水中脉冲放电产生过氧化氢及其影响因素

采用介质涂覆的球-筒电极结构,用以脉冲电压条件下在水中产生放电,通过比色法检测放电产生的过氧化氢,研究了不同电压脉冲幅值、脉冲宽度（储能电容的大小）、水的电导率以及脉冲频率对过氧化氢产生速率的影响,实验结果表明过氧化氢的产率随电压脉冲幅值的增大而增大。当电压脉冲幅值足够高时,水中放电由流注放电形式转换为电弧放电形式,此时过氧化氢产率也大幅提高,而在相同电压条件下,随水的电导率的增大,过氧化氢的产率减小。在相同电压下,脉冲频率的增大,导致放电平均功率增大,水中放电产生过氧化氢的浓度提高。在3.3 W功率时,120 min后水中过氧化氢浓度达到0.2 mmol/L,从而证明了所用电极结构的优越性。     

Destabilization of Thiolated Gold Clusters for the Growth of Single‐Crystalline Gold Nanoparticles and Their Self‐Assembly for SERS Detection

Thiolate‐protected gold nanoclusters with high chemical stability are exploited extensively for fundamental research and utility in chosen applications. Here for the first time, the controlled destabilization of extraordinarily stable thiolated gold clusters for the growth of single‐crystalline gold nanoparticles (AuNPs) is demonstrated, which was achieved simply via the oxidation of surface‐protecting thiolates into disulfides by hydrogen peroxide under basic condition. By combining with our experimental observations over the entire destabilization and growth process, the new growth mechanism from clusters to AuNPs is revealed by density functional theory (DFT) calculations. It is found that the size of AuNPs decreases with the increase of hydrogen peroxide concentration due to the generation of more nuclei at the higher hydrogen peroxide concentrations. In addition, the preparation of AuNPs is tuned by changing the concentration of hydrogen peroxide, and they are self‐assembled into microspheres via an evaporation‐mediated process, which can induce strong plasmonic coupling between adjacent AuNPs for ultrasensitive surface‐enhanced Raman scattering detection. The present work demonstrates a facile route to functionalize and engineer AuNPs via controlling the reaction conditions and the ratio of precursors, and thus bring new possibilities for using more clusters as precursors to construct novel nano/microstructures for various applications.     

BPR氧化减色法测定过氧化氢亨利常数

利用冷阱收集气-液平衡管出来的气相过氧化氢,以及氯化血红素(Hemin)催化下溴邻苯三酚红(bromopyrogallolred,BPR)被过氧化氢氧化减色的分光光度法检测,测定了温度依赖的过氧化氢亨利常数。在10~35℃的范围内,过氧化氢亨利常数KH(mol·L-1·atm-1)表达为lnKH=a/T-b,其中a=7269±22,b=13·26±0·08,T为温度(K)。过氧化氢溶解焓ΔH为60·43±0·18kJ·K-1·mol-1。     

Kinetics and mechanisms of the sonolytic destruction of non-volatile organic compounds: investigation of the sonochemical reaction zone using several OH* monitoring techniques

This study investigates the sonolytic degradation mechanism of non-volatile organic compounds and reaction sites for its degradation using various tools that allow OH* to be monitored, such as: the spin-trapping method of OH* detection using non-volatile nitrone trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the hydrogen peroxide analytical methods and the p-chlorobenzoic acid (pCBA)-probe method. These methods can successfully monitor OH* produced during sonochemical processes, and identify the major reaction sites involving OH* of the three proposed reaction zones--within the cavity, in the bulk solution, and at the gas-liquid interfacial (shell) region. The patterns of hydrogen peroxide accumulation under the various conditions suggest that peroxides pre-form at the interfacial region, but the self-scavenging reaction by hydrogen peroxide simultaneously takes place in the same region. The simultaneously measured peroxide concentration, in the absence and presence of DMPO, and that of the DMPO-OH adduct indicated the peroxide production and DMPO-OH adduct formation reaction occur at the shell region. The sonolytic destruction efficiency of ultrasound coupled with Fe(II) has been also investigated. The coupled Fe(II)/ultrasound process was found to enhance the OH* production rate by 70% compared to the ultrasound process alone due to the reaction of Fe(II) with sonochemically produced hydrogen peroxide (Fenton's reaction). This accelerated reaction was also found to occur at the shell region rather than in the bulk solution. The enhancement effect of Fe(II)/ultrasound was also examined using pCBA as a probe. 2.8-fold and 3.6-fold increases of the pCBA degradation rate were observed at Fe(II) concentrations of 10 and 20 microM, respectively.     

