罗丹明6G/MCM-41纳米复合物的发光蓝移

介孔分子筛MCM-41具有规则排列的纳米量级的孔道，可以作为宿主封装其他材料。利用这一性质，将激光染料罗丹明6G分子封装在介孔分子筛MCM-41中形成了纳米复合物。用透射电镜、小角度X射线衍射和荧光光谱等方法对纳米复合物的性质进行了分析。用波长为480nm的光对纳米复合物进行激发，得到的发光峰为531nm。与无限稀罗丹明6G乙醇溶液的发光峰相比，这一发光峰有15nm的蓝移和明显的宽化。我们认为当罗丹明6G分子封装在MCM-41的介孔中时，罗丹明6G分子与介孔分子筛孔道表面分子之间存在较强的相互作用(包括氢键、静电吸引等)，导致电子云被局域在具有较强吸引力的分子筛表面原子周围。引起激发态能量升高，发光峰蓝移。     

不对称卟啉共价固载于硅基介孔薄膜材料模拟RS触发器的研究

合成了5-(4-氨基苯基)-10,15,20-三苯基卟啉(ATPP),并成功将其以共价嫁接的形式固载于介孔二氧化硅薄膜。基于卟啉化合物对酸碱的特异性响应,实现了对RS触发器逻辑功能的模拟。卟啉化合物被共价固载于介孔薄膜材料使得该分子逻辑器件具有相对较大的表面积、周期性排布的均一孔道结构以及高的光透过性等介孔薄膜材料的优异性质。这种混合多孔结构不但有利于嫁接于介孔材料中的卟啉与酸碱的更有效相互作用,而且还使酸碱输入能够被更加彻底地清除。     

Preparation and Acid Catalytic Activity of TiO2 Grafted Silica MCM-41 with Sulfate Treatment

采用连续嫁接方法对纯硅MCM-41孔道表面分别进行一次和两次TiO2修饰,并进行了硫酸根促进,制备了具有规整介孔结构的硫酸根促进型复合金属氧化物ST/MCM-41和d-ST/MCM-41;同时制备了经一次钛修饰但未经硫酸根促进的样品T/MCM-41作为对比. 利用XRD、氮吸附-脱附、元素分析、拉曼光谱和红外光谱等表征手段,对所制样品的结构和表面酸性进行考察;利用假性紫罗兰酮环化这一典型的酸催化反应对其催化活性进行评价,并与工业应用的大孔磺酸树脂Amberlyst-15进行催化性能比较. 表征结果显示,纯     

介孔二氧化硅双重孔隙的导热特性研究

介孔二氧化硅颗粒的双重孔隙分布特征对材料的导热性能具有显著影响。本文通过微观形态表征分析了介孔二氧化硅的复合孔道，并基于受限空间内的气体分子动力学理论，构建了双重孔隙结构的热导率关联模型。为了验证理论模型的合理性与准确性，采用瞬态热带法测量了介孔二氧化硅材料(MCM-41和SBA-15)在0～30 MPa和20～550℃的环境压力及温度变化下的有效热导率。实验测量结果表明，本文理论模型可以有效预测介孔二氧化硅颗粒热导率的变化规律。进一步根据模型分析可知，材料热导率随着环境温度及压力的升高而增长，表现出明显的正相关性，同时其微观结构的差异也是热导率变化的决定性因素。     

α-Al_2O_3介孔材料导热特性的模拟

本文针对α-Al2O3有序介孔材料的导热特性开展分子动力学模拟分析.提出了一种保证电中性的孔道结构构造方法;采用逆非平衡分子动力学方法(muller-plathe法),选取Matsui势为作用势,模拟计算了Al2O3介孔晶体材料在不同环境温度下沿孔道轴向方向的热导率;并借助全面实验分析法,设计了模拟条件,以考察孔径和孔隙率对热导率的影响.模拟结果显示:介孔Al2O3热导率先随温度的升高呈上升趋势,并在200—400 K之间取得极值;而后在400—1400 K范围内,热导率随温度的升高几乎呈线性下降.孔隙率一定时,随孔径增大,介孔Al2O3材料比表面积降低,界面散射的抑制作用减弱,使材料热导率略有上升;孔径一定时,随孔隙率上升,孔道壁面声子数减少,材料热导率下降明显;相对于孔径因素,材料孔隙率对声子导热影响更大.     

