Synthesis and Characterization of Novel Layered Lithium Sodium Silicate （Silinaite） and the Mesoporous Materials from Silinaite

Novel layered silinaite has been synthesized using an aqueous mixture of water glass, LiOH and NaOH under hydrothermal crystallization. Subsequently transformation of silinaite into mesoporous materials (SDM) was achieved at mild condition using cetyltrimethylammonium bromide as structure-directing agents. The resulting samples were characterized by XRD, SEM, FTIR nitrogen adsorption-desorption isotherms and catalytic performance in bulky molecular involved reaction. The results revealed that synthesized mesoporous materials derived from the silinaite exhibited an ordered hexagonal crystal structure with average pore diameter 2.7 nm and BET surface area 817m2/g. The SDM-supported ZnCl2 catalyst, prepared by impregnation-evaporation method, retained the mesoporous structure and showed high selectivity in alkylation of benzene with benzyl chloride.     

Synthesis of Tin Oxide Through Thermal Decomposition of Sn2 （NH4）2 （ C2 O4 ）3 and Its Gas Sensing Property

Nanocrystalline tin oxide samples were prepared by using Sn2 （NH4 ）2 （C2O4）3 as the precursor. The thermal decompositions were respectively conducted at 250,450 and 650 ℃. TG-DTA, XRD, TEM, FTIR were used to characterize the samples. The indirect heating sensors by using these materials as sensitive bodies were fabricated on an alumina tube with Au electrodes and platinum wires. Sensing properties of these sensors were investigated. It was found that the tin oxide sample obtained by thermal decomposition at 450 ℃ has a higher sensitivity to C2H5OH and a higher selectivity to hexane and ammonia than those obtained via the conventional precipitate method and the working temperatures needed were greatly decreased.     

A Novel,Efficient and Facile Method for the Template Removal from Mesoporous Materials

A new catalytic-oxidation method was adopted to remove the templates from SBA-1 5 and MCM-4 1 me- soporous materials via Fenton-like techniques under microwave irradiation. The mesoporous silica materials were treated with different Fenton agents based on the template＇s property and textural property. The samples were cha- racterized by powder X-ray diffraction（XRD） measurement, N2 adsorption-desorption isotherms, infrared spectro- scopy, 29Si MAS NMR and thermo gravimetric analysis（TGA）. The results reveal that this is an efficient and facile approach to the thorough template-removal from mesoporous silica materials, as well as to offering products with more stable structures, higher BET surface areas, larger pore volumes and larger quantity of silanol groups.     

Synthesis of some new bis-3,4-dihydropyrimidin-2(1H)-ones by using silica-supported tin chloride and titanium tetrachloride

<正>Silica-supported tin chloride and titanium tetrachloride were prepared by the reaction of tin chloride and titanium tetrachloride with activated silica gel in refluxing toluene.These solid acids have been employed as the catalysts for the synthesis of bisdihydropyrimidin -2(1H)-ones from aromatic dialdehydes,1,3-dicarbonyl compounds and urea at 90℃under solvent-free conditions.     

Synthesis and Gas-sensing Performance of Nanosized SnO2

Nanosized tin dioxide particles were prepared by sol-gel dialytic processes with tin(Ⅳ) chloride and alcohol as start materials. The nanoparticles of tin dioxide were charactered by thermogravimetry and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET. The results show that the average diameter of tin dioxide particles dried at 353 K was about 2nm. Even if the tin dioxide particles were calcined at 873 K, the average diameter of particles was less than 10 nm. The removal of Cl^- was solved by using this kind of method. The mechanism of the formation of tin dioxide nanosized particles was proposed and analyzed in this paper. We also measured the sensitivity of the sensor based on the tin oxide powder calcined at 673K to NH3, alcohol, acetone, hexane and CO. The gas-sensing performance results indicate that this sensor has a higher sensitivity to alcohol and acetone, and selectivity for NH3, hexane and CO at an operating temperature of 343 K.     

