基于金属有机和元素有机化合物参与的新合成方法学的研究

包括下列研究工作:碱催化形成碳-碳双键的合成方法学;双烯化反应的合成方法学;立体选择性地控制合成烯炔和丙烯类化合物的合成方法学;连串反应的合成方法学.

Fabrication and characterization of tungsten-containing mesoporous silica for heterogeneous oxidative desulfurization

A series of functional,tungsten-containing mesoporous silica materials（W-SiO2） have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction（XRD）,transmission electron microscopy（TEM）,Raman spectroscopy,Fourier transform infrared spectra（FTIR）,diffuse reflectance spectra（DRS）,and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm（2.9 nm）.The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene（DBT）,which is able to achieve deep desulfurization within 40 min under the optimal conditions（Catalyst（W-SiO2-20）= 0.01 g,temperature = 60℃,oxidant（H2O2）= 20 μL）.For the removal of different organic sulfur compounds within oil,the ability of the catalyst（W-SiO2-20） under the same conditions to remove sulfur compounds decreased in the order：4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.

One-pot cascade conversion of xylose to furfuryl alcohol over a bifunctional Cu/SBA-15-SO3H catalyst

The conversion of hemicellulose-derived xylose to furfuryl alcohol is a practical procedure for producing value-added chemicals from biomass.In this study,a bifunctional Cu/SBA-15-SO3 H catalyst was employed for the one-pot catalytic conversion of xylose to furfuryl alcohol with a yield of up to 62.6% at the optimized conditions of 140℃,4 MPa,and for 6 h in a biphasic water/n-butanol solvent.A high reaction temperature resulted in further hydrogenation to 2-methyl furan,while a high hydrogen pressure led to a side hydrogenation reaction to xylitol.The biphasic solvent allowed xylose solvation as well as furfuryl product extraction.The acidic-SO3 H sites and Cu sites co-existed,maintained a balance,and cooperatively catalyzed the cascade conversion.Excessive acidic sites and large pores could promote the xylose conversion,although a low furfuryl alcohol yield was obtained.This catalytic system could be potentially applied to the one-pot synthesis of furfuryl alcohol from hemicellulose-derived xylose.

Microwave radiation one-pot synthesis of chloropropyl-functionalized mesoporous MCM-41

Chloropropyl-functionalized mesoporous MCM-41（MCM-41-（CH2）3Cl） was synthesized in alkaline medium by the microwave radiation one-pot method, using cetyltrimethy-lammoniumbromide （CTAB） as novel template, tetraethoxysilane （TEOS） as silica source, and chloropropyltriethoxysilane （C1PTES） as the coupling agent. The microstructure of MCM-41-（CH2）3Cl was characterized by the means of X-ray diffraction （XRD）, nitrogen absorption-desorption, Fourier transform infrared spectroscopy （FT-IR）, scanning electron microscopy （SEM）, and transmission electron microscopy （TEM）. The results show that a successful synthesis of MCM-41-（CH2）3Cl with well structure is obtained. The optimal microwave power is 120 W and the best microwave time is 50 rain. The dosage of chloropropyltriethoxysilane on the structure of chloropropyl-functionalzed MCM-41 was also investigated. It is found that the chloropropyltriethoxysilane volume between 0.8 mL and 1.6 mL is favorable for the formation of highly ordered MCM-41-（CH2）3Cl mesostructure.

Synthesis of Substituted u-Oxo-bis[tetra-phenyl porphyrinatoiron] Compounds from Free Base Porphyrins by a One-pot Method

A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4-7H2O and TRPPH2, the molar ratio of FeSO4-7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93% 98% could be obtained under the following optimal conditions： the reaction time of FeSOn-7H2O with TRPPH2 was about 10 h, the molar ratio of FeSOn-7H2O/TRPPH2 about 5 ： 1, and the volume ratio of H2O/DMF exceeded 2 ： 1. Further research indicated that only TRPPFeCI were formed once FeSOn-7H2O was replaced by FeCl2-4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method.

