Removal of Copper‐phthalocyanine from Aqueous Solution by Cationically Templated MCM‐41 and MCM‐48 Nanoporous Adsorbents

The effect of cationic template on the adsorption of copper-phthalocyanine-3,4’,4",4"’-tetrasulfonic acid tetra-     

Tubular Morphology of Mesoporous Silica MCM‐41

We investigated detailed conditions for synthesizing the tubular form of MCM‐41 mesoporous aluminosilicate. The method is the delayed neutralization method in which the rate of neutralization is one of the controlling factors. Rapid neutralization results in the particulate form while gradual neutralization leads to tubules. It is found that the tubule morphology has several sub‐categories. There are thick‐walled, think‐walled hollow tubular MCM‐41 and solid core tubules. There are void structures in the channel framework that makes the nanochannels to be effectively interconnected.     

Efficient Liquid‐Phase Oxidation of Diphenylmethane to Benzophenone over Vanadium‐Containing MCM‐41 Catalysts

The liquid‐phase oxidation of diphenylmethane with tert‐butylhydroperoxide has been studied using vanadium‐containing MCM‐41 materials, which were prepared by direct hydrothermal (V‐MCM‐41) and wet impregnation (V/MCM‐41) methods. These catalysts were characterized in detail by ICP‐AES, N₂‐sorption, XRD, FT‐IR, ²⁹Si and ⁵¹V NMR, TPD of ammonia, TPR of hydrogen, and chemisorption of oxygen. Both series of catalyst show good catalytic results, which are attributed to their highly ordered mesoporous structure, large BET surface area as well as the presence of easily accessible vanadium‐oxygen species as active centers in the catalyst. Further, V‐MCM‐41 exhibit superior catalytic activity (based on turnover number) than V/MCM‐41 mainly due to well‐dispersed tetrahedral vanadium‐oxygen species with higher oxidation ability. The effect of reaction parameters, i.e., temperature, time, solvent, etc. were investigated. Catalyst recycling test reveals good stability with only slight extent of leaching during the reaction.     

Mesoporous Molecular Sieve MCM‐41 as a Novel and Efficient Catalyst to Synthesis of 2‐Substituted Benzimidazoles

o‐Phenylenediamine derivatives readily react with benzoyl chloride derivatives in the presence of MCM‐41 as catalyst to yield 2‐substituted benzimidazoles in very good yields.     

Mesoporous Silica MCM‐41 Supported N‐Heterocyclic Carbene‐Pd Complex for Heck and Sonogashira Coupling Reactions

Heterocyclic carbene‐Pd complex was anchored onto the mesoporous silica MCM‐41 which exhibits high catalytic activity in Heck reaction under phosphine free reaction conditions for the reaction of iodo/bromoarenes with olefinic compounds such as butyl acrylate, isopropyl acrylate and styrene. This catalytic system also showed high activity for Sonogashira coupling reaction of various aryl halides under copper, phosphine and solvent‐free reaction conditions. The air and thermally stable catalyst were reused several times without significant loss of its activity. High efficiency of the catalyst along with its recycling ability and the rather low Pd‐loading demonstrated in both Heck and Sonogashira coupling reactions are the merits of the presented catalyst system.     

Synthesis of Spiro‐dihydrofuran in the Presence of a Novel and Reusable Nanocatalyst Cu (II)‐Glycerol/MCM‐41

The use of supported Cu complex on mesoporous as a novel, efficient, heterogeneous, reusable and green catalyst for the synthesis of spiro‐dihydrofuran derivatives is reported. This methodology is effective for the reaction of dimedone with a wide range of aldehyde in the presence of BrCN and triethylamine. The structure of catalyst was characterized by different techniques such as EDX, SEM, TGA, ICP‐OES, XRD, TEM, FT‐IR, and BET. The recycled nanocatalyst was used at least five times with no significant loss of its activity.     