Catalytic activity of copper (II) oxide prepared via ultrasound assisted Fenton-like reaction

Copper (II) oxide nanoparticles were synthesized in an ultrasound assisted Fenton-like aqueous reaction between copper (II) cations and hydrogen peroxide. The reactions were initiated with the degradation of hydrogen peroxide by ultrasound induced cavitations at 0 °C or 5 °C and subsequent generation of the OH radical. The radical was converted into hydroxide anion in Fenton-like reactions and copper hydroxides were readily converted to oxides without the need of post annealing or aging of the samples. The products were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Brunauer–Emmett–Teller (BET) surface area analysis. Catalytic activity of the nanoparticles for the hydrogen peroxide assisted degradation of polycyclic aromatic hydrocarbons in the dark was tested by UV–visible spectroscopy with methylene blue as the model compound. The rate of the reaction was first order, however the rate constants changed after the initial hour. Initial rate constants as high as 0.030 min⁻¹ were associated with the high values of surface area, i.e. 70 m²/g. Annealing of the products at 150 °C under vacuum resulted in the decrease of the catalytic activity, underlying the significance of the cavitation induced surface defects in the catalytic process.     

孔雀石绿-铁(Ⅱ)体系催化动力分光光度法测定雨水中微量过氧化氢

基于在pH 4.0的H₂SO₄介质中,Fe（Ⅱ）对H₂O₂氧化孔雀石绿褪色反应的催化作用,建立了一种在常温下测定H₂O2浓度的催化光度分析方法。在孔雀石绿吸收峰618nm波长处测得的吸光度降低值（△A）与过氧化氢浓度在0—50μmol·L^-1范围内呈线性相关,回归方程为△A=0.0171C+0.0191,检出限为1.0μmol·L^-1（s/n=3）。本法可以方便、快捷的用于雨水中微量过氧化氢的测定,结果满意。     

A new development of dyestuffs degradation system using ultrasound

Dyestuffs are often present in industrial wastewaters and can consist of hazardous substances which have a serious impact on the environment and personal health. This report describes a system developed to degrade these substances using sonochemical reactions. Ultrasonic frequencies of 118, 224, 404 and 651 kHz and power input values of 11.4, 29.0 and 41.5 W were tested on Rhodamine B and Orange II dyestuff solutions in order to find the best degradation conditions. The ultrasonic irradiation of air-saturated solutions produces free radicals that combine and generates hydrogen peroxide, and compared to the production of hydrogen peroxide when irradiating water, a decrease was found during the irradiation to dyestuff solutions, indicating that some of the free radicals were consumed in the dyestuffs degradation process. The effects of the ultrasonic irradiation conditions on the pH, nitric and nitrous acid formations as well as the total organic carbon value (TOC) were also investigated. For the ultrasonic frequencies of 224, 404 and 651 kHz, the degradation rates were very similar, however, the 118 kHz system presented a degradation rate of about one-third that of the higher frequencies for both dyestuffs. The Rhodamine B solutions were decolorized within 2 h of ultrasonic irradiation for all systems with the exception of the 118 kHz one. For Orange II, except for the 118 kHz system, all solutions were decolorized within 4 h of ultrasonic irradiation. All reactions were carried out at 25 degrees C and the total ultrasonic irradiation time was 10 h.     

