(纳米MCM-41)-CdS主-客体复合材料的制备及光学性质

以水热法制备了纳米微粒MCM-41分子筛，通过离子交换法将Cd(II)交换到分子筛中，然后采用硫代乙酰胺作硫化氢前驱体对(MCM-41)-Cd进行硫化，制备出主-客体复合材料(MCM-41)-CdS．化学分析表明，客体成功地组装到分子筛中．粉末X射线衍射结果表明，组装过程并未破坏所制备的主-客体材料中分子筛的骨架，分子筛骨架完整且结晶度仍然很高．红外光谱表明所制备材料骨架保持完好．低温N2吸附-解吸附研究表明，相对于MCM-41分子筛主体所制备的复合材料孔体积、孔尺寸及比表面积降低，表明客体在分子筛孔道内组装成功．制备的主-客体复合材料固体扩散漫反射吸收光谱相对于CdS体相呈现某些蓝移，说明客体处于分子筛孔道内，也表明分子筛主体对纳米硫化镉客体表现出明显的立体限域效应．(纳米MCM-41)-CdS及(微米MCM-41)-CdS样品呈现明显发光．     

Optical oxygen sensing materials based on a novel dirhenium(I) complex assembled in mesoporous silica

A new dirhenium(I) complex fac-[{Re(CO)₃(4,7-dinonadecyl-1,10-phenanthro -line)}₂ (4,4′-bipyridyl)] (trifluoromethanesulfonate)₂ (denoted as D-Re(I) ) is assembled in MCM-41 and SBA-15 type mesoporous silica support. The emission peaks of D-Re(I) in D-Re(I)/MCM-41 and D-Re(I)/SBA-15 are observed at 522 and 517 nm, respectively. Their long excited lifetimes, which are of the order of microseconds, indicate the presence of phosphorescence emission arising from the metal to ligand charge-transfer (MLCT) transition. The luminescence intensities of D-Re(I)/MCM-41 and D-Re(I)/SBA-15 decrease remarkably with increase in the oxygen concentration, meaning that they can be used as optical oxygen sensing materials based on luminescence quenching. The ratios I₀/I₁₀₀ of D-Re(I)/MCM-41 and D-Re(I)/SBA-15 are estimated to be 5.6 and 20.1, respectively. The obtained Stern-Volmer oxygen quenching plots of the mesoporous sensing materials could be fitted well to the two-site Demas model and Lehrer model.     

Luminescence properties of Euβ-diketonates incorporated in cubic mesoporous silica

Luminescent materials have been prepared by wet impregnation of Europium (III) dibenzoylmethane complexes in either non-silylated or silylated mesoporous MCM-48 silica. Silylation and incorporation of the Eu (III) complex were confirmed by Nuclear Magnetic Resonance, N₂-sorption, X-ray diffraction and Infrared spectroscopy. The luminescence properties were investigated at room and high temperatures up to 200 °C. Information on host-guest interactions were collected by analyzing the optical characteristics of the Eu (III) ions in the different media. In particular, the intensity parameter Ω₂ is confirmed to be a useful spectroscopic probe for Eu (III) first coordination shell interaction. The role of the O²⁻—Eu³⁺ charge transfer band and the impact of the silylation on the luminescence properties at room and high temperatures is demonstrated.     

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.     

Photoactive Ru Complex Embedded in Mesostructured MCM-41 Nanoparticles

The synthesis and characterization of photoactive hybrid materials based on [Ru(bpy)₃]²⁺ physically adsorbed within the channels of mesoporous MCM-41 silica nanoparticles is presented. A set of photoactive mesostructured hybrids with different guest loading has been prepared and characterized by X-ray diffraction, High Resolution Transmission Electron Microscopy, volumetric analyses, Diffuse Reflectance UV-Vis and Photoluminescence spectroscopies and lifetime measurements. The hybrids synthesis and the washing procedures, performed to investigate the host-guest interaction and the stability of the complex within the mesopores, didn??t affect the integrity of the structure and morphology of MCM-41 nanoparticles. The dispersion of [Ru(bpy)₃]²⁺ within the channels varied depending on the loading value and this is reflected in the different and peculiar photoluminescence features of the resulting hybrid materials. Photoluminescence spectroscopy evidenced that the use of MCM-41 nanoparticles ensures a better dispersion of the complex within the mesopores, if compared with traditional MCM-41. Further studies are in progress to investigate the interesting and promising features exhibited by such photoactive systems for advanced applications of electrochemiluminescence in optoelectronics and diagnostics.     

