氯柱硼镁石在硼酸溶液中溶解转化的Raman光谱

利用Raman光谱对氯柱硼镁石在30 ℃时,4.5%的硼酸水溶液中溶解相转化过程进行了研究。研究结果表明相转化产物为库水硼镁石(2MgO·3B₂O₃·15H₂O)。根据Raman光谱位移对溶液中各种聚硼酸根B(OH)-₄,B₂O(OH)2-₆,B₃O₃(OH)-₄等阴离子的Raman峰进行了归属以及它们间的相互作用分别进行了讨论分析。提出了溶液中硼氧配阴离子的存在形式及其相互作用机理和我国青藏高原盐湖区库水硼镁石形成的地球化学成盐条件和机理。     

利用红外光谱分析有机羧酸在均相反应中的配位作用机理

利用红外(IR)光谱、X射线衍射(XRD)及透射电子显微镜(TEM)等手段,对有机羧酸在尿素及硝酸铈的均相反应混合溶液中所起的配位作用进行了分析,并对产品的物相和形貌进行了测试与表征。实验结果表明：在尿素及硝酸铈的混合溶液中分别加入一元羧酸硬脂酸,二元羧酸酒石酸和三元羧酸柠檬酸时,一元羧酸硬脂酸在混合溶液中只起表面活性剂的作用,其产物为斜方晶系的单晶Ce₂O(CO₃)₂·H₂O微粉,且表面活性剂硬脂酸的加入使得晶体的晶化程度明显提高;而二元羧酸酒石酸与三元羧酸柠檬酸在均相反应中则起螯合剂的作用,分别与Ce3+形成螯合物酒石酸铈和柠檬酸铈,这些结果的造成是由于其反应机理的不同所导致的。     

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.     

茜素应用于识别硼酸的研究

应用紫外-可见分光光度法研究了茜素与硼酸之间的识别行为,结果表明,在pH 9.0Na2HPO4-NaH2PO4缓冲介质中,茜素与硼酸形成1∶1稳定络合物,使茜素的吸收光谱发生明显蓝移,溶液颜色由玫红色变为橙黄色,阴离子F-、Cl-、Br-、I-、Ac-、NO-3、C2O24-等均未引起茜素的吸收光谱及溶液颜色发生明显变化,因此茜素可以选择性识别硼酸。初步探讨了茜素与硼酸之间的相互作用机理,并对茜素识别硼酸与茜素识别阴离子的机理进行了比较。     

(Au)_核(Ag)_壳纳米微粒-火焰原子吸收光谱法测定过氧化氢

在90 ℃水浴条件下,以粒径为10 nm的纳米金做晶种,用柠檬酸三钠还原硝酸银,制备了平均粒径为30 nm的（Au）核（Ag）壳纳米微粒,用高速离心纯化除去过量的柠檬酸三钠获得了较纯的（Au）核（Ag）壳纳米微粒。在pH 3.8的HAc-NaAc缓冲溶液中,Fe2＋催化H2O2反应产生的羟基自由基可氧化（Au）核（Ag）壳纳米微粒生成银离子。离心后,离心液中的银离子可用火焰原子吸收光谱法在328.1 nm波长处测量。随着H2O2浓度增大,离心液中银离子浓度增加,其吸光度值增加。H2O2浓度在2.64～42.24 μmol·L-1范围内与上清液中银离子的原子吸收值ΔA呈良好的线性关系,回归方程为ΔA=0.014c-0.013 1, 相关系数为0.998 4,检出限为0.81 μmol·L-1 H2O2。当用于水样中H2O2的测定,获得了满意的结果。     

Synthesis and formation mechanism of pinnoite by the phase transition process

Pinnoite (MgB₂O(OH)₆) for the first time was synthesized using the solid–liquid–solid conversion method. The effects of reaction time, pH value and concentrations of magnesium and borate were investigated. Pinnoite was synthesized under the optimum condition of 8 mmol hungtsaoite and 1% boric acid solution at 80 °C. The products were determined using X-ray diffraction, Fourier-transform infrared spectroscopy, TG-DSC and a UV–vis spectrometer. The change processes of the surface morphology of pinnoite were investigated using scanning electron microscopy. In addition, the formation mechanism of pinnoite was discussed according to the changes in the content of precipitation and pH value.     

