不同涂层电极和抑制剂对电化学氧化降解苯酚的影响

采用热分解法和电沉积法2种工艺制得4个二氧化铅电极,用扫描电镜（SEM）观察了电极表面形貌.以水杨酸(2-HBA)为捕获剂,用高效液相色谱仪测定羟基自由基与水杨酸的羟基化产物2,5-二羟基苯甲酸(2,5-DHBA)的量作为产生的羟基自由基的浓度.通过羟基自由基的浓度的测定和苯酚的降解,研究了不同涂层电极和抑制剂对电化学氧化对苯酚降解的影响.热分解电极、无掺杂电极、掺铋电极和掺镧电极产生羟基自由基的最大浓度分别为0.781、1.048、1.838、2.044 μmol/L,以这4个电极为阳极对苯酚进行电解, 1.5　h苯酚去除率分别为87.30%、93.55%、97.95%、98.70%,5　h　TOC去除率分别为86.75%、94.26%、98.53%、99.60%;以掺镧电极为阳极,加入抑制剂CO^2-₃、PO^3-₄、CH₃ＣＯＯ^-产生的羟基自由基的最大浓度分别为无检出、0.170 μmol/L、0.270 μmol/L,对苯酚进行电解,5 h苯酚去除率分别为99.06%、99.98%、99.79%.电沉积法制得电极对苯酚的降解效果优于热分解法制得的电极,而掺杂的电极优于无掺杂的电极,掺镧电极对苯酚降解效果最好,抑制剂CO^2-₃、PO^3-₄、CH₃ＣＯＯ^-存在时会对苯酚的降解起到阻碍作用,CO^2-₃阻碍作用最强.不同制备方法和掺杂不同添加剂制得的电极的催化性能不同,对苯酚的降解效果也不同;羟基自由基的浓度越大,苯酚的降解效果越好,抑制剂捕获了产生的羟基自由基,不利于苯酚的降解.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Reactive oxygen species metabolism during the cadmium hyperaccumulation of a new hyperaccumulator Sedum alfredii （Crassulaceae）

Sedum alfredii Hance, a newly discovered hyperaccumulator, could serve as a good material for phytoremediation Cd polluted sites. Malondialdehyde (MDA), reactive oxygen species (ROS) and antioxidases (catalase (CAT); superoxide dismutase (SOD); peroxidase (POD)) in the leaf were determined when S. alfredii was treated for 15 d with various CdCl2 concentrations ranging from 0 to 800 μmol/L. The results showed that the production rate of 2′,7′-dichlorofluorescein (DCF), which is an indicator of ROS level, reached up to the maximum at 400 μmol/L CdCl2 and then declined with the increase of CdCl2 concentration, while MDA accumulation tended to increase. CAT activity was significantly inhibited at all tested CdCl2 concentrations and SOD activity was sharply suppressed at 800 μmol/L CdCl2. However, the enhancement of POD activity was observed when CdCl2 concentration was higher than 400 μmol/L. In addition, its activity increased when treated with 600 μmol/L CdCl2 for more than 5 d. When sodium benzoate, a free radical scavenger, was added, S. alfredii was a little more sensitive to Cd toxicity than that exposed to Cd alone, and the Cd accumulation tended to decline with the increase of sodium benzoate concentration. It came to the conclusions that POD played an important role during Cd hyperaccumulation, and the accumulation of ROS induced by Cd treatment might be involved in Cd hyperaccumulation.     

利用激光诱导荧光技术测量大气氢氧自由基的研究进展

激光诱导荧光技术是目前测量大气ＯＨ 自由基中使用最多的方法。本文总结了２０ 多年的研究成果,论述了激光诱导荧光技术用于测定大气ＯＨ 自由基的研究进展,讨论了测量中的不确定因素及其对策,并着重介绍了目前最常用的基于气体扩张的低压荧光（ＦＡＧＥ） 技术。     

氟里昂替代品降解产物三氟乙酸的环境影响

氟里昂替代品在大气中的降解反应将产生大量的三氟乙酸,其在大气中可与ＯＨ 自由基反应生成三氟甲烷和二氧化碳,主要的去除机制是沉降和雨除,并在地面水中累积;本文还对其在地表水中的积累预测和背景值监测做了描述     

苯甲酸类光催化降解和羟基自由基反应的关系

研究了13种苯甲酸类化合物在固定膜平板反应器中的光催化降解,探讨了光降解速率与化合物结构之间的定量关系（QSAR）,同时分析了苯甲酸类化合物和羟基自由基反应的速率常数与结构的关系结果表明,Hammett常数（σ）和摩尔对数溶解度（lgS）是影响本甲酸类光降解速率lgK的重要因素,其定量关系式为：lgK＝-0．309σ＋0.125lgS－2.612,苯甲酸类与羟基自由基反应的定量关系式为lgK_OH＝－0.414σ＋9．816,证实了羟基自由基在本甲酸类光催化过程中的重要作用.     

