Progress in Pore-Size Control of Mesoporous MCM-41 Molecular Sieve Using Surfactant Having Different Alkyl Chain Lengths and Various Organic Auxiliary Chemicals

Pore-size control of mesoporous silica MCM-41 molecular sieve is described on the basis of the use of surfactant having different alkyl chain lengths and various organic auxiliary chemicals during the hydrothermal synthesis process. The BJH pore diameter of MCM-41 can be tuned from 1.6 to 4.2 nm using single or mixture of two surfactant(s) with alkyl chain lengths varied from C₈ to C₂₂. By the addition of different organic auxiliary chemicals: 1,3,5-trimethylbenzene, isopropylbenzene or tridecane into the synthesis medium, the BJH pore size of MCM-41 can be tailored up to 12.0 nm.     

水热法合成MCM-41分子筛时添加辅助烃的影响

０前言中孔ＭＣＭ－４１分子筛是Ｍｏｂｉｌ公司１９９２年开发的一种具有２－１０ｎｍ孔径的新型分子筛材料。由于其独特的孔径范围和表面特性,相关研究已经成为国际分子筛研究领域的热点课题,对它的合成、表征和催化作用已进行了许多研究［１～７］。Ｍｏｂｉｌ公司的...     

New Routes to the Synthesis of Mesoporous Materials and Their Properties

The factors that influence the hydrothermal synthesis of MCM-41 were investigated, and it was found that compared with those from high H₂O/SiO₂ systems(designated MCM-41-A), the products from low H₂O/SiO₂ systems(designated MCM-41-B) exhibited a less-defined X-ray powder diffraction (XRD) pattern with a broader main reflection peak at a lower 2θ diffraction angle. MCM-41-B possesses a smaller surface area but a larger pore size than MCM-41-A. New routes including direct thermal treatment, room-temperature crystallization and microwave heating were developed for the formation of MCM-41, and the properties of the products prepared from these new routes were compared with those of the MCM-41 hydrothermally synthesized. The pore sizes of MCM-41 materials are uniformly distributed with an effective pore diameter that falls into the range of 2-4 nm, where as the products from wet-gel thermal treatment possess two kinds of mesopores:the well-defined smaller pores distributed at 3 nm and the larger one within 8-20 nm. The MAS NMR spectroscopy revealed that after calcination to remove the organic template in Al-containing MCM-41, a small part of the tetrahedrally-coordinated framework aluminum atoms became octahedrally-coordinated and a considerable amount of Si-OH species were generated.     

纳米介孔分子筛MCM-41的微波辐射合成法

报导了纳米介孔分子筛MCM-41的微波辐射合成法,运用XRD、HRTEM、IR、TG、荧光光谱和低温N2吸附等技术对其进行了表征.研究结果表明,利用微波技术合成MCM-41,操作便利,节能省时.所得产物具有六方介孔排列结构,孔径约2.5 nm;颗粒大小分布均匀,平均粒径约40 nm;比表面积和孔隙率高,吸附量大,热稳定性好;在近紫外光激发下,显示出纳米粒子的量子发光效应.     

中孔沸石新材料MCM－41──Ⅰ．合成、酸性及稳定性

中孔沸石新材料ＭＣＭ－４１──Ⅰ．合成、酸性及稳定性赵修松，王清遐，徐龙伢，谢紊娟（中国科学院大连化学物理研究所，大连１１６０２３）李新生（中国科学院大连化学物理研究所催化基础国家重点实验室，大连１１６０２３）关键词ＭＣＭ－４１沸石，合成，酸性，稳定...     

Study of the Adsorption Properties of MCM-41 Molecular Sieves Prepared at Different Synthesis Times

The variation of surface properties of SiMCM-41 and AlMCM-41 nanoporous materials as function of synthesis time was examined. The main properties studied were: surface area, pore diameter, pore volume, mesoporous parameter, and wall thickness. Siliceous MCM-41 molecular sieves were synthesized starting from hydrogels with the following molar compositions: 4.58SiO₂:0.435Na₂O:1 CTMABr:200 H₂O for SiMCM-41, and 4.58SiO₂:0.485 Na₂O:1 CTMABr:0.038 Al₂O₃:200 H₂O, for AlMCM-41. Cetyltrimethylammonium bromide (CTMABr) was used as the structural template. The crystallographic parameters were obtained from XRD data and by nitrogen adsorption using the BET and BJH methods. The results obtained showed a significant variation of the surface properties of the MCM-41 materials as a function of the synthesis time reaching silica wall thickness of ca. 2 nm on the fourth day.     