SYNTHESIS OF HYBRID MESOPOROUS POLYSTYRENE-SILICA MATERIALS WITH NON-SURFACTANT CITRIC ACID AS TEMPLATE VIA SOL-GEL PROCESS

Hybrid mesoporous polystyrene-silica materials were successfully prepared through HCl-catalyzed sol-gelreactions of tetraethyl orthosilicate (TEOS) and triethoxysilyl-functionalized polystyrene obtained via atom transfer radicalpolymerization (ATRP) of styrene, in the presence of citric acid (CA) as non-surfactant template or pore-forming agent andfollowed by ethanol extraction to remove template molecules. The materials were characterized by infrared spectroscopy(IR), N_2 adsorption-desorption measurements, powder X-ray diffraction (XRD), thermogravimetric analysis (TGA) andtransmission electron microscopy (TEM). The results indicate that the materials prepared with 50 wt%-60 wt% templatecontents have average pore sizes of 2-3 nm and large surface areas (ca. 886 m~2/g) as well as high pore volumes (ca.0.53 cm~3/g). The mesoporosity arises from interconnected channels and pores with disordered arrangements. The porediameters and pore volumes increase as the template content is increased. The pore diameters show a little change uponheating at 200℃ overnight. However, the materials do not have good hydrothermal stability.     

Fabrication of Tubular Structure Agglomerates of Calcium Carbonate by Using Collodion Film

A novel and simple method for preparing tubular structure agglomerates of calcium carbonate (CC-tube) is described. Calcium chloride and sodium carbonate aqueous solutions were used as reactants separated by a collodion film (a nitrocellulose material) in aqueous solution. The effects of the concentrations of calcium chloride and sodium carbonate aqueous solutions on the morphology and phase structure of the as-obtained samples were investigated. The CC-tube growth was prevented with the increase of reactant concentration from 0.5 to 1.0 mol•L－1. Compared with Na2CO3 aqueous solution, it is favourable to grow calcite crystals in CaCl2 aqueous solution. The products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron- microscopy.     

Synthesis of monodispersed Fe3O4@C core/shell nanoparticles

We report a facile method to synthesize dispersed Fe₃O₄@C nanoparticles（NPs）. Fe₃O₄ NPs were firstly prepared via the high temperature diol thermal decomposition method. Fe₃O₄@C NPs were fabricated using glucose as a carbon source by hydrothermal process. The obtained products were characterized by X-ray diffraction（XRD）, transmission electron microscopy（TEM）, vibrating sample magnetometer（VSM） and Raman spectra. The results indicate that the original shapes and magnetic property of Fe₃O₄ NPs can be well preserved. The magnetic particles are well dispersed in the carbon matrix. This strategy would provide an efficient approach for existing applications in Li-ion batteries and drug delivery. Meanwhile, it offers the raw materials to assemble future functional nanometer and micrometer superstructures.     

RAPID DETERMINATION OF PROTEIN IN MILLET BY FOURIER TRANSFORM NEAR-INFRARED(FTNIR)DIFFUSE REFLECTANCE SPECTROSCOPY

In this paper,the Fourier transform near-infrared(FTNIR)diffuse reflectance spectroscopy is applied for therapid determination of protein in millet.The partial least-squares(PLS)regression is successfully used as aneffective multivariate calibration technique.The calibration set is composed of 20 standard millet samples thatthe protein contents were determined by the traditional Kjeldahl method.The optimal model dimension is foundto be 5 by cross-validation.22 millet samples were determined by the proposed FTNIR-PLS method.Thecorrelation coefficient between the concentration values obtained by the FTNIR-PLS method and the traditionalKjeldahl method is 0.9805.The standard error of prediction(SEP)is 0.28% and the mean recovery is 100.2%.Theproposed method has been successfully applied for the routine analysis of protein in about 10,000 grain samples.     

Distereoselective one-pot synthesis of pyrimidopyrimidines using sulfated tin oxide as a reusable catalyst： An extension of Biginelli-type reaction

The Biginelli-type compounds 4,5,8a-triarylhexahydropyrimido[4,5-d]pyrimidine-2,7（1H,3H）-diones were synthesized by a one-pot three-component reaction using sulfated tin oxide as a reusable catalyst. This method has the advantages of high yields, short reaction time, simple starting materials and reusability of catalyst for several times.     

