电化学方法生成羟基自由基及其在酸性铬蓝降解脱色中的应用1)

在电解槽中,以Ｎａ２ＳＯ４为支持电解质,多孔石墨电极为阴极,金属铁为阳极,在１０ｍＡ·ｃｍ－２的阴极电流密度下,电解生成的过氧化氢与阳极溶解的Ｆｅ２＋进行反应,生成羟基自由基(Ｆｅｎｔｏｎ试剂),进而对有机染料进行氧化反应,使其不饱和双键断裂,从而达到有机染料降解、脱色的目的,在生成Ｆｅｎｔｏｎｎ试剂的反应中,Ｆｅ２＋被氧化为 Ｆｅ３＋,生成的 Ｆｅ３＋在阴极得电子后重新被还原为Ｆｅ２＋,因此,在电解槽中 Ｆｅ２＋起着催化剂的作用．ＣＯＤ的去除率大于８０%,脱色率达１００%．脱色速率的测定表明其为一级反应,反应速度常数ｋ等于ｌ．９８ × １０－４ｓ－１．     

黄磷诱发氧化新技术

黄磷诱发氧化是一种有效的氧化方法，已开始应用于气相和液相污染控制。反应过程中生成一系列活性物种，臭氧是其中之一。黄磷诱发氧化反应主要在气相中进行，多相间接触条件是反应的关键因素。考察了对两种典型有毒物多氯联苯和三甲基环已烯酮的氧化效果，两小时左右，去除率达９０％以上。这项新技术具有设备简单、条件缓和等优势，因而有一定的应用前景，并对开拓新的氧化领域具有重要意义。     

纳米级Fe^o与普通Fe^o还原降解偶氮染料的比较

采用Fe^o对偶氮染料进行催化还原处理是染料废水脱色的一种重要方法．经过Fe^o降解．偶氮染料的N=N双键断裂．还原生成芳香胺，增加了废水的可生化性，有利于后续处理．因此，提高Fe^o的催化还原效率是进一步研究的方向．1996年，Johnson等人在研究了一系列氯代脂肪烃的Fe^o脱氯速     

针铁矿对几种氧化锰矿物氧化As(Ⅲ)特性的影响

用氧化还原平衡法研究了水钠锰矿、钙锰矿和黑锰矿等三种不同结构类型氧化锰矿物对As(Ⅲ)的氧化特性，以及针铁矿对上述氧化的影响。结果表明，水钠锰矿、钙锰矿和黑锰矿对As(Ⅲ)的最大氧化量分别为480．4、279．6和117．9mmol／kg，其氧化能力与氧化锰矿物的结构、Mn氧化度、表面电荷性质以及结晶度等因素有关；体系中存在针铁矿时，它们对As(Ⅲ)的最大氧化量分别增加到651．0、332．3和159．4mmol／kg；针铁矿本身并不氧化As(Ⅲ)，体系氧化能力增强是通过针铁矿对氧化生成的As(Ⅴ)的吸附来实现的。     

含氮有机物在Pt／HM,Pd／HM和CuO／HM催化剂上的氧化降解

本文考虑了乙腈、硝基甲烷和乙二胺在Ｐｔ／ＨＭ，Ｐｄ／ＨＭ和ＣｕＯ／ＨＭ催化剂上氧化降解产物随反应温度的变化。在实验温度范围内，含氮产物在Ｎ２，Ｎ２Ｏ和ＮＯ２。随着反应温度的升高，硝基甲烷氧化降解的Ｎ２选择性呈单调下降；而乙腈和乙二胺的Ｎ２选择性出现极小值；高温时Ｎ２选择性升高可能是氧化生成的ＮＯ在高温时更在利于和ＣＮ基或ＮＨ２基相互反应生成Ｎ２的缘故。对于乙腈和乙二胺的催化氧化降解活性为：Ｐｔ／Ｈ     

纳米级Fe0与普通Fe0还原降解偶氮染料的比较

采用Fe0 对偶氮染料进行催化还原处理是染料废水脱色的一种重要方法 .经过Fe0 降解 ,偶氮染料的N =N双键断裂 ,还原生成芳香胺 ,增加了废水的可生化性 ,有利于后续处理 .因此 ,提高Fe0的催化还原效率是进一步研究的方向 .1 996年 ,Johnson等人在研究了一系列氯代脂肪烃的Fe0 脱     

