Investigation on the mechanism of the photoluminescence of MCM-41

Pure siliceous MCM-41 sample was synthesized in ethylenediamine (EDA) medium. MCM-41 sample calcined at 813 K showed the most strong photoluminescent (PL) effect, while those calcined at 1073 K and 1323 K only showed weak photoluminescence. The intensity of photoluminescence decreased as the calcined temperature increased. By nuclear magnetic resonance (NMR) spectroscopy and infrared (IR) investigation, it was demonstrated that both the Al-depleted defect sites and silanol contents were responsible for the strong PL effect of the investigated MCM-41 samples. It was also suggested that the mesoporous channel structure of MCM-41 influences the investigated PL effect.     

Compatibilizing effect of mesoporous fillers on the mechanical properties and morphology of polypropylene and polystyrene blend

Polypropylene(PP)/Polystyrene(PS) (PP/PS = 80/20) blend with different types of fillers were prepared by using melt method. Four different types of fillers, namely mesoporous MCM-41 (without template), nano-SiO₂, Polymethylmethacrylate (PMMA)/MCM-41 and PMMA/SiO₂ were considered. For PMMA/MCM-41 filler, the synthesis of the filler consisting of entrapped strand of PMMA within the pores of mesoporous MCM-41 (without template) was described. The mechanical properties of the blend determined as the nano-fillers contents and the different types of blend were found to vary with the different interface between fillers and the matrix. SEM revealed a good interaction between the matrix phases and PMMA/MCM-41 or MCM-41 (without template). The decreased T_g of PS implied that the good adhesion between PP and PS blend was obtained by adding PMMA/MCM-41 nano-filler.     

SiC-dopped MCM-41 materials with enhanced thermal and hydrothermal stabilities

SiC-dopped MCM-41 mesoporous materials were synthesized by the in situ hydrothermal synthesis, in which a small amount of SiC was added in the precursor solvent of molecular sieve before the hydrothermal treatment. The materials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, N₂ physical adsorption and thermogravimetric analysis, respectively. The results show that the thermal and hydrothermal stabilities of MCM-41 materials can be improved obviously by incorporating a small amount of SiC. The structure collapse temperature of SiC-dopped MCM-41 materials is 100 °C higher than that of pure MCM-41 according to the differential scanning calorimetry analysis. Hydrothermal treatment experiments also show that the pure MCM-41 will losses it's ordered mesoporous structure in boiling water for 24 h while the SiC-dopped MCM-41 materials still keep partial porous structure.     

Development and characterization of the composites based on mesoporous MCM-41 and polyethylene glycol and their properties

Novel MCM-41/polyethylene glycol composites have been synthesized using different ratios of MCM-41. The structure of the different composites was confirmed by using various characterization tools, including: thermal analyses (TGA and DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and field emission scanning electron microscopy (FE-SEM). The XRD and FT-IR results indicated that PEG interacts with MCM-41 via the formation of hydrogen bonds where no new phase was detected. The TGA analysis results demonstrated that the presence of MCM-41 practically affects the temperature of the main step of degradation. The DTA analysis demonstrated that an increase in the MCM-41 content up to 30 wt.% is accompanied by a continuous decrease in the melting point of PEG.     

Ultrasonic-assisted synthesis and magnetic studies of iron oxide/MCM-41 nanocomposite

