根据近年来离子液体在分子筛材料合成方面取得的进展,对离子热法合成分子筛的机理研究、新型分子筛的合成及合成方法的创新等进行多方面的论述,离子液体的独特性质及独特合成环境在新型分子筛合成领域具有很大优势,预期离子热合成法在分子筛材料的合成研究领域会有更大的发展空间.

Selective oxidation of ethyl lactate (EL) with molecular oxygen as oxidant is an alternative route to produce ethyl pyruvate (EP). However, to obtain pyruvate with high yield under mild conditions remains challenging due to the troublesome over oxidation issue. Here, a highly efficient photocatalytic strategy was firstly developed to obtain EP at room temperature. ZnIn sulfides (ZIS) with different Zn/In ratios were synthesized as the catalysts. Under the irradiation of visible light, 100% EL conversion with 88.4% EP yield could be obtained. The optimized ZIS catalyst shows the highest surface area (215.7 m2 g-1) as well as much higher separation and transport efficiency of the electron-hole pairs. Combining radical trapping experiments with characterization results, a reaction mechanism was proposed. The mild reaction conditions with efficient generation of singlet oxygen contribute the high yield of EP. Kinetic isotope experiments indicate that the cleavage of C(OH)-H bond probably was involved in the rate determining step.

采用等体积浸渍的方法对HZSM-5分子筛进行磷改性。通过将磷改性前后的HZSM-5分别与SAPO-34分子筛通过机械混合法和水热晶化法制备成复合分子筛，分别用XRD、SEM、FTIR、NH 3 -TPD、BET等手段对分子筛样品的物化性质、酸性和孔结构进行表征分析。对比分析了磷改性和复合分子筛的两种制备方法对甲醇制丙烯（MTP）反应催化性能的影响。结果表明，磷改性HZSM-5分子筛的强酸强度和数量明显下降，丙烯选择性也得到了提升。而分子筛的机械混合改变了催化剂的酸性和孔结构，使得其在MTP反应中有较高的丙烯选择性和较长的催化寿命。在磷改性后的HZSM-5与SAPO-34分子筛机械混合得到的S/PZ-M分子筛上，MTP反应结果表明，反应进行30 h时，丙烯的选择性高达51.34%,丙烯/乙烯比为3.93。

Silicoaluminophosphate zeolite SAPO-34 with a CHA topological structure has been highlighted for its high methanol conversion and excellent selectivity for light olefins in the methanol-to-olefin (MTO) reaction. In this work, hierarchical porous SAPO-34 zeolite with excellent catalytic properties was first prepared by introducing water-soluble polyacrylamide (PAM) hydrogel into the synthesis system of conventional SAPO-34 by using a one-step hydrothermal synthesis method. The effects of PAM concentration and PAM type on the morphology and pore structure of hierarchical SAPO-34 catalysts and the formation mechanism of hierarchically structured zeolites were studied. Compared to conventional microporous SAPO-34, the hierarchically structured SAPO-34 exhibits excellent performance in the MTO reaction with an approximately three times longer catalytic lifetime (740 min) and remarkably improved selectivity for light olefins of up to 87.5%.

A triclinic SAPO-34 molecular sieve was synthesized ionothermally. The as-synthesized products were characterized by powder X-ray diffraction (XRD), scanning electron microscope (SEM), nuclear magnetic resonance (NMR), fourier infrared spectrometer (FT-IR) and thermogravimetric (TG) analyses. The formation mechanism of the hierarchical porous triclinic SAPO-34 zeolites and the factors affecting the morphology of the SAPO-34 molecular sieve were investigated. The results show that the formation mechanism of the hierarchical pores is in accordance with Ostwald ripening theory, and the accumulation of grains constitutes the existence of mesopores and macropores. The crystallization temperature, ionic liquid type, and organic amines can effectively change the morphology and crystallinity of the SAPO-34 molecular sieve. The crystallization temperature, ionic liquid and template have great influence on the (111) crystal plane, thus affecting the morphology of the molecular sieve. Moreover, it can be proven through NMR and TG analyses that ionic liquids and organic amines can be used as structure directing agents together.