稀土离子对超氧阴离子自由基生成的抑制作用

利用肾上腺素在碱性条件下自氧化产生超氧阴离子自由基（O^.-2）的性质，研究了稀土硝酸盐对生成O^.-2的抑制作用。稀土硝酸盐与超氧化物歧化酶（SOD）具有相似的性质，对肾上腺素自氧化生成的O^.-2有明显的抑制作用。抑制率在16．3％－78．4％之间，而且体系中稀土硝酸盐的浓度与其对O^.-2的抑制率之间有明显的剂量效应关系。     

头孢曲松氯化消毒转化产物鉴定及机理研究

以头孢曲松为目标化合物,探索其在氯消毒处理中的转化机理.结果显示头孢曲松在氯化处理中主要发生两种反应,一种为氧化反应,另一种为氯化反应.头孢曲松分子中的硫醚官能团经氧化生成亚砜产物,消毒剂中的氯原子与噻唑环中的4-C原子发生亲电取代反应生成氯代产物.更为重要的是,本研究还探讨了低浓度头孢曲松在环境水体基质中的氯化转化特征,结果表明,本文所推测的反应机理在含头孢曲松的实际环境水样的氯化处理中同样发生.     

仲辛醇吸收NOx尾气的GC／MS研究

本文采用GC/MS法研究了仲辛醇氧化还原法吸收NO_x尾气后的化学组成,鉴定出的组份达37种,并且对一些主要组份的生成机理进行了简单的探讨。     

有机污染物综合指标(一)

水体有机污染是水质污染的主要问题。衡量有机污染的程度,最好进行有机污染的全分析,但十分困难。除规定的有毒有机污染物外,一般只测定有机污染综合指标来定量地反映水质有机污染程度。 有机污染综合指标主要有:生化需氧量(BOD) 是间接表示水体中可被生物降解的有机物含量的指标。化学需氧量(COD)是表征水中能被强氧化剂氧化分解的有机物含量的参数。总有机碳(TOC) 是以水样中的含碳量来表示有机物含量的,总需氧量(TOD)表示水中含C、N、H、S、P、M(金属) 的有机物完全氧化生成稳定无机氧化态的需氧量。紫外吸收(UVA或UV)是利用芳香族和一些具有不饱和双键的化合物对220—250nm波段的紫外光有强烈吸收的特性来测定污水中有机物的含量。此外尚有碳-氯仿提取物(CCE)和碳-醇提取物 (CAE),它们是先用活性碳吸附,再用氯仿或乙醇提取,脱去溶剂,恒重残渣即得结果。此法对含有杀虫剂的水样测定有明显的优点。主要有机污染综合指标测定方法的比较见表1。     

A Pt-Bi bimetallic nanoparticle catalyst for direct electrooxidation of formic acid in fuel cells

Direct formic acid fuel cells are a promising portable power-generating device, and the development of efficient anodic catalysts is essential for such a fuel cell. In this work Pt-Bi nanoparticles supported on micro-fabricated gold wire array substrate were synthesized using an electrochemical deposition method for formic acid oxidation in fuel cells. The surface morphology and element components of the Pt-Bi/Au nanoparticles were characterized, and the catalytic activities of the three Pt-Bi/Au nanoparticle electrodes with different Pt/Bi ratios for formic acid oxidation were evaluated. It was found that Pt₄Bi₉₆/Au had a much higher catalytic activity than Pt₁₁Bi₈₉/Au and Pt₁₃Bi₈₇/Au, and Pt₄Bi₉₆/Au exhibited a current density of 2.7 mA·cm^-2, which was 27-times greater than that of Pt/Au. The electro-catalytic activity of the Pt-Bi/Au electrode for formic acid oxidation increased with the increasing Bi content, suggesting that it would be possible to achieve an efficient formic acid oxidation on the low Pt-loading. Therefore, the Pt-Bi/Au electrode offers a promising catalyst with a high activity for direct oxidation of formic acid in fuel cells.     