Ultrasound assisted phase-transfer catalytic epoxidation of 1,7-octadiene - a kinetic study

An ultrasound assisted phase-transfer catalyzed epoxidation of 1,7-octadiene is greatly enhanced by using a cocatalyst of phosphotungstic acid in the presence of hydrogen peroxide in an organic solvent/aqueous solution two-phase medium. An active intermediate of the catalyst (Q3PW12(O)nO40, where Q = R4N+) produced from the reaction of phosphotungstic acid, hydrogen peroxide, and Aliquat 336. A rational mechanism of epoxidation is proposed to account for the reaction from the experimental evidence. The organic-phase reactions, including two series reactions, are the rate-controlling steps to produce two products, viz., 1,2-epoxy-7-octene and 1,2,7,8-diepoxyoctane. The kinetics of epoxidation, including the characteristics of the catalyst and the effect of the amount of cocatalyst, agitation speed, quaternary ammonium salts, amount of Aliquat 336, amount of hydrogen peroxide, amount of chloroform, pH value, organic solvents, and temperature on the conversion of 1,7-octadiene were investigated in detail. A kinetic model was built, from which a pseudo-first-order rate law is sufficient to describe the behavior of the reaction.     

水中脉冲放电产生过氧化氢及其影响因素

采用介质涂覆的球-筒电极结构,用以脉冲电压条件下在水中产生放电,通过比色法检测放电产生的过氧化氢,研究了不同电压脉冲幅值、脉冲宽度(储能电容的大小)、水的电导率以及脉冲频率对过氧化氢产生速率的影响,实验结果表明过氧化氢的产率随电压脉冲幅值的增大而增大。当电压脉冲幅值足够高时,水中放电由流注放电形式转换为电弧放电形式,此时过氧化氢产率也大幅提高,而在相同电压条件下,随水的电导率的增大,过氧化氢的产率减小。在相同电压下,脉冲频率的增大,导致放电平均功率增大,水中放电产生过氧化氢的浓度提高。在3.3 W功率时,120 min后水中过氧化氢浓度达到0.2 mmol/L,从而证明了所用电极结构的优越性。     

The effect of hydrogen peroxide on polishing removal rate in CMP with various abrasives

The effect of hydrogen peroxide in chemical mechanical planarization slurries for shallow trench isolation was investigated. The various abrasives used in this study were ceria, silica, alumina, zirconia, titania, silicon carbide, and silicon nitride. Hydrogen peroxide suppresses the polishing of silicon dioxide and silicon nitride surfaces by ceria abrasives. The polishing performances of other abrasives were either unaffected or enhanced slightly with the addition of hydrogen peroxide. The ceria abrasives were treated with hydrogen peroxide, and the polishing of the work surfaces with the treated abrasive shows that the inhibiting action of hydrogen peroxide is reversible. It was found that the effect of hydrogen peroxide as an additive is a strong function of the nature of the abrasive particle.     

Understanding the mechanism of DNA deactivation in ion therapy of cancer cells: hydrogen peroxide action*

Changes in the medium of biological cells under ion beam irradiation has been considered as a possible cause of cell function disruption in the living body. The interaction of hydrogen peroxide, a long-lived molecular product of water radiolysis, with active sites of DNA macromolecule was studied, and the formation of stable DNA-peroxide complexes was considered. The phosphate groups of the macromolecule backbone were picked out among the atomic groups of DNA double helix as a probable target for interaction with hydrogen peroxide molecules. Complexes consisting of combinations including: the DNA phosphate group, H₂O₂ and H₂O molecules, and Na⁺ counterion, were considered. The counterions have been taken into consideration insofar as under the natural conditions they neutralise DNA sugar-phosphate backbone. The energy of the complexes have been determined by considering the electrostatic and the Van der Waals interactions within the framework of atom-atom potential functions. As a result, the stability of various configurations of molecular complexes was estimated. It was shown that DNA phosphate groups and counterions can form stable complexes with hydrogen peroxide molecules, which are as stable as the complexes with water molecules. It has been demonstrated that the formation of stable complexes of H₂O₂-Na⁺-PO₄ ^- may be detected experimentally by observing specific vibrations in the low-frequency Raman spectra. The interaction of H₂O₂ molecule with phosphate group of the double helix backbone can disrupt DNA biological function and induce the deactivation of the cell genetic apparatus. Thus, the production of hydrogen peroxide molecules in the nucleus of living cells can be considered as an additional mechanism by which high-energy ion beams destroy tumour cells during ion beam therapy.     