介孔二氧化钛光催化降解乙醛及其影响因素

"应用溶剂蒸发自组装的方法合成了具有蠕虫状孔道的介孔二氧化钛粉末和薄膜．考察了不同焙烧温度对材料介孔结构和光催化性能的影响．乙醛光催化降解实验用来表征不同焙烧温度下介孔材料的光催化性能．结果表明实验中合成的介孔二氧化钛材料的光催化活性明显高于颗粒二氧化钛(Degussa P25)．其中400 oC焙烧的样品具有平均孔径为6.0 nm的窄的孔径分布和117 m2/g的大的比表面积．通过对光催化活性结果的分析,发现介孔二氧化钛的活性主要受其比表面积和结晶性的共同影响．对介孔二氧化钛薄膜材料进行了同样的光催化表     

载体表面修饰对芯材相变特性的影响

本文以金属有机骨架Cr-MIL-101和介孔二氧化硅MCM-41为载体,采用物理共混和浸渍法实现常规相变芯材十八酸(Stearic Acid,SA)和聚乙二醇(Polyethylene glycol, PEG)的有效复合。基于FT-IR、DSC对材料进行结构表征与相变特性测量。探讨孔道表面修饰对复合材料负载量以及结晶特性的影响,并借助分子模拟手段深入分析修饰基的作用机理和机制。研究表明,可通过修饰基强化载体-芯材之间相互作用以实现负载量提升;而载体-芯材之间相互作用力过强,则可能导致芯材在受限空间内运动被束缚,降低结晶率甚至无法结晶相变。本文研究意义在于明晰基于修饰基进行相变材料性能调控的原理并尝试提出可行的方法。     

不对称卟啉共价固载于硅基介孔薄膜材料模拟反馈回路的研究

将具有氨基功能团的不对称中位四苯基卟啉以共价嫁接的形式固载于介孔二氧化硅薄膜.当将含有卟啉化合物的介孔薄膜材料置于酸性或碱性溶液中并取出时,卟啉在酸性或碱性环境中的状态会被完整的保存下来,进而实现对具有逻辑记忆功能的反馈回路(Feedback loop)的模拟.这种分子逻辑器件兼具了介孔薄膜材料的优异性质:相对较大的表面积不但有利于输入介质与响应单元更有效地接触,还有益于输入介质的彻底清除,避免其残留下来影响下次逻辑输入;周期性排布的均一孔道结构更加有利于器件的后期加工;高的透过性使得输出(Output)更容易被光学仪器所检测.     

介孔材料MCM-41的导热研究

文章根据二氧化硅介孔材料MCM-41纳米孔结构特点,首先建立和验证了纳米结构单元模型,然后使用平衡分子动力学方法模拟了孔壁热导率;接着耦合孔隙内气体导热,开展了一维传热分析,最终提炼出MCM-41的有效热导率表达式;并对壁厚、孔径和孔隙率对热导率的影响进行了分析.研究结果表明,MCM-41具有良好的绝热性能,其有效热导率随孔隙率增大近似呈线性减小,且表现出各向异性;导热性能沿孔道长度方向表现出准一维特性. 关键词： 有效热导率 介孔材料 MCM-41 平衡分子动力学     

用于测定介孔的Kelvin方程及其修正述评

介绍了物理吸附法评价介孔材料孔结构参数的理论基础、孔介质模型及吸附质对测量结果准确性的影响因素.讨论了 Kelvin 公式,以及从不同方面对 Kelvin 公式进行的修正,并以此为基础,评述采用物理吸附法测定介孔材料各种孔结构测试方法,着重探讨物理吸附法的理论基础、模型建立及其不足之处,分析和探讨介孔材料孔结构表征中存在的问题及原因,为建立新的理论模型探讨思路与可能.     

Synthesis of multi-wall carbon nanotubes by the pyrolysis of ethanol on Fe/MCM-41 mesoporous molecular sieves

Ordered hexagonal arrangement MCM-41 mesoporous molecular sieves were synthesized by the traditional hydrothermal method, and Fe-loaded MCM-41 mesoporous molecular sieves (Fe/MCM-41) were prepared by the wet impregnation method. Their mesoporous structures were testified by X-ray diffraction (XRD) and the N₂ physical adsorption technique. Carbon nanotubes (CNTs) were synthesized by the chemical vapor deposition (CVD) method via the pyrolysis of ethanol at atmospheric pressure using Fe/MCM-41 as a catalytic template. The effect of different reaction temperatures ranging from 600 to 800 ^°C on the formation of CNTs was investigated. The resulting carbon materials were characterized by various physicochemical techniques such as transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The results show that multi-wall carbon nanotubes (MWCNTs) with an internal diameter of ca. 7.7 nm and an external diameter of ca. 16.9 nm were successfully obtained by the pyrolysis of ethanol at 800 ^°C utilizing Fe/MCM-41 as a catalytic template.     