无机离子对左旋葡聚糖光降解的影响

左旋葡聚糖(LG)被广泛作为生物质燃烧的示踪剂.然而,近年来研究表明左旋葡聚糖在大气中不稳定而会发生光降解.此外,对于大气中含量较高的SO₄^2-、NO₃-、NO₂-无机离子对LG光解的影响罕有报到.为此,本文模拟了液相中SO₄^2-、NO₃-、NO₂-对LG光氧化行为的影响.结果表明,Na2SO₄、NaNO₃、NaNO₂条件下LG光解速率常数分别为0.208、0.182、0.165 min^-1,均低于对照组(0.266 min-1),这表明无机离子的存在会减缓LG光降解速率.此外,这3种无机离子对LG光解产物中的低分子脂肪酸分布,甲酸/乙酸(C1/C2)比率均有重要的影响.其中,SO₄^2-存在下产物中戊二酸较多、NO₃-存在下产物中甲酸较多、NO₂-存在下产物中乙酸较多;NO₂-存在下产物中的C1/C2比率小于1与一般二次源中的C1/C2比率不一致,这表明由单一反应引起的C1/C2并不总是大于1.这些结果对于我们深刻理解大气液相中的有机物转化具有重要的参考价值.     

Anaerobic treatment of wastewater containing methanol in upflow anaerobic sludge bed (UASB) reactor

The direct conversion of methanol into methane is the main process in anaerobic treatment of methanol containing wastewater. However, acetic acid can also be produced from methanol theoretically, which may probably result in an abrupt pH drop and deteriorate the anaerobic process. Therefore, it is interesting to know what would really happen in an anaerobic reactor treating methanol wastewater. In this study, an up-flow anaerobic sludge bed (UASB) reactor treating methanol wastewater was operated. The chemical oxygen demand (COD), acetic acid and pH of the effluent were monitored at different loadings and influent alkalinity. The results showed that the anaerobic reactor could be operated steadily at as low as 119 mg/L of influent alkalinity and high organic loading rate with no obvious pH drops. Volatile fatty acids accumulation was not observed even at strong shock loadings. The microorganisms in the sludge at the end of the test became homogeneous in morphology, which were mainly spherical or spheroidal in shape.     

Chloroacetic acids in environmental processes

The fate of chloroacetic acids (CAA) in forest soils was studied using radio-indicator methods. We showed that chloroacetic acids are both microbially degraded and simultaneously formed by chloroperoxidase-mediated chlorination of acetic and humic acids. The degree of biodegradation of chloroacetic acids in soil depends on their concentration. Dichloroacetic acid (DCA) is degraded faster than trichloroacetic acid (TCA). Chlorination of acetic acid led to a fast formation of dichloroacetic acid, whereas chlorination of humic acids gave rise to trichloroacetic acid. Both processes lead to a steady state in soil, participate in the chlorine cycle and possibly also in decomposition of organic matter in forest ecosystems.     

Solvent-free biodiesel epoxidation

Biodiesel emerged again recently as an alternative for fossil fuels. Besides energy, biodiesel can be used as raw material to synthesize high value products such as epoxides. Indeed, epoxides are versatile intermediates in organic synthesis for numerous reactions due to the high reactivity of the oxirane ring. Actually common epoxidation by peracids in organic solvent can last several hours according to the double bonds number. The solvent confers selectivity to the reaction, preventing di-hydroxylation. Alternatively solvent-free reactions can be done in shorter times, but hydroxylation is less controlled. Here, we set up the synthesis of epoxides from methyl and ethyl esters of waste cooking oil, without solvent or metal catalyst. We tested molar ratio of hydrogen peroxide and formic acid, double bond number, reaction time, and temperature. Results show that the highest epoxide yields and selectivity, with high conversion of the double bonds, were obtained for temperature reactions between 50 and 65 °C, reaction times from 2 to 3 h, and molar ratio of 20/2/1. For those conditions, the double bonds conversion is equal or near 100 %, with epoxide yield and selectivity between 85 and 93 %. Organic solvent suppression, besides being environmentally friendly, also saves reaction time and subsequent purification steps.     

