185nm UV降解水中4-CP、4-NP和RhB的研究

本文以对氯苯酚(4-CP)、对硝基苯酚(4-NP)和罗丹明B(Rh B)为模型有机物(以4-CP和4-NP为小分子模型有机物,以Rh B为大分子模型有机物),分别研究了185 nm UV对水中这3种模型有机物的降解规律、性能和效果.研究结果表明,185 nm UV直接对水中4-CP、4-NP和Rh B有很好的降解效果.研究内容包括:185 nm UV降解模型有机物的浓度、TOC(Total organic carbon)浓度、185 nm UV降解模型有机物过程中溶液pH及电导率变化、以及降解模型有机物过程中产生的无机离子等几个方面.

Preparation of bismuth oxide/titania composite particles and their photocatalytic activity to degradation of 4-chlorophenol

Bismuth oxide/titania, one interfacial composite semiconductor with high photocatalytic activity under solar light, was prepared at low temperature. The structure was characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, brunauer-emmett-teller （BET）, X-ray photoelectron spectroscopy （XPS） and diffuse reflection spectra （DRS）. The results indicate that deposited titania nanoparticles on bismuth oxide surface have micro-nano structure, and this composite material exhibits porosity and increased surface hydroxyl groups. Furthermore, the as-prepared photocatalyst shows higher photocatalytic activity to the degradation of 4-chlorophenol than pure titania or P25 under sunlight.

Iron-glutamate-silicotungstate ternary complex as highly active heterogeneous Fenton-like catalyst for 4-chlorophenol degradation

A novel iron-glutamate-silicotungstate ternary complex（FeШGluS iW） was synthesized from ferric chloride（FeI II）,glutamic acid（Glu）,and silicotungstic acid（SiW）,and used as a heterogeneous Fenton-like catalyst for 4-chlorophenol（4-CP） degradation at neutral pH value. The prepared FeШGluS iW was characterized using inductively coupled plasma atomic emission spectroscopy,thermogravimetry,Fourier-transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,X-ray diffraction,and field-emission scanning electron microscopy. The results showed that FeШGluS iW has the formula [Fe（C5H8NO4）（H2O）]2SiW 12O40？13H2O,with glutamate moiety and Keggin-structured SiW 12O404- heteropolyanion. The catalyst showed high catalytic activity in 4-CP degradation in the dark and under irradiation. Under the conditions of 4-CP 100 mg/L,FeШGluS iW 1.0 g/L,H2O2 20 mmol/L,and pH = 6.5,4-CP was completely decomposed in 40 min in the dark and in 15 min under irradiation. When the reaction time was prolonged to 2 h,the corresponding total organic carbon removals under dark and irradiated conditions were ca. 27% and 72%,respectively. The high catalytic activity of FeI IIGluS iW is resulted from hydrogen bonding of H2O2 on the FeI IIGluS iW surface. The enhanced degradation of 4-CP under irradiation arises from simultaneous oxidation of 4-CP through Fenton-like and photocatalytic processes respectively catalyzed by ferric iron and the SiW 12O404- hetropolyanion in FeШGluS iW.

4-CPS/UPU并联机构运动学分析与仿真

提出了一种用于并联机床领域的4-CPS/UPU并联机构。基于旋量理论,建立了该并联机构的运动和约束螺旋系,该机构具有5个自由度,可实现三移两转功能;通过修正的K-G公式对其自由度进行了验证;进一步分析了并联机构的位置正逆解、工作空间;运用Adams软件对其进行了仿真分析。该机构工作空间连续,形状近似四棱台,规则对称,无空洞,且仿真得到的位移和速度曲线光滑,表明该机构具有良好的运动性能。研究结果为其在并联机床领域的参数化设计提供了一定的理论基础。

Effect of Sb dopant amount on the structure and electrocatalytic capability of Ti/Sb-SnO_2 electrodes in the oxidation of 4-chlorophenol

