Enhanced photocatalytic and adsorptive degradation of organic dyes by mesoporous Cu/Al2O3-MCM-41: intra-particle mesoporosity, electron transfer and OH radical generation under visible light

Mesoporous Cu/Al(2)O(3)-MCM-41 composite was synthesized by two step processes; in situ incorporation of high surface area mesoporous Al(2)O(3) (MA) into the framework of MCM-41 (in situ method) followed by impregnation of Cu(II) by incipient wetness method. The interesting thing is that starch was used for the first time as template for the preparation of high surface area MA. To evaluate the structural and electronic properties, these catalysts were characterized by low angle X-ray diffraction (LXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), UV-vis DRS, FTIR and photoluminescent (PL) spectra. The various cationic dye such as methylene blue (MB), methyl violet (MV), malachite green (MG) and rhodamine 6G (Rd 6G) of high concentration 500 mg L(-1) were degraded and adsorbed very efficiently (100%) using the 5 Cu/Al(2)O(3)-MCM-41 composite within 30 and 60 min, respectively. The high and quick removal of such concerted cationic organic dyes and also mixed dyes (MB+MV+MG+Rd 6G) by means of photocatalysis/adsorption is basically due to the combined effect three characteristics of synthesized mesoporous 5 Cu/Al(2)O(3)-MCM-41 composite. These characteristics are intra-particle mesoporosity, electron transfer and ˙OH radical generation under solar light.     

The Synthesis and Characteristics of Vanadoaluminosilicate MCM-41 Mesoporous Molecular Sieves

A series of vanadoaluminosilicate MCM-41 mesoporous molecular sieves with various compositions have been hydrothermally synthesized. Hexadecyltrimethylammonium bromide was used as a surfactant in the synthesis. The samples were characterized with nitrogen sorption, X-ray diffraction, differential thermal analysis, thermogravimetric analysis, Fourier transform-Infrared spectroscopy, UV-visible spectroscopy, scanning electron microscopy, transmission electron microscopy, and solid state NMR. The solid products had the MCM-41 structure and contained only atomically dispersed vanadium and aluminum consistent with framework vanadium and aluminum. The samples were hydrophobic and contained large amount of surfactant in the as-synthesized samples. The surfactant could be removed upon calcination at 450°C. N₂ sorption measurements and TEM demonstrate the high mesoporosity of [V, Al]-MCM-41. The incorporation of vanadium and aluminum into MCM-41 decreased the surface area to some extent. The morphologies of all the samples were the agglomerate of plates. ²⁹Si MAS NMR shows that the pore wall is amorphous. ²⁷Al MAS NMR shows that all of aluminum species were tetrahedrally coordinated even after calcination at 550°C.     

Immobilization of palladium in mesoporous silica matrix: preparation, characterization, and its catalytic efficacy in carbon-carbon coupling reactions

Palladium(0) has been immobilized into the silica-based mesoporous material to develop catalyst Pd(0)-MCM-41, which is found to be highly active in carbon-carbon coupling reactions. [Pd(NH3)4]2+ ions have been incorporated into the mesoporous material during synthesis of MCM-41 and subsequently upon treatments with hydrazine hydrate Pd2+ ions present in mesoporous silica matrix were reduced to Pd(0) almost instantaneously. The catalyst has been characterized by small-angle X-ray diffraction, N2 sorption, and transmission electron microscopy (TEM). TEM and surface area measurements clearly demonstrate that the immobilization of Pd(0) into the mesoporous silica has a significant effect on pore structure of the catalyst. Nevertheless, after immobilization of palladium the meso-porosity of the material is retained, as evidenced in the nitrogen sorption measurement. The TEM micrograph shows that both MCM-41 and Pd(0)-MCM-41 have similar types of external surface morphology; however, Pd(0)-MCM-41 was less ordered. Pd(0)-MCM-41 showed high catalytic activity toward carbon-carbon bond formation reactions like Heck and Sonogashira coupling, as evidenced in high turn-over numbers. In contrast to many other Pd-based catalysts reported so far, Pd(0)-MCM-41 acts as a truly heterogeneous catalyst in C-C coupling reactions. Notably, the new heterogeneous catalyst is found to be efficient in the activation of arylchloride to give impressive conversion in cross coupling (15-45% for Heck and 30% for Sonogashira) reactions under mild conditions.     

