Baeyer-Villiger oxidation of cyclohexanone to epsilon-caprolactone in airlift sonochemical reactor

Baeyer-Villiger oxidation of cyclohexanone to epsilon-caprolactone was studied in a new type reactor--the airlift loop sonochemical reactor. The reactor plays a synergistic effect of sonochemsity and higher oxygen transfer rate. The influences of ultrasound intensity, reaction temperature, the molar ratio of benzaldehyde to cyclohexanone and oxygen gas flow rate on the conversion and selectivity of cyclohexanone were investigated and discussed. Under ultrasound, the amount of benzaldehyde can be reduced from 75% to 67%. Ultrasound not only intensified the rates of reactions but also increased the yield of product. The optimized operation conditions are listed as follows: the reaction temperature is 30 degrees C, the molar ratio of cyclohexanone to benzaldehyde is 1:2, the oxygen gas flow rate is 1.15 cm s(-1), and ultrasonic irradiations 2h at 40 kHz, 2.25 W cm(-2). Under the optimum operation conditions, the average molar yield of epsilon-caprolactone comes up to 87.7%.     

Baeyer–Villiger oxidation of cyclohexanone to ε-caprolactone in airlift sonochemical reactor

Baeyer–Villiger oxidation of cyclohexanone to ε-caprolactone was studied in a new type reactor – the airlift loop sonochemical reactor. The reactor plays a synergistic effect of sonochemsity and higher oxygen transfer rate. The influences of ultrasound intensity, reaction temperature, the molar ratio of benzaldehyde to cyclohexanone and oxygen gas flow rate on the conversion and selectivity of cyclohexanone were investigated and discussed. Under ultrasound, the amount of benzaldehyde can be reduced from 75% to 67%. Ultrasound not only intensified the rates of reactions but also increased the yield of product. The optimized operation conditions are listed as follows: the reaction temperature is 30 °C, the molar ratio of cyclohexanone to benzaldehyde is 1:2, the oxygen gas flow rate is 1.15 cm s⁻¹, and ultrasonic irradiations 2 h at 40 kHz, 2.25 W cm⁻². Under the optimum operation conditions, the average molar yield of ε-caprolactone comes up to 87.7%.     

Ultrasonic effects on electroorganic processes. Part 27. Electroreduction of acrylonitrile at suspended lead particle-electrode

Ultrasonic effect on the electroreduction of acrylonitrile at suspended lead particle-electrode was examined. The product selectivity for adiponitrile, which was formed as the corresponding hydrodimeric product along with propionitrile as the hydromonomeric one in the cathodic reduction of acrylonitrile, was increased by addition of lead particles as a particle-electrode, and moreover the selectivity was further increased under ultrasonication. This ultrasonic effect is rationalized as due to not only mass transport of lead particles to the feeder cathode but also an increase in the effective surface area of particle-electrode by ultrasonic dispersion. A mechanism for the ultrasonic effect is discussed in detail on the basis of the reaction system.     

Improved synthesis of sucrose fatty acid monoesters under ultrasonic irradiation

Sucrose fatty acid esters were synthesized by the transesterification of sucrose with aliphatic esters under ultrasound irradiation in good yield (?73%). The optimum reaction conditions for the transesterification reaction include a molar ratio of sucrose to fatty acid ethyl ester of 2:1 and the use of a 13% mol anhydrous K₂CO₃ catalyst. The optimum reaction temperature was set at 70 °C, the optimum reaction time was 2 h, and the optimum reaction pressure was 11 kPa. The reaction had excellent monoester selectivity. The proportion of monoester (6-monoester + 6′-monoester) in the purified products was up to 92–95% via flash column chromatography over silica gel, the ratios of 6-monoester/6′-monoester are 2.1–2.7, and the sucrose monoesters were identified by HPLC–MS, NMR and IR.     