无机基质MCM-41掺杂Yb~(3+)对组装体中客体Tb(aspirin)_3 phen发光性能的影响

在室温下,以掺Yb3+的MCM-41作为主体,"热处理"后的Tb(aspirin)3phen作为发光客体,将其进行组装,通过XRD和N2-吸附脱附和IR对组装体的结构和物理性质进行了研究.利用激发和发射光谱分析了组装体的光致发光性能和主客体关系.采用了一种新型的掺杂方法"直接焙烧法",用以避免在试样合成中掺杂离子的损失.在Yb/MCM-41和Tb(aspirin)3phen-Yb/MCM-41的XRD谱图中同时在20=2.6时出现了(100)晶面衍射峰,表明试样为规则有序,六方结构的MCM-41材料.Tb(aspirin)3phen进入Yb/MCM-41孔道后,无机骨架的有序性进一步增加.相对于MCM-41,Yb/MCM-41在IR谱图中波数963cm-1的谱带减弱,表明Yb3+已经进入无机骨架.另外,波数1 384 cm-1的吸收谱带也能提供组装体Tb(as-pirin)3phen-MCM-41中成键的特征信息.PL测试结果表明,Tb(aspirin)3phen在240～375 nm区间的宽激发吸收分别归属于配体aspirin羰基n→π跃迁,苯环,π→π跃迁和phen的杂菲基团吸收.对客体Tb(aspirin)3phen进行热处理,能增强Tb(aspirin)3phen在MCM-41孔道中的发光效率,并且当基质MCM-41硅骨架掺杂Yb3+后,组装体的发光强度进一步增强,当Yb/Si=7.579×10-3时,发光强度最高.     

介孔组装体Alq3-MCM-41的光学性质

将有机发光小分子8-羟基喹啉铝(Alq₃)组装进介孔MCM-41中,采用XRD、IR、荧光光谱等测试方法对组装体Alq₃-MCM-41进行表征。XRD表明,Alq₃-MCM-41保持了有序的介孔骨架结构;IR谱图中,在波数1542 cm^-1处出现的特征吸收谱带表明组装体中Alq₃在孔道中与羟基成键;荧光光谱表明,组装体中MCM-41与Alq₃分子间发生了能量转移,从而使Alq₃-MCM-41具有优异的发光性能;荧光强度随组装量的增多而显著增强,这主要是由于在Alq₃-MCM-41中,MCM-41有序孔道的微环境使Alq₃分子分散性提高,减弱了Alq₃分子间的聚集或缔合现象,从而有效地提高了其发光强度。     

Fe_3O_4-β-环糊精聚合物固相萃取紫外可见光谱法分离分析孔雀石绿

合成并以元素分析、红外及电镜等方法表征Fe_3O_4/羟丙基-β-环糊精聚合物磁性纳米材料(CM-HP-β-CDCP-MNPs),以此作为固相萃取剂,建立磁性固相萃取-紫外可见光谱法分离分析孔雀石绿的新方法。考察影响吸附和洗脱的条件(pH,萃取剂用量,洗脱剂类型用量,萃取用洗脱时间等)。结果表明:室温下,pH 7.0时,CM-HP-β-CDCP-MNPs能快速定量吸附孔雀石绿(吸附率92%);乙醇在30min内可脱附孔雀石绿(脱附率90%);CM-HP-β-CDCP-MNPs可重复使用5次。在最佳实验条件下,该方法的富集倍数为7.5,检出限为5.6ng·mL~(-1),线性范围为0.08~8.00μg·mL~(-1),测定样品中的孔雀石绿结果令人满意。利用红外光谱初步讨论Fe_3O_4/羟丙基-β-环糊精聚合物纳米材料吸附机理。     

