Stability and textural properties of cobalt incorporated MCM-48 mesoporous molecular sieve

Transition metal cobalt incorporated MCM-48 mesoporous molecular sieves (CoMCM-48) with different Co contents were synthesized hydrothermally at 120 °C for 24 h by directly adding fluoride ions to the initial gel. The resulting materials were characterized by means of XRD, TEM, FT-IR, UV-vis, TPR and N₂ physical adsorption, respectively. The effect of various factors, such as the Si/Co molar ratio, calcination temperature and hydrothermal treatment time, on the crystalline structure and textural properties of CoMCM-48 was investigated in detail. The results show that the CoMCM-48 mesoporous materials with high specific surface area were successfully synthesized. A small amount substitution of Co for Si in MCM-48 did not significantly change the textural properties while the higher cobalt incorporated leads to decrease of the surface area and deterioration of structural regularity. Furthermore, the resulting CoMCM-48 still retained the cubic mesoporous framework even after calcination at 800 °C for 4 h or hydrothermal treatment at 100 °C for 24 h.     

Effect of the thermal and hydrothermal treatment on textural properties of Zr-MCM-41 mesoporous molecular sieve

Zr-containing mesoporous molecular sieves were synthesized by hydrothermal method using cetyltrimethyl ammonium bromide as a template and sodium silicate and zirconium sulfate as raw materials. The structure and morphology of the synthesized samples were characterized via various physicochemical methods, including X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, solid state nuclear magnetic resonance (²⁹Si MAS-NMR) techniques, thermal gravimetric-differential scanning calorimeter (TG-DSC) and N₂ physical adsorption, respectively. The effect of the different initial ZrO₂:SiO₂ molar ratio, the different thermal treatment temperature and the different hydrothermal treatment time on textural property was investigated. The experimental results reveal that the as synthesized samples possess a typical mesoporous structure of MCM-41. On the other hand, the specific surface area and pore volume of the synthesized Zr-MCM-41 mesoporous molecular sieve decrease with the increase of the amount of zirconium incorporated in the starting material, the rise of thermal treatment temperature and the prolonging of hydrothermal treatment time, the mesoporous ordering becomes poor. Also, when the molar ratio of ZrO₂:SiO₂ in the starting material is 0.1, the mesoporous structure of the Zr-MCM-41 mesoporous molecular sieve still retains after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 6 d, and have specific surface areas of 423.9 and 563.9 m²/g, respectively.     

Effect of the Si/Ce molar ratio on the textural properties of rare earth element cerium incorporated mesoporous molecular sieves obtained room temperature

Rare earth Ce-incorporated MCM-41 mesoporous molecular sieves (CeMCM-41) were synthesized via a direct and nonhydrothermal method at room temperature from sodium silicate and ammonium cerium (IV) nitrate as raw materials. Cetyltrimethyl ammonium bromide (CTAB) was used as a template. The resultant samples were characterized by means of powder X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), diffuse reflectance ultraviolet–visible spectroscopy (UV–vis) and N₂ physical adsorption, respectively. The effect of the Si/Ce molar ratio on the crystalline structure and textural properties of CeMCM-41 was also investigated. The experimental results show that ordered CeMCM-41 mesoporous molecular sieves were successfully synthesized at room temperature and the resultant mesoporous materials have specific surface areas in the range of 594–1369 m²/g and average pore sizes in the range of ca. 2.5–2.8 nm. It has been found that the structural properties are strongly related to the amounts of cerium incorporation. When the cerium content increased in the samples, the intensity of the peak (1 0 0) was gradually reduced, and the surface area and structural regularity were diminished.     

镧掺杂的介孔分子筛的合成及其光学性能研究

以十六烷基三甲基溴化铵(CTAB)为表面活性剂,正硅酸乙酯(TEOS)为硅源,采用水热晶化法,合成了镧掺杂的MCM-41介孔分子筛。通过X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱、透射电镜(TEM)、紫外-可见(UV-Vis)光谱等测试手段对其孔结构和镧原子的存在状态进行了表征。XRD和TEM结果表明,合成样品具有典型的二维六方有序介孔结构,样品的傅里叶变换红外光谱和紫外-可见光谱表明镧被成功的引入到介孔骨架中。     

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.     

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.     

超声波酸性体系下MCM-41的合成及表征

以十六烷基三甲基溴化铵(CTAB)为模板剂,正硅酸乙酯(TEOS)为硅源,以超声波为辅助手段于酸性介质中制备出了MCM-41介孔分子筛,采用XRD、TEM、FTIR等手段对样品进行了分析表征.结果表明,所合成样品具备MCM-41所特有的六方排列的一维孔道结构和较高的有序度,所合成的MCM-41平均粒径为11nm,孔径约为2.7nm.     