不同有机胺修饰MCM-41的CO2吸附性能和热稳定性

将乙二胺(EDA,60 g/mol)、四乙烯五胺(TEPA,189 g/mol)和两种聚乙烯亚胺600(PEI600g/mol; PEI1800g/mol)分别负载在MCM-41上制备氨基功能化介孔材料,研究其对CO₂的吸附性能和热稳定性.结果表明,除了EDA-MCM41,其他三种材料随着胺分子量增大CO₂吸附性能下降,但是热稳定性却有所提高,其中,TEPA-MCM41的吸附容量最大,达到2.7 mmol/g.同时发现,乙二胺在制备过程中随溶剂挥发而难以完全负载在MCM-41上.在纯N₂气氛和再生温度100 ℃条件下,经10次循环实验后,TEPA-MCM41的吸附能力下降了7.4%,而PEI600-MCM41和PEI1800-MCM41吸附能力保持不变,且质量变化在1%以内,表现出良好的再生稳定性.采用80%CO₂/20%N₂对吸附饱和的材料进行再生,四种材料的再生温度将提高到160 ℃以上,高分子量PEI600-MCM41和PEI1800-MCM41相比于TEPA-MCM41具有更好的热稳定性.     

Pd/NH2C3H6-MCM-41催化水介质中的碘苯Ullmann反应

 采用室温共缩聚法合成了胺基改性MCM-41杂化材料(NH2C3H6-MCM-41), 并以此材料为载体制备了负载型Pd催化剂 (Pd/NH2C3H6-MCM-41). 采用X射线衍射、核磁共振、红外光谱、透射电镜、X射线光电子能谱和N2吸附等方法对催化剂进行了表征. 结果表明,催化剂仍保持有MCM-41的孔结构,但其有序度随着 NH2C3H6-基团和Pd含量的增加而降低. 催化剂在以水为溶剂的碘苯偶联反应(Ullmann反应)中显示出优良的催化性能,联苯收率可达63%, 有望为清洁有机合成提供高效非均相催化剂. 胺基修饰的促进作用可归因于催化剂Pd分散度的提高和表面化学性质的改变.     

Selective synthesis of α-substituted β-keto esters from aldehydes and diazoesters on mesoporous silica catalysts

The titled reactions are effectively catalyzed on mesoporous silica MCM-41 but not on amorphous silica prepared from the same starting materials as those of MCM-41. The ordered porous structure was essential to generate the acid catalysis. Planting of Al or Ti ion improved not only the catalytic activity but also the tolerance to basic functional groups of substrates. The catalytic activity of Al- or Ti-MCM-41 was better than that of SnCl₂ and NbCl₅ in the homogeneous phase. In particular, Al (or Ti)-MCM-41 was characteristically active for the reaction of aldehydes with α-substituted diazoesters to give 2-substituted-3-oxo propionic acid esters.     

An investigation of gold adsorption from a binary mixture with selective mesoporous silica adsorbents