Palladium chloride anchored on organic functionalized MCM‐41 as a catalyst for the Heck reaction

Palladium chloride was grafted to amino‐functionalized MCM‐41 to prepare heterogeneous catalysts. XRD, N₂ adsorption–desorption isotherms, IR, ¹³C and ²⁹Si cross‐polarization magic‐angle spinning NMR spectroscopy and XPS techniques were employed to characterize the catalytic materials. The heterogeneous palladium catalyst exhibited excellent catalytic activity for the Heck vinylation of iodobenzene with methyl acrylate, giving 92% yield of methyl cinnamate in the presence of N‐methylpyrrolidone (NMP) and triethylamine (Et₃N). The stability of the heterogeneous catalyst was also studied in detail. The catalytic tests showed that the palladium leaching correlated to solvent, base and palladium loading. The heterogeneous catalyst exhibited excellent stability towards loss of activity and palladium leaching was not observed during six recycles in the presence of toluene and Na₂CO₃. Copyright © 2007 John Wiley & Sons, Ltd.     

Vapor‐Phase Reaction of Citronellal over Mesoporous Molecular Sieves MCM‐41 and Zeolites

The vapor‐phase reaction of citronellal (CTN) at 220 °C and atmospheric pressure has been studied using mesoporous molecular sieves and zeolites in a fixed‐bed reactor. The primary products included isopulegol (IPG), menthone, and pulegol with subsequent reactions to form cyclic hydrocarbons. The CTN conversion and the product selectivity depend on the acidity and the textural property of catalysts. Lewis and/or Brönsted acid sites are essential for catalyzing this reaction. An increase of SiO₂/Al₂O₃ mol ratio diminishes the acid amount of all catalysts and enhances both the surface area and the structural order of MCM‐41. The catalytic activity follows the order of MCM‐41 > HZSM‐5 > Hβ > USY, in accordance with the relative total acid amount except that of MCM‐41. Despite its low acidity, Si‐MCM‐41 exhibits the best catalytic performance due to its uniform mesopores, large surface area and good stability; the CTN conversion and the IPG yield attain 91.9% and 58.6%, respectively, after at least 25 h time‐on‐stream.     

MCM‐41‐Supported Bidentate Phosphine Rhodium Complex: An Efficient and Recyclable Heterogeneous Catalyst for the Hydrosilylation of Olefins

MCM‐41‐supported bidentate phosphine rhodium complex (MCM‐41‐2P‐RhCl₃) was conveniently synthesized from commercially available and cheapγ‐aminopropyltriethoxysilane via immobilization on MCM‐41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. It was found that the title complex is a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity.     

Liquid Phase Hydrogenation of t,t,c‐1,5,9‐Cyclododecatriene over Ni/MCM‐41 and Ni/SiO2 Catalysts

Ni‐loaded pure siliceous and aluminosilicate MCM‐41 (Ni/MCM‐41) and nickel‐loaded silica (15Ni/SiO₂) were synthesized via wet impregnation and were characterized by various techniques. The H₂ consumption in the TPR analysis was found to be proportional to the Ni amount in the calcined samples. After reduction the average Ni particle sizes of 15Ni/MCM‐41 and 15Ni/SiO₂ were 9–12 and 16 nm, respectively, by means of XRD and TEM measurements. All catalysts owned weak and intermediate Lewis acid sites that increased slightly with increasing the Ni amount and the Al content. In the liquid phase hydrogenation of t,t,c‐1,5,9‐cyclododecatriene over Ni/MCM‐41, the catalytic activity was parallel to the Ni content and enhanced slightly with the acid amount of the catalysts. Consequently, it was proposed that the Ni metallic sites contributed the major effect to the catalytic activity while the Lewis acid sites promoted a small but significant influence on the catalytic performance. It is noteworthy that all 15Ni/MCM‐41 catalysts exhibited remarkably higher activity than that of the conventional 15Ni/SiO₂ catalyst.     