One-pot synthesis of cyclic aldol tetramer and ?, β-unsaturated aldol from linear aldehydes using quaternary ammonium combined with sodium hydroxide as catalysts

One-pot synthesis of cyclic aldol tetramer and α, β-unsaturated aldol from C3-C8 linear aldehydes using phase-transfer catalyst（PTC）, quaternary ammonium, combined with sodium hydroxide as catalysts was investigated. Butanal was subjected for detail investigations to study the effect of parameters. It was found that the selectivity of cyclic aldol tetramer depends greatly on the operating conditions of the reaction, especially the PTC/butanal molar ratio. The average selectivity of 2-hydroxy-6-propyl-l, 3, 5-triethyl-3-cyclohexene-1-carboxaldehyde（HPTECHCA） was 54.41% using tetrabutylammonium chloride combined with 14%（mass fraction） Na OH as catalysts at 60 ℃for 2 h with a PTC-to-butanal molar ratio of 0.09：1. Pentanal was more likely to generate cyclic aldol tetramer compared with other aldehydes under the optimum experimental conditions. Recovery of the PTC through water washing followed by adding enough sodium hydroxide from the washings was also demonstrated.

Synthesis of 2-Methyl-4-methoxyaniline from o-Nitrotoluene Using Pt/C and Acidic Ionic Liquid as Catalyst System

2-Methyl-4-methoxyaniline （MMA） was synthesized by one-pot method through the hydrogenation and Bamberger rearrangement of o-nitrotoluene in methanol using acidic ionic liquid and 3% Pt/C as catalyst system. The effects of ionic liquid type, dosage of ionic liquid and 3% Pt/C, reaction temperature and reaction pressure on o-nitrotoluene conversion and MMA selectivity were investigated. The results indicated that the imidazolium-based acidic ionic liquid which contains SO3H-functionalized cation showed higher selectivity to MMA than other acidic ionic liquids used in this work. Using 1-（propyl-3-sulfonate）-3-methylimidazolium hydrosulfate （[HSO3-pmim][HSO4]） as the acid catalyst, the selectivity to MMA was as high as 67.6% at 97.8% of o-nitrotoluene conversion. As 3% Pt/C increased from 0.01 g to 0.025 g, the selectivity to MMA decreased from 73.4% to 62.5%, because of the hydrogenation of intermediate o-methyl-phenylhydroxylamine to o-toluidine becoming more dominant. An increase in hydrogen pressure also had obviously dramatic effect in lowering the MMA selectivity. After easy separation from the products, the catalyst system could be reused at least 3 times.

Amberlyst-15 in PEG：A novel catalytic system for the facile and efficient one-pot synthesis of benzothiazolo-[2,3-b]-quinazolinone derivatives

A simple and convenient approach for the synthesis of tetraheterocyclic benzothiazolo-[2,3-b]-quinazolin-1-ones has been developed utilizing the MCR methodology, which involves the condensation of 2-aminobenzothiazole, cyclic-diketones and various aldehydes using Amberlyst-15 in PEG 400 as an environmentally benign and reusable catalyst system. Environmental benignity, recyclability, cost-effectiveness, easy workup and excellent yields are the major attributes of this one-pot procedure.

Facile and efficient one-pot synthesis of 2-arylbenzoxazoles using hydrogen tetrachloroaurate as catalyst under oxygen atmosphere

In this paper, we presented a novel method for the facile and efficient one-pot synthesis of 2-arylbenzoxazoles, which were directly synthesized from 2-aminophenol and aldehydes catalyzed by hydrogen tetrachloroaurate (HAuCl4·4H2O) under an oxygen atmosphere with anhydrous tetrahydrofuran (THF) as solvent or in solvent-free condition. The results show that this method could bring excellent yields as high as 96%. THF was proven to be the best choice among several solvents screened and the reaction was tolerated with a variety of aromatic aldehydes possessing electron-donating or withdrawing groups. The advantages of the present method lie in catalytic process using economic and environmentally benign dioxygen as oxidant.