Ultrasonic coal-wash for de-sulfurization

Coal is the one of the world's most abundant fossil fuel resources. It is not a clean fuel, as it contains ash and sulfur. SOx as a pollutant are a real threat to both the ecosystem and to human health. There are numerous de-sulfurization methods to control SO(2) emissions. Nowadays, online flue gas de-sulfurization is being used as one such method to remove sulfur from coal during combustion. The biggest disadvantage associated with this method is formation of by-products (FGD gypsum). A way for effective usage of FGD gypsum has not yet been found. This will lead to acute and chronic effects to humans as well as plants. Power ultrasound can be used for the beneficiation of coal by the removal of sulfur from coal prior to coal combustion. The main effects of ultrasound in liquid medium are acoustic cavitation and acoustic streaming. The process of formation, growth and implosion of bubbles is called cavitation. Bulk fluid motion due to sound energy absorption is known as acoustic streaming. In addition, coupling of an acoustic field to water produces OH radicals, H(2)O(2), O(2), ozone and HO(2) that are strong oxidizing agents. Oxidation that occurs due to ultrasound is called Advanced Oxidation Process (AOP). It converts sulfur from coal to water-soluble sulphates. Conventional chemical-based soaking and stirring methods are compared here to ultrasonic methods of de-sulfurization. The main advantages of ultrasonic de-sulfurization over conventional methods, the mechanism involved in ultrasonic de-sulfurization and the difference between aqueous-based and solvent-based (2N HNO(3), 3-volume percentage H(2)O(2)) de-sulfurization are investigated experimentally.     

Effect of Fenton-like oxidation on enhanced oxidative degradation of para-chlorobenzoic acid by ultrasonic irradiation

Sonolysis, Fenton-like oxidation (FeOOH-H2O2), and a combination of the two processes were used to facilitate the degradation of para-chlorobenzoic acid (a model compound for free radical mediated reactions). The objective of this study was to investigate the effect of FeOOH and H2O2 dosages on the degradation of para-chlorobenzoic acid (p-CBA) using ultrasound/FeOOH-H2O2. The oxidation rate of p-CBA was measured at various concentrations of H2O2 and FeOOH particles and pH conditions. pH's below the pKa of p-CBA (3.98), showed significantly better degradation of p-CBA than at higher values from 5 to 9. The rates of degradation of p-CBA by FeOOH-H2O2 were enhanced in the presence of ultrasound. The first-order rate constant, k for p-CBA degradation by ultrasound was 4.5 x 10(-3) min(-1), and in the presence of FeOOH-H2O2 this was found to be substantially faster (1.54 x 10(-2) min(-1)). The observed rate enhancements for the degradation of p-CBA can be attributed primarily to the continuous cleaning and chemical activation of the FeOOH surfaces by acoustic cavitation and the accelerated mass transport rates of reactants and products between the solution phase and the FeOOH surface. This new process provides a viable alternative to existing oxidation technologies.     

Secondary sonochemical effect on Mo-catalyzed bromination of aromatic compounds

The Molybdate-catalyzed bromination of various aromatic compounds in the presence of KBr/H(2)O(2) in an aqueous/chloroform biphasic system occurred under ultrasonic irradiation, whereas the reaction did not take place under conventional mechanical stirring (1400 rpm). The sonochemical activation was found to be of secondary effect, attributed to lowering pH by sonolysis of CHCl(3)-H(2)O solvents mixture.     

Ultrasonic-assisted synthesis of chrysin derivatives linked with 1,2,3-triazoles by 1,3-dipolar cycloaddition reaction

The 1,3-dipolar cycloaddition reaction between 7-(3-azidopropoxy)-5-hydroxyflavone and phenylacetylene was carried out to investigate the synthesis of 7-(3-(4-phenyl-1,2,3-triazol-1-yl)propoxy)- 5-hydroxyflavone in presence of ultrasound (sono-synthesis) and absence of ultrasound (conventional method) under relatively optimized solvent and catalyst conditions. The reaction rate was notably accelerated with the help of ultrasound irradiation. An experiment was especially carried out for investigating the acceleration mechanism of ultrasound on the cycloaddition. A novel series of chrysin derivatives linked with 1,2,3-triazoles were obtained by the copper(I)-catalyzed 1,3-dipolar Huisgen cycloaddition reaction using t-BuOH/H(2)O (1:1 v/v) as reaction solvents and CuSO(4)·5H(2)O/sodium ascorbate as the catalyst at room temperature in the presence of ultrasound irradiation. Their structures are elucidated by NMR, ESI MS, IR and Elemental analysis.     