Ti/Sb-SnO2 anodes were prepared by thermal decomposition to examine the influence of the amount of Sb dopant on the structure and electrocatalytic capability of the electrodes in the oxidation of 4-chlorophenol. The physicochemical properties of the Sb-SnO2 coating were markedly influenced by different amounts of Sb dopant. The electrodes, which contained 5% Sb dopant in the coating, presented a much more homogenous surface and much smaller mud-cracks, compared with Ti/Sb-SnO2 electrodes containing 10% or 15% Sb dopant, which exibited larger mud cracks and pores on the surface. However, the main microstructure remained unchanged with the addition of the Sb dopant. No new crystal phase was observed by X-ray diffraction （XRD）. The electrochemical oxidation of 4-chlorophenol on the Ti/SnO2 electrode with 5% Sb dopant was inclined to electrochemical combustion; while for those containing more Sb dopant, intermediate species were accumulated. The electrodes with 5% Sb dopant showed the highest efficiency in the bulk electrolysis of 4-chlorophenol at a current density of 20 mA/cm^2 for 180 min; and the removal rates of 4-chlorophenol and COD were 51.0% and 48.9%, respectively.

Biodegradation of 4-Chlorophenol by Candida albicans PDY-07 under Anaerobic Conditions

Candida albicans PDY-07 was isolated from activated sludge under anaerobic conditions and identified as a member belonging to the genus Candida. Pure culture of C. albicans PDY-07, biodegradation of 4-chlorophenol (4-CP) was carried out under anaerobic conditions in Erlenmeyer flasks at 35°C, with an initial pH of 7.0–7.2 and a starting inoculum of 10%(by volume). The results showed that, under the above-mentioned conditions, C. albicans PDY-07 could thoroughly biodegrade 4-CP up to a concentration of 300mg·L?1 within 244h and that it had a high tolerance potential of up to 440mg·L?1 for 4-CP. With the increase in the initial concentrations of 4-CP, substrate inhibition was obviously enhanced. There was increased consumption of 4-CP, which was not assimilated by the cell for growth but was used to counteract the strong substrate inhibition. In addition, the cell growth and substrate-degradation kinetics of 4-CP as the sole source of carbon and energy for the strain in batch cultures were also investigated over a wide range of substrate concentrations (2.2–350mg·L?1), using the proposed cell growth and degradation kinetic models. The results recorded from these experiments showed that the proposed kinetic models adequately described the dynamic behavior of 4-CP biodegradation by C. albicans PDY-07.

Biodegradation of Phenol and 4-Chlorophenol by the Mutant Strain CTM 2

The biodegradations of phenol and 4-chlorophenol （4-cp） were studied using the mutant strain CTM 2 obtained by the He-Ne laser irradiation on wild-type Candida tropicalis. The results showed that the capacity of the CTM 2 to biodegrade 4-cp was increased up to 400 mg·L^-1 within 59.5 h. In the dual-substrate biodegradation both velocity and capacity of the CTM 2 to degrade 4-cp increased with low-concentration phenol. A totalof 400 mg·L^-1 4-cp was completely degraded within 50.＇5 h in thepresence of 300 mg·L^-1 phenol. The maximum 4：cp biodegegradation could reach 440 mg·L^1 with 120 mg·L^1 phenol. Low-concentration 4-cp caused great inhibition on the CTM 2 to degrade phenol. In addition, the kinetic behaviors were described using the kinetic model proposed in this lab.

Oxidative Degradation of 4-chlorophenol in Aqueous Induced by Plasma with Submersed Glow Discharge Electrolysis

The oxidative degradation of 4-chlorophenol （4-CP） in aqueous solution induced by plasma with submersed glow discharge has been investigated. The concentration of 4-CP and the reaction intermediates were determined by high performance liquid chromatography （HPLC）. Various influencing factors such as the initial pH, the concentration of 4-CP and the catalytic action of Fe^2＋ were examined. The results indicate that 4-CP is eventually degraded into inorganic ion, dioxide carbon and water. The attack of hydroxyl radicals on the benzene rings of 4-CP in the initial stage of oxidative reactions is presumed to be a key step. They also suggest that the reaction is of a pseudo-first order kinetic reaction and the proposed method is an efficient way for the 4-CP degradation,

Biodegradation of 4-Chlorophenol by Candida albicans PDY-07 under Anaerobic Conditions