Main reaction process simulation of hydrogen gas discharge in a cold cathode electric vacuum device

Based on the related theory of plasma discharge process and the COMSOL multiphysics software, and considering the corresponding boundary conditions, the related reaction types in the hydrogen plasma discharge were simulated and analysed, and the main reactions of hydrogen discharge in small electric vacuum components at low pressure and weak ionization were confirmed. Among the 21 types of reactions in hydrogen discharge process, 11 of them play important roles under low pressure and weak ionization in cold cathode electric vacuum device. The simulated results are consistent with the test result.     

A novel sodium iodide and ammonium molybdate co-catalytic system for the efficient synthesis of 2-benzimidazoles using hydrogen peroxide under ultrasound irradiation

The reaction of aldehydes and o-phenylenediamine for the preparation of 2-benzimidazoles has been studied using hydrogen peroxide as an oxidant under ultrasound irradiation at room temperature in this paper. The combination of substoichiometric sodium iodide and ammonium molybdate as co-catalysts, together with using small amounts of hydrogen peroxide, makes this transformation very efficient and attractive under ultrasound. Thus, a mild, green and efficient method is established to carry out this reaction in high yield.     

Influence of particles on sonochemical reactions in aqueous solutions

Numerous publications deal with the possible application of ultrasound for elimination of organic pollutants as a tool for water pollution abatement. Most of the experiments were performed in pure water under laboratory conditions. For developing technologies that hold promise it is necessary to investigate the effect of ultrasound in natural systems or waste water where particulate matter could play an important role. In this paper the influence of quartz particles (2-25 microm) on the chemical effects of ultrasound in aqueous system using a high power ultrasound generator (68-1028 kHz, 100 W, reactor volume 500 ml) is reported. In pure water in dependence on particle size, concentration and frequency the formation rate of hydrogen peroxide under Ar/O2 (4:1) shows a maximum using 206 kHz in presence of 3-5 microm quartz particles (4-8 g/l). Under these conditions the yield of peroxide is higher than without quartz. Additionally under N2/O2 (4:1) besides hydrogen peroxide the formation of nitrite/nitrate was measured. Compared to pure water quartz particle depressed the formation of nitrite/nitrate up to 10-fold but not the formation of H2O2. According to the results of H2O2 formation the elimination of organic compounds by sonolysis (206 kHz) and the influence of quartz particles were investigated. As organic compounds salicylic acid, 2-chlorobenzoic acid and p-toluenesulfonic acid were used. The influence of quartz on the oxidation of organic compounds (206 kHz) is similar to that on the formation of H2O2.     

On the possibility of realization of reactions in the regime of superintense bubble boiling

The possibility of occurrence of various chemical reactions during superintense bubble boiling due to the formation of shock waves and cavitation was demonstrated. More than 20 individual liquids, mixtures thereof, solutions of dyes and inducators, bromoform, etc., were tested. The formation of hydrogen peroxide during SBB in distilled water was investigated. It was demonstrated that the nature of the heater material plays an important role. A critical character of the dependence of the hydrogen peroxide yield on the power applied to the heater was revealed. SBB in aqueous solutions of ethanol was shown to produce high-boiling compounds, primarily ethyl cellosolve and acetyl cellosolve, according to chromatographic analysis. In the acetone-water system, polycondensation products, in particular, acetone dimers and trimers, such as isophorone, were produced.     

