在无有机导向剂条件下采用乙醇为助剂合成高硅沸石

高硅沸石具有优异的热稳定性、水热稳定性、大的微孔体积、高表面积和均匀的微孔孔道,因而广泛应用于催化领域.然而,高硅沸石的合成往往需要使用有机结构导向剂,不但增加了沸石合成成本,而且还产生了大量的三废排放.为了解决这个问题,我们发展了在无有机导向剂存在条件下采用沸石晶种诱导合成沸石的方法,但是该方法合成的沸石产物骨架富铝...     

A priori phase prediction of zeolites: case study of the structure-directing effects in the synthesis of MTT-type zeolites

This study first uses molecular modeling to examine the structure-directing effects of small amines that are selective for the crystallization of MTT-type zeolite phases. The optimized van der Waals interactions of these small amines are compared within the one-dimensional pore zeolites with the MTT, TON, and MTW frameworks. From these results and our previous molecular modeling studies of structure-directing agents (SDA) for MTT-type zeolites, a large number of amines or quaternary ammonium molecules are successfully predicted to be selective for MTT phases. These molecules were chosen by matching the crystallographic periodicity of the pore structure with the distances between the centers of branched groups in these molecules. These molecules vary in length and in the number of branched moieties, and a few of these molecules are polymeric or oligomeric. In test cases where the distances between the branched groups are not multiples of the pore periodicity, with few exceptions these molecules usually do not produce MTT phases. Finally, we discuss the inorganic conditions necessary for crystallization of MTT phases in borosilicate preparations with some of the diamines in this investigation.     

高硅沸石合成中四氢呋喃模板作用的初步研究

在四氢呋喃(THF)-Na~2O-SiO~2-Al~2O~3-H~2O体系中,水热条件下合成出的沸石相,随配料硅铝比提高,依次为MOR(丝光沸石),ZSM-35,ZSM-5和ZSM-39,1^3^CCP/MASNMR谱,TG/DTG/DTA和EDX成分分析方法对沸石中的THF进行表征,1^3^C谱化学位移的显著变化,以及THF高的脱除温度,证明作为模板剂的THF分子进入所合成的沸石结构,并与骨架发生强的相互作用。     

Multi-objective de novo molecular design of organic structure-directing agents for zeolites using nature-inspired ant colony optimization

Organic structure-directing agents (OSDAs) are often employed for synthesis of zeolites with desired frameworks. A priori prediction of such OSDAs has mainly relied on the interaction energies between OSDAs and zeolite frameworks, without cost considerations. For practical purposes, the cost of OSDAs becomes a critical issue. Therefore, the development of a computational de novo prediction methodology that can speed up the trial-and-error cycle in the search for less expensive OSDAs is desired. This study utilized a nature-inspired ant colony optimization method to predict physicochemically and/or economically preferable OSDAs, while also taking molecular similarity and heuristics of zeolite synthesis into consideration. The prediction results included experimentally known OSDAs, candidates having structures closely related to known OSDAs, and novel ones, suggesting the applicability of this approach.

Inspired by the exploratory methods of ant colonies, adaptive optimization was employed to explore the chemical space for organic molecules that guide zeolite crystallization, giving both physicochemically and economically promising molecules.     

Molecular simulations of host-guest interactions between zeolite framework STW and its organic structure-directing agents

Zeolites have been widely applied in many chemical processes owing to their featured microporous framework structures. Organic structure-directing agents (OSDAs) play an important role during of the formation of zeolite frameworks via non-bonding host-guest interactions. Understanding these interactions is crucial to the design of OSDAs and the synthesis of target zeolites. Here, we report a molecular simulation study in the host-guest interactions between zeolite framework STW and 21 alkylated imidazolium and pyrazolium cations that have been used as the OSDAs for the synthesis of STW-type zeolites. We find that OSDAs that have successfully directed the formation of STW exhibit stronger host-guest interactions than unsuccessful ones. Furthermore, we find all successful OSDAs possess relatively more negative atomic charges on nitrogen atoms and smaller dipole moments. According to this finding, we have designed seven new alkylated imidazolium and pyrazolium cations that may be suitable for zeolite STW, and verified their structure-directing capability by molecular simulation calculations.     

