporated in zeolite L is single exponential with a lifetime of 3 ns. The much longer lifetime in zeolite L than in solution is due to the fact, that the diethyl groups are sterically restricted when the dye is inside the host.     

Electronic and vibrational properties of fluorenone in the channels of zeolite L

Fluorenone (C13H8O) was inserted into the channels of zeolite L by using gas-phase adsorption. The size, structure, and stability of fluorenone are well suited for studying host-guest interactions. The Fourier transform IR, Raman, luminescence, and excitation spectra, in addition to thermal analysis data, of fluorenone in solution and fluorenone/zeolite L are reported. Normal coordinate analysis of fluorenone was performed, based on which IR and Raman bands were assigned, and an experimental force field was determined. The vibrational spectra can be used for nondestructive quantitative analysis by comparing a characteristic dye band with a zeolite band that has been chosen as the internal standard. Molecular orbital calculations were performed to gain a better understanding of the electronic structure of the system and to support the interpretation of the electronic absorption and luminescence spectra. Fluorenone shows unusual luminescence behavior in that it emits from two states. The relative intensity of these two bands depends strongly on the environment and changes unexpectedly in response to temperature. In fluorenone/zeolite L, the intensity of the 300 nm band (lifetime 9 micros) increases with decreasing temperature, while the opposite is true for the 400 nm band (lifetime 115 micros). A model of the host-guest interaction is derived from the experimental results and calculations: the dye molecule sits close to the channel walls with the carbonyl group pointing to an Al3+ site of the zeolite framework. A secondary interaction was observed between the fluorenone's aromatic ring and the zeolite's charge-compensating cations.     

Enhanced NIR Luminescence of Nanozeolite L Loading Lanthanide β‐Diketonate Complexes

Herein, we report the preparation of zeolite NIR luminescence materials with a remarkable increase of luminescence intensity by attaching stopper molecule (an imidazolium salt) to the channel entrances of zeolite L loading with NIR lanthanide (Er³⁺ or Nd³⁺) β‐diketonate complexes. This results from the formation of Ln³⁺‐β‐diketonate complexes (Ln=Er or Nd) with high coordination numbers through the decreasing of the proton strength in the zeolite channels. The obtained materials were characterized with SEM and photoluminescence spectroscopy. We believe that this hybrid material will be an appealing candidate for the applications of optical fiber, telecommunications and bio‐imaging.     

Interplay of bonding and geometry of the adsorption complexes of light alkanes within cationic faujasites. Combined spectroscopic and computational study

A FT-IR spectroscopic study of methane, ethane, and propane adsorption on magnesium and calcium forms of zeolite Y reveals different vibrational properties of the adsorbed molecules depending on the exchanged cation. This is attributed to different adsorption conformations of the hydrocarbons. Two-fold eta(2) coordination of light alkanes is realized for MgY, whereas in case of CaY zeolite quite different adsorption modes are found, involving more C-H bonds in the interaction with the cation. The topological analysis of the electron density distribution function of the adsorption complexes shows that when a hydrocarbon coordinates to the exchanged Mg(2+) ions, van der Waals bonds between H atoms of the alkane and basic zeolitic oxygens significantly contribute to the overall adsorption energy, whereas in case of CaY zeolite such interactions play only an indirect role. It is found that, due to the much smaller ionic radius of the Mg(2+) ion as compared to that of Ca(2+), the former ions are significantly shielded with the surrounding oxygens of the zeolitic cation site. This results in a small electrostatic contribution to the stabilization of the adsorbed molecules. In contrast, for CaY zeolite the stabilization of alkanes in the electrostatic field of the partially shielded Ca(2+) cation significantly contributes to the adsorption energy. This is in agreement with the experimentally observed lower overall absorption of C-H stretching vibrations of alkanes loaded to MgY as compared to those for CaY zeolite. The preferred conformation of the adsorbed alkanes is controlled by the bonding within the adsorption complexes that, in turn, strongly depends on the size and location of the cations in the zeolite cavity.     

High-resolution sorption studies of argon and nitrogen on large crystals of microporous zeolite ZSM-5

Summary High resolution adsorption (HRADS) with argon and nitrogen at 77 K were performed on large crystals of zeolite ZSM-5 using a novel volumetric device. Multi-step isotherms for both adsorptives could be observed for the first time. The micropore filling was followed by low temperature microcalorimetry. Exothermic heats of adsorption were found to be correlated with steps in the adsorption isotherms. Based on results from atom-atom potential energy calculations (AAP) as well as from independent model building it is shown that 24 kinetic adsorbate molecules can be situated in a ZSM-5 unit cell. Localized adsorption is presented as possible filling mechanisms. Experimental results are reasonably interpreted assuming primary filling of narrow channels and secondary adsorption in the wider channel intersections. At least for nitrogen there is evidence for a transition of fluid-like to a solid-like adsorbate phase.Compared to argon, Henry's constants and the initial isosteric heat of adsorption indicate a stronger adsorption of nitrogen which is thought to be due to additional interactions of the nitrogen quadrupole moment with the zeolite framework.