Degradation of C.I. Acid Orange 7 by the advanced Fenton process in combination with ultrasonic irradiation

The combination of ultrasound and the advanced Fenton process (AFP, zero-valent iron and hydrogen peroxide) for the degradation of C.I. Acid Orange 7 was studied. The effect of hydrogen peroxide concentration, initial pH, ultrasonic power density, dissolved gas, and iron powder addition on the decolorization of C.I. Acid Orange 7 was investigated. A modified pseudo-first order kinetic model was used to simulate the experimental results. The results showed that the decolorization rate increased with the increase of hydrogen peroxide concentration and power density, but decreased with the increase of initial pH value. There existed an optimal iron powder addition when decolorization rate was concerned. The decolorization efficiency also increased with the increase of hydrogen peroxide concentration, but decreased with the increase of initial pH value. It varied little at different power densities or iron powder additions at the fixed hydrogen peroxide concentration. The presence of dissolved gas would enhance color removal, and the enhancement was more significant when dissolved oxygen was present. More hydrogen peroxide dosage and reaction duration are required to achieve a relatively high COD removal than those employed to simply break the chromophore group.     

纳米TiO2叶片状阵列电极的制备及其在染料敏化太阳电池中电子的输运性能

在低温条件下采用定向刻蚀技术, 对金属Ti片表面用H₂O₂溶液进行刻蚀氧化, 制备了垂直生长的纳米TiO₂叶片状阵列薄膜电极. 通过X射线衍射分析表明, 纳米TiO₂叶片状阵列薄膜经500 ℃下烧结1 h后, 从无定型转变为锐钛矿相. 场发射扫描电子显微镜观察表明: 在80 ℃下的H₂O₂溶液刻蚀氧化, 经1 d制备得到的是Ti片表面垂直生长的叶片状阵列, 其形貌均匀且完整地 关键词： 2')" href="#">纳米TiO₂ 叶片状阵列电极 染料敏化太阳电池 电子传输     

分光光度法测定食盐中的碘

采用分光光度法对食盐中碘含量进行定量分析.对反应条件进行试验及优化,得最佳测定条件为:测定波长565nm,0.5mol/L盐酸2.00mL、3%双氧水3.00mL、10g/L淀粉1.00mL,显色时间10min.在此条件下测得碘含量为29.32mg/kg,符合国家标准.本方法操作简便,可靠,重现性好,专属性强,具有广泛...     

NH3/H2预混旋流火焰稳定性及燃烧极限实验研究

采用叶轮型旋流燃烧器,选取氢气作为燃料添加剂,研究了掺氢比对氨气旋流火焰稳定性的影响,分析了不同旋流数、叶片数、当量比以及预混气总流量条件下,旋流火焰形态变化.测定并分析了不同参数对旋流火焰燃烧极限范围的影响,结果表明,随掺氢比的增大,火焰逐渐由"V"型转化为稳定的"M"型,燃烧反应愈发充分;高旋流数(1.27)或低叶...     

Sonochemical enantioselective hydrogenation of ethyl pyruvate over platinum catalysts

Chiral sonochemical hydrogenation of an aliphatic -ketoester, ethyl pyruvate to ethyl lactate was carried out over various platinum catalysts in different solvents under atmospheric hydrogen pressure. The reaction rates and the enantiomeric excesses were determined over Pt/C, Pt/SiO₂ and Pt/K-10 catalysts both under conventional and sonochemical conditions. The effect of ultrasounds on the catalytic activity and enantioselectivity was tested applying sonochemical pretreatment before the reaction. The ultrasonic irradiation was found to be highly advantageous in these hydrogenations. After insonation of the catalysts, the enantioselectivity was highly improved over Pt/SiO₂ and Pt/K-10 catalysts. In addition, the reactions took place in quantitative yield and with complete chemoselectivity and the hydrogenation rates increased with one order of magnitude despite the very mild (atmospheric hydrogen pressure, room temperature) experimental conditions.