无有机模板剂体系水热合成Beta沸石中晶种的导向机理(英文)

在无有机模板剂体系中研究了不同硅铝比和晶粒度Beta沸石晶种的结构导向行为,采用X射线衍射、X射线荧光光谱、扫描电镜、透射电镜、紫外-拉曼光谱、红外光谱和N2物理吸附等方法对不同晶化时间固相产物和Beta沸石产物进行了表征.结果表明,不同Beta沸石晶种,包括全硅晶种,均能够导向合成Beta沸石,而且晶种在晶化诱导期都发生溶解.但是,晶种的硅铝比、晶粒度、预处理(焙烧)以及晶种加入的时间对晶种的溶解行为、Beta沸石晶化过程和产物都有重要影响.形貌研究还发现,含铝晶种不仅溶解后的残体通过提供晶核聚集的"固载化"表面导向了新生Beta沸石小晶体的密集生长,而且溶解下来的结构片段也提供了分散的晶核导向形成相对分散的Beta沸石小晶体;全硅晶种则仅通过溶解下来的结构片段提供分散的晶核.在无模板体系中,使用适当高硅铝比、小晶粒和经过焙烧处理的Beta沸石作为晶种有利于合成得到高结晶度的Beta沸石纯相.     

Synthesis of ferrierite-type zeolite by microwave method using ethylenediamine as an organic structure-directing agent

A new method for the synthesis of ferrierite-type zeolite has been developed using microwave irradiation in the presence of structure-directing agents (templates). The physicochemical characteristics of the synthesized zeolites were investigated by X-ray diffraction analysis, low-temperature nitrogen adsorption–desorption and SEM-EDX. When comparing the synthesis products, it was found that microwave irradiation significantly reduces the crystallization time of the synthesized zeolites compared to traditional hydrothermal treatment     

Porphyrin covalent organic framework for photocatalytic synthesis of tetrahydroquinolines

A metal-free porphyrin covalent organic framework was employed as the heterogeneous photocatalyst for the synthesis of tetrahydroquinolines under aerobic conditions. With visible light irradiation of a catalytic amount of H₂P-Bph-COF at room temperature, various substituted N,N-dimethylanilines and N-aryl maleimides were transformed to tetrahydroquinoline derivatives in moderate to good yields. This was the first example of the synthesis of tetrahydroquinolines via the photocatalytic aerobic annulation reaction employing the metal-free COF as the heterogeneous photocatalyst.     

Eco-friendly synthesis of high silica zeolite Y with choline as green and innocent structure-directing agent

Zeolite synthesis in contemporary chemical industries is predominantly conducted using organic structure-directing agents (OSDAs), which are chronically hazardous to humans and the environment. It is a growing trend to develop an eco-friendly and nuisanceless OSDA for zeolite synthesis. Herein, choline is employed as a non-toxic and green OSDA to synthesize high silica Y zeolite with SiO₂/Al₂O₃ ratios of 6.5–6.8. The prepared Y zeolite samples exhibited outstanding (hydro)thermal stability at ultrahigh temperature owing to the higher SiO₂/Al₂O₃ ratio. The XRF, SEM, ²⁹Si-NMR and ¹³Na+ results suggested that choline plays a structure-directing role in the synthesis of Y zeolite, while the feed molar fraction of Na⁺ is a crucial determinant for the framework SiO₂/Al₂O₃ ratio and the crystal morphology.     

Tripentaerythritol in the synthesis of new types of framework bicyclophosphites

Regioselective reaction of tripentaerythritol with phosphorous hexaethyltriamide resulted in the preparation of singular framework bisbicyclophosphite. A study of chemical characteristics of the obtained product is started.     