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Sorptionsuntersuchungen zur Hochauflösung von Argon und Stickstoff an großen Kristallen von mikroporösem Zeolit ZSM-5

     

Supramolecular Organization of Dye Molecules in Zeolite L Channels: Synthesis,Properties, and Composite Materials

Sequential insertion of different dyes into the 1D channels of zeolite L (ZL) leads to supramolecular sandwich structures and allows the formation of sophisticated antenna composites for light harvesting, transport, and trapping. The synthesis and properties of dye molecules, host materials, composites, and composites embedded in polymer matrices, including two‐ and three‐color antenna systems, are described. Perylene diimide (PDI) dyes are an important class of chromophores and are of great interest for the synthesis of artificial antenna systems. They are especially well suited to advancing our understanding of the structure–transport relationship in ZL because their core fits tightly through the 12‐ring channel opening. The substituents at both ends of the PDIs can be varied to a large extent without influencing their electronic absorption and fluorescence spectra. The intercalation/insertion of 17 PDIs, 2 terrylenes, and 1 quaterrylene into ZL are compared and their interactions with the inner surface of the ZL nanochannels discussed. ZL crystals of about 500 nm in size have been used because they meet the criteria that must be respected for the preparation of antenna composites for light harvesting, transport, and trapping. The photostability of dyes is considerably improved by inserting them into the ZL channels because the guests are protected by being confined. Plugging the channel entrances, so that the guests cannot escape into the environment is a prerequisite for achieving long‐term stability of composites embedded in an organic matrix. Successful methods to achieve this goal are described. Finally, the embedding of dye–ZL composites in polymer matrices, while maintaining optical transparency, is reported. These results facilitate the rational design of advanced dye–zeolite composite materials and provide powerful tools for further developing and understanding artificial antenna systems, which are among the most fascinating subjects of current photochemistry and photophysics.     

分子模拟噻吩、苯、正己烷混合物在MFI和MOR中的吸附行为

采用GCMC方法模拟了噻吩-苯二元组分和噻吩-苯-正己烷三元组分在MFI和MOR沸石中的吸附分离性能. 结果表明, 对于噻吩-苯二元体系, 在MFI孔道中, 噻吩分子比苯分子都优先定位于孔道的交叉部分, 当总压升高时, 苯的吸附量增加, 噻吩的吸附量保持不变, 苯分子被噻吩分子“挤”到直型孔道之中, 该二元体系符合Clark等提出的竞争吸附模型. 而对于在MOR中的吸附, 噻吩和苯分子没有表现出明显不同的优先吸附位, 符合Clark等提出的体积填充模型. 对于噻吩-苯-正己烷三元体系, 在MFI沸石中, 正己烷的吸附量最大, 噻吩和苯的吸附量很小. 而对于MOR沸石, 噻吩的吸附量最大, 苯和正己烷的吸附量小, 对于这三种较大尺寸的分子, 只能位于MOR主孔道中, 当存在着少量的正己烷分子时, 就影响到了苯的吸附, 而正己烷对噻吩在MOR孔道中填充的影响要比苯小, 噻吩的吸附量影响不大.     

A study of binary adsorption of aromatics in completely siliceous zeolite ZSM-5 by FT-Raman spectroscopy

In the present work, binary adsorption of p-xylene and toluene in completely siliceous zeolite ZSM-5 was examined by FT-Raman spectroscopy in combination with powder X-ray diffraction. The results indicate that at total loadings of < or = 4 molecules per unit cell (u.c.) both p-xylene and toluene molecules prefer to reside at the intersections of straight and zigzag channels. The structure of the sorbate/sorbent complexes likely belongs to orthorhombic. At high loadings of 7 and 8 molecules/u.c., the framework of the zeolite transforms to another orthorhombic phase. In this high-loaded phase, toluene molecules are distributed evenly in both the channel intersection and the midsection of straight channel. Although p-xylene has access to both the channel intersection and the zigzag channel, it does show a slight preference for the channel intersection. The adsorptive behavior of these aromatics at intermediate total loadings of 5 and 6 molecules/u.c. is more complicated because the zeolitic framework is a mixture of two different orthorhombic phases.     