MCM-41负载磷钨酸的制备与表征

以十六烷基三甲基溴化铵(CTAB)为表面活性剂,以正硅酸乙酯(TEOS)为硅源,采用水热合成法制备了介孔分子筛MCM-41,并利用浸渍法将磷钨酸(HPW)负载在MCM-41分子筛上,得到HPW/MCM-41催化剂f采用X射线衍射、傅里叶变换红外光谱、透射电镜等手段对负载型催化剂进行了表征.结果表明,磷钨酸负载到MCM-...     

Effects of different Ti-doping methods on the structure of pure-silica MCM-41 mesoporous materials

Pure-silica mesoporous materials doped by titanium have been prepared by direct synthesis method and post-synthetic impregnation method. The effects of different Ti-doping methods on the structure of pure-silica mesoporous materials have been researched. X-ray diffraction, transmission electron microscopy, scanning electronic microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray absorption spectrum and nitrogen adsorption-desorption isotherms have been employed to characterize the products. It has been found that structural properties were strongly related to the amount and the way of titanium introduction. The mesoporous ordering of the samples that have been prepared by direct synthesis method and post-synthetic method became poor with the increasing of titanium amount. The XANES and EXAFS spectra confirmed that the titanium have been inserted into the framework of MCM-41. The titanium grafted in the Ti-MCM-41 in fourfold coordination, and the titanium doped in the Ti/MCM-41 in higher coordination sites.     

Adsorptive removal and kinetics of methylene blue from aqueous solution using NiO/MCM-41 composite

Highly ordered mesoporous material MCM-41 was synthesized from tetraethylorthosilicate (TEOS) as Si source and cetyltrimethylammonium bromide (CTAB) as template. Well-dispersed NiO nanoparticles were introduced into the highly ordered mesoporous MCM-41 by chemical precipitation method to prepare the highly ordered mesoporous NiO/MCM-41 composite. X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and high-resolution TEM (HRTEM), and nitrogen adsorption–desorption measurement were used to examine the morphology and the microstructure of the obtained composite. The morphological study clearly revealed that the synthesized NiO/MCM-41 composite has a highly ordered mesoporous structure with a specific surface area of 435.9 m² g⁻¹. A possible formation mechanism is preliminary proposed for the formation of the nanostructure. The adsorption performance of NiO/MCM-41 composite as an adsorbent was further demonstrated in the removal azo dyes of methyl orange (MO), Congo red (CR), methylene blue (MB) and rhodaming B (RB) under visible light irradiation and dark, respectively. The kinetics and mechanism of removal methylene blue were studied. The results show that NiO/MCM-41 composite has a good removal capacity for organic pollutant MB from the wastewater under the room temperature. Compared with MCM-41 and NiO nanoparticles, 54.2% and 100% higher removal rate were obtained by the NiO/MCM-41 composite.     

Ag2S nanoparticle encapsulated in mesoporous material nanoparticles and its application for photocatalytic degradation of dye in aqueous solution

Semiconductor loaded mesoporous materials in general possess greater photocatalytic activity than pure semiconductors. Hence, with an attempt to achieve higher photocatalytic activity, Ag₂S/MCM-41 photocatalysts were prepared by ion exchange method and used for the photocatalytic degradation of methylene blue. The materials were characterized by different analytical techniques such as transmission electron microscopy (TEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and BET (Brunauer-Emmert-Teller) experiments. The effect of Ag₂S, MCM-41 support and different wt% of Ag₂S over the support on the photocatalytic degradation and influence of parameters such as Ag₂S loading, catalyst a mount, pH and initial concentration of dye on degradation are evaluated. The degradation reaction follows pseudo-first order kinetics. It was seen that 0.6 g/L of photocatalyst is an optimum value for the dosage of photocatalyst. The degradation efficiency was decreased in dye concentration above 3.2 ppm for dye.     

Effects of NiTiO3 nanoparticles supported by mesoporous MCM-41 on photoreduction of methylene blue under UV and visible light irradiation

In this work, we report the synthesis of nickel titanate nanoparticles loaded on nanomesoporous MCM-41 nanoparticles to determine the effect of MCM-41 nanoparticles on the photocatalytic activities of nickel titanate (NiTiO₃) nanoparticles by using simple solid-state dispersion (SSD) method. Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and UV–Vis diffuse reflectance spectra (DRS) analysis were used to characterize the size and morphology of the obtained nanocomposite. The photocatalytic activity (PA) of the as-prepared NiTiO₃ loaded on MCM-41 was evaluated by degradation of the methylene blue under irradiation of UV and visible light. The results showed that NiTiO₃ loaded on nanosize MCM-41 has higher photocatalytic activity than that of NiTiO₃ nanoparticles.     