高比表面积蠕虫状介孔SnO2的合成与表征

 以聚乙二醇 (PEG) 为模板剂, 氯化锡为锡源, 尿素为沉淀剂, 采用水热法合成出高比表面积的蠕虫状介孔四方相金红石型 SnO2. 考察了 PEG 分子量及其浓度、水热温度和焙烧温度对 SnO2 孔结构和形貌的影响. 采用 X 射线衍射、N2 吸附-脱附、透射电镜、红外光谱和紫外-可见光谱等技术对样品进行了表征. 结果表明, 模板剂可被水洗除去, PEG 分子量对介孔 SnO2 的比表面积影响不大, 而 PEG 浓度、水热温度和焙烧温度的影响较大. 在以分子量为 6000 的 PEG 与 Sn 的摩尔比为 0.01 的条件下, 于 120 oC 水热处理 29 h 后可合成出比表面积高达 161 m2/g 和平均孔径为 2.6 nm 的蠕虫状介孔 SnO2. 所制得样品具有较好的紫外光吸收性能, 适宜用作催化剂、载体和气体传感器等.     

Effect of hydrothermal treatment on the structure, stability and acidity of Al containing MCM-41 and MCM-48 synthesised at room temperature

The effect of hydrothermal treatment of the synthesis gel on the structure, hydrothermal and mechanical stabilities and acidity of MCM-41 and MCM-48 aluminosilicates synthesised at room temperature has been investigated by X-ray diffraction, nitrogen adsorption at 77 K and DRIFTS with pyridine as probe molecule. The influence of the Al content and pore size on the structure of the resulting treated Al-MCM-41 materials has also been studied. For all samples improvement of the structural ordering and increase of the pore size, was observed, with pore wall thickness remaining practically unchanged. For Al-MCM-48 an improvement of the pore size uniformity occurs during the treatment. Only a small loss of pore size uniformity occurred for Al-MCM-41 prepared with hexadecyltrimethylammonium bromide, but with samples prepared with tetra and octadecyltrimethylammonium bromide the treatment generated a bimodal pore size distribution. The pore volume increased (17%) in the case of Al-MCM-48 but decreased (5.5–14%) for Al-MCM-41, suggesting a decrease in surface roughness resulting from increase of the degree of condensation of the pore walls. Both treated and untreated samples presented relatively strong Brønsted sites and increase of the Lewis acidity was found to occur upon treatment. Treated samples were found to be more resistant to refluxing in boiling water and mechanical compaction, which was attributed to more polymerised pore walls, with Al-MCM-41 samples tested demonstrating higher stability than Al-MCM-48. However, the differences in stability of samples prepared with or without hydrothermal treatment were not significant. Both treated and untreated samples presented high hydrothermal stability. Although refluxing in boiling water lead to some loss of structural ordering, only a small decrease of pore volume (3–5.5% for Al-MCM-41 and 8-14% for Al-MCM-48) occurred, with practically no alterations in pore size and wall thickness. Ordered mesopore structure, with narrower pores and thicker walls, was still observed after compression at 590 MPa for most of the samples tested.     

Adsorption properties of ordered mesoporous silicas synthesized in the presence of block copolymer Pluronic F127 under microwave irradiation

Ordered mesoporous silicas (OMSs) were prepared at different temperatures by using tetraethyl orthosilicate (TEOS) as a silica source, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (Pluronic F127) as a structure directing agent and sodium chloride as an additive under acidic conditions and microwave irradiation. The small angle X-ray diffraction patterns of these samples indicate the presence of ordered mesopores, while adsorption studies show that they possess high volumes of pores, bimodal pore size distributions and large pore sizes. There is an interesting change in the hysteresis loop of nitrogen adsorption isotherms with increasing temperature of hydrothermal treatment; a delayed desorption characteristic for cage-like mesostructures is observed for the OMS samples treated at 100 and 120?°C, while the hydrothermal treatment at 140 and 160?°C leads to the samples having hysteresis loops characteristic for channel-like materials.     

Preparation of Silica Supported Tin Chloride: As a Recyclable Catalyst for the Silylation of Hydroxyl Groups with HMDS

Silica‐supported tin chloride [SiO₂‐Sn(Cl)_4‐n] has been prepared by mixing tin chloride with activated silica gel in toluene under refluxing conditions for one day. A range of primary, secondary, and tertiary alcohols as well as phenolic hydroxyl groups were converted into their corresponding trimethylsilyl ethers with hexamethyldisilazane in the presence of catalytic amounts of silica‐supported tin chloride at room temperature. An excellent chemoselective silylation of hydroxyl groups in the presence of other functional groups was also observed. This catalyst could be recycled and reused fifteen times without loss of efficiency.     