Ultrasound assisted enzyme catalyzed hydrolysis of waste cooking oil under solvent free condition

The present work demonstrates the hydrolysis of waste cooking oil (WCO) under solvent free condition using commercial available immobilized lipase (Novozyme 435) under the influence of ultrasound irradiation. The process parameters were optimized using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound intensity. It has been observed that ultrasound-assisted lipase-catalyzed hydrolysis of WCO would be a promising alternative for conventional methods. A maximum conversion of 75.19% was obtained at mild operating parameters: molar ratio of oil to water (buffer pH 7) 3:1, catalyst loading of 1.25% (w/w), lower ultrasound power 100 W (ultrasound intensity – 7356.68 W m⁻²), duty cycle 50% and temperature (50 °C) in a relatively short reaction time (2 h). The activation energy and thermodynamic study shows that the hydrolysis reaction is more feasible when ultrasound is combined with mechanical agitation as compared with the ultrasound alone and simple conventional stirring technique. Application of ultrasound considerably reduced the reaction time as compared to conventional reaction. The successive use of the catalyst for repetitive cycles under the optimum experimental conditions resulted in a loss of enzymatic activity and also minimized the product conversion.     

Electrochemical promotion of NO reduction by C3H6 and CO on Rh/YSZ catalyst — Electrodes

The selective catalytic reduction of NO by propylene or CO in the presence of excess oxygen is a system of great technological importance. The effect of Electrochemical Promotion (or Non-faradaic Electrochemical Modification of Catalytic Activity — NEMCA) was used to promote this reaction (C₃H₆ or CO/NO/O₂) on Rh/YSZ catalyst-electrodes. It was found that both the catalytic activity and the selectivity of the Rh catalyst-electrode is affected dramatically upon varying its potential with respect to a Au pseudoreference electrode. Catalytic rate enhancements up to 15000% and 6000% were observed in the case of NO reduction by propylene, while the product selectivity to N₂ production is affected significantly (up to 200%) upon positive potential application. Remarkable promotion of the catalytic activity was also observed in the case of NO reduction by CO, since up to 20-fold increases both in catalytic rates and in NO conversion were obtained under NEMCA conditions. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Ultrasound assisted intensification of biodiesel production using enzymatic interesterification

Ultrasound assisted intensification of synthesis of biodiesel from waste cooking oil using methyl acetate and immobilized lipase obtained from Thermomyces lanuginosus (Lipozyme TLIM) as a catalyst has been investigated in the present work. The reaction has also been investigated using the conventional approach based on stirring so as to establish the beneficial effects obtained due to the use of ultrasound. Effect of operating conditions such as reactant molar ratio (oil and methyl acetate), temperature and enzyme loading on the yield of biodiesel has been investigated. Optimum conditions for the conventional approach (without ultrasound) were established as reactant molar ratio of 1:12 (oil:methyl acetate), enzyme loading of 6% (w/v), temperature of 40 °C and reaction time of 24 h and under these conditions, 90.1% biodiesel yield was obtained. The optimum conditions for the ultrasound assisted approach were oil to methyl acetate molar ratio of 1:9, enzyme loading of 3% (w/v), and reaction time of 3 h and the biodiesel yield obtained under these conditions was 96.1%. Use of ultrasound resulted in significant reduction in the reaction time with higher yields and lower requirement of the enzyme loading. The obtained results have clearly established that ultrasound assisted interesterification was a fast and efficient approach for biodiesel production giving significant benefits, which can help in reducing the costs of production. Reusability studies for the enzyme were also performed but it was observed that reuse of the catalyst under the optimum experimental condition resulted in reduced enzyme activity and biodiesel yield.     

Preparation of highly ordered mesoporous AlSBA-15-SO3H hybrid material for the catalytic synthesis of chalcone under solvent-free condition