Preparation, characterization, and luminescence properties of novel hybrid material containing europium(III) complex covalently bonded to MCM-41

In this paper, a novel luminescent organic-inorganic hybrid material containing covalently bonded ternary europium complex in mesoporous silica MCM-41 has been successfully prepared by co-condensation of tetrethoxysilane (TEOS) and the modified ligand 2-phenyl-1H-imidazo[4,5-f][1,10]phen-3-(triethoxysilyl)propylcarbamate (PIP-Si) in the presence of cetyltrimethylammonium bromide (CTAB) surfactant as template. PIP-Si containing 1,10-phenanthroline covalently grafted to 3-(triethoxysilyl)propyl isocyanate is used not only as a precursor but also as the second ligand for Eu(TTA)₃·2H₂O (TTA: 2-thenoyltrifluoroacetate) complex to prepare a novel functionalized mesoporous material. The resulted mesoporous composite materials, which demonstrate strong characteristic emission lines of Eu³⁺⁵D₀-⁷F_J (J=0, 1, 2, 3, 4), were characterized by Fourier transform infrared (FT-IR), small-angle X-ray diffraction, excited-state decay analysis. Emission intensity of the Eu(III) complex covalently linked to MCM-41 (Eu-MCM-41) increases with the increasing irradiation time, demonstrating better photostability compared with both pure Eu(III) complex and physically incorporated sample.     

Sonochemical assisted hydrothermal synthesis of ZnO: Cr nanoparticles loaded activated carbon for simultaneous ultrasound-assisted adsorption of ternary toxic organic dye: Derivative spectrophotometric,optimization, kinetic and isotherm study

Chromium doped zinc oxide nanoparticles (ZnO: Cr-NPs) was synthesized by ultrasonically assisted hydrothermal method and characterized by FE-SEM, XRD and TEM analysis. Subsequently, this composite ultrasonically assisted was deposited on activated carbon (ZnO: Cr-NPs-AC) and used for simultaneous ultrasound-assisted removal of three toxic organic dye namely of malachite green (MG), eosin yellow (EY) and Auramine O (AO). Dyes spectra overlap in mixture (major problem for simultaneous investigation) of this systems was extensively resolved by derivative spectrophotometric method. The magnitude of variables like initial dyes concentration, adsorbent mass and sonication time influence on dyes removal was optimized using small central composite design (CCD) combined with desirability function (DF) approach, while pH was studied by one-a-time approach. The maximized removal percentages at desirability of 0.9740 was set as follow: pH 6.0, 0.019 g ZnO: Cr-NPs-AC, 3.9 min sonication at 4.5, 4.8 and 4.7 mg L⁻¹ of MG, EY and AO, respectively. Above optimized points lead to achievement of removal percentage of 98.36%, 97.24%, and 99.26% correspond to MG, EY and AO, respectively. ANOVA for each dyes based p-value less than (<0.0001) suggest highly efficiency of CCD model for prediction of data concern to simultaneous removal of these dyes within 95% confidence interval, while their F-value for MG, EY and AO is 935, 800.2, and 551.3, respectively, that confirm low participation of this them in signal. The value of multiple correlation coefficient R², adjusted and predicted R² for simultaneous removal of MG is 0.9982, 0.9972 and 0.9940, EY is 0.9979, 0.9967 and 0.9930 and for AO is 0.9970, 0.9952 and 0.9939. The adsorption rate well fitted by pseudo second-order and Langmuir model via high, economic and profitable adsorption capacity of 214.0, 189.7 and 211.6 mg g⁻¹ for MG, EY and AO, respectively.     

White luminescence of a system based on poly(9,9-di(ethylhexyl)fluorene) activated by fluorescent dyes

Luminescence has been studied for poly(9,9-di(ethylhexyl)fluorene) containing laser dyes which fluoresce in the green and red spectral regions. It has been shown that white luminescence can be obtained as a result of singlet-singlet energy transfer from the polymer matrix to the dyes at certain concentrations of the latter. Two systems are proposed that make it possible to obtain equi-energy white emission and white emission, taking into account the characteristics of the spectral sensitivity of the human eye. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 37–41, January–February, 2007.     