Gold-selective adsorbents were prepared from mesoporous MCM-41 silica by grafting organic amine groups (i.e., RNH2, R2NH, and R3N; R=propyl). NH2-MCM-41, NRH-MCM-41, and NR2-MCM-41 displayed strong affinity for gold and at 1 mmol/g loading adsorbed 0.40, 0.33, and 0.20 mmol/g of gold. Copper and nickel were not adsorbed on these adsorbents. Grafting surface chemical moieties introduces heterogeneity on an otherwise uniform MCM-41 pore surface and metal adsorption is best described by the Freundlich adsorption model. A series of binary adsorption equilibrium studies with NH2-MCM-41 containing 2.2 mmol RNH2/g shows that NH2-MCM-41 adsorbs only gold from solutions containing copper and nickel with an adsorption capacity of 0.6 mol of Au/mol of RNH2 (1.1 mmol of Au/g of NH2-MCM-41). Copper and nickel were not adsorbed by NH2-MCM-41 regardless of the solution concentration, composition, and pH (i.e., 2 to 4) in the presence of gold. The LeVan and Vermeulen adsorption model based on a single component Freundlich isotherm and corrected for the anion effect accurately predicted the binary adsorptions. The adsorbed gold was completely recovered by a simple acid wash and the recovered gold solution is 99% pure. The regenerated NH2-MCM-41 remained 100% selective for gold removal and exhibited the same adsorption capacity even after several uses.     

Synthesis of an Ni<Subscript>2</Subscript>P catalyst supported on Na-MCM-41 with highly activity for dibenzothiophene HDS under mild conditions

A novel and simple method to synthesize supported Ni₂P/Na(x)-MCM-41 catalysts (where x is the mass fraction of Na-to-MCM-41 in terms of percentage) at a lower reduction temperature by incorporation of Na was described. The catalysts were characterized by H₂ temperature-programmed reduction (H₂-TPR), X-ray diffraction (XRD), N₂ adsorption–desorption, CO uptake, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The effect of Na on the structure of catalysts and catalytic properties for the dibenzothiophene (DBT) hydrodesulfurization (HDS) was investigated, which confirmed that a suitable amount of Na can promote highly dispersed Ni₂P particles. The Na preferentially interacts with phosphate to generate the sodium phosphate and therefore suppresses the formation of stronger P–O–P bonds, which enables the phosphide catalyst to be easily formed at a lower reduction temperature. Compared with conventional phosphate (973–1273 K), the reduction temperature of Ni₂P/Na(x)-MCM-41 catalyst was relatively low (773 K). The Ni₂P/Na(x)-MCM-41 catalyst with x?=?1.0 showed the maximum DBT conversion of 91.6%, which is higher than that of Ni₂P/M41 without Na (80.3%).     

C18-MCM-41复合介孔材料的合成及其在固相微萃取中的应用

以十八烷基三氯硅烷为偶联剂,采用分步合成法合成了烷基官能化的介孔分子筛C18-MCM-41,用元素分析、傅立叶红外光谱(FT-IR)、X射线衍射(XRD)对合成的复合材料进行表征,结果表明,有机官能化后材料仍保持介孔材料的结构特性。以该材料为固相微萃取涂层材料对水中的多环芳烃(萘、蒽、菲)进行了分析,方法的线性范围分别为5.0~250、0.4~300、0.5~400μg/L,检出限分别为5.0、0.10、0.25μg/L,加标回收率在94.3%~104.4%之间,分析结果令人满意,说明C18-MCM-41介孔材料可作为涂层材料用于固相微萃取。     

Thermal stability of amine-functionalized MCM-41 in different atmospheres

In the present work, we report on the thermal stability of NH₂-MCM-41 hybrid material under different atmospheres (nitrogen and air). The thermal stability of this hybrid material is very important because of its common use in catalysis, adsorption, biomedical and biotechnological applications, based on mesoporous and aminopropyl functionalities. Samples were prepared by one pot co-condensation method with different loadings of 3-aminopropyltriethoxysilane (APTES). The thermal stability of hybrid samples (NH₂-MCM-41) heat treated in nitrogen and air at 30–800 °C has been investigated. Samples were synthesized under basic media in the presence of cetyltrimethylammonium bromide (CTABr) as structure-directing agent, tetraethyl orthosilicate as silica source, and APTES as functionalizing agent with molar composition of 0.055 CTABr:045 SiO₂:0.054 APTES:5.32 NH₄OH:14.99 H₂O at 50 °C for 24 h at pH 12.4. The obtained hybrid materials have been characterized by thermogravimetric analysis (TG), derivative thermogravimetric analysis, differential scanning calorimetry, X-ray powder diffraction, Fourier-transform infrared spectroscopy, transmission electron microscopy, and surface area determination by the BET method. Based on TG measurements of the treated samples, it was found out that the thermal stability varied greatly in different atmospheres.     