Single-step preparation of SBA-15 materials functionalized with both propylsulfonic acid groups and aluminum species (AlSBA-15-SO₃H) was carried out by hydrothermal treatment of a mixture of aluminum isopropoxide, 3-mercaptopropyltriethoxysilane, tetraethoxysilane, and triblock copolymer surfactant. At Si/Al molar ratio of 11-96, the materials exhibited well-ordered hexagonally arranged mesopores with pore diameter of ca. 9 nm, BET surface area of 546.9-666.0 m² g⁻¹, and pore volume of 0.82-1.03 cm³ g⁻¹. As-prepared AlSBA-15-SO₃H was successfully used in the Claisen-Schmidt condensation reaction of benzaldehyde with acetophenone to produce chalcone under solvent-free condition, and the influence of the reaction parameters including temperatures, molar ratios of BZD to APN, and aluminum loadings were considered during the chalcone synthesis procedure. It showed that AlSBA-15-SO₃H exhibited significantly high catalytic activity and selectivity, outperforming the reference catalysts such as sulfuric acid, ZSM-5, and acidic MCM-49. In addition, the catalytic stability and regeneration of AlSBA-15-SO₃H was studied.     

Mechanistic study of the formation of quercetine cycloadducts under microwave conditions: a theoretical approach

A theoretical mechanistic investigation of the cycloaddition reaction of quercetine with 3,5-di-tert-butyl-o-quinone has been carry out employing density functional calculations at M06-2X/6-31G(d,p) level of theory. This computational study was performed in order to gain insight in the energetic and structural parameters that rule the observed experimental selectivity in the synthetised cyclodimers obtained under classical heating and microwave irradiation conditions and the influence of the solvent on their chemical reactivity. The effect of the solvent in the selectivity was studied implicitly using the polarisable continuum model in absence and presence of one explicit solvent’s molecule. The theoretical results explain the main issues of the classical heating and the MWI reaction and suggest that thermal effects are directly responsible for the reaction selectivity observed. The comparison of the mechanistic pathway and the non-covalent interactions, shows that a dioxane assisted mechanism can explain the observed experimental selectivity of the two synthetised compounds, thus the dioxane molecule play a catalytic role on this hetero Diels–Alder reaction.     

Dry etching of MgCaO gate dielectric and passivation layers on GaN

MgCaO films grown by rf plasma-assisted molecular beam epitaxy and capped with Sc₂O₃ are promising candidates as surface passivation layers and gate dielectrics on GaN-based high electron mobility transistors (HEMTs) and metal-oxide semiconductor HEMTs (MOS-HEMTs), respectively. Two different plasma chemistries were examined for etching these thin films on GaN. Inductively coupled plasmas of CH₄/H₂/Ar produced etch rates only in the range 20-70 Å/min, comparable to the Ar sputter rates under the same conditions. Similarly slow MgCaO etch rates (∼100 Å/min) were obtained with Cl₂/Ar discharges under the same conditions, but GaN showed rates almost an order of magnitude higher. The MgCaO removal rates are limited by the low volatilities of the respective etch products. The CH₄/H₂/Ar plasma chemistry produced a selectivity of around 2 for etching the MgCaO with respect to GaN.     

Electrochemical promotion of Pt during the oxidation of ethanol

The reaction of ethanol oxidation has been examined over a Pt polycrystalline film deposited on an yttria stabilized zirconia (YSZ) electrochemical reactor. Experiments were carried out at 325 °C at atmospheric total pressure and under open and closed circuit conditions. It was found that the electrochemically-induced change in the catalytic rate of ethanol consumption is four orders of magnitude higher than the rate of ion transport through the solid electrolyte. The galvanostatic transient behavior of the consumption rates of ethanol and oxygen and of the formation rates of carbon dioxide and acetaldehyde have been also recorded. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Non-faradaic electrochemical modification of catalytic activity in solid electrolyte cells

The catalytic activity and selectivity of metal catalysts used as electrodes in high temperature solid electrolyte cells can be altered dramatically and in a reversible manner. This is accomplished by electrochemically supplying oxygen anions onto catalytic surfaces via polarized metal-solid electrolyte interfaces. Oxygen anions, forced electrochemically to adsorb on the metal catalyst surface, alter the catalyst work function in a predictable way and lead to reaction rate increases as high as 4000%. Changes in catalytic rates typically exceed the rate of O^2– transport to or from the catalyst surface by 10²-3 · 10⁵. Significant changes in product selectivity have been also observed. The case of several catalytic reactions in which this new phenomenon has been observed is presented and the origin of the phenomenon is discussed.     