Preparation and characterization of carbamoylphosphonate(CMPO) silane grafted on various mesoporous silicas

The carbamoylphosphosphonate silane (CMPO analogue; 2-(diphenylphosphoryl)-N-(3-(triethoxysilyl)propyl) acetamide) modified mesoporous silica was prepared via a post-synthesis grafting method for the effective purification of rare earth elements. The guest CMPO analogue was synthesized by direct coupling reaction of 2-(diphenylphosphoryl) acetic acid and 3-(triethoxysilyl)propan-1-amine. Various mesoporous silicates such as MCM-41, SBA-15, or amorphous silica nanoparticles were adopted as host materials. The resulting surface-modified mesoporous materials were characterized with respect to their structural integrity, surface area, and pore size and the concentration of the CMPO silane species. These CMPO functionalized periodic mesostructured silicates offer the potential of applications as catalysts, sensors, or environmental sorbents.     

Photophysical Properties of Lanthanide Hybrids Covalently Bonded To Functionalized MCM-41 by Modified Aromatic Carboxylic Acids

MCM-41 mesoporous silica has been functionalized with aromatic carboxylic acids salicylic acid (Sal) and 2-hydroxyl-3-methylbenzoic acid (HMBA) through co-condensation approach of tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as a template. Organic ligands salicylic acid or 2-hydroxyl-3-methylbenzoic acid grafted to the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TEPIC) was used as the precursor for the preparation of an organic–inorganic hybrid materials. Novel organic–inorganic mesoporous luminescent hybrid containing Ln³⁺ (Tb³⁺, Eu³⁺) complexes covalently attached to the functionalized ordered mesoporous MCM-41, which were designated as Ln-Sal-MCM-41 and Ln-HMBA-MCM-41, respectively, were obtained by sol–gel process. The luminescence properties of these resulting materials were characterized in detail, and the results reveal that luminescent mesoporous materials have high surface area, uniformity in the mesopore structure and good crystallinity. Moreover, the mesoporous material covalently bonded Tb³⁺ complex (Tb-Sal-MCM-41 and Tb-HMBA-MCM-41) exhibit the stronger characteristic emission of Tb³⁺ and longer lifetime than the corresponding Eu-containg materials Eu-Sal-MCM-41 and Eu-HMBA-MCM-41 due to the triplet state energy of modified organic ligands Sal-TEPIC and HMBA-TEPIC match with the emissive energy level of Tb³⁺ very well. In addition, the luminescence lifetime and emission quantum efficiency of ⁵D₀ Eu³⁺ excited state also indicates the efficient intramolecular energy transfer process in Tb-SAL-MCM-41 and Tb-HMBA-MCM-41.     

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.     

(NaZSM-5)-AgI主体-客体纳米复合材料的研究

用热扩散法成功地把AgI组装于NaZSM5的孔道中,对制备的样品(NaZSM5)AgI进行了化学分析、粉末XRD分析、化学吸附、红外光谱表征,研究了所制备的样品固体扩散漫反射吸收光谱及发光性质.化学分析表明,AgI已进入NaZSM5主体中.粉末XRD分析显示了组装AgI后NaZSM5沸石骨架依然存在,红外光谱表明了(NaZSM5)AgI样品骨架振动与NaZSM5的骨架振动有细微差别,这主要是由组装了AgI引起的.吸附研究说明了AgI已进入NaZSM5的孔道.固体扩散漫反射吸收光谱表明,主体NaZSM5对制备的主体客体样品光吸收几乎没有影响,(NaZSM5)AgI的吸收光谱受AgI尺寸大小的影响.发光研究表明,制备的样品能带隙很高,辐射过程很强,(NaZSM5)AgI样品系具有发光功能的复合材料.     