Iron oxide nanoparticles were stabilized within the pores of mesoporous silica MCM-41 amino-functionalized by a sonochemical method. Formation of iron oxide nanoparticles inside the mesoporous channels of amino-functionalized MCM-41 was realized by wet impregnation using iron nitrate, followed by calcinations at 550 °C in air. The effect of functionalization level on structural and magnetic properties of obtained nanocomposites was studied. The resulting materials were characterized by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy and selected area electron diffraction (HRTEM and SAED), vibrating sample and superconducting quantum interface magnetometers (VSM and SQUID) and nitrogen adsorption–desorption isotherms measurements. The HRTEM images reveal that the most of the iron oxide nanoparticles were dispersed inside the mesopores of silica matrix and the pore diameter of the amino-functionalized MCM-41 matrix dictates the particle size of iron oxide nanoparticles. The obtained material possesses mesoporous structure and interesting magnetic properties. Saturation magnetization value of magnetic iron oxide nanopatricles stabilized in MCM-41 amino-functionalized by in situ sonochemical synthesis was 1.84 emu g⁻¹. An important finding is that obtained magnetic nanocomposite materials exhibit enhanced magnetic properties than those of iron oxide/MCM-41 nanocomposite obtained by conventional method. The described method is providing a rather short preparation time and a narrow size distribution of iron oxide nanoparticles.     

Influence of pH on the sorption behaviour of uranyl ions in mesoporous MCM-41 and MCM-48 molecular sieves

The sorption of uranyl ions in mesoporous MCM-41 and MCM-48 was accomplished with the help of a direct-template-exchange route, and the progress was monitored as a function of pH of the precursor uranyl nitrate solution. Under identical conditions of synthesis, around one and a half times larger amount of uranium was found to be sorbed in MCM-48 (∼12.5 wt.%) as compared to MCM-41 (∼9.5 wt.%). Further, the powder X-ray diffraction (XRD) data revealed that the expansion of unit cell parameters and broadening of reflections of the uranium containing samples depended on the pH of the precursor uranyl solution. Likewise, the Fourier transform infrared spectroscopy (FT-IR) studies showed a progressive decrease in the frequency of the axial OUO asymmetric stretching vibrational band, ν_a(UO) of the anchored uranyl groups with the increase of pH of the exchanging uranyl solution. The presence of two bands at ∼920 and 879 cm⁻¹ for uranyl exchanged samples prepared at pH > 5 indicated the presence of trinuclear (UO₂)₃⁺₅(OH) species. The occlusion of uranium thus depends upon the pore structure of the host material and the nature and dimension of the hydrolysis species formed at a particular pH of uranyl solution. Furthermore, the template-exchange of hexavalent uranium in MCM-41 and MCM-48 not only results in the formation of bulky hydrolysis species in the mesovoids, but also substitutes (isomorphously) in the silicate matrix resulting in the formation of UMCM-41 and UMCM-48.     

Synthesis and characterization of Co-Fe Prussian blue nanoparticles within MCM-41

A Prussian blue analogue, K_0.84Co_1.08[Fe(CN)₆] is prepared by reaction between [Fe(CN)₆]³⁻ in aqueous solution and ion-exchanged Co²⁺ in the channels of MCM-41. Powder X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, nitrogen adsorption/desorption isotherms, diffuse reflectance UV-vis absorption spectroscopy and magnetic measurements were employed to characterize the product. The results show that the Prussian blue analogue is in nanoparticles within the channels and the hexagonal phase of MCM-41 remains intact during the reactions. A particle size effect on optical and magnetic properties of the nanoparticles was observed.     

氟化MCM-41的制备及超声触发释药性能研究

采用微波法制备了MCM-41,并将其与NH4F反应制得氟化MCM-41(F-MCM-41),采用浸渍法将抗肿瘤药物5-氟尿嘧啶(5-FU)分别组装到MCM-41和氟化MCM-41中。采用XRD、FT-IR、低温N2吸附和TG对MCM-41、氟化MCM-41和药物组装体进行了表征,考察了常规条件和超声条件下组装体在人工模拟胃液中的药物释放行为。结果表明,药物组装体超声条件下的药物释放速率明显优于常规释放。     

Synthesis of mesoporous silica materials (MCM-41) from iron ore tailings

Highly ordered mesoporous materials were successfully synthesized by using the iron ore tailings as the silica source and n-hexadecyltrimethyl ammonium bromide as the template. The samples were detail characterized by powder X-ray diffraction, scanning electron microscope, high-resolution transmission electron microscopy and N₂ physisorption. The as-synthesized materials had high surface area of 527 m² g⁻¹ and the mean pore diameter of 2.65 nm with a well-ordered two-dimensional hexagonal structure. It is feasible to prepare mesoporous MCM-41 materials using the iron ore tailings as precursor.     