辅助有机胺对介孔分子筛MCM-41合成及其性质的影响

采用阳离子表面活性剂十六烷基三甲基溴化铵为模板剂、硫酸铝为铝源、硅溶胶为硅源，分别使用中等链长的有机胺和正己烷作为辅助添加剂，用水热晶化法在碱性介质中合成了介孔分子筛MCM-41，通过XRD、N2吸附-脱附、SEM测试手段对得到的样品进行了对比表征分析。实验结果表明，除三乙胺外，向反应体系中加入适量的三正丙胺、三正丁基胺、三正辛胺和二异丁胺后，均能够使介孔 MCM-41的d100值和孔径增大，且具有较大的BET表面积（>1 000 m2/g）和孔容（>1 cm3/g）；加入正己烷后，也可以使得MCM-41孔径变大，但是和加入有机胺相比较，合成的样品具有较小的BET表面积（887.3 m2/g）和孔容（0.81 cm3/g）。     

MCM-41分子筛的合成及129Xe核磁共振的研究

Purely siliceous MCM-41 with a narrow pore-size distribution, different pore size, high surface area was synthesized . As prepared, calcined and catalytically tested MCM-41 materials have been comprehensively characterized by N₂ adsorption/desorption at 77K and ¹²⁹Xe NMR. By adding mesitylene during the synthesis, the pore size of MCM-41 was enlarged to 5.2nm. The chemical shift in ¹²⁹Xe NMR spectroscopy of adsorbed xenon indicates that the MCM-41 is one dimensional pore channels .     

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。     

以CTMABr和CTMAOH为共模板剂合成MCM-41

采用共模板剂水热合成了MCM-41.分别用X射线粉末衍射(XRD)、固体核磁共振(²⁷AlMASNMR)和N₂吸附等温线技术考察了用该方法和传统方法所制备的Si-MCM-41和Al-MCM-41样品的晶相结构、孔结构以及Al在分子筛中的化学环境.结果表明,用共模板剂方法合成的MCM-41样品,其纯度和孔径均一性显著提高,特别是当样品中Al含量较高时,仍可保证Al原子以四配位结合在MCM-41的硅骨架上.还就采用共模板剂的理论依据进行了讨论.     

Influence of the incorporated metal on template removal from MCM-41 type mesoporous materials

Al-modified MCM-41, La-modified MCM-41, and Ce-modified MCM-41 mesoporous materials were prepared with different molar ratios (Si/M = 10; 25; 50; 100 and 200) at room temperature. The materials were characterized using XRD, BET–BJH, and TG–DTA. The XRD showed four peaks, due to the ordered hexagonal array of parallel silica tubes, which could be indexed as (100), (110), (200), and (210), assuming a hexagonal unit cell. The surface area decreased as the concentration of the metal incorporated in the material increased. The thermal stability of the materials was around 650 °C. The CeO₂ phase made the mass transfer process more difficult, hindering Hofmann degradation and favoring oxidation.     

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.     

以离子液体为模板剂合成MCM-41的研究——不同扩孔剂对介孔分子筛MCM-41孔径结构的影响

以离子液体为模板剂, 正硅酸乙酯为硅源, 研究了扩孔剂三甲苯, 癸烷, 以及三甲苯与癸烷1∶1的混合物对介孔分子筛MCM-41结构的影响, 采用XRD以及氮吸附-脱附分析技术对合成的介孔分子筛MCM-41进行了表征.结果表明: 三种扩孔剂中以三甲苯与癸烷1∶1的混合物效果最优, MCM-41的孔径可达到4.5 nm, 并且可以提高介孔分子筛的比表面积与结晶度.扩孔剂的最佳添加量为: 扩孔剂与模板剂之比等于1.0;最佳晶化温度120 ℃.     

(MCM-41)-La_2O_3纳米复合材料的制备、表征及光学性质

借助水热法,以正硅酸乙酯为硅源,十六烷基三甲基溴化铵为模板剂,在碱性条件下制备了纳米MCM-41分子筛。通过固相热扩散法将La2O3组装到MCM-41介孔孔道中,制备出含La2O3不同浓度的(MCM-41)-La2O3主-客体纳米复合材料。采用化学分析、粉末XRD、FTIR、77K低温N2吸附-解吸附、固体扩散漫反射吸收光谱、拉曼光谱、扫描电镜和发光光谱对主-客体复合材料进行表征。粉末XRD结果表明,La2O3组装到MCM-41分子筛的孔道后并未破坏分子筛骨架,在所制备的(MCM-41)-La2O3主-客体纳米复合材料中MCM-41骨架结构仍然具有较高的有序性,并且,随着植入客体材料浓度的增加复合材料的有序度有所降低。红外光谱表明所制备的纳米复合材料主体分子筛骨架完好;低温氮气吸附-解吸附技术表明La2O3已经部分地占据了MCM-41分子筛孔道,导致分子筛的比表面积和孔体积都有所降低;固体扩散漫反射吸收光谱表明吸收光谱的吸收峰发生了蓝移现象,并表现出量子限域效应,说明La2O3已经组装到了MCM-41分子筛的孔道中;拉曼光谱表明所制备的复合材料没有出现新的特征峰,表明La2O3已经组装到了MCM-41分子筛的孔道中;扫描电镜表明(MCM-41)-La2O3样品的外观非常规整,主要呈现的是球状结构,La2O3含量为10%时,(MCM-41)-La2O3的平均粒径为(114±10)nm。发光光谱研究结果表明,所制备的复合材料(MCM-41)-La2O3样品在396nm处具有较好的发光性质,因而具有作为发光材料潜在应用前景。     

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.     