Amino-functionalized mesoporous silica modified glassy carbon electrode for ultra-trace copper(II) determination

This paper described a facile and direct electrochemical method for the determination of ultra-trace Cu²⁺ by employing amino-functionalized mesoporous silica (NH₂-MCM-41) as enhanced sensing platform. NH₂-MCM-41 was prepared by using a post-grafting process and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and fourier transform infrared (FTIR) spectroscopy. NH₂-MCM-41 modified glassy carbon (GC) electrode showed higher sensitivity for anodic stripping voltammetric (ASV) detection of Cu²⁺ than that of MCM-41 modified one. The high sensitivity was attributed to synergistic effect between MCM-41 and amino-group, in which the high surface area and special mesoporous morphology of MCM-41 can cause strong physical absorption, and amino-groups are able to chelate copper ions. Some important parameters influencing the sensor response were optimized. Under optimum experimental conditions the sensor linearly responded to Cu²⁺ concentration in the range from 5 to 1000 ng L⁻¹ with a detection limit of 0.9 ng L⁻¹ (S/N = 3). Moreover, the sensor possessed good stability and electrode renewability. In the end, the proposed sensor was applied for determining Cu²⁺ in real samples and the accuracy of the results were comparable to those obtained by inductively coupled plasma optical emission spectrometry (ICP-OES) method.     

A rational approach in the design of selective mesoporous adsorbents

Two MCM-41 derived adsorbents have been tailor-made for the separation of silver and copper ions using the hard-soft, acid-base (HSAB) principle as the design guideline. NH2-MCM-41 containing "hard" Lewis base adsorption sites (i.e., RNH2) was prepared for the adsorption of the "hard" Lewis acid, Cu2+, and SH-MCM-41 with a grafted "soft" thiolpropyl base was prepared for the selective removal of Ag+, a "soft" Lewis acid. Single- and binary-component adsorption studies were conducted at different metal concentrations, solution compositions, and pH values. The experimental results showed that SH-MCM-41 has excellent affinity and capacity for silver adsorption and adsorbed only the silver ions with copper remaining in the solution. The selectivity was not affected by the metal concentration and composition, anion, and pH. Under similar experimental conditions, NH2-MCM-41 selectively adsorbed copper from the binary solution. The selectivity of NH2-MCM-41 remained for the copper at different pH values, although the adsorption capacity diminished at lower pH values. The type of anions used affected copper adsorption on NH2-MCM-41 with an increased copper uptake in the presence of the sulfate ions. A simple Freundlich adsorption model was sufficient to describe metal adsorption on SH-MCM-41 and NH2-MCM-41, and the LeVan and Vermeulen model was successfully used to predict the adsorption capacity and selectivity for binary-component adsorptions.     

高纯度中孔分子筛MCM-41的合成与表征

用不同pH值的混合物制备了不同孔径的全硅MCM-41和不同金属离子取代的M-MCM-41(M=Al,Mn,Fe和V)分子筛.这些试样均呈现MCM-41的X射线粉末衍射特征峰和Ⅳ型氮气吸附等温线,但混有不同含量的无定形氧化硅.样品中MCM-41晶体的含量与溶胶的pH值和所用表面活性剂的碳链链长有关.骨架硅的金属离子取代降低了MCM-41的有序度,并且(100)面衍射峰强度从Al到V依次减弱.     