大气压非平衡等离子体甲烷干法重整零维数值模拟

大气压非平衡等离子体由于其独特的非平衡特性,可为甲烷和二氧化碳稳定温室气体分子活化和重整提供非热平衡和活化环境.本文采用了零维等离子体化学反应动力学模型,考虑了详细的CH₄/CO₂等离子体化学反应集,重点研究了反应气体CH₄/CO₂摩尔分数(5%—95%)对大气压非平衡等离子体甲烷干法重整制合成气和重要含氧化合物的影响.首先,给出了进料气体不同体积比时电子密度和温度随时间的演化规律,结果表明初始甲烷摩尔分数的提高有利于获得较高的电子密度和电子温度.随后,讨论了主要自由基和离子数密度在不同的甲烷摩尔分数下随着时间的变化规律,并给出了反应气体的转化率、合成气体和重要含氧化合物的选择性.此外,还明确了合成气和含氧化合物主要生成和损耗的化学反应路径,发现甲基和羟基是合成含氧化合物的关键中间体.最后,归纳总结给出了主要等离子体粒子之间的总体等离子体化学反应流程图.     

Synthesis of Cu2ZnSnSe4 compound powders by solid state reaction using elemental powders

The solid state reaction method was used to synthesize single phase and near stoichiometric Cu₂ZnSnSe₄ compound from elemental Cu, Zn, Sn and Se powders in a quartz tube furnace under an Ar flow at atmospheric pressure. These elemental powders were initially milled using zirconia balls. The α-CuSe phase was present in all of the milled powders because of the mechanical alloying effect between the Cu and Se powders. The solid state reaction mechanism was examined for the synthesis process. The phase analysis suggested that the Cu₂ZnSnSe₄ powder crystallized into the stannite phase with a high degree of crystallinity after near stoichiometric molar ratios of the powders was reacted at 500 °C for 6 h. This study showed that the solid state reaction method was a straightforward technique for the synthesis of the Cu₂ZnSnSe₄ compound powders from the elemental powders.     

氯铝酸离子液体的酸性及其催化烷基化反应研究

分别采用吡啶探针和乙腈探针红外光谱法研究了氯铝酸离子液体的酸性,结合固体酸表征方法,研究了离子液体的酸性对吡啶探针各振动模式的影响。发现当氯铝酸离子液体AlCl₃的摩尔分数x为0.4～0.5时,离子液体显弱Lewis酸性,强碱性吡啶探针分子能很好地表征离子液体的酸性,而弱碱性乙腈探针分子只适用于表征酸性较强的离子液体。考察了氯铝酸离子液体酸强度对苯与长链烯烃烷基化反应的影响,结果发现,AlCl₃的摩尔分数x≤ 0.5时,离子液体没有催化活性;x>0.55时,随着离子液体酸性的增强,烯烃转化率升高,但2位烷基苯选择性下降。结合离子液体的酸强度对烷基化反应机理进行初步分析认为具有催化活性的物质是强Lewis酸Al₂Cl-₇。     

CdTe量子点功能化玻片的制备及其对Pb2+浓度的检测

通过羟基化和氨基硅烷化处理,得到表面接枝氨基的玻片载体。水相合成巯基乙酸修饰的CdTe量子点(CdTe-TGA),采用EDC/NHS活化反应,将量子点偶联到氨基化玻片表面,制备出具有荧光性能的功能化玻片。考察了量子点与EDC的量比、活化时间、偶联温度以及偶联时间对偶联效果的影响。结果表明,在量子点与EDC的量比为1:30、活化时间1 h、偶联温度30 ℃、偶联时间4 h条件下获得的功能化玻片具有最佳的荧光性能。将该条件下制备的功能化玻片用于水溶液中Pb²⁺的浓度检测,得到玻片相对荧光猝灭强度随Pb²⁺浓度变化的线性曲线,线性范围为1.0×10^-9~4.0×10^-8mol·L^-1,检出限为3.8×10^-9mol·L^-1,且具有良好的选择性。该方法可以灵敏而准确地检测Pb²⁺浓度。     

Ruthenium-Catalyzed Hydrogenation of Nitrobenzene in a Supercritical Carbon Dioxide Medium

Catalytic hydrogenation of nitrobenzene in the medium of isopropanol and supercritical (SC) carbon dioxide using hypercrosslinked polystyrene-based ruthenium catalysts was studied. Carrying out this process in a SC-CO₂ medium allows higher reaction rates and selectivity for the target product, aniline.     

