Efficient synthesis of isoindoles using supercritical carbon dioxide

Bicyclopyrroles were efficiently converted to the corresponding isoindoles by a retro Diels-Alder reaction in supercritical carbon dioxide. By adding ethylene gas as an oxygen scavenger, the isoindole yield was further improved.     

Microwave-induced synthesis of highly dispersed gold nanoparticles within the pore channels of mesoporous silica

Highly dispersed gold nanoparticles have been incorporated into the pore channels of SBA-15 mesoporous silica through a newly developed strategy assisted by microwave radiation (MR). The sizes of gold are effectively controlled attributed to the rapid and homogeneous nucleation, simultaneous propagation and termination of gold precursor by MR. Diol moieties with high dielectric and dielectric loss constants, and hence a high microwave activation, were firstly introduced to the pore channels of SBA-15 by a simple addition reaction between amino group and glycidiol and subsequently served as the reduction centers for gold nanoparticles. Extraction of the entrapped gold from the nanocomposite resulted in milligram quantities of gold nanoparticles with low dispersity. The successful assembly process of diol groups and formation of gold nanoparticles were monitored and tracked by solid-state NMR and UV-vis measurements. Characterization by small angle X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated that the incorporation of gold nanoparticles would not breakup the structural integrity and long-range periodicity of SBA-15. The gold nanoparticles had a narrow size distribution with diameters in the size range of 5-10 nm through TEM observation. The average particles size is 7.9 nm via calculation by the Scherrer formula and TEM measurements. Nitrogen adsorption and desorption isotherms gave further evidence that the employed method was efficient and gold nanoparticles were successfully incorporated into the pore channels of SBA-15.     

Asymmetric synthesis using hydrolytic enzymes in supercritical carbon dioxide

The use of hydrolytic enzymes in supercritical carbon dioxide (scCO₂), an environmentally friendly solvent with many uses, is an attractive approach to asymmetric synthesis: several examples are reviewed here.     

Biphasic synthesis of colloidal mesoporous silica nanoparticles using primary amine catalysts

Evanescent wave-cavity ring-down spectroscopy (EW-CRDS) is employed to characterize micellization of anionic surfactants and the related capability of removing cationic substance off the silica surface. Crystal violet (CV(+)) cationic dye is used as a molecular probe to effectively determine critical hemimicelle concentration (HMC) of surfactants on the surface. The HMC results are 1×10(-2), 4×10(-3), 8×10(-4), and 2.5×10(-4) mol/L for sodium sulfate salts with a carbon-chain length of C-10, C-12, C-14, and C-16, respectively. A stronger hydrophobic interaction results in a less concentration required to undergo micellization. The HMC values on the surface are about half of those in solution. When NaCl solution is added, the electrolyte helps reduce the electrostatic repulsion between the anionic sulfate heads to facilitate the surfactant aggregation, and thus, the subsequent HMC is reduced. Furthermore, the probable phase change for dye-surfactant interactions on the surface at the concentration below HMC is observed, and the desorption rates of CV(+) are measured as a function of concentration and carbon-chain length of surfactants above HMC. Given each surfactant concentration at its respective HMC, the corresponding desorption rates are along the order of C-12相似文献   

Synthesis of mesoporous silica nanobamboo with highly dispersed tungsten carbide nanoparticles

By controlling the interaction between cationic surfactant micelles and ammonium metatungstate during the formation of mesoporous silica structure, highly dispersed tungsten carbide (WC) nanoparticles of 2.0 nm in diameter on mesoporous silica nanospheres were synthesized at lower concentration of ammonium metatungstate. With additional ammonium metatungstate, a novel mesoporous silica nanobamboo structure was formed with bimodal size-distributed WC nanoparticles, in which 2.0 nm WC was homogeneously distributed in nanobamboo's mesoporous silica wall and those with larger diameter (10.0-20.0 nm) were only formed on the nanobamboo's inner surface and at its internodes. The mesoporous silica nanobamboo also had a very high tensile strength due to its bamboo-like structure.     

Solvation forces between silica bodies in supercritical carbon dioxide

We report Monte Carlo simulations of the solvation pressure between two planar surfaces, which represent the interface of spherical silica nanoparticles in supercritical carbon dioxide. Carbon dioxide (CO2) was modeled as an atomistic dumbbell or a spherical Lennard-Jones particle. The interaction between CO2 molecules and silica surfaces was characterized by the standard Steele potential with energetic heterogeneities representing the hydrogen bonds. The parameters for the solid-fluid interaction potentials were obtained by fitting our simulations to the experimental isotherms of CO2 sorption on mesoporous siliceous materials. We studied the dependence of the solvation force on the distance between planar silica surfaces at T = 318 K, at equilibrium bulk pressures p(bulk) ranging from 69 to 200 atm. At 69 atm, we observed a long-range attraction between the two surfaces, and it vanished when the pressure was increased to 102 and then 200 atm. The results obtained with different fluid models were consistent with each other. According to our observations, energetic heterogeneities of the surface have negligible influence on the solvation pressure. Using the Derjaguin approximation, we calculated the solvation forces between spherical silica nanoparticles in supercritical CO2 from the solvation pressures between the planar surfaces.     