Optical properties of (nanometer MCM-41)-(malachite green) composite materials

Nanosized materials loaded with organic dyes are of interest with respect to novel optical applications. The optical properties of malachite green (MG) in MCM-41 are considerably influenced by the limited nanoporous channels of nanometer MCM-41. Nanometer MCM-41 was synthesized by tetraethyl orthosilicate (TEOS) as the source of silica and cetyltrimethylammonium bromide (CTMAB) as the template. The liquid-phase grafting method has been employed for incorporation of the malachite green molecules into the channels of nanometer MCM-41. A comparative study has been carried out on the adsorption of the malachite green into modified MCM-41 and unmodified MCM-41. The modified MCM-41 was synthesized using a silylation reagent, trimethychlorosilane (TMSCl), which functionalized the surface of nanometer MCM-41 for proper host-guest interaction. The prepared (nanometer MCM-41)-MG samples have been studied by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, low-temperature nitrogen adsorption-desorption technique at 77 K, Raman spectra and luminescence studies. In the prepared (nanometer MCM-41)-MG composite materials, the frameworks of the host molecular sieve were kept intact and the MG located inside the pores of MCM-41. Compared with the MG, it is found that the prepared composite materials perform a considerable luminescence. The excitation and emission spectra of MG in both modified MCM-41 and unmodified MCM-41 were examined to explore the structural effects on the optical properties of MG. The results of luminescence spectra indicated that the MG molecules existed in monomer form within MCM-41. However, the luminescent intensity of MG incorporated in the modified MCM-41 are higher than that of MG encapsulated in unmodified MCM-41, which may be due to the anchored methyl groups on the channels of the nanometer MCM-41 and the strong host-guest interactions. The steric effect from the pore size of the host materials is significant. Raman spectra firmly demonstrated the stable form obtained after the MG incorporation into the nanometer MCM-41. Therefore, nanometer MCM-41 appears to have a good potential for its use as a support for dyes and the (nanometer MCM-41)-MG composite materials may give a wide optical application.     

Hydrocarbon oxidation catalyzed by vanadium polyoxometalate supported on mesoporous MCM-41 under ultrasonic irradiation

Vanadium polyoxometalate (PVMo) supported on mesoporous MCM-41, MCM-41-NH(2), as efficient and heterogeneous catalysts, with large surface area, for hydrocarbon oxidation with hydrogen peroxide is reported. Oxidation of the alkenes and alkanes gave product selectivities, which are similar to those observed for corresponding homogeneous catalyst. PVMo-MCM was prepared by introduction of PVMo into the mesoporous molecule sieves of MCM-41 by impregnation and adsorption techniques. The samples were characterized by X-ray diffraction (XRD), thermal gravimetric-differential thermal analysis (TG-DTA), FT-IR, scanning electron microscopy (SEM), UV-Vis and cyclic voltametry (CV). Ultrasonic irradiation has a particular effect on MCM-41 structural uniformity and reduced the reaction times and improved the product yields. In addition, the solid catalysts could be recovered and reused several times without loss of its activity.     

荧光光谱法研究左氧氟沙星与MCM-41的相互作用

采用微波辅助水热法制备介孔分子筛MCM-41,并用浸渍法将左氧氟沙星(LVFX)组装在MCM-41均一的六方形孔道中,制备出新型载药复合物LVFX/MCM-41。用粉末X射线衍射(XRD)、低温氮吸附、傅里叶变换红外光谱(FTIR)及差热-热重(TGA-DTA)分析对MCM-41以及LVFX/ MCM-41复合物进行表征,合成的介孔分子筛MCM-41的孔径为2.382 nm,比表面积为1 015 m2·g-1。对MCM-41、LVFX/MCM-41、LVFX(固态)及LVFX(溶液)的荧光光谱研究结果显示,LVFX/MCM-41的荧光光谱比组装前发生明显红移,表明MCM-41孔道内表面的羟基和LVFX形成氢键,羟基上的电子云向LVFX分子上的吸电子基团转移;同时MCM-41和LVFX之间形成新环,使电子云能在更大的环上移动,药物分子的共轭体系扩大,荧光光谱峰红移。MCM-41与左氧氟沙星之间强的相互作用为研发以MCM-41为载体的新型释药系统提供了理论依据。