铝离子和钛离子化学改性MCM-41介孔材料的制备及其对污水中镉离子的吸附性能(英文)

通过在MCM-41材料中引入Al 3+和Ti 4+两种诱因金属离子合成了化学改性介孔材料Al-Ti-MCM-41和Ti-Al-MCM-41;评价了两种介孔材料对污水中镉离子的吸附行为.利用氮气吸附-脱附等温线对Al-Ti-MCM-41(1∶1)样品的吸附行为进行了详细分析,考察了吸附剂投加量、Cd2+初始质量浓度和吸附温度对其吸附行为的影响.结果表明:改性Al-Ti-MCM-41(1∶1)介孔材料的最可几孔径和比孔容分别为16nm和0.04cm3/g,由BJH法计算得到的平均孔径为17.02nm;其对污水中Cd2+的吸附率达99.8%.Cd2+的吸附率随Al-Ti-MCM-41(1∶1)介孔材料投加量的增加先增加而后降低最终达到平衡,吸附容量随Cd2+初始浓度的增大而增加;吸附温度对吸附行为基本无影响.     

Assessment of the intrinsic interactions of mesoporous silica with carbon dioxide

Three mesoporous silica, SBA-16, SBA-15 and MCM-41, with different structures and porosities were synthesized via a hydrothermal method and their interactions with carbon dioxide (CO₂) were investigated through thermal programmed desorption (TPD) and differential scanning calorimetry. TPD measurements provided precise assessments of the intrinsic affinity towards CO₂, without the influence of moisture. All silica materials were found to exhibit intrinsic affinity towards carbon dioxide, but the surface basicity, expressed in terms of retained CO₂ amount, is markedly influenced by increases in pore size and framework structures. SBA-15 displayed the highest CRC values, explained in terms of larger pore size, lower numbers of acidic out-of plane Si–OH and higher numbers of much less acidic in-plane silanols. These findings provide valuable information for a better understanding of the role of the silica structure in the intrinsic basicity, prior to further modifications for improving the affinity towards CO₂ or merely for catalysis purposes involving CO₂ as reagents, intermediates or products.     

Prearation of Highly Ordered Mesoporous Silica Materials and Application as Enzeme Supports

An enzyme, horseradish peroxidase (HRP), was adsorbed in the manner of single immersion method on the silica mesoporous materials, FSM-16, MCM-41 and SBA-15 with various pore diameters from 27 to 92 and their enzymatic activity in an organic solvent and the thermal stability were studied. FSM-16 and MCM-41 showed larger amount of adsorption of HRP than SBA-15 or silica gel,when the pore sizes were larger than the spherical molecular diameter of HRP (ca 64×37). The increased enzyme adsorption capacity may be due to the surface characteristics of FSM-16 and MCM-41, which would be consistent with the observed larger adsorption capacity of cationic pigment compared with anionic pigment for these materials. The immobilized HRP on FSM-16 and MCM-41 with pore diameter above 50 showed the highest enzymatic activity in an organic toluene and thermal stability in aqueous solution at the temperature of 70℃. The immobilized enzymes on the other mesoporous materials including large or small pore sized FSM-16 showed lower enzymatic activity in an organic solvent and the thermal stability. Both surface character and size matching between pore sizes and the molecular diameters of HRP were important in achieving high enzymatic activity in organic solvent and high thermal stability.     

预置晶种合成MCM-41/ZSM-3复合分子筛

以十六烷基三甲基溴化铵和四甲基氢氧化铵为模板剂，以ZSM-3为晶种，在水热条件下合成了同时具有中孔和微孔的复合分子筛MCM-41/ZSM-3。通过XRD、IR、N2吸附脱附等温线和SEM表征，样品的XRD图谱在小角度衍射区和大角度衍射区同时出现了MCM-41和ZSM-3的衍射峰；IR图谱上也同时出现了MCM-41和ZSM-3的吸收谱带，并且合成样品与两种分子筛的机械混合物有明显差别；N2吸附脱附等温线证明样品含中孔和微孔结构，并且微孔直径集中分布在0.7 nm左右，中孔直径集中分布在3.3 nm左右；从SEM照片可以看出，复合分子筛和机械混合物形貌不同，前者为附晶生长或再结晶，后者为均匀分散。     

Characterization of CoMCM-41 mesoporous molecular sieves obtained by the microwave irradiation method

CoMCM-41 mesoporous molecular sieves with different amounts of cobalt were synthesized via the microwave irradiation method. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), temperature programmed reduction (TPR), transmission electron microscopy (TEM) and N₂ adsorption-desorption technique, and thermal and hydrothermal stabilities of synthesized CoMCM-41 samples were also investigated. Results show that these synthesized materials have typical mesoporous structure of MCM-41. Also, specific surface area and pore volume of synthesized CoMCM-41 decrease with increasing amount of cobalt added, and mesoporous ordering also decreases. When the molar ratio of SiO₂:CoO in the starting material is 1.0:0.05, mesoporous ordering of synthesized CoMCM-41 is the best among the four doping contents. On the other hand, results of thermal and hydrothermal tests show that CoMCM-41 after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 5 days still retains mesostructure. However, mesoporous framework is entirely damaged after calcination at 850 °C for 3 h.