Encapsulated ultrafine and highly dispersed molybdenum dioxide nanoparticles in hollow mesoporous silica spheres as an efficient epoxidation catalyst for alkenes

A facile post-synthetic strategy was developed to functionalize the preformed hollow mesoporous silica spheres by encapsulating the molybdenum dioxide (MoO₂) nanoparticles inside the interior cavity. Hollow mesoporous silica spheres were prepared and employed as carriers, and the encapsulation of MoO₂ nanoparticles was achieved through a one-pot hydrothermal protocol. After characterization, the encapsulated MoO₂ nanoparticles were certified to be ultrafine and highly dispersed, which greatly promoted the catalytic activity. The as-prepared catalysts were utilized in epoxidation of alkenes and exhibited as a promising catalyst in this reaction. After reacting for 10 h, the optimal catalyst MoO₂@SiO₂-1 achieved a conversion above 95% and selectivity above 95%, respectively. Moreover, the catalysts also exhibited good reusability, conversion of 78% and selectivity of 89% (reaction time 4 h) were still obtained after recycling for 5 times. Meanwhile, the employed facial and efficient hydrothermal approach could be expanded to other molybdenum modified heterogeneous catalysts in various applications.     

Sorption of butane, propane, ethane, methane, and carbon dioxide on asphaltene

Isotherms of sorption of butane, propane, ethane, methane, and carbon dioxide on an asphaltene sample of known elemental composition were measured. The effect of the pressure and temperature on the shape the sorption isotherms for all the adsorption systems studied was examined. The values of the initial heat of sorption were determined and compared to the energies of interaction of the molecules with asphaltene. The results obtained suggest that asphaltene is a swellable amorphous sorbent.     

Molecular level dispersed Pd clusters in the carbon walls of ordered mesoporous carbon as a highly selective alcohol oxidation catalyst

Ordered mesoporous carbon containing molecular-level dispersed Pd clusters in the carbon walls can be synthesized by the nanocasting pathway, which shows high selectivity for the oxidation of alcohols to aldehydes.     

Preparation of silica/perfluoroalkyl methacrylate polymer inorganic/organic particles in supercritical carbon dioxide

Silica/perfluoroalkyl methacrylate polymer (PHDFDMA) particles were prepared using various types of silica by polymerization in supercritical carbon dioxide. There are three steps in the fabrication of inorganic/organic hybrid composites: silane treatment, polymerization, and soxhlet extraction. After these steps, we observed the morphology of silica/PHDFDMA particles using field emission scanning electron microscope and transmission electron microscope. From these analyses, we can confirm that the silica/PHDFDMA core/shell particles were obtained when we used Ludox and silica gel as a silica template. On the other hand, core/shell particles were not formed when using fused silica and precipitated silica. In addition, to confirm the amount of polymer on silica, we performed an analysis using thermogravimetric analysis and electron probe micro-analyzer. In this case, PHDFDMA was approximately 20 wt.% on the silica gel and 40 wt.% on the Ludox, respectively. When using fused silica and precipitated silica as a template, amount of PHDFDMA on silica was maximum 5 wt.% and over 40 wt.%, respectively. From these results, to obtain enough PHDFDMA encapsulated silica particle, colloidal silica, Ludox is the best template in four different types of silica.     

Preparation of polydivinylbenzene microspheres in supercritical carbon dioxide using acetone as cosolvent

Monodisperse polydivinylbenzene (PDVB) microspheres with clean surface were prepared by precipitation polymerization without stabilizer in supercritical carbon dioxide using acetone as cosolvent. Effects of the cosolvent, reaction time and pressure, and monomer concentration on the polymerization were studied. It was found that the conversions in all polymerization systems were above 95%. Examination by scanning electron microscopy showed that reaction pressure, divinylbenzene concentration, and level of the cosolvent had pronounced effects on the morphology of the microspheres. When 6?～?7 ml of acetone was used in a reactor of 50 ml, monodisperse PDVB microspheres of around 2.1 μm in diameter were obtained. Thermal gravimetrical analysis showed the products were of good thermostability up to about 400 °C.     

Controlled synthesis of highly dispersed platinum nanoparticles in ordered mesoporous carbons

A novel route has been developed to fabricate ordered carbon mesoporous materials with well-dispersed, highly stable Pt nanoparticles of ca. 2-3 nm on the pore walls using platinum acetylacetonate as the co-feeding carbon and Pt precursor.     