高骨架铝含量Al-MCM-41的合成

制备了不同Al含量的Al-MCM-41试样，其中Si/Al比值最小为3，即最高含铝量x~A~l=0.303。X射线粉末衍射(XRD)分析表明样品具有MCM-41的特征结构，氮气吸附研究表明，样品呈现Ⅳ型吸附等温线，具有孔径分布均一的中孔结构。文中还利用^2^7AlMASNMR研究了试样中Al的化学环境，结果表明，即使在高铝含量的情况下，样品中的铝原子仍以四配位结合在MCM-41的硅骨架上，未能检测出骨架外六配位铝的存在。文中还就Al含量对孔结构的影响以及Al-MCM-41形成机理作了讨论。     

Synthesis of [Si]-MCM-41 from TEOS and water glass: the water glass-enhanced condensation of TEOS under alkaline conditions

Mesoporous [Si]-MCM-41 molecular sieve systems have been fabricated by aging silica gels in CTAB both at RT and under hydrothermal conditions with or without stirring. For the synthesis involving water glass as a SiO₂ source, optimal conditions (100 °C, pH 10, crystallization time 2–3 days) gave reproducible, highly ordered [Si]-MCM-41 materials in multi gram scale with high lattice parameter values and BET surface areas. The synthesis with TEOS as silica source produced an inferior quality material. A novel synthesis route involving the use of mixtures of the two precursors gave [Si]-MCM-41 with improved structural (XRD) and microstructural (HRTEM) long-range order. Addition of small amounts of water glass to a TEOS-based synthesis gel under stirred conditions produced [Si]-MCM-41 with excellent mesoporosity, long-range microstructural order, XRD and S _BET properties. These properties are reminiscent of those for materials obtained from water glass as a sole SiO₂ source. The advantage of this route is that it gave high-quality materials at relatively lower temperatures (80 °C) and shorter crystallization times (6 h) after 21 h aging at RT. The variation of the XRD d ₁₀₀ peak position, BET and HRTEM properties with [TEOS]/[water glass] ratio revealed that a ratio = 3.95 gave optimal production of the highly ordered materials. The data suggests that water glass acts as a structure-directing agent for the TEOS and is incorporated into the final structure.     

Inorganic/organic mesoporous silica as a novel fiber coating of solid-phase microextraction

Mesoporous materials were employed as fast, sensitive and efficient fiber coatings of solid-phase microextraction (SPME) for the first time. Three micrometer as-synthesized C₁₆-MCM-41 particles were immobilized onto stainless steel wire with 100 μm coating thickness. In combination with high performance liquid chromatography (HPLC), extraction efficiency and selectivity of C₁₆-MCM-41 were investigated using aromatic hydrocarbons. Effect of extraction and desorption time, extraction temperature, stirring rate and ionic strength on extraction efficiency were examined. Aanalytical merits of SPME with C₁₆-MCM-41 coating were evaluated. The chromatographic peak area is proportional to the concentration of anthracene in the range 0.5-150 μg l⁻¹. The limit of detection was 0.05 μg l⁻¹ (S/N=3) and the relative standard deviation (R.S.D.) was 0.033%.     

MoO<Subscript>2</Subscript>(acac)<Subscript>2</Subscript> supported on MCM-41: An efficient and reusable catalyst for alkene epoxidation with <Emphasis Type="Italic">tert</Emphasis>-BuOOH

A new heterogeneous catalyst prepared by immobilization of MO₂(acac)₂ on Mobil Catalytic Material, MCM-41, is reported. This catalyst, MoO₂(acac)₂-MCM-41, was successfully applied for efficient epoxidation of olefins with tert-BuOOH in 1,2-dichloroethane as solvent. The catalyst was characterized by elemental analysis, FT-IR, UV-Vis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). This catalyst can be reused several times without significant loss of its catalytic activity.     

Rare earth (Eu, Tb) mesoporous hybrids with calix[4]arene derivative covalently linking MCM-41: Physical characterization and photoluminescence property