Co3O4纳米晶的制备和表征

发现了一种新制备Co3O4纳米晶的新方法。这种方法是先将高分子聚乙烯吡咯烷酮(PVP)和乙酸钴溶解到溶剂中缓慢蒸发溶剂,然后干燥形成的前驱体,最后在400℃温度下煅烧制备了Co3O4纳米晶。生成的产物用XRD,SEM,TEM等测试方法进行了表征。结果发现在不同的溶剂中形成前驱体所制备的Co3O4纳米晶具有不同的形貌特征,使用乙醇溶剂时生成了大量的由Co3O4纳米晶自组装形成的Co3O4微米球;而使用水溶剂时则生成的全都是Co3O4纳米晶。实验结果表明在不同溶剂中形成的前驱体对于最终制备的Co3O4纳米晶形态有着很大的影响。     

腐植酸溶液的声化学降解研究

采用频率为1.8MHz的超声波在固定式声化学反应器内研究了声化学降解腐植酸的自由基氧化历程。通过采用TA溶液作为OH自由基捕获剂,吡啶溶液作HO2自由基捕获剂,以及KI溶液的I2释放法分别确定出实验条件下反应溶液中OH自由基的浓度为10^-7M,HO2自由基浓度为10^-5M及H2O2浓度为10^-5M。在此基础上研究了均相与多相催化条件下声化学降解腐植酸溶液的TOC削减情况。发现CeO2和Cu2O催化作用下腐植酸的降解效率分别较均相条件下提高40％和20％。并就反应机理和反应动力学过程进行了描述。     

直接沉淀法中不同晶型钛酸锌的X射线粉末衍射研究

以Ti(SO₄)₂和Zn(NO₃)₂·6H₂O为原料,碳酸铵为沉淀剂,采用直接沉淀法制备了钛酸锌的粉体。探讨了反应条件对所得钛酸锌晶体结构的影响,并对样品进行了XRD和TG-DTA等分析。钛酸与碳酸锌分子生成的先后顺序影响得到的钛酸锌的结构。在钛酸优先生成的体系中,碳酸锌分子生成之后与周围足量的钛酸分子发生碰撞反应,由于钛酸优先生成且沉淀剂足量,碰撞反应充分且在碰撞反应中钛酸保持过量,反应生成了亚钛酸锌(Zn₂Ti₃O₈)。在碳酸锌优先生成的体系中,钛酸分子生成之后与周围足量的碳酸锌分子发生碰撞反应,由于碳酸锌优先生成且沉淀剂足量,碰撞反应充分且在碰撞反应中碳酸锌保持过量,反应生成了正钛酸锌(Zn₂TiO₄)。另外,沉淀剂用量和反应温度都影响着最终产物的种类和晶型。沉淀剂用量越多、反应温度越高,越易于生成Zn₂Ti3O₈或Zn₂TiO₄。只有在沉淀剂不足、反应温度较低的情况下,才能生成偏钛酸锌(ZnTiO₃)。     

C and O stable isotopic signatures of fast-growing dripstones on alkaline substrates: reflection of growth mechanism, carbonate sources and environmental conditions

Secondary carbonate precipitates (dripstones) formed on concrete surfaces in four different environments--Mediterranean and continental open-space and indoor environments (inside a building and in a karstic cave)--were studied. The fabric of dripstones depends upon water supply, pH of mother solution and carbonate-resulting precipitation rate. Very low δ(13)C (average-28.2‰) and δ(18)O (average-18.4‰) values showed a strong positive correlation, typical for carbonate precipitated by rapid dissolution of CO(2) in a highly alkaline solution and consequent disequilibrium precipitation of CaCO(3). The main source of carbon is atmospheric or biogenic CO(2) in the poorly ventilated karstic cave, which is reflected in even lower δ(13)C values. Statistical analysis of δ(13)C and δ(18)O values of the four groups of samples showed that the governing factor of isotope fractionation is not the temperature, but rather the precipitation rate.     

Detection and characterization of boric acid and borate ion binding to cytochrome c using multiple quantum filtered NMR

The application of multiple quantum filtered (MQF) NMR to the identification and characterization of the binding of ligands containing quadrupolar nuclei to proteins is demonstrated. Using relaxation times measured by MQF NMR multiple binding of boric acid and borate ion to ferri and ferrocytochrome c was detected. Borate ion was found to have two different binding sites. One of them was in slow exchange, k(diss) = 20 +/- 3 s(-1) at 5 degrees C and D(2)O solution, in agreement with previous findings by (1)H NMR (G. Taler et al., 1998, Inorg. Chim. Acta 273, 388-392). The triple quantum relaxation of the borate in this site was found to be governed by dipolar interaction corresponding to an average B-H distance of 2.06 +/- 0.07 A. Other, fast exchanging sites for borate and boric acid could be detected only by MQF NMR. The binding equilibrium constants at these sites at pH 9.7 were found to be 1800 +/- 200 M(-1) and 2.6 +/- 1.5 M(-1) for the borate ion and boric acid, respectively. Thus, detection of binding by MQF NMR proved to be sensitive to fast exchanging ligands as well as to very weak binding that could not be detected using conventional methods.     