Synthesis and characterization of ionic liquid-functionalized alumino-silicate MCM-41 hybrid mesoporous materials

Ionic liquid-functionalized alumino-silicate MCM-41 hybrid mesoporous materials have been synthesized with two-step approach, by means of in situ skeleton doping with aluminium and post surface grafting with N-methylimidazole ionic liquid groups. The samples were characterized by X-ray diffraction (XRD), high resolution transmission electron microscope (HRTEM), N₂ adsorption-desorption, Fourier transform infrared (FTIR) spectra, ²⁷Al and ¹³C MAS NMR spectra and temperature-programmed desorption (TPD) of NH₃. The results indicated that the bifunctionalized MCM-41 possessed ordered mesostructure. Aluminium was efficiently introduced into the framework of the mesostructure, generating Lewis and Brönsted acid sites. N-methylimidazole ionic liquid groups were covalently grafted onto the surface of mesoporous materials. The as-synthesized bifunctional MCM-41 showed good catalytic performance in the coupling reaction of CO₂ and propylene oxide.     

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.     

Stability and characterization of mesoporous molecular sieve using natural clay as a raw material obtained by microwave irradiation

Mesoporous molecular sieve was synthesized via microwave irradiation method, and using natural clay, sodium silicate and aluminum chloride as raw materials and cetyl trimethyl ammonium bromide (CTAB) as a template agent under alkaline condition. The samples were characterized by various analytic and spectroscopic tools such as XRD, FT-IR, TEM, TG-DSC and N₂ physical adsorption, respectively. The results show that the synthesized sample has typical mesoporous structure and exhibits good mesoporous ordering. On the other hand, the as synthesized sample after calcination at 550 °C for 10 h has a surface area of 576.0 m²/g and an average pore size of 4.83 nm. Furthermore, the synthesized mesoporous molecular sieve still exhibits good mesoporous ordering after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 10 days.     

Synthesis and characterization of MCM-41 decorated with CuO particles

CuO particles have decorated on the external surface of MCM-41 by in situ introducing cupric nitrate during the hydrothermal synthesis followed by the calcination. The textural and structural properties of CuO/MCM-41 are compared with those of pure MCM-41. The results show that CuO particles are about 40 nm in size and are not agglomerated. The addition of cupric nitrate to the synthesis gel leads to materials with somewhat reduced quality as evidenced from X-ray diffraction patterns and nitrogen adsorption measurements. CuO/MCM-41 is less ordered relative to pure MCM-41 and there are inter-aggregate pores resulting in a higher average pore diameter in the material. The formation of CuO particles on the external surface of MCM-41 and the possible reason for the less ordered structure of CuO/MCM-41 are also discussed in the present paper.     

Removal of naphthalene from petrochemical wastewater streams using carbon nanoporous adsorbent

Ordered mesoporous carbon, OMC, was synthesized using ordered mesoporous silica MCM-48 as hard template, the structural order and textural properties of the synthesized materials were studied by XRD, SEM, and nitrogen adsorption-desorption analysis. Adsorption of naphthalene over various porous adsorbents such as OMC, MCM-48, and commercial activated carbon was studied from solutions with different concentration at ambient temperature (25 ± 2 °C) and pH 7. The adsorption isotherms of naphthalene were in agreement with a Langmuir model, moreover, the uptake capacity of naphthalene followed the order: OMC > commercial activated carbon > mesoporous silica (MCM-48).     

Template synthesis and characterisation of MCM-41 mesoporous molecular sieves containing various transition metal elements—TME (Cu,Fe, Nb,V, Mo)

A series of metallosilicates (transition metal elements—TME) MCM-41 (TME=Fe, Cu, Nb, V, Mo) mesoporous molecular sieves with variable Si/TME ratios have been synthesized and characterised by low temperature N₂ adsorption/desorption, XRD, XPS, H₂-TPR, FTIR combined with NO+NO₂ adsorption, diffuse reflectance UV–Vis spectroscopy, and ESR study. All the materials exhibit hexagonal arrangement of uniform mesopores (with exception of CuMCM-41). Defect holes amid the nanochanels besides well-ordered mesopores characterise mainly Fe-containing materials, in which the highest TME loading was reached. Similar but smaller defects take place in NbMCM-41. The amount of TME included into MCM-41 structure under the preparation conditions used in this work changes in the order: Fe>Nb>Cu≫V≫Mo. This sequence is not related to the oxidation state of metals which was estimated in calcined materials as Fe³⁺, Nb⁵⁺, Cu²⁺, V⁵⁺, Mo⁶⁺. It does not also correlate with cation sizes in a simple way. The possibility of forming tetrahedral coordination seems to limit the TME incorporation into the MCM-41 skeleton if free metal cations are used in the gel (Cu²⁺, Fe³⁺, Nb⁵⁺). Al in the gel makes the isomorphously substitution of silicon by copper easier, but part of Cu occupies extra framework cationic positions in the final material.     