Intensification of heterogeneously catalyzed Suzuki-Miyaura cross-coupling reaction using ultrasound: Understanding effect of operating parameters

Palladium-catalyzed Suzuki-Miyaura cross-coupling reaction is a significant reaction for obtaining industrially important products. The current research work deals with intensification of reaction of 4-bromoanisole and phenylboronic acid catalyzed with 5 wt% Pd/C (5% by weight Pd supported on C available as commercial catalyst) using ultrasound and more importantly, without use of any additional phase transfer catalyst. Heterogeneous catalyst has been selected in the present work so as to harness the benefits of easy separation and the possible limitations of heterogeneous operation are minimized by introducing ultrasonic irradiations. The effect of operating parameters such as ultrasound power, temperature, catalyst loading and molar ratio on the progress of reaction has been investigated. It has been observed that an optimum power, temperature and catalyst loading exist for maximum benefits whereas higher molar ratio was found to be favourable for the progress of the reaction. Also, the use of ultrasound reduced the reaction time from 70 min required in conventional approach to only 35 min under conditions of frequency of 22 kHz, power dissipation of 40 W and catalyst loading as 1.5 mol% (refers to total quantum of catalyst used in the work) in ethanol-water system under ambient conditions. The work also demonstrated successful results at ten times higher volume as compared to the normally used volumes in the case of simple ultrasonic horn. Overall, the work has successfully demonstrated process intensification benefits obtained due to the use of ultrasound for heterogeneously catalyzed Suzuki-Miyaura cross-coupling reaction.     

Ultrasound-assisted reaction of 2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl bromide with potassium salt of curcumin under PTC conditions

Reaction of 2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl bromide with potassium salt of curcumin [bis-1,7-(3'-methoxy-4'-hydroxy)phenyl-5-hydroxy-1,4,6-heptatrien-3-one] under either thermal or high pressure conditions affect the labile substrate, curcumin, thus resulting in drastic reduction in the yields of the glucosides. This drawback could be effectively overcome by carrying out the biphasic reaction in the presence of a phase transfer catalyst under the effect of ultrasound. The reaction under the sonochemical conditions was faster and resulted in the increased yield of the glucoside products. The reaction was investigated in detail with a view to optimizing the yield of the glucosides. The detailed study clearly indicated the important role of the nature and quantity of the phase transfer catalyst employed in the reaction. Also, the selectivity with respect to the formation of mono- or di-beta-glucosides under both mono- and biphasic reaction conditions was clearly discernable. The study establishes a simple synthetic protocol for the glucoside derivatives of curcumin in high yields and selectivity using ultrasonic waves.     

羟胺浸提-可见分光光度法测定土壤无定形铁

采用羟胺浸提-可见分光光度法测定了土壤无定形铁。与草酸-草酸铵浸提法相比,羟胺浸提法排除磁性铁矿物的干扰,克服了原方法实验结果偏高的缺点。该法相对标准偏差RSD<2.0％,回收率为97.5％～101.5％,实验的精密度稍好于草酸-草酸铵法,且具有快速、简便、显色时间短等特点。同时进行了土壤厌氧恒温培养实验,结果显示铁还原启动期、快速期和稳定期的还原速率分别为0.030～0.053 g·d-1·kg-1,0.186～0.333 g·d-1·kg-1和0.015～0.030 g·d-1·kg-1。回归分析结果表明,羟胺浸提法测定结果与土壤培养实验中测得的快速期铁还原速率显著相关(r=0.990 7,p＜0.01),说明在浸提土壤无定形铁的过程中,羟胺法比草酸-草酸铵法具有更好的选择性。