Sonophotocatalytic decomposition of water using TiO(2) photocatalyst

Sonophotocatalytic reaction is a photocatalytic reaction with ultrasonic irradiation or the simultaneous irradiation of ultrasound and light with a photocatalyst. The possibility of the effect of hybrid of sonochemical and photocatalytic reactions was examined. Liquid water was hardly decomposed to H(2) and O(2) by photocatalysis or sonolysis, independently. In order to decompose water, powdered TiO(2) photocatalyst suspended in distilled water should be simultaneously irradiated by light and ultrasound. This sonophotocatalytic reaction was effective on the decomposition of water to H(2) and O(2).     

Preliminary results on the effect of power ultrasound on nitrogen oxide and dioxide atmosphere in nitric acid solutions.

The effect of ultrasound (20 kHz, 3 W cm-2) on the kinetics of HNO2 and H2O2 formation was investigated in a 1 M HNO3 medium for NO2-Ar and NO-Ar gas mixtures in various volume fractions (f(NO2) < 1.7 vol% and f(NO) < 1.1 vol%, respectively). The H2O2 formation rate measured in 1 M HNO3 in the presence of N2H5NO3 was observed to be much lower than that of HNO2 without N2H5NO3, and was relatively independent of the NO2 or NO gas volume fractions in the argon atmosphere. The HNO2 formation rate increased under ultrasound, and was higher with NO than with NO2. The induction period observed without ultrasound disappeared when ultrasound was applied. The first step in the sonochemical mechanism of HNO2 formation in the presence of NO2 involves thermal decomposition of NO2 into NO within the cavitation bubble. In the second step of HNO2 formation, NO reacts either with HNO3 in the cavitation bubble, or with NO2 in the cavitation bubble or at the bubble/solution interface.     

Dawson结构磷钨钒杂多酸有机铵盐的合成及光谱研究

以偏钒酸铵、磷酸二氢钠和钨酸钠为原料,调节溶液的pH值为4,控制反应时间为10 h,合成了三钒取代的Dawson结构磷钨钒杂多酸,然后以化学反应计量的5倍量加入抗衡离子K+,制备了母体杂多酸盐K9P2W15V3O62·41H2O。在不断的搅拌下,将母体杂多酸盐的酸性溶液缓慢滴加到十六烷基三甲基溴化铵溶液中,合成了目标化合物磷钨钒杂多酸有机铵盐(C19H42N)6H3[P2W15V3O62]。经元素分析、红外光谱、X射线粉末衍射、差热-热重等手段进行了表征,表明目标化合物仍保持Dawson结构,为未见文献报道的杂多化合物。     

L-苏糖酸及其金属化合物的红外光谱研究

制备了高纯度的L-苏糖酸及其与钙、镁、锰、钴、镍和锌的化合物,用化学分析和元素分析确定了它们的组成;通过红外光谱分析研究,确定金属离子与L-苏糖酸的羰基氧配位,同时与羧基脱质子配位,而醇羟基质子不解离,金属离子为sp~3杂化,配位数为4。     

Measurement of hydroxyl radical production in ultrasonic aqueous solutions by a novel chemiluminescence method

Measurement methods for ultrasonic fields are important for reasons of safety. The investigation of an ultrasonic field can be performed by detecting the yield of hydroxyl radicals resulting from ultrasonic cavitations. In this paper, a novel method is introduced for detecting hydroxyl radicals by a chemiluminescence (CL) reaction of luminol-hydrogen peroxide (H2O2)-K5[Cu(HIO6)2](DPC). The yield of hydroxyl radicals is calculated directly by the relative CL intensity according to the corresponding concentration of H2O2. This proposed CL method makes it possible to perform an in-line and real-time assay of hydroxyl radicals in an ultrasonic aqueous solution. With flow injection (FI) technology, this novel CL reaction is sensitive enough to detect ultra trace amounts of H2O2 with a limit of detection (3sigma) of 4.1 x 10(-11) mol L(-1). The influences of ultrasonic output power and ultrasonic treatment time on the yield of hydroxyl radicals by an ultrasound generator were also studied. The results indicate that the amount of hydroxyl radicals increases with the increase of ultrasonic output power (< or = 15 W mL(-1)). There is a linear relationship between the time of ultrasonic treatment and the yield of H2O2. The ultrasonic field of an ultrasonic cleaning baths has been measured by calculating the yield of hydroxyl radicals.