c-Axis-oriented HZSM-5 zeolites were directly synthesized by introducing crosslinked polyacrylamide (C-PAM) hydrogels into ZSM-5 synthesis gels. The growth orientation of the crystals as well as the acidity of ZSM-5 could be modulated by the C-PAM content in the synthesis gel. The crystal growth along the a-axis and b-axis was obviously restricted, whereas c-axis growth was distinctly promoted with increasing C-PAM content, which was probably due to the C-PAM having stronger interactions with the {010} and {100} facets than the {101} facet. Sample Z-2, which was prepared with 2% C-PAM exhibited the shortest b-axis length elongated prism structure and strong acid sites. Furthermore, Z-2 exhibited excellent catalytic performance in the methanol-to-olefin (MTO) reaction showing the highest methanol conversion (100%) and the light olefin selectivity (TOS) (81.2%), as well as the longest lifetime (>23 h).

Amphiphilic hyper-crosslinked porous cyclodextrin polymer (PBCD-B-D) with a surface area of 1445 m(2) g(-1) was synthesized for rapid removal of organic micropollutants. Partially benzylated cyclodextrin was crosslinked with 4,4'-bis(chloromethyl)-1,1'-biphenyl and alpha,alpha'-dichloro-p-xylene by the Friedel-Crafts alkylation reaction. The hydrophilicity of the PBCD-B-D surface is modulated by controlling the number of hydroxyl groups on cyclodextrin. Benzylation reaction is more likely to occur at the C-2 and C-6 positions of cyclodextrin hydroxyl groups according to Gaussian computation. Four different water-soluble pollutants (3-phenylphenol, 2-naphthol, p-nitrophenol, and 4-chlorophenol) were selected for adsorption study. The adsorption rate of PBCD-B-D is extremely high, and the removal efficiency reaches above 95% in 1 min. For the adsorption of 3-phenylphenol and 2-naphthol, the rate constants of PBCD-B-D are 827-1187 and 396-413 times larger than those of granular activated carbon (GAC) and beta-cyclodextrin polymer crosslinked with epichlorohydrin (EPI-CDP), respectively. The adsorption capacity of PBCD-B-D is 2 and 4 times higher than that of GAC and EPI-CDP, respectively. The combination of cyclodextrin inclusion mechanism, hydrophobic attraction, and hydrogen bonding allows PBCD-B-D to adsorb both hydrophobic and hydrophilic pollutants. PBCD-B-D can be easily regenerated at room temperature using methanol as eluent. In addition, PBCD-B-D showed excellent adsorption performance towards mixed pollutants at environmentally relevant concentrations. According to the thermodynamic study, the adsorption of organic compounds onto PBCD-B-D belongs to physical adsorption and is spontaneous. PBCD-B-D is a potential novel adsorbent for water treatment owing to its excellent adsorption performance, low cost, and good regenerability.

Methyl pyruvate (MPA) was synthesized from dihydroxyacetone (DHA), the oxidation product of glycerol, over Sn-β and TS-1 hybrid molecular sieves at low temperature. Sn-β and TS-1 provide the active sites for conversion of DHA to methyl lactate (MLA) and oxidation of MLA to MPA, respectively. Synergism of Lewis acid sites on Sn-β and TS-1 realize the production of MPA from DHA. After optimization, 71% yield of MPA can be obtained under 50 °C. This is the first report for the synthesis of MPA from DHA directly.

Simple synthesis of a swellable porous β-cyclodextrin-based polymer in the aqueous phase for the rapid removal of organic micro-pollutants from water.