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。     

Cu(II) recognition materials: Fluorophores grafted on mesoporous silica supports

There were designed and synthesized naphthalene and pyrene derivatives consisting of fluorophore group and of receptor fragment with donor N and O atoms. These fluorosensors were covalently attached by grafting carboxyl group to surfaces of silica xerogel or mesoporous silicas (MCM-41 and MCM-48) functionalized either with 3-aminopropyl or 3-glycidoxypropyl groups. The pyrene derivatives 2 and 3 covalently grafted on MCM-48 silica functionalized with 3-aminopropyl groups are potential recognition elements of a fluorescence chemical sensor.Fluorescence emission of the prepared recognition materials is quenched specifically owing to photoinduced electron transfer (PET) effect after coordination reactions with Cu(II) ions. Moreover, both the materials exhibit selectivity for Cu(II) ions in aqueous solutions in presence of such metal ions as: alkali, alkaline earth and transition. During UV irradiation the studied recognition elements undergo slowly photochemical degradation.     

Mesoporous silica (MCM-41) effect on (PEO + LiAsF6) solid polymer electrolyte

Composite polymer electrolyte films consisting of polyethylene oxide (PEO), LiAsF₆ and mesoporous silica (MCM-41) with fixed PEO/LiAsF₆ = 90/10 but different weight percent ratios of MCM-41 were prepared using the solution casting method. The polymer electrolyte films were characterized using XRD, DSC, SEM and electrical impedance spectroscopy. In corporation of MCM-41 in a (PEO + LiAsF₆) polymer electrolyte facilitates salt dissociation, enhances ion conductivity, and improves miscibility between organic and inorganic moieties. The scanning electron microscopy (SEM) photographs indicates the electrolytes are miscible and homogeneous up to 10 wt.% of MCM-41, and an optimized conductivity is found at this composition (10 wt.%). However, at higher weight ratios (>10 wt.%), the Li/MCM-41-rich domain developed, and the conductivity decreased with increasing mesoporous material. The electrochemical performance of fabricated electrochemical cells of configuration Li/(PEO + LiAsF₆ + MCM-41)/(MoO₃ + C + PTFE) were investigated.     

Study of optical and nanostructural metal-induced changes in erythrocyte membranes by scattering and atomic force microscopy

The surface topography of erythrocyte membranes is studied by atomic force microscopy. Differences in fine structure of membranes are found. The structure of profiles of erythrocyte membranes modified by metals is smoother compared to unmodified erythrocytes. The autocorrelation function of irregularity pro-files of erythrocyte membranes and its parameter (the correlation length) are informative parameters of the action of toxic metals on the erythrocyte membrane surface. The content of metal in an erythrocyte membrane is determined from optical investigations of a suspension of membranes subjected to the action of lead and zinc ions. It is revealed that the luminescence of erythrocyte membranes is enhanced compared to reference data. The absorption spectra of erythrocyte membranes in the range 325–740 nm are calculated from the diffuse transmission and reflection coefficients of samples taking into account their luminescence. The possibility of determining the content of metals in erythrocyte membranes from optical measurements is demonstrated.     

Key factor affecting the structural and textural properties of ZSM-5/MCM-41 composite

ZSM-5/MCM-41 micro/mesoporous composite materials were synthesized by the hydrothermal technique with alkali-treated ZSM-5 zeolite as source of silica and aluminum and characterized by various physico-chemical techniques such as X-ray diffraction (XRD), nitrogen sorption at 77 K, transmission electronic microscopy (TEM), FTIR spectroscopy and NH₃ temperature programmed desorption (TPD) techniques. The effect of concentration of CTAB in the synthesis of these solids has been investigated, the mesopore volume, surface area and surface acidity decrease with increasing the concentration of CTAB. Increasing the CTAB concentration causes the recrystallization of zeolite ZSM-5 and it disadvantage the formation of mesoporous materials MCM-41. The catalytic activity of ZSM-5/MCM-41 materials has been evaluated in the Friedel–Crafts acylation of anisole with benzoyl chloride as alkylating agent. The results revealed the reaction to be influenced by surface area, pore volume and surface acidity.