Organic modified mesoporous MCM-41 through solvothermal process as drug delivery system

MCM-41 materials modified by organic aminopropyl groups have been successfully prepared through solvothermal process and have been used as drug-controlled delivery system of aspirin. The results show that the releasing properties of this delivery system are affected by the amount of aminopropyl groups on the pore wall and the ordered structure of mesoporous materials. These materials were characterized by XRD, TG, FT-IR, TEM, UV and N₂ adsorption.     

Room temperature synthesis of Si-MCM-41 using polymeric version of ethyl silicate as a source of silica

Synthesis of mesoporous MCM-41 materials at room temperature using less expensive polymeric version of ethyl silicate (40 wt% SiO₂) as a source of silica was established. The influence of crucial synthesis parameters such as molar ratios of H₂O/NH₄OH, NH₄OH/SiO₂ and CTMABr/SiO₂ in gel on the quality of the phase formed was investigated. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and low temperature N₂ adsorption-desorption isotherms have been employed to characterize the products. The magnitude of orderness, textural properties and thermal stability of the Si-MCM-41 samples prepared under identical judiciously pre-controlled synthesis conditions using ethyl silicate and conventional tetraethyl orthosilicate (TEOS) were assessed. Even though, ethyl silicate has proved to be suitable source for the preparation of MCM-41 at room temperature, there exists an optimum value of H₂O/NH₄OH for different NH₄OH/SiO₂ molar ratios in the gel. Changes in the morphology were observed when NH₄OH/SiO₂, H₂O/NH₄OH molar ratios in the gels were changed.     

纳米介孔MCM-41-M/偶联剂体系对天然橡胶性能的影响

制备了天然橡胶(NR)/MCM-41-M、NR/偶联剂化学改性纳米介孔MCM-41-M、NR/MCM-41-M/偶联剂复合材料,研究了不同含量的MCM-41-M、不同种类偶联剂对MCM 41-M的改性以及偶联剂的添加方式对NR复合材料性能的影响.结果表明;MCM-41-M在NR中有明显的补强作用,当代替3份炭黑时NR基复合材料的拉伸强度达到最大值,比纯NR提高了12.7%。与MCM-41-M和KH-570直接添加到NR中相比,MCM-41-M经偶联剂KH-570改性使拉伸强度提高了50%。将MCM-41-M用偶联剂KH 570改性后添加到NR中,使NR的玻璃化转变温度升高、玻璃化转变区的损耗角减小、储能模量提高到最大。     

Electrochemical Behavior of Heteropoly Acid Anions Adsorbed in Electrodes Modified with Mesoporous Molecular Sieve Silica

Heteropoly acid H4SiW12O48 (denoted as SiW12) was assembled with the mesoporous materials MCM-41 modified with 3-aminopropyltriethoxysilane (APTES) (denote MCM-41((m))). The electrochemical behavior of SiW12/MCM-41((m)) complexes-based electrode indicated SiW12 anion was adsorbed by MCM-41((m)). In MCM-41((m)) electrode, large voltammetric waves, showing that the electrostatic bound ions adsorbed in MCM-41((m)) were electrochemically active. The potential application as amperometric sensors for nitrite is anticipated.     