Uniform silver nanoparticles on tunable porous N‐doped carbon nanospheres for aerobic oxidative synthesis of aryl nitriles from benzylic alcohols

Tunable N‐doped carbon nanospheres from sucrose as carbon source and Tris(2‐aminoethyl)amine (TAEA) as nitrogen source by a simple and easily reproducible method were prepared. It was demonstrated that the tunable N‐doping of carbon spheres could be realized by altering the ratio of TAEA in the raw materials. The content of doped nitrogen, surface area, pore volume and pore size of carbon nanospheres were increased with the increasing of TAEA amount in the hydrothermal process. Prepared N‐doped carbon nanospheres act as solid ligand for anchoring of Ag NPs which generated via chemical reduction of Ag ions. Benzylic alcohols and aldehydes were converted into the aryl nitriles by using Ag/N‐CS‐1 nanospheres as the catalyst and O₂ as the oxidant, efficiently. This catalyst was stable and could use for 6 successful runs.     

锌锡双金属掺杂MCM-41的合成及表征

以硅酸钠为硅源, 锡酸钠，硝酸锌为金属源，十六烷基三甲基溴化铵为模板剂，采用直接水热合成法合成出了锌锡双金属同时掺杂的介孔MCM-41。通过ICP﹑XRD、TG-DTA﹑FTIR﹑HRTEM以及BET等技术对材料的结构和性质进行了表征。结果表明，合成的材料具有典型的六方介孔结构，比表面高，孔分布窄，热稳定性较高，且锌锡可能进入介孔MCM-41骨架中。该材料对苯酚羟基化反应具有良好的催化性能，双金属修饰MCM-41催化活性明显优于单组分掺杂。     

Sn掺杂MoO_3的制备、表征及气敏性能

以仲钼酸铵和四氯化锡为原料,采用水热法制备了不同Sn掺杂比例的MoO_3;利用X射线衍射(XRD),扫描电子显微镜(SEM)和Brunauer-Emmett Teller(BET)测试等手段对材料进行了物相、形貌结构和孔径表征;测试了其对乙醇、二氯甲烷、甲醇、甲醛、甲酸、四氯化碳、氨气和丙酮等气体的传感性能.结果表明,Sn掺杂未改变MoO_3的结构;290℃为气体传感测试的最佳测试温度;掺杂后的MoO_3对乙醇气体的灵敏度和响应时间均优于纯相MoO_3,Sn掺杂摩尔比为5%时效果最好,500 mg/m~3测试条件下对乙醇的灵敏度为19.64,响应时间为1.1 s.     

以MCM-22为原料合成高水热稳定性的介孔材料

以合成的微孔分子筛MCM-22为原料,将其与表面活性剂及氢氧化钠一起回流溶解,再调节溶液的pH值至7～9, 使MCM-22转化为高水热稳定性的介孔材料. 所得介孔材料具有蠕虫状的均匀孔道,骨架中不含有MCM-22的微观结构单元. 该介孔材料至少含有18%的表面活性剂,经823 K焙烧脱除表面活性剂后,其孔径为2 2 nm, 比表面积为 1 038 m2/g, 孔容为0 97 cm3/g. 焙烧后的介孔材料具有非常高的水热稳定性,经沸水回流100 h后其比表面积为896 m2/g, 孔容为0 90 cm3/g, 孔径为2 1 nm, 即使经过300 h的回流,该材料仍能保持698 m2/g的比表面积和0 90 cm3/g的孔容. 固体 29Si MAS NMR结果表明,该介孔材料的高水热稳定性与其高表面缩合度有关.     

Size-controlled synthesis of SnO2 nanoparticles using reverse microemulsion method

Tin oxide nanoparticles were prepared using an ionic surfactant (sodium dodecyl sulfate) and tin (IV) chloride as an inorganic precursor via the reverse microemulsion method. The size of the nanoparticles is controlled by variation of water-to-surfactant ratio. Eliminating of surfactant in prepared nanoparticles was confirmed by the infrared spectroscopy after sequential calcinations. Transmission electron microscopy, surface area, pore volume, average pore diameter, pore size distribution and X-ray diffraction results were used for evaluation of size distribution, shape and structure of prepared SnO₂ nanoparticles. Transmission electron micrographs confirmed that the obtained materials are spherical nanoparticles. The X-ray diffraction results show the crystalline phases of all samples are SnO₂ with tetragonal structured crystal. In addition, the X-ray diffraction and transmission electron microscopy data showed that the size of SnO₂ nanoparticles decreased with decreasing the water-to-surfactant ratio.