One-pot synthesis of Li_3VO_4@C nanofibers by electrospinning with enhanced electrochemical performance for lithium-ion batteries

Electrospinning is firstly used to one-pot synthesis of Li3VO4@C nanofibers in a large scale. Although with the presence of organic sources in synthesis process, the pure phase Li3VO4 with superior nanofibrous morphology is still successfully obtained through adjusting different heat treatment processes and different vanadium sources. The prepared Li3VO4@C nanofibers exhibit a unique structure in which nanosized Li3VO4 particles are uniformly embedded in amorphous carbon matrix. Compared with LiBVO4/C powder, Li3VO4@C nanofibers display enhanced reversible capacity of 451 mAhg^-1 at 40mAg^-1 with an increased initial coulombic efficiency of 82.3%, and the capacity can remain at 394 mAh g ^-1 after 100 cycles. This superior electrochemical performance can be attributed to its unique structure which ensures a high reactivity by nanosized Li3VO4, more stable electrode/electrolyte interface by carbon encapsulation, improved electronic conductivity and buffered volume changes by flexible carbon matrix. The electrospinning technology provides an effective method to obtain high performance Li3VO4 as a promising anode material for lithium-ion batteries.

A facile one-pot synthesis of supercubes of Pt nanocubes

A facile one-pot synthetic strategy is developed to prepare high-quality Pt supercubes. The as-synthesized Pt supercubes are composed of the uniform Pt nanocubes arranged in a primitive cubic structure. The shape and size of the Pt superparticles are readily tuned by varying the structures of pyridyl-containing ligands used in the synthesis. The co-presence of CO and nitrogen-containing ligands is critical to the formation of Pt supercubes. While CO molecules play an important role in the synthesis of Pt nanocube, introducing nitrogen-containing ligands is essential to the successful assembly of those nanocubes into Pt supercubes. Our systematic studies reveal that the electrostatic attraction between positively charged ligands and nega- tively charged Pt nanocubes is the main driving force for the assembly of Pt nanocubes into supercubes. More importantly, the ligands within the Pt supercubes are readily removed at relatively low expected to exhibit unique size-selective catalysis. temperature to yield surface-clean supercubes which are

One-pot synthesis of Bi2Se3 nanostructures with rationally tunable morphologies

Shape control has proven to be a powerful and versatile means of tailoring the properties of Bi2Se3 nanostructures for a wide variety of applications. Here, three different Bi2Se3 nanostructures, i.e., spiral-type nanoplates, smooth nanoplates, and dendritic nanostructures, were prepared by manipulating the supersaturation level in the synthetic system. This mechanism study indicated that, at low supersaturation, defects in the crystal growth could cause a step edge upon which Bi2Se3 particles were added continuously, leading to the formation of spiral-type nanoplates. At intermediate supersaturation, the aggregation of amorphous Bi2Se3 particles and subsequent recrystallization resulted in the formation of smooth nanoplates. Furthermore, at high supersaturation, polycrystalline Bi2Se3 cores formed initially, on which anisotropic growth of Bi2Se3 occurred. This work not only advances our understanding of the growth mechanism but also offers a new approach to control the morphology of Bi2Se3 nanostructures.

Ultrathin ZnO membranes a few atomic layers in thickness

For the first time we fabricated ZnO membranes with thicknesses of 2.4 nm by a facile one-pot synthesis in aqueous solution.The crystal analysis revealed that the hexagonal ZnO membranes were about 10 atomic layers in thickness.The ZnO membranes bent,scrolled,intersected with each other,and self-assembled to particles in micrometre size.The hierarchical assemblies showed sponge-like structures with room inside.In the growth process,a cationic polyelectrolyte was utilized to modulate growth behavior of the ZnO crystals.As a result,the preferred growth direction of ZnO membranes is along 0110,which was perpendicular to[0001]growth direction in a typical hydrothermal synthesis.The growth mechanism of the membranes was also discussed.