在SAPO-17分子筛的合成母液中加入工业级HZSM-22分子筛,采用水热法制备了一系列不同HZSM-22质量分数的SAPO-17/HZSM-22复合分子筛。利用XRD、SEM、FT-IR、NH3-TPD等手段对复合分子筛的微观结构和酸性进行表征,并考察其在甲醇制烯烃（MTO）反应中的催化性能。结果表明,HZSM-22的质量分数对复合分子筛的物化性质和MTO性能均具有较大影响。当添加质量占混合凝胶总质量的1/10时,SAPO-17/HZSM-22复合分子筛结晶度最高,形成部分粘连结构,且在MTO反应中复合分子筛催化剂的寿命较长,反应进行11 h时,其低碳烯烃选择性仍可保持在75%左右,丙烯/乙烯的比值为1.19。

首先用一定浓度的Na2 CO3溶液处理ZSM-22分子筛,然后再用HCl溶液进行酸洗,得到多级孔ZSM-22分子筛.采用XRD、SEM、BET、FTIR、NH3-TPD等手段研究碱酸处理对ZSM-22分子筛物化性能的影响,并将其作为催化剂用于甲醇制低碳烯烃(MTO)反应.结果表明,碱酸处理后的样品结晶度维持较好,且拥有较高的比表面积和微孔-介孔结构.碱酸处理可选择性地脱除分子筛的部分强酸中心.其中利用0.2 mol/L Na2 CO3处理后再用0.1 mol/L HCl酸洗得到的ZSM-22分子筛催化剂,在其低碳烯烃选择性基本保持不变的基础上,MTO反应寿命可显著提高.

复合分子筛是一类能将两种或多种分子筛的孔道结构和酸性质结合在一起的新型催化材料,该类材料往往具有单一分子筛所不具有的优势.复合分子筛的高比表面积和孔体积比使其在反应过程中具有高的扩散系数和较少的传输限制,能比单一分子筛表现出更高的催化活性,因此被广泛应用于石油化工领域.重点综述了复合分子筛在催化裂化、异构化、芳构化、烷基化、甲醇制烃等领域的应用进展情况,并对复合分子筛的应用进行了展望.

SAPO-5 molecular sieves (E-SAPO-5) were synthesized ionothermally in 1-ethyl-2,3-dimethylimidazolium bromides ([EMMIM]Br) ionic liquid (IL). The samples were characterized by X-ray diffraction (XRD), nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), N-2 isothermal adsorption-desorptionand, temperature-programmed desorption of ammonia (NH3-TPD) and fourier transform infrared (FT-IR) spectroscopy. Moreover, the catalytic performances of the samples in the methanol conversion reaction were investigated. Relative to the hydrothermal method, ionothermal synthesis favored the formation of large silica islands mainly by the SM3 substitution mechanism and decreased the B acid sites and the strong acid and total acid amounts of E-SAPO-5, which significantly influenced the distribution of the products in the methanol conversion reaction. Methanol underwent the methanol-to-dimethyl-ether (MTD) reaction and methanol-to-olefin (MTO) reaction over the E-SAPO-5 and hydrothermally synthesized SAPO-5, respectively. E-SAPO-5 exhibited high MTD activity at the high temperature of 450 degrees C with methanol conversion of 100% and dimethyl ether (DME) selectivity of 86.6%.

An impregnation approach was used to prepare SmCoO3/SBA-15 composite. SBA-15 was employed as a hard template and SmCoO3 was grown in its pores via sol-gel method. It has been observed that the microstructure, morphology and photothermal properties of the composite powder strongly depend on the hard template. There is a close correlation among specific surface area, elemental composition and properties of the sample. Furthermore, it was demonstrated that SBA-15 plays an important role in the characteristics of the structure, micromorphology and photothermal properties of the composite from the template to the final. This new type composite can be applied in various fields such as environment, energy and chemical industry. (C) 2018 Elsevier B.V. All rights reserved.

SAPO-17 molecular sieve is synthesized through the hydrothermal synthesis process.By adding hydrofluoric acid and potassium chloride during the synthesis process,the crystallization time of samples is shortened greatly and the synthesized SAPO-17 molecular sieve has a higher silica-alumina ratio.The effects of HF and KC1 on the synthesis of molecular sieves are investigated by XRD and SEM.The physiochemical properties and catalytic performance of the SAPO-17 molecular sieves synthesized under the optimal conditions of Al2O3∶P2O5∶SiO2∶CHA ∶H2O ∶HF ∶KCl=1 ∶1∶0.1∶1.1∶50∶0.9∶0.01 are characterized by XRD,SEM,FT-IR and NH3-TPD.The results show that this SAPO-17 molecular sieve has excellent catalytic performance to MTO reaction,with a selectivity of low-carbon olefins being 84.03％.