Adsorption of mycotoxins by organozeolites

Adsorption of zearalenone (ZEN), ochratoxin A (OCHRA) and aflatoxin B1 (AFB1) on natural zeolite, clinoptilolite, modified with different amounts of octadecyldimethylbenzyl ammonium (ODMBA) ions was investigated. Results showed that adsorption of hydrophobic ionizable ZEN on unmodified zeolite tuff was very low and that adsorption on organozeolites increased with increasing hydrophobicity of the zeolitic surface. The adsorption was independent of the form of ZEN in solution and the solution pH, indicating that hydrophobic interactions with ODMBA are responsible for ZEN adsorption. Adsorption of low polar ionizable OCHRA on organozeolites also increased with increasing hydrophobicity of the zeolitic surface, however, OCHRA showed moderate adsorption on unmodified zeolitic tuff at pH 3. OCHRA adsorption on unmodified zeolite as well as on lower surface coverage of organozeolite was dependent on the form of OCHRA in solution; there was a decrease of adsorption at high pH, where OCHRA is in the anionic form. It indicated that at acidic pH, low surface coverage allows some combination of hydrophobic interaction with ODMBA and interactions with the surface of the zeolite. At higher surface coverage, the OCHRA adsorption was higher and practically independent of pH, indicating that the hydrophobic interactions of OCHRA with ODMBA are responsible for its adsorption. Nonionizable low polar AFB1 had a high affinity for the unmodified zeolitic tuff and the adsorption of AFB1 was greatly reduced for organozeolites, indicating that AFB1 does not have high tendency for hydrophobic interactions with ODMBA. pH dependence of AFB1 adsorption, while AFB1 has the same form at all pHs, demonstrated that the surface modification of the zeolite depends on pH and that these modifications have influence on its adsorption. The calculated dipole moments of neutral mycotoxin molecules: AFB1-9.5D, OCHRA-6.9D and ZEN-2.2D are in qualitative agreement with adsorption experimental data.     

Host-guest antenna materials

The focus of this review is on host-guest composites with photonic antenna properties. The material generally consists of cylindrical zeolite L crystals the channels of which are filled with dye molecules. The synthesis is based on the fact that molecules can diffuse into individual channels. This means that, under the appropriate conditions, they can also leave the zeolite by the same way. In some cases, however, it is desirable to block their way out by adding a closure molecule. Functionalization of the closure molecules allows tuning of, for example, wettability, refractive index, and chemical reactivity. The supramolecular organization of the dyes inside the channels is a first stage of organization. It allows light harvesting within a certain volume of a dye-loaded nanocrystalline zeolite and radiationless transport to both ends of the cylinder or from the ends to the center. The second stage of organization is the coupling to an external acceptor or donor stopcock fluorophore at the ends of the channels, which can trap or inject electronic excitation energy. The third stage of organization is the coupling to an external device through a stopcock molecule. The wide-ranging tunability of these highly organized materials offers fascinating new possibilities for exploring excitation-energy-transfer phenomena, and challenges for developing new photonic devices.     

A new aluminosilicate molecular sieve with a system of pores between those of ZSM-5 and beta zeolite

A new aluminosilicate zeolite (ITQ-39) has been synthesized. This is an extensively faulted structure with very small domains that makes the structure elucidation very difficult. However, a combination of adsorption spectroscopy and reactivity studies with selected probe molecules suggests that the pore structure of ITQ-39 is related to that of Beta zeolite, with a three-directional channel system with large pores (12-MR), but with an effective pore diameter between those of Beta and ZSM-5, or a three-directional channel system with interconnected large (12-MR) and medium pores (10-MR). The pore topology of ITQ-39 is very attractive for catalysis and shows excellent results for the preparation of cumene by alkylation of benzene, while it can be a promising additive for FCC.     

Investigations of the adsorption of n-pentane in several representative zeolites

We have examined the adsorption of n-pentane in several representative zeolites such as silicalite (MFI), ferrierite (FER), zeolite L (LTL), and faujasite zeolites with FAU structure including siliceous Y (Si-Y) and Na-Y by using FT-Raman spectroscopy in combination with thermogravimetric analysis (TGA) with particular attention being paid to the conformational and dynamic behavior of the guest molecule. The results indicate that the framework topology mainly dictates the conformation of n-pentane in a zeolite. For the zeolites with channel systems such as silicalite, ferrierite, and zeolite L, the population of the all-trans conformer increases upon loading, given that the geometry of the isomer fits better in the channel. When n-pentane is adsorbed in zeolites with a large cavity, such as Si-Y and Na-Y, the distribution of the all-trans (TT) and trans-gauche (TG) conformers is similar to that of pure liquid, suggesting that the large supercage in the framework imposes minimal effect on the conformational equilibrium. The dynamics of the guest molecule is, however, influenced significantly by the existence of cations. Adsorption of n-pentane in a siliceous framework such as silicalite and Si-Y results in extensive molecular motion at room temperature, the degree of which decreases with decreasing temperature. In zeolites ferrierite, L, and Na-Y, the presence of cations in the framework markedly hinders the overall molecular motion. The cations clearly play a role in the observed static disorder of the guest molecule in zeolite L. Important information regarding the location of the n-pentane molecules within silicalite and ferrierite is also obtained.     