Heterogeneous strong base catalysis in supercritical carbon dioxide by mesoporous alumina and sulfated mesoporous alumina

The development of solid strong base catalysts utilizable in green but acidic medium of scCO₂ is reviewed. The strong base sites on mesoporous alumina and sulfated mesoporous alumina that had been generated by severe treatment at 773 K under vacuum (10^?4 Torr) were not neutralized by the compressed Lewis acidic molecules of CO₂, promoting a representative strong base-catalyzed reaction of the Tishchenko reaction as well as a typical base-catalyzed reaction of the Knoevenagel reaction in scCO₂. Infrared spectroscopy of the adsorbed pyrrole, temperature-programmed desorption of CO₂, and the poisoning by a very weak Brönsted acid of methanol have revealed that the average strengths of the base sites on mesoporous alumina and sulfated mesoporous alumina are weaker than that on conventional γ-alumina like JRC-ALO-4, but that they have a small number of strong base sites which function even in scCO₂ medium. It was found that the addition of a slight amount of THF cosolvent into scCO₂ remarkably accelerates the Tishchenko reaction over sulfated mesoporous alumina; the reaction rate in the scCO₂–THF medium was 1.5-fold and 2-fold faster than those in ordinary organic solvents such as benzene and THF and that in pure scCO₂, respectively. The unique structures of mesoporous alumina and sulfated mesoporous alumina have been fully characterized by N₂ adsorption–desorption measurements and XRD analyses.     

One-step synthesis of highly dispersed gold nanocrystals on silica spheres

Highly dispersed gold nanocrystals decorating silica spheres were prepared from HAuCl4 and NaOH via a deposition-precipitation (DP) process, in which the isoelectric point (IEP) of the substrate was adjusted during sphere synthesis by interaction of the surface with ammonia molecules. Through the systematic variation of pH (4-8), reaction temperature (65-96 degrees C), and time (10-30 min), a superior product with small (2-5 nm), homogeneously distributed gold crystals was obtained at pH 7 and a reaction temperature of 96 degrees C. These materials will offer enhanced performance as catalysts and contrast enhancers in biomedical imaging.     

The synthesis of polyacrylamide nanoparticles in supercritical carbon dioxide

Polyacrylamide nanoparticles, 50 to 200 nm, were created by inverse emulsion polymerization of acrylamide in supercritical carbon dioxide. The cross-linked polyacrylamide was produced by intermolecular imidization.     

超临界二氧化碳中组氨酸催化合成环状碳酸酯

研究了超临界二氧化碳中α-氨基酸催化二氧化碳与环氧化物环加成反应合成环状碳酸酯,发现组氨酸的催化活性最高.在二氧化碳压力为8MPa、反应温度130℃、反应时间48h、组氨酸加入量为0.8mol%的条件下,二氧化物可以顺利的与各种环氧化物反应,以高的选择性和产率生成相应的环状碳酸酯.     

Preparation of micron-size polystyrene particles in supercritical carbon dioxide

The dispersion polymerization of styrene in supercritical CO₂ utilizing poly(1,1-dihydroperfluorooctyl acrylate) (p-FOA) as a polymeric stabilizer was investigated as well as poly(1,1-dihydroperfluorooctyl methacrylate) (p-FOMA). The resulting high yield (>85%) of spherical and relatively uniform polystyrene (PS) particles with micron-size range (2.9–9.6 µm) was formed for 40 h at 370 bar using various amounts of p-FOA and p-FOMA as a stabilizer with good stability until the end of the reaction. The particle diameter was shown to be dependent on the weight percent of added stabilizer. Previously, we reported that p-FOA was not effective for the dispersion polymerization of styrene as a stabilizer. Here, we find that p-FOA can indeed be an effective stabilizer for the dispersion polymerization of styrene in supercritical CO₂, but the pressure necessary to achieve good stability is higher than pressure used by us previously. This study suggests the possibility that fluorinated acrylic homopolymers are effective for the dispersion polymerization of various kinds of monomers as a stabilizer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2429–2437, 1999     

Histidine-catalyzed synthesis of cyclic carbonates in supercritical carbon dioxide

The coupling reaction of carbon dioxide with epoxides was investigated using naturally occurring α-amino acids as the catalyst in supercritical carbon dioxide and it was found that L-histidine is the most active catalyst. In the presence of 0.8 mol% of L-histidine at 130 °C under 8 MPa of CO₂, the reaction of carbon dioxide with epoxides proceeded smoothly, affording corresponding cyclic carbonates in good to excellent yields.     

Catalytic performance of silica-supported chromium oxide catalysts in ethane dehydrogenation with carbon dioxide

The oxidative dehydrogenation of ethane into ethylene by CO₂ over a series of silica-supported chromium oxide catalysts was investigated. The results showed that the catalysts were effective for the reaction and CO₂ in the feed promoted the catalytic activity. The 5%Cr/SiO₂ catalyst exhibited the excellent performance with 30.7% ethane conversion and 96.5% ethylene selectivity at 700^oC. ESR and UV-DRS were used to probe the active sites and the species with high valent states (Cr⁵⁺ and/or Cr⁶⁺) were found to be important for the reaction.