MoO3在介孔分子筛MCM-41上分散和存在状态的研究

在773K加热MoO3和MCM－41的机械混合物，可以实现MoO3分散在介孔分子筛MCM－41表面，用透射电镜和选区电子衍射，配合XRD和液氮温度下氮吸附－脱附曲线和BJH孔径分布，研究了活性组分MoO3在有序介 材料MCM－41上的存在状态，以及MoO3分散到MCM－41表面后MCM－41的结构变化情况。结果表明：当MoO3的含量小于单层分散阈值，加热后MoO3的XRD衍射峰彻底消失，用HRTEM观察不到分散在MCM－41表面或孔道中的MoO3颗粒，而EDS能谱证明在MCM－41的孔道中有呈分散态的MoO3存在。MoO3的含量大于单层分散阈值，通过加热不能使MoO3完全分散在MCM－41表面，而且XRD、HRTEM、氮吸附－脱附等温线和孔径分布都表明由于MoO3的分散量较大，载体MCM－41的有序介孔结构遭到破坏。     

不同偶联剂对介孔分子筛MCM-41的表面修饰及对MCM-41/环氧树脂性能的影响

使用2种硅烷偶联剂(KH550和KH792)对介孔分子筛MCM-41进行表面改性,采取氮气吸附-脱附、FTIR和TGA等进行表征,并采用原位聚合法制备了MCM-41/环氧树脂复合材料,研究了偶联剂种类和MCM-41用量等对复合材料固化过程及性能的影响。结果表明:硅烷偶联剂可与MCM-41表面的硅羟基反应,在分子筛内外表面接枝上功能化基团。经表面修饰的MCM-41比表面积下降为原来的1/5,KH550在MCM-41表面接枝率仅为KH792的一半。KH550与MCM-41外表面反应得更充分,KH792对MCM-41孔道内壁的修饰效果更强。固化动力学结果表明:KH792的功能化基团有伯胺和仲胺,与环氧树脂具有更高的反应活性,但不利于环氧大分子进入孔道,仅以球形粒子的形式添加在环氧树脂中;KH550表面修饰的MCM-41可使环氧大分子进入孔道内形成互穿结构。KH550表面修饰体系更多体现出MCM-41多孔的特征,形成了有机-无机互穿结构的复合体系,大幅度提高了储能模量和玻璃化转变温度。KH792表面修饰体系则呈常规球形纳米粒子的特征,其储能模量和玻璃化转变温度较纯环氧树脂有所提高但幅度不大。     

Functionalization of mesoporous MCM-41 for the delivery of curcumin as an anti-inflammatory therapy

In this study, mesoporous silica nanoparticles (MSNs) composed of MCM-41 were synthesized and modified with amine groups (i.e., NH₂) to form NH_2/MCM-41, which was loaded with curcumin (CUR) to form CUR@NH₂/MCM-41 to create an efficient carriers in drug delivery systems (DDSs). The three samples (i.e., pure MCM-41, NH₂/MCM-41, and CUR@NH₂/MCM-41) were characterized using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transition electron microscopy (TEM), and a thermogravimetric analyzer (TGA). The study investigated the effect of the carrier dose, CUR concentration, pH, and contact time on the drug loading efficiency (DLE%) by adsorption. The best DLE% for MCM-41 and NH₂/MCM-41 was found to be 15.78 and 80%, respectively. This data demonstrated that the Langmuir isotherm had a greater correlation coefficient (R²) of 0.9840 for MCM-41 and 0.9666 for NH₂/MCM-41 than the Freundlich and Temkin isotherm models. A pseudo-second-order kinetic model seems to fit well with R² = 0.9741 for MCM-41 and R² = 0.9977 for NH₂/MCM-41. A phosphate buffer solution (PBS) with a pH of 7.4 was utilized to study CUR release behavior. As a result, the full release after 72 h was found to have a maximum of 74.1% and 29.95% for pure MCM-41 and NH₂/MCM-41, respectively. The first-order, Weibull, Hixson-Crowell, Korsmeyer-Peppas, and Higuchi kinetic release models were applied to releasing CUR from CUR@MCM-41 and CUR@NH₂/MCM-41. The Weibull kinetic model fit well, with R² = 0.944 and 0.96912 for pure MCM-41 and NH₂/MCM-41, respectively.     