超声波对合成介孔材料Al-MCM-41的有序度的影响

在超声频率为20 kHz,电功率为500 W的超声波作用下,分别以Al（NO₃）₃和Al₂ （SO₄）₃做铝源合成了具有不同Si/Al比的Al-MCM-41。XRD结果显示,尽管超声波作用下,掺杂杂原子Al也要降低介孔材料的有序度,但其有序度降低的程度比普通水热法要小,超声波的辅助可以在同样反应时间内得到比普通水热法具有更高有序度的Al-MCM-41,即在掺杂过程中,超声波要比普通搅拌有利于介孔材料保持其骨架稳定性。此外考察了超声波作用时间对产品有序度和粒度的影响。     

Adsorption characterization of surfactant-templated ordered mesoporous silicas synthesized with and without hydrothermal treatment

This work reports a systematic study of ordered mesoporous silicas (OMSs) synthesized with and without hydrothermal treatment at 373 K for a series of surfactants of different alkyl chain length (from C10 to C18). For these samples nitrogen adsorption and small angle X-ray scattering (SAXS) data were measured to characterize their adsorption and surface properties. Namely, nitrogen adsorption isotherms were used to evaluate their specific surface area, pore volume and pore size distribution, whereas SAXS data provided information about their structural ordering. It is shown that while the room temperature synthesis afforded OMS samples with cubic MCM-48 structure, an additional 5-day hydrothermal treatment of these samples at 373 K caused their transformation to MCM-41 (two-dimensional hexagonal structure) and improved their pore uniformity, which was manifested by reducing the width of pore size distribution.     

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.     

Continuous one-step synthesis of N-doped titania under supercritical and subcritical water conditions for photocatalytic reaction under visible light

N-doped titania was prepared continuously by one-step synthetic method under supercritical and subcritical water conditions using titanium(IV)tetraisopropoxide (TTIP) and nitric acid as a titania precursor and nitrogen source, respectively. The synthesized N-doped titania particles were characterized by XRD, N₂-adsorption, TEM, XPS, UV-vis diffuse reflectance spectroscopy. N-doped titania was successfully synthesized and its crystalline structure was homogenous anatase phase with high surface area. The absorption edge of synthesized N-doped titania shifted into the visible light region compared with commercial titania P25. All synthesized N-doped titania have higher photocatalytic activity than P25 under visible light irradiation. The photocatalytic activity of N-doped titania synthesized under supercritical water condition was the highest for the degradation of methyl orange under visible light due to the larger crystallite size compared with the N-doped titania synthesized under subcritical water condition.     

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。     

Sol-gel derived S,I-codoped mesoporous TiO2 photocatalyst with high visible-light photocatalytic activity

A mesoporous S,I-codoped TiO₂ photocatalyst with high visible light photocatalytic activity was synthesized through the hydrolysis and condensation of titanium isopropoxide with thiourea and iodic acid as the precursors. The as-prepared catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-vis diffuse reflectance (DRS), X-ray photoelectron spectroscopy (XPS), Fourier translation infrared spectroscopy (FT-IR), and N₂ adsorption. The results showed that the cations of S⁶⁺ and I⁵⁺ could substitute for some of the lattice titanium (Ti⁴⁺). The S,I-codoping forms the new bands above the valence band and narrows the band-gap of the TiO₂, then shifts the absorption edge from UV light region to visible light range. The activity of the catalyst was examined by photodegradation of methylene blue in an aqueous solution under visible light irradiation. The activity of the S,I-codoped catalyst is far superior to that of single S or I-doped TiO₂ counterpart. The high visible light photocatalytic activity could be attributed to the strong absorption of light, well-crystalline anatase phase, and mesoporous microstructure.     

Chemisorption of hydrogen sulphide on zinc oxide modified aluminum-substituted SBA-15

Aluminum silicate mesoporous material, ZnO/Al-SBA-15, was synthesized by post-synthesis and immobilization method via microwave-assisted route. Desulphurization tests from a gas mixture with low content H₂S were carried out as the probing reaction on these materials. Chemical effects and the nature of the ZnO additive and textural properties on desulphurization capacity were studied over this material. Material was characterized using N₂ adsorption, XRD, TEM, FTIR, XPS, ICP and other techniques. The analysis suggests that the as-synthesized material had well-ordered hexagonal mesopores and was abundant in micropores. ZnO nanoparticles dispersed well and anchored both in the channel and the wall of mesoporous silica. The material with 2.1 wt.% zinc loading presented the highest H₂S uptake capacity. Both micropores and mesopores are active sites for H₂S capture, especially micropores. The enhancement of H₂S removal capacity was attributed to the integration of the pore structure of mesoporous material and the promising desulphurization properties of ZnO nanoparticles. ZnO/Al-SBA-15 could be an effective alternative to remove H₂S from gaseous streams and it also extends the research of mesoporous material.