Sonochemical synthesis of library benzodiazepines using highly efficient molecular ionic liquid supported on Fe‐MCM‐41 nanocomposites as a recyclable catalyst

In this study, library substituted benzodiazepines was synthesized using molecular ionic liquid supported on Fe‐MCM‐41 nanocomposites (Fe‐MCM‐41‐IL). This protocol using ultrasound provided advantages such as rapid, clean conversion and simplicity in experimental setup that led to rapid generation of benzodiazepines under mild condition. The catalyst can be easily isolated by using an external magnetic field and reused in the next reaction up to six cycles without obvious activity decreasing.     

Synthesis and characterization of MCM‐41‐Biurea‐Pd as a heterogeneous nanocatalyst and using its catalytic efficacy in C–C,C–N and C–O coupling reactions

MCM‐41‐Biurea‐Pd is introduced as a new, heterogeneous and reusable catalyst for C–C and C–heteroatom bond formation between various aryl halides, phenols and amines, in the presence of Ph₃SnCl (Stille reaction) in PEG‐400 as a green solvent at room temperature. The structure of the functionalized MCM‐41 was analysed using various techniques.     

Control of Wall Thickness and Extraordinarily High Hydrothermal Stability of Nanoporous MCM‐41 Silica

Wall thickness of siliceous MCM‐41 could be controlled systematically up to 36.1 Å. A reasonable model explaining formation of thicker MCM‐41 walls, not enlarging pore channel is proposed on the basis of TGA and ¹³C MAS NMR data of samples. Thermal restructuring process under mild basic condition favors the silica redeposition on silica wall and building up thicker wall. Most mesostructure of calcined MCM‐41 with thicker wall was retained even after hydrothermal treatment in boiling water for 14 days. To our best knowledge, the excellent hydrothermal stability of the MCM‐41 silica reported herein has not been described before and facilitates practical applications of mesoporous molecular sieves in future.     

Dehydration of Castor Oil over NaHSO4/MCM‐41 Catalyst Modified by n‐Dodecyltriethoxysilane

n‐Dodecyltriethoxysilane (DTEOS) modified NaHSO₄/MCM‐41 catalysts (silanized catalysts) were synthesized by different impregnation sequences and evaluated in the liquid‐phase dehydration of castor oil. The samples were evaluated by X‐ray diffraction, nitrogen adsorption‐desorption, SEM, TEM, FT‐IR spectroscopy, XPS, ²⁹Si MAS NMR spectroscopy, contact angle measurements, NH₃‐TPD, and pyridine‐FT‐IR spectroscopy. The analyses demonstrated that silanization enhanced the hydrophobicity of the catalysts, and the impregnation sequence of silanized catalysts had a significant effect on the NaHSO₄ dispersion, surface area, acid distribution, and hydrophobicity of the silanized catalysts. The catalytic activity of the silanized catalysts was much higher than that of NaHSO₄/MCM‐41. Among the silanized catalysts, the catalyst prepared by simultaneous impregnation with DTEOS and NaHSO₄ showed the highest iodine value of 141.8 [g(I₂) per 100 g] and lowest hydroxyl value of 11.3 [mg(KOH) · g^–1].     

Detection of NADH and Ethanol at Titanium Containing MCM‐41 with Low Overpotential

Titanium‐containing MCM‐41 (Ti‐MCM‐41) modified glassy carbon electrode (GCE) can exhibit an excellent electrocatalytic activity towards the oxidation of β‐Nicotinamide adenine dinucleotide (NADH). A dramatic decrease in the overvoltage of NADH oxidation reaction is observed at 0.28 V vs. SCE. The application in the amperometric biosensing of ethanol using alcohol dehydrogenase enzyme (ADH) also has been demonstrated with this material. The proposed sensor shows a highly sensitivity, an acceptable reproducibility and a good stability. The linear range of ethanol is 25–1000 μM and the detection limit is 8.0 μM. Ti‐MCM‐41 modified electrode not only can be used to detect the concentration of NADH in biochemical reaction, but also as the potential matrix for the construction of dehydrogenases sensor.     