MCM-41 mesoporous silica has been functionalized with two kinds of macrocylic calixarene derivatives Calix[4] and Calix[4]Br (Calix[4]=P-tert-butylcalix[4]arene, Calix[4]Br=5.11,17.23-tetra-tert-butyl-25.27-bihydroxy-26.28-bibromopropoxycalix[4]arene) through condensation approach of tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as a template. Novel organic-inorganic mesoporous luminescent hybrid containing RE³⁺ (Eu³⁺, Tb³⁺) complexes covalently attached to the functionalized ordered mesoporous MCM-41, which are designated as RE-Calix[4]-MCM-41 and RE-Calix[4]Br-MCM-41, respectively, are obtained by sol-gel process. It is found that they all have high surface area, uniform in the mesostructure and good crystallinity. Measurement of the photoluminescence properties show the mesoporous material covalently bonded Tb³⁺ complexes (Tb-Calix[4]-MCM-41 and Tb-Calix[4]Br-MCM-41) exhibit the stronger characteristic emission of Tb³⁺ and longer lifetime than the corresponding Eu-containing materials Eu-Calix[4]-MCM-41 and Eu-Calix[4]Br-MCM-41 due to the triplet state energy of modified organic ligands Calix[4]-Si and Calix[4]Br-Si match with the emissive energy level of Tb³⁺ very well.     

Removal of Cr(VI) from aqueous solutions using EDCC-MCM-41: Isotherm,kinetics and thermodynamic evaluation

Abstract

EDCC-MCM-41, a novel ethylenediamine derivative of MCM-41 was synthesized from a sugar industry waste, bagasse fly ash. Studies were carried out on its ability to remove Cr(VI) from aqueous solution. Its performance was also compared with that of unmodified MCM-41 and an already known derivative NH₂-MCM-41 (both also synthesized from bagasse fly ash) at the same experimental conditions. Results show that the novel adsorbent produced a better sorption performance (adsorption capacity of 49.04?mg g^?1) than MCM-41 and NH₂-MCM-41 which produced adsorption capacities of 13.78?mg g^?1 and 25.29?mg g^?1 respectively. Thermodynamics, kinetics and isotherm studies confirm that the sorption process involving the novel adsorbent is favorable for Cr(VI) and can best be represented by pseudo-second-order kinetics model. The sorption process was also found to be multistep, involving both film diffusion and intraparticle diffusion into the pores on the adsorbent’s surface.

Abbreviations: BFA: Bagasse Fly Ash; MCM-41: Mobil Composition of matter no. 41; NH2-MCM-41: mine functionalized MCM-41; EDCC-MCM-41: Ethylenediamine grafted MCM-41; qe: Mass of material adsorbed at equilibrium per mass of adsorbent; qt: Mass of material adsorbed at any time t per mass of adsorbent; C0: The initial concentration; Ce: The residual concentration at equilibrium; Ct: Residual concentration at any time t; W: The weight of adsorbents; rRMSD: Root mean square deviation; R: Gas constant     

Surface characterization and catalytic evaluation of copper-promoted Al-MCM-41 toward hydroxylation of phenol

The Mobil Composition of Matter No. 41 (MCM-41) containing Cu and Al with Si/Al ratios varying from 100 to 10 and 1 to 6 wt.% of Cu was synthesized under hydrothermal and impregnation conditions, respectively. The samples were characterized by nitrogen adsorption–desorption measurements, X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS), temperature-programmed reduction (TPR), temperature-programmed desorption (TPD), and ²⁹Si and ²⁷Al magic-angle spinning–nuclear magnetic resonance (MAS–NMR) spectra. X-ray diffraction patterns indicate that the modified materials retain the standard MCM-41 structure. TPR patterns show the two-step reduction of Cu species. TPD study shows that Cu-impregnated Al-MCM-41 samples are more acidic than Al-MCM-41. From the MAS–NMR it was confirmed that most of the Al atoms are present tetrahedrally within the framework and some are present octahedrally in extraframework position. Impregnation of Cu shifted Al to the extraframework position. The catalytic activity of the samples toward hydroxylation of phenol in aqueous medium was evaluated using H₂O₂ as the oxidant at 80 °C. The effects of reaction parameters such as temperature, catalyst amount, amount of H₂O₂, and solvent were also investigated. Sample containing 4 wt.% copper-loaded Al-MCM-41-100 showed high phenol conversion (78%) with 68% catechol and 32% hydroquinone selectivity.