UV/H2 O2光氧化降解水中邻二氯苯的研究

通过UV/H2O2氧化法,对水中邻二氯苯的降解动力学、降解反应的影响参数进行研究,结果表明,UV/H2O2氧化法能有效降解邻二氯苯,其反应符合准一级反应动力学规律;弱酸性或中性环境有利于降解反应的进行,H2O2的投入量在特定条件下具有一个最佳值通过IC,GC/MS鉴定出降解中间产物主要为2,3二氯苯酚、3,4二氯苯酚、甲酸、乙酸和乙二酸等,据此推导出邻二氯苯在UV/H2O2体系中的降解途径和机理     

Degradation of chlorinated phenols by nanoscale zero-valent iron

Chlorophenols (CPs), as important contaminants in groundwater, are toxic and difficult to biodegrade. Recently nanoscale zero-valent iron received a great deal of attention because of its excellent performance in treating recalcitrant compounds. In this study, nanoscale zero-valent iron particles were prepared using chemical reduction, and the reductive transformations of three kinds of chlorinated phenols (2-CP, 3-CP, and 4-CP) by nanoscale zero-valent iron under different conditions were investigated. The transformation process of the CPs was shown to be dechlorination first, then cleavage of the benzene ring. The removal efficiency of the CPs varied as follows: 2-CP > 3-CP > 4-CP. The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit (E _LUMO). With the increase in initial concentrations of CPs, removal efficiency decreased a little. But the quantities of CPs reduced increased evidently. Temperature had influence on not only the removal efficiency, but also the transformation pathway. At higher temperatures, dechlorination occurred prior to benzene ring cleavage. At lower temperatures, however, the oxidation product was formed more easily.     

Surface characterization of acid-oxidized multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) oxidized with sulfuric acid, nitric acid, and the mixture of sulfuric and nitric acids were characterized by thermogravimetric analysis (TGA), Raman spectroscopy, elemental analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The TGA data showed that the MWNTs were more resistant to oxidation than C₆₀ or activated carbon fibers. Catalyst particles could be removed by the oxidants containing sulfuric acid, and thus indicative of the tip opening of MWNTs. The sulfuric acid had a propensity to create defect sites and introduce the surface oxides at those defects that already exist or be newly generated on MWNTs. However, the acid mixture could open the caps of MWNTs but preserve the structure homogeneity. The treatment with nitric acid gave rise to the highest bulk oxygen content in MWNTs, while the most abundant surface oxides were provided by sulfuric acid oxidation. In addition, nitric acid exhibited the best ability to transform the phenolic groups into carboxyl groups.     

Green chemistry approach to analysis of formic acid and acetic acid in aquatic environment by headspace water-based liquid-phase microextraction and high-performance liquid chromatography

A simple and totally organic-free (green) method, viz. headspace water-based liquid-phase microextraction combined with high-performance liquid chromatography-ultraviolet detection has been successfully developed for analysis of formic acid and acetic acid in environmental water samples. A microdrop of an aqueous solution of sodium hydroxide was suspended from the tip of a microsyringe needle over the headspace of the stirred sample solution containing the analytes at pH 1.0 for a given time. The microdrop was then retracted into the microsyringe, diluted with HPLC mobile phase, and injected to HPLC. Optimum efficiency has been achieved for: 3.0 µL NaOH microdrop (0.1 mol L^?1) exposed for 15 min over the headspace of an aqueous sample of 6.5 mL at 55 °C, containing 15% w/v of Na₂SO₄, adjusted to pH = 1.0 and stirred at 750 rpm. Under these conditions, enrichment factors of 162 and 187, limits of detection of 0.3 and 0.1 µg L^?1 (S/N = 3) with dynamic linear ranges of 1–500 and 0.5–500 µg L^?1 were obtained for formic acid and acetic acid, respectively. A reasonable repeatability (5.8% ≤ RSD ≤ 8.8%, n = 6) and satisfactory linearity (r² ≥ 0.997) illustrated the performance of the method.     

Comparison of different probe molecules for the quantification of hydroxyl radicals in aqueous solution

We show that the transformation of benzene into phenol is a more selective probe for the hydroxyl radical than the transformation of nitrobenzene or the generation of 4-hydroxybenzoic acid from benzoic acid. The benzene to phenol system showed adequate performance as a probe upon irradiation of lake water samples and humic acids. We show that the use of nitrobenzene and benzoic acid as hydroxyl probes should be avoided because of poor selectivity. Moreover, all the tested probe molecules underwent important interference by irradiated antraquinone-2-sulphonate, and considerably overestimated the formation of the hydroxyl radicals.