Candida albicans PDY-07 was isolated from activated sludge under anaerobic conditions and identified as a member belonging to the genus Candida. Pure culture of C. albicans PDY-07, biodegradation of 4-chlorophenol 4-CP was carried out under anaerobic conditions in Erlenmeyer flasks at 35℃, with an initial pH of 7.0—7.2 and a starting inoculum of 10% by volume. The results showed that, under the above-mentioned con- ditions, C. albicans PDY-07 could thoroughly biodegrade 4-CP up to a concentration of 300mg·L-1 within 244h and that it had a high tolerance potential of up to 440mg·L-1 for 4-CP. With the increase in the initial concentrations of 4-CP, substrate inhibition was obviously enhanced. There was increased consumption of 4-CP, which was not assimilated by the cell for growth but was used to counteract the strong substrate inhibition. In addition, the cell growth and substrate-degradation kinetics of 4-CP as the sole source of carbon and energy for the strain in batch cultures were also investigated over a wide range of substrate concentrations 2.2—350mg·L-1, using the proposed cell growth and degradation kinetic models. The results recorded from these experiments showed that the proposed kinetic models adequately described the dynamic behavior of 4-CP biodegradation by C. albicans PDY-07.

Laccase immobilized on magnetic nanoparticles by dopamine polymerization for 4-chlorophenol removal

In this work, a new immobilization method based on dopamine(DA) self-polymerization was developed for laccase immobilization on magnetic nanoparticles(Fe_3O_4 NPs). To optimize the immobilization condition including reaction pH, DA concentration and enzyme concentration, a central composite response surface method was applied. The optimal condition was determined as p H value of 5.92, laccase concentration of 0.25 mg mL^(-1) and DA concentration of 12.74 mg mL^(-1), under which a high enzyme activity recovery of 88.17% was obtained.By comparing with free laccase, the stabilities of immobilized laccase towards p H, thermostability, storage were enhanced significantly.Approximately 60% of relative activity for immobilized laccase was remained after being incubated for 6 h at 50℃, but the free laccase only remained 25%. After 40 days of storage at 4℃, the laccase immobilized by DA kept about 89% of its original activity, but the free laccase only retained 48%. After recycled 10 times, the relative activity of immobilized laccase still retained 70%. The immobilized laccase was then applied to catalyze the degradation of 4-chlorophenol(4-CP), 86% percentage of 4-CP was removed within 2 h. After degraded 10 times, the relative activity of immobilized laccase still remained 64% of its initial activity, which exhibits an excellent reusability and operational stability.

负载型铜掺杂TiO2催化剂的制备及其光催化去除水中4-CP的研究

以CuCl2为铜源,用溶胶凝胶法制备了不同载体的负载型铜掺杂TiO2催化剂,用SEM、XRD和BET对催化剂进行表征与分析。以催化剂对水中4-CP的去除率为评价标准,研究其催化性能。结果表明:当以粗孔硅胶为载体,焙烧温度为500℃,焙烧时间为2h,Cu^2+和TiO2的质量比为0.5%时,催化剂对氧化4-CP的效果最好,催化剂中TiO2以钛矿型为主。

零价铁对土壤中4-氯苯酚还原脱氯研究

氯苯酚是常见的环境污染物,它们在土壤中的加速分解可以减少对人类健康的危害。以恒温培养为方法,GC-MS为检测手段,研究了在常温常压下土壤中4-氯苯酚(4-CP)在零价铁作用下的还原脱氯反应。结果表明:4-CP可以被来自零价铁的电子还原,零价铁能够有效促进土壤中的4-CP脱除苯环上的氯原子,从而达到降低毒性、增加可生化性目的。反应条件如初始pH、时间、零价铁用量等均对4-CP还原脱氯效率有重要影响,特别是当初始pH值控制在偏酸时更有利于反应的进行。在零价铁加入量500mg、初始pH=4、反应时间7d的条件下,零价铁对土壤中4-CP还原脱氯效率最高可以达到65%。利用实验数据,对零价铁作用下4-CP还原脱氯的反应机理也进行了初步探讨。