Seed-directed synthesis of zeolites with enhanced performance in the absence of organic templates

We demonstrate here a seed-directed synthesis (SDS) of Beta, Levyne, and Heulandite zeolites in the absence of organotemplates, where the seeds drive crystallization of the zeolites. Compared with conventional Beta synthesized in the presence of organic templates, Beta-SDS exhibits large textural parameters, stable Al species, and unprecedentedly high density of active sites, resulting in superior catalytic activity and selectivity for valuable products in catalysis.     

无模板剂法制备沸石分子筛和分子筛膜的研究进展

随着新无机材料和处理技术的发展,无有机模板剂法制备沸石分子筛和分子筛膜得到了广泛的关注.与有模板剂法相比,无有机模板剂法保持了沸石晶体的结晶度和骨架结构,合成过程更加简单、廉价和绿色.尤其无模板剂二次生长法制备分子筛膜避免了分子筛膜在高温煅烧脱除模板剂过程中缺陷的产生.本文作者综述了国内外制备沸石分子筛和分子筛膜的研究进展,着重介绍了晶种诱导法、自发成核法和晶型转化法制备沸石分子筛,以及无模板剂二次生长法制备分子筛膜,分析了存在的问题和可能的解决措施,并对其发展趋势进行了展望.     

The location and ordering of fluoride ions in pure silica zeolites with framework types IFR and STF; implications for the mechanism of zeolite synthesis in fluoride media

Single-crystal X-ray diffraction studies carried out at a synchrotron radiation source have allowed the structure solution and location of fluoride ions inside as-made pure silica zeolites with the IFR and STF framework structures. The local environment of the fluoride has been identified, and unusual ordering of the fluoride ions has been discovered in both cases. The details of the crystal structures are used to suggest structural features that are important in determining the ordering of fluoride ions in zeolites. A mechanism for how the fluoride ordering occurs is suggested for IFR and STF based on the local structure of small cages that make up these zeolites, and the implications for the mechanism of crystal growth are discussed.     

One-pot synthesis of MWW zeolite nanosheets using a rationally designed organic structure-directing agent

A new material MIT-1 comprised of delaminated MWW zeolite nanosheets is made in a one-pot synthesis using a rationally designed organic structure-directing agent (OSDA). The OSDA consists of a hydrophilic head segment that resembles the OSDA used to synthesize the zeolite precursor MCM-22(P), a hydrophobic tail segment that resembles the swelling agent used to swell MCM-22(P), and a di-quaternary ammonium linker that connects both segments. MIT-1 features high crystallinity and surface areas exceeding 500 m² g^–1, and can be synthesized over a wide synthesis window that includes Si/Al ratios ranging from 13 to 67. Characterization data reveal high mesoporosity and acid strength with no detectable amorphous silica phases. Compared to MCM-22 and MCM-56, MIT-1 shows a three-fold increase in catalytic activity for the Friedel–Crafts alkylation of benzene with benzyl alcohol.     

Targeted synthesis of a porous borazine-linked covalent organic framework

The first microcrystalline borazine-linked polymer, BLP-2(H), has been synthesized. BLP-2(H) crystallizes into 2D sheets that stack in an eclipsed AA fashion, has high thermal stability (～420 °C) and high porosity (SA(BET) = 1178 m(2) g(-1)) and it can store up to 2.4 wt% of hydrogen at 77 K and 15 bar with isosteric heat of adsorption of 6.8 kJ mol(-1).     

Microscale synthesis system for regulation and prediction of metal organic framework morphologies

Metal organic frameworks (MOFs) have attracted lot of attention. Traditional synthesis processes are usually conducted in beaker systems that always result in high reagents cost and time waste. Here, we introduce a microscale synthesis platform that integrated ultrasound unit array to solve the micro-stirring problem, and explore the influences of multi-parameters on the synthesis of Cu-MOFs. On such platform, the mini-pillars with high adhesion ability can be used for anchoring microdroplets (1–20 μL), and the ultrasound unit is applied for rapid micro-stirring of reagents. Such an integrated platform with low consumption of reagents can explore the influences of multiple synthesis parameters (e.g., ultrasound time and power, reagents concentration, solvents ratios, environmental humidity, and temperature) for precisely controlling and guiding Cu-MOF synthesis, and further to predict the specific Cu-MOFs nanostructures fabrication based on the miniature model database. We expect that such a platform can help the researchers to explore the relationships between the final morphology and input parameters, so as to achieve accurate material synthesis, which holds great potentials in future fully automated and robot-based laboratory.     