Synthesis and characterization of super-microporous material with enhanced hydrothermal stability

Super-microporouos silicon material with high hydrothermal stability denoted as MCM-41-T has been prepared from mesoporous MCM-41 by high temperature treatment. The structural and chemical property of MCM-41-T has been characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption-desorption, infrared spectroscopy and ²⁹Si MAS NMR. The characteristic results show that Si-OH groups are forced to condense by high temperature treatment, and the pore size of MCM-41-T is around 1.5 nm in the super-microporous range. Compared with the original material MCM-41, the hydrothermal stability of MCM-41-T has been significantly enhanced.     

杂多酸固载催化剂的合成及窄分子量纤维素制备的研究

通过水热合成法制备MCM-41型介孔分子筛,采用浸渍法负载磷钨酸于MCM-41介孔分子筛中,煅烧得到新型HPW/MCM-41固载催化剂。利用傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、热重分析(TG)和扫描电镜(SEM)对固载催化剂进行表征;考察催化剂对棉纤维催化降解反应的性能。结果表明,新型HPW/MCM-41固载催化剂即持有了磷钨酸的Keggin结构,同时又保持了分子筛的完整介孔结构,具有催化、筛分双重性能。棉纤维催化降解反应数据显示,磷钨酸负载量、反应温度、催化剂用量、液固比及停留时间均影响HPW/MCM-41降解纤维素的性能。在单因素实验最佳反应条件下,棉纤维素降解产物的分子量分布较为均匀,降解产物的产率较优。     

TiO_2在MCM-41内表面单层及双层分散的结构表征

首次以有机物钛酸丁酯为前驱体,合成了ＴｉＯ２呈单层分散状态（Ｔｉ／Ｓｉ＝０.２０）或双层分散状态（Ｔｉ／Ｓｉ＝０．３９）的介孔分子筛ＭＣＭ－４１（Ｓｉ／Ａｌ＝３５）,并以 ＸＲＤ,ＦＴＩＲ,Ｎ２吸附－脱附,固体ＵＶ－ｖｉｓ 漫反射等表征手段对其结构特征和氧化钛分散状态进行了研究．结果表明： ＴｉＯ２在介孔分子筛ＭＣＭ－４１孔道中分散, ＭＣＭ－４１骨架结构结晶度降低,但是附着二层ＴｉＯ２后,仍能保持长程有序结构; ＴｉＯ２与ＭＣＭ－４１孔道表面的ＳｉＯ２以化学键连接,生成Ｓｉ－Ｏ—Ｔｉ键;无论是单层还是双层分散的 ＴｉＯ２在 ＭＣＭ－４１内孔壁均匀分散;且由于ＴｉＯ２粒子的减小使其对紫外光的吸收发生明显的蓝移现象．     

配合物[Fe(bipy)2]3+修饰的MCM-41的合成与表征

以γ－氨丙基修饰介孔分子筛ＭＣＭ－４１内孔壁,将引入的γ－氨丙基与金属配位离子［Ｆｅ（ｂｉｐｙ）_２］^３＋通过配位键首次合成了金属配位化合物修饰的ＭＣＭ－４１（ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２）．通过ＸＲＤ,７７Ｋ氮气吸附－脱附曲线,固体ＵＶ－ｖｉｓ漫反射光谱和循环伏安曲线表征了复合物ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２。由于［Ｆｅ（ｂｉｐｙ）_２］^３＋的引入,使 ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２的结晶度降低, ＢＥＴ比表面积、孔容和最可几孔径急剧下降．γ－氨丙基与Ｆｅ^３＋的配位而使其ＵＶ－ｖｉｓ漫反射吸收光谱与ＭＣＭ－Ｆｅ（ｂｉｐｙ）_２不同;循环伏安特性曲线表明ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２在电化学上比浸渍法制备的ＭＣＭ－Ｆｅ（ｂｉｐｙ）_２稳定．