纳米Fe^0作用下4-氯酚的脱氯特性及机理

采用化学还原法制备了纳米Fe0,ESEM测定结果表明其颗粒在1～100nm内.实验表明这些纳米Fe0能在20h内将初始浓度为20mg/L的4-氯酚完全降解,Fe0对4-CP的还原脱氯是主要去除途径.苯酚是脱氯反应的主要产物.当4-CP的初始浓度由20mg/L增大到50,100,150mg/L时,其相对去除率明显降低,但绝对降解量有较大提高.温度不仅影响脱氯速率,而且影响4-CP去除的途径.30℃时,脱氯反应为主要反应;10℃时,较易产生氧化产物.Fe原子的迁移过程在4-CP的降解中也是一个重要的限速步骤.此外,纳米Fe0具有很好的稳定性,在受试的379h内,纳米Fe0能够应对不同浓度冲击及反复投加的4-氯酚冲击的能力.

5,10,15,20-四(3-氯-4-磺酸苯基)卟啉的合成及其与银显色反应的研究

报道了水溶性卟啉T(3-CP)PS_4的合成方法,研究了试剂与银离子的显色反应条件,测定了试剂的离解常数pKa_3,4为3.90。当Pb^(2+)和CTMAB存在时,配合物的最大吸收波长位于427.2nm处,表观摩尔吸光系数为3.23×10~5,配合比为1:1,稳定常数K=4.91×10~7,银含量在0～6μg/25ml范围内符合朗伯—比尔定律。本法可用于阳极泥和光谱底片中微量银的测定。

新型含能化合物3,5-二硝基吡唑-4-硝酸酯的合成与表征

以4-氯吡唑(4-CP)为原料,经过硝硫混酸硝化制得4-氯-3,5-二硝基吡唑(4-CDNP),再以硝酸银为亲核试剂进行亲核取代反应得到一种新型的含能化合物3,5-二硝基吡唑-4-硝酸酯(DNPN),并采用红外光谱、核磁共振、元素分析对产物结构进行了表征,计算了其爆轰性能,考察了硝硫混酸组成、硝化温度对硝化反应的影响,得到较佳的合成条件:硝硫混酸组成为V(98%硝酸):V(98%硫酸)=1∶4,反应温度为100℃,反应时间为5 h,产率为65.1%。4-CDNP与硝酸银的反应很快,在40℃下反应1h产率就可达到35.6%。DNPN的爆速为8.78 km·s^(-1),爆压35.12 GPa,优于TNT。

ZnO/CeO_(2)/carbon xerogel composites with direct Z-scheme heterojunctions:Enhancing photocatalytic remediation of 4-chlorophenol under visible light

This paper aims to create visible light driven ternary photocatalysts using zinc oxide(ZnO),cerium(IV)oxide(CeO_(2)),and carbon xerogel(CX) as constituent materials.The use of CeO_(2) is based on the creation of direct-Z-scheme heterojunctions with the ZnO and the consequent diminishing of charge recombination,whereas the carbon xerogel inclusion is predicted to minimize bandgap energy,decrease electro n-hole reco mbination,and boost specific surface area.Furthermo re,the choice of the black-wattle tannin as a carbonaceous precursor was targeted at the development of an environmentally friendly and affordable composite.The existence of the hexagonal phase of zinc oxide and cubic structure of the cerium(IV) oxide in the ternary material was confirmed by X-ray diffractometry and X-ray photoelectron spectroscopy,with the latter also suggesting chemical bonding between the ZnO and the CX due to the creation of zinc oxycarbide complexes.The inclusion of the carbon xerogel provokes a significant modification in the morphology of the ternary material,resulting in an increased surface area and smaller particle aggregates.The CX/ZnO-CeO_(2) ternary composite obtains the highest photocatalytic efficiency among all the materials studied,degrading 100% of 4-chlorophenol under simulated sunlight and 68% under visible radiation,after 5 h.The increased photocatalytic activity can be attributed to the formation of direct Z-scheme heterojunctions between the semiconductors,higher visible light response,and higher specific surface area,as evidenced by the results obtained by active radical scavenging,chronoamperometry,diffuse reflectance spectroscopy,and N_(2) adsorption-desorption isotherms.