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.     

Structure of Nanochannel Entrances in Stopcock‐Functionalized Zeolite L Composites

Multifunctional hybrid materials are obtained by modifying zeolite L (ZL) with stopcock molecules, consisting of a tail group that can enter the ZL nanochannels and a head group too large to pass the channel opening. However, to date no microscopic‐level structural information on modified ZL materials has been reported. Herein we draw atomistic pictures of channel openings and stopcock‐functionalized ZL based on first‐principles calculations. We elucidate the interactions of the tail group with the inner surface of ZL channels and the space‐filling properties of the stopcocks, revealing cork‐ or lid‐sealing modes. Water is essential to obtain stable modifications. Al? OH groups are the preferred modification sites, bipodal modifications suffer from strain, and tripod binding is ruled out. Our results suggest the viability of recursive functionalization by cross‐linking.     

Nanochannels: hosts for the supramolecular organization of molecules and complexes

Nanochannels have been used as hosts for supramolecular organization for a large variety of guests. The possibilities for building complex structures based on 2D and especially 3D nanochannel hosts are larger than those based on 1D nanochannel hosts. The latter are, however, easier to understand and to control. They still give rise to a rich world of fascinating objects with very distinguished properties. Important changes are observed if the channel diameter becomes smaller than 10 nm. The most advanced guest-nanochannel composites have been synthesized with nanochannels bearing a diameter of about 1 nm. Impressive complexity has been achieved by interfacing these composites with other objects and by assembling them into specific structures. This is explained in detail. Guest-nanochannel composites that absorb all light in the right wavelength range and transfer the electronic excitation energy via FRET to well-positioned acceptors offer a unique potential for developing FRET-sensitized solar cells, luminescent solar concentrators, color-changing media, and devices for sensing in analytical chemistry, biology, and diagnostics. Successful 1D nanochannel hosts for synthesizing guest-host composites have been zeolite-based. Among them the largest variety of guest-zeolite composites with appealing photochemical, photophysical, and optical properties has been prepared by using zeolite L (ZL) as a host. The reasons are the various possibilities for fine tuning the size and morphology of the particles, for inserting neutral molecules and cations, and for preparing rare earth complexes inside by means of the ship-in-a-bottle procedure. An important fact is that the channel entrances of ZL-based composites can be functonalized and completely blocked, if desired, and furthermore that targeted functionalization of the coat is possible. Different degrees of organizational levels and prospects for applications are discussed, with special emphasis on solar energy conversion devices.     

沸石分子筛上程序升温脱附谱的Monte Carlo模拟研究Ⅱ．不同晶粒的沸石分子筛

沸石分子筛上程序升温脱附谱的ＭｏｎｔｅＣａｒｌｏ模拟研究＊Ⅱ．不同晶粒的沸石分子筛王建国李永旺陈诵英彭少逸（中国科学院山西煤炭化学研究所，太原０３０００１）关键词沸石分子筛，程序升温脱附，ＭｏｎｔｅＣａｒｌｏ模拟沸石分子筛被广泛用作吸附剂和催化剂的根...     

水在NanZSM-5型分子筛中吸附的研究: 分子模拟

利用分子动力学(MD)模拟退火的方法和巨正则系综Monte Carlo模拟方法(GCMC)研究了水在NanZSM-5型分子筛中的吸附行为, 计算结果与文献中报道的实验结果吻合较好. 在此基础上, 进一步预测了水在不同硅铝比的NanZSM-5型分子筛中的吸附性质, 计算结果显示: 分子筛骨架上的硅铝比会显著影响水分子的吸附量和吸附等温线, 随着硅铝比的降低, 水的吸附量增加; 水分子的吸附位置是在钠离子和铝原子的周围, 平均每个钠离子周围吸附4个水分子, 而当水的吸附量增大时, 水分子与分子筛骨架上的氧原子之间发生了氢键作用; 在吸附量相同的条件下, 水的吸附热随着硅铝比的降低而升高.     

Prediction of adsorption of small molecules in porous materials based on ab initio force field method

Computational prediction of adsorption of small molecules in porous materials has great impact on the basic and applied research in chemical engineering and material sciences. In this work,we report an approach based on grand canonical ensemble Monte Carlo(GCMC) simulations and ab initio force fields. We calculated the adsorption curves of ammonia in ZSM-5 zeolite and hydrogen in MOF-5(a metal-organic-framework material). The predictions agree well with experimental data. Because the predictions are based on the first principle force fields,this approach can be used for the adsorption prediction of new molecules or materials without experimental data as guidance.