Hollow AlPO4-5 spheres (E-AP and B-AP) are synthesized ionothermally in tri-substituted imidazolium bromide ionic liquids (ILs), that is, 1-ethyl-2,3-dimethylimidazolium bromide and 1-butyl-2,3-dimethylimidazolium bromide, respectively. Moreover, the morphologies of the hollow AlPO4-5 particles vary with the type of ILs and the amounts of ILs, phosphoric acid, amine, and hydrofluoric acid. The thicknesses of the shells of the hollow spheres are substantially affected by the length of the alkyl chain on the imidazole ring of the ILs. The shell thicknesses significantly increase from 300-500 nm to 4-5 mu m as the alkyl chain length increases, and solid AlPO4-5 spheres (H-AP) are generated in 1-hexyl-2,3-dimethylimidazolium bromide IL. Furthermore, the experimental results suggest that the formation of hollow AlPO4-5 spheres in an IL is consistent with Ostwald ripening theory. In addition, compared with ordinary solid AlPO4-5 (S-AP) prepared by hydrothermal methods, the hollow E-AP particles are small and spherical. Moreover, the Co-loaded hollow AlPO4-5 (Co/E-AP) catalyst exhibits excellent catalytic activities in the selective oxidation of tetralin. The reaction conversions are 73.5 and 5.7% over the Co/E-AP catalyst and Co-loaded solid AlPO4-5 (Co/S-AP) catalyst, respectively, which means that the hollow structure facilitates the mass transfer of the reactants and products in the catalytic reaction.

ZSM-5/AlPO4-5 composite zeolites were prepared in polyacrylamide (PAM) hydrogels and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), N2 isothermal adsorption-desorption, nuclear magnetic resonance (NMR) and temperature-programmed desorption of ammonia (NH3-TPD). In addition, the catalytic performances of the composite zeolites in the methanol-to-olefin (MTO) reaction were examined. The results indicate that introducing PAM into the synthesis gel of ZSM-5/AlPO4-5 facilitates both the formation of the ZSM-5/AlPO4-5 composite zeolite and the improvement of the catalyst performance. Moreover, the catalyst acidities are closely related to their selectivities for the MTO reaction. The composite zeolite obtained in the PAM hydrogel has a lower density of total acid sites and a higher selectivity for light olefins compared with the composite zeolite prepared without the PAM.

空心材料由于其具有较大的比表面积和孔体积,广泛应用在化学和材料科学等领域.本文综述了近年来在离子液体中合成空心材料的研究进展,详细介绍了各种合成方法的特点及空心材料的形成机理,探讨了离子液体中制备空心材料的发展趋势.

Blue light emission from hydrogenated amorphous silicon carbideproduced by organic sourceJun Xu, Kunji Chen, Tianfu Ma, Jiafang Du, Xinfan Huang, Wei Li and Duan FengDept. ofPhysics and National Laboratory of Solid State Microstructures, Nanjing University,Nanjing 210093, ChinaCenter For Advanced Studies in Science and Technology ofMicrostructures, Nanjing 210093,ChinaABSTRACTHydrogenated amorphous silicon carbide (a-SiC:H) alloys were produced by using organiccarbon source, xylene, instead of generally used methane. It was found that the optical band gap ofpresent samples is significantly increased and reaches as high as 3 .

Imitating natural rod or cone cells in human eyes inspires a novel biomimetic design of filter-free RGB color sensing photodetectors. A radial tandem junction super-rod structure is developed in article number 1700390 by Junzhuan Wang, Linwei Yu, Yi Shi, and co-workers that consists of coaxially stacking hydrogenated amorphous silicon PIN junctions upon silicon nanowires, resembling to the retinal cells in terms of both geometry and dimensions.