Use of different types of mesoporous materials as tools for organic synthesis

Mesoporous materials have been investigated as auxiliary agents for organic synthesis comprising reactants with widely different solubility characteristics. The finely divided oxide material was immersed in an aqueous solution of a water-soluble reactant, potassium iodide, and the loaded particles were kept under stirring in the hydrophobic reactant, 4-tert-butylbenzyl bromide, or in a hydrocarbon solution of this reactant. The reaction proceeded well in alumina and silica of either bicontinuous cubic or hexagonal geometry. It was shown for silica that the particle size was an important parameter; the smaller the size the faster the reaction. Titania gave a much lower reaction rate than alumina and silica. It was found that the hexagonal mesoporous alumina could be reused either as a slurry or in a column procedure. Attempts were also made to use hydrophobic mesoporous materials, either mesoporous graphite or mesoporous oxide treated with chlorotrimethylsilane, in the reversed mode. The hydrophobic solid was then immersed in a solution of the hydrophobic reactant and subsequently dispersed in an aqueous solution of the water-soluble reactant. Two nucleophilic substitution reactions and one oxidation reaction were investigated but the yields were low in all cases.     

A general framework for the measurement of band broadening properties of GC capillary columns

In the approach to the developement of a practical procedure for the evaluation of band broadening properties of gas capillary columns, the expression for the variance of a solute band is cast in a dimensionless form. This expression supplies the basis for a valid bench mark for column evaluation. Experimental results demonstrate the applicability of the method.     

Macrocyclic amines as structure-directing agents for the synthesis of three-dimensional antimony-sulfide frameworks

A new family of antimony sulfides, incorporating the macrocyclic tetramine 1,4,8,11-tetraazacyclotetradecane (cyclam), has been prepared by a hydrothermal method. [C10N4H26][Sb4S7] (1), [Ni(C10N4H24)][Sb4S7] (2), and [Co(C10N4H24)]x[C10N4H26](1-x)[Sb4S7] (0.08 < or = x < or = 0.74) (3) have been characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetry, and analytical electron microscopy. All three materials possess the same novel three-dimensional Sb4S7(2-) framework, constructed from layers of parallel arrays of Sb4S8(4-) chains stacked at 90 degrees to one another. In 1, doubly protonated macrocyclic cations reside in the channel structure of the antimony-sulfide framework. In 2 and 3, the cyclam acts as a ligand, chelating the divalent transition-metal cation. Analytical and X-ray diffraction data indicate that the level of metal incorporation in 2 is effectively complete, whereas in 3, both metalated and nonmetalated forms of the macrocycle coexist within the structure.     

Templated synthesis of imine-based covalent organic framework hollow nanospheres for stable potassium-ion batteries

Covalent organic frameworks (COFs), as highly tunable porous crystalline materials, have promising applications in potassium-ion batteries (PIBs) due to their abundant charge carrier transport channels and excellent structural stability. However, the excessive stacking of interlayer electron clouds makes it difficult to expose internal active sites. Strategies to design functional COFs with controllable morphology and copious active sites are promising but still challenging. Herein, by utilizing the condensation between 1,3,5-triformylbenzene (TFB) and p-phenylenediamine (PPD) and using amino-modified SiO₂ nanospheres as templates, we synthesize core-shell NH₂-SiO₂@TP-COF. Through NaOH etching of NH₂-SiO₂@TP-COF, we obtain imine-based TP-COF hollow nanospheres, which shows excellent potassium storage performance when applied to the anode for PIBs. Ex-situ analysis and density functional theory calculations reveal that CN groups and benzenes are active sites for K⁺ storage.