Reductive Dechlorination of p-Chlorophenol by Nanoscale Iron

Objective To investigate reductive dechlorination of 4-chlorophenol （4-CP） by nanoscale Fe^0 under different conditions. Methods Nanoscale Fe^0 was synthesized by using reductive method. 4-CP and its intermediate products were analyzed by HPLC. Chlorine ion was quantified with DX-100 ion chromatograph. Nano-iron particles were observed under a FEI Quanta 200 FEG environmental scanning electron microscope （ESEM）. Results The size of the particles was in the range of 10-100 nm. The nano-iron particles could reduce 4-CP effectively. The initial concentration of 4-CP increased with the decrease of the relative degradation rate, whereas the reduced amount of 4-CP increased. Temperature could influence both the dechlorination rate and the reaction pathway. Moreover, the stability and durability of nanoscale Fe^0 was evaluated through batch studies over extended periods of time. Conclusion The nanoscale Fe^0 can be used for sustainable treatment of contaminants in groundwater.

新型光催化氧化体系UV/Fe^(2+)/空气降解4-CP废水

报道了新型光催化氧化体系UV/Fe2+/空气对4-CP废水的降解.该体系利用廉价空气为氧化剂,在紫外光照过程中产生H2O2,与溶液中存在的Fe2+形成Fenton反应,使污染物得到快速彻底的降解.反应40min时,溶液中几乎检测不到4-CP.和初始H2O2浓度为22mg/L的UV/Fenton相比,UV/Fe2+/空气体系能更快速彻底地降解4-CP.因此,对于能受紫外光激发的污染物,UV/Fe2+/空气是一种廉价有效的光催化氧化处理方法.

Degradation of 4-chlorophenol in aqueous solution by γ-radiation and ozone oxidation

The degradation of 4-chlorophenol (4-CP) by using gamma rays generated by a 60Co source in the presence of O3 was investigated. The radiolysis of 4-CP and the kinetics of 4-CP min-eralization were analyzed based on the determination of total organic carbon (TOC). The influence of initial 4-CP concentration and the free radicals scavengers (such as NaHCO3 and t-butanol) on the 4-CP degradation was also studied. The results showed that when the radiation rate was 336 Gy·min?1, 4-chlorophenol at concentration of 10 mg·L?1 could be completely degraded at the radiation dose of 2 kGy. The degradation of 4-chlorophenol could be described by a first-order reaction model, the rate constant of 4-CP degradation by combined ozonation and radiation was 0.1016 min?1, which was 2.4 times higher than the sum of radiation (0.0294 min?1) and ozonation (0.0137 min?1). It re-vealed that the combination of radiation and ozonation resulted in synergistic effect, which can re-markably increase the degradation efficiency of 4-CP.

Photocatalytic degradation of 4-chlorophenol under P-modified TiO2/UV system: Kinetics, intermediates, phytotoxicity and acute toxicity

A series of phosphorus-modified titanium dioxide samples with varying P/Ti atomic ratio were conveniently prepared via a conventional solgel route. The effects of phosphorus content and calcination temperature on the crystalline structure, grain growth, surface area, and the photocatalytic activity of P-modified TiO2 were investigated. The XRD results showed that P species slow down the particle growth of anatase and increase the anatase-to-rutile phase transformation temperature to more than 900°C. Kinetic studies on the P-modified TiO2 to degraded 4-chlorophenol had found that the TP5500 prepared by adopting a P/Ti atomic ratio equal to 0.05 and calcined at 500°C had an apparent rate constant equal to 0.0075 min 1, which is superior to the performance of a commercial photocatalyst Degussa P25 Kapp = 0.0045 min 1 and of unmodified TiO2 （TP0500） Kapp = 0.0022 min 1. From HPLC analyses, various hydroxylated intermediates formed during oxidation had been identified, including hydroquinone （HQ）, benzoquinone （BQ） and （4CC） 4-chlorocatechol as main products. Phytotoxicity was assessed before and after irradiation against seed germination of tomato （Lycopersicon esculentum） whereas acute toxicity was assessed by using Folsomia candida as the test organism. Intermediates products were all less toxic than 4-chlorophenol and a significant removal of the overall toxicity was accomplished