Asymmetric Transfer Hydrogenation Catalyzed by Mesoporous MCM‐41‐Supported Chiral Ru‐Complex

Chiral N‐sulfonyldiamine was successfully anchored on mesoporous MCM‐41 silica. The MCM‐41‐supported chiral N‐sulfonyldiamine was used as an efficient heterogeneous chiral ligand in the asymmetric transfer hydrogenation of ketones. This heterogeneous system offered satisfactory enantioselectivities up to 94 % with excellent conversions.     

Low Potential Detection of NADH at Titanium‐Containing MCM‐41 Modified Glassy Carbon Electrode

Titanium‐containing MCM‐41 (Ti‐MCM‐41) modified glassy carbon electrode (GCE) can exhibit an excellent electrocatalytic activity towards the oxidation of β‐Nicotinamide adenine dinucleotide (NADH). A dramatic decrease in the over‐voltage of NADH oxidation reaction is observed at 0.28 V (vs. SCE). The modified electrode is found to be stable and reproducible. The electrode shows a linear response for a wide range of 10–1200 μM NADH and the detection limit is 8.0 μM. Ti‐MCM‐41 mesoporous molecular sieves provide an efficient matrix for development of NADH biosensors and the prepared electrode not only can be used to detect the concentration of NADH in biochemical reaction, but also as the potential matrix of the construction of dehydrogenases biosensor.     

Detailed Structural Characterizations of SBA‐15 and MCM‐41 Mesoporous Silicas on a High‐Resolution Transmission Electron Microscope

Using high‐resolution transmission electronic micrograph (HR‐TEM) observation, one can clearly see the pore geometry of the MCM‐41 and SBA‐15 mesoporous silicas to determine that their pore shapes are hexagonal and round, respectively. With the perpendicular orientations of the nanochannels to the electron beam, parallel line images of the (100) and (110) repeating spacings were observed. In the SBA‐15 mesoporous silicas, there are byproducts of the granular silica and disordered mesostructures, attributed to the weak hydrogen interactions between Pluronic 123 blockcopolymer and the silica species. There are also many different and significant +π disclination defects in SBA‐15 and MCM‐41 surfactant‐silica composites. The SBA‐15 with a thicker silica wall is more stable under irradiation by high‐energy electron beams compared to MCM‐41, which has thinner wall thickness. Some carbon nanostructure impurities were found in some carbon films on the metal grids.     

Synthesis of Fe‐MCM‐41 from silatrane and FeCl3 via sol–gel process and its epoxidation acivity

An iron‐containing mesoporous molecular sieve, or Fe‐MCM‐41, was successfully synthesized the via sol–gel technique using silatrane and FeCl₃ as the silicon and iron sources, and was characterized using various techniques. Many factors were investigated, namely, reaction temperature and time, calcination rate, and iron amount in the reaction mixture. It was found that the optimum conditions in which to synthesize Fe‐MCM‐41 was to carry out the reaction at 60 °C for 7 h using a 1 °C min^?1 calcination rate and a 550 °C calcination temperature. The catalytic activity and selectivity of styrene epoxidation using hydrogen peroxide showed that the selectivity of the styrene oxide reached 65% at a styrene conversion of 22% over the 1%wt catalyst. Copyright © 2008 John Wiley & Sons, Ltd.     

MCM‐41‐Immobilized [Rh(cod)OCH3]2 Complex – A Hybrid Catalyst for the Polymerization of Phenylacetylene and Its Ring‐Substituted Derivatives

The immobilization of [Rh(cod)OCH₃]₂ (cod = cycloocta‐1,5‐diene) on mesoporous molecular sieves MCM‐41 provides the first inorganic‐type hybrid catalyst, which affords heterogeneous polymerization of phenylacetylene and its ring‐substituted derivatives, – 2‐fluorophenylacetylene, 4‐fluorophenylacetylene, and 4‐pentylphenylacetylene – into readily isolable high‐molecular‐weight (M̄_w from 50 000 to 180 000) substituted polyvinylenes of high cis‐transoid structure. The activity of this catalyst is compared with that of homogeneous catalyst [Rh(cod)OCH₃]₂.