新型二氧化铅电极处理硝基苯废水

采用高压塑片的方法制备了一种PbO₂电极,用X衍射、扫描电镜、火焰原子吸收分光光度法对该电极性能进行了考察,并探讨了该电极降解硝基苯的机理和工艺条件.结果表明,该电极与普通石墨电极相比,COD_Cr去除率更高,电解5 h COD_Cr去除率最高可达65%.由于PbO₂电极具有较高的析氧电位,在阳极极化下,PbO₂电极表面易生成·OH,这是其电解效率高的主要原因.该电极电解硝基苯的最适条件:ρ(硝基苯)为501.5 mg/L,电极间距为3 cm,溶液pH为7.利用该电极处理含磷酸盐和氯离子的硝基苯废水效果尤为突出,但由于阴极的还原作用,电解过程中硝基苯不能被完全氧化.      

电极喷嘴布置对NO电晕氧化过程影响的试验研究

使用湿空气作为自由基源物质 ,研究了电极喷嘴布置对电晕放电特性、NO电晕氧化过程的影响 .结果表明 ,随着电极喷嘴数的增加 ,总电晕区域变大 ,流光的脉动重复率增加 ,NO的氧化率提高 .试验条件下 ,对应B(14 )、B(8)、A(7)、A(4 )的放电电极 ,电晕反应器NO的氧化率最高可分别达到 65 3 %、5 0 5 %、5 1 3 %、2 7 5 % .采用喷嘴数较多的电极时 ,NO电晕氧化的能量效率较高 ,有效工作区内 ,对应B(14 )、B(8)、A(7)、A(4 )的放电电极 ,电晕反应器NO氧化的能量效率最高分别为 5 3 1g·kWh- 1 、5 0 2g·kWh- 1 、5 0 7g·kWh- 1 、3 8 0g·kWh- 1 ,它们对应的NO氧化率分别为 5 3 8%、42 5 %、48 8%、2 3 0 % .喷嘴数目相同时 ,A型电极所形成的电晕流光在电晕反应器内具有更好的充满度 ,更有利于烟气NOx 脱除 .     

Aqueous free radical chemistry of mercury in the presence of iron oxides and ambient aerosol

The effect of goethite (α-FeOOH), hematite (α-Fe₂0₃) and maghemite (γ-Fe₂0₃) on the aqueous photoreduction of divalent mercury with organic acids (oxalate, formate and acetate) is investigated. Laboratory photochemistry experiments with synthetic iron oxides and simulated sunlight were performed to assess the role of the oxides on the photoreduction. Ambient aerosol was also collected and introduced as the solid phase to compare its effect with that of synthetic oxides. It is observed that the presence of various iron oxides or aerosol particles enhances the photoreduction. It is also found that the hydroxyl radicals produced in the hematite-oxalate systems can re-oxidize the reduced mercury back to Hg(II). Based on the experimental observations, mechanisms responsible for the Hg(II) reduction are proposed. The kinetics of Hg⁰ oxidation by hydroxyl radicals was also studied by a steady-state kinetic technique using nitrate photolysis as the * OH radical source. The second-order rate constant is determined to be 2.0 × 10⁹ M⁻ s⁻¹. The implications of the studied reactions on the atmospheric chemistry of mercury are discussed.     

甲醇蒸汽在CaO颗粒脱硫反应中的作用机理实验研究

通过在模拟烟气中添加微量的甲醇蒸汽产生自由基从而发生链式反应的方法提高循环流化床干法脱硫反应速率。该实验结果和理论分析表明 :甲醇蒸汽在 90 0℃以下不可能通过热均裂产生自由基 ,而甲醇蒸汽的不完全燃烧过程可以产生自由基 ,引发快速的链式脱硫反应 ,脱硫反应的合理温度为 80 0℃