壬基酚聚氧乙烯醚在水溶液中的光降解行为研究

采用模拟日光灯和长波紫外灯（UVA-365nm）2种光源,对水溶液中壬基酚聚氧乙烯醚（NPEOs）的光降解动力学、降解过程中NPEO同系物成分的变化、以及氧化剂过氧化氢的加入对光降解的影响进行了研究,并采用LC-MS对光降解的产物进行了分析.研究表明,实验周期内NPEOs在模拟日光和长波紫外光下均发生不同程度的光降解,降解速率常数分别为6.20×10^-3　μmol/(L·h)和1.18×10^-2　μmol/(L·h).在模拟日光下,在NPEOs降解过程中观察到短链的NPEO_1,3分布比例的增加,而在长波紫外光下的降解过程中并没有发现NPEO成分分布的变化.过氧化氢的加入对NPEOs的光降解具有明显的促进作用,特别是在模拟日光下,0.01 mmol/L和1.00 mmol/L H₂O₂的加入使NPEOs的96h降解率由20.9%分别提高至44.4%和91.5%.通过LC-MS分析,初步认为壬基酚三乙氧基乙酸的烷基氧化产物(CA_3～9PEC₃)是溶液中NPEOs光降解的主要产物,并据此推断了可能的反应历程.     

紫外驱动高级氧化法降解水体中的磷酸三苯酯

有机磷酸酯（OPEs）作为备受关注的一类新污染物,已对偏远的南极地区水环境引发了中等风险.磷酸三苯酯（TPHP）是水体中常见的OPEs,已被证实具有毒性效应、生物富集和放大效应,对环境和人体健康威胁较大.利用傅里叶红外光谱仪（FT-IR）和液相色谱-串联质谱联用仪（LC-MS/MS）探究TPHP在紫外-过氧化氢（UV-H₂ O₂）、紫外-二氧化钛（UV-TiO₂）和紫外-过硫酸盐（UV-PS）这3种高级氧化体系（UV-AOPs）中的降解过程,创新性地利用FT-IR实现了TPHP降解过程中红外特征峰变化的在线观测,并对其降解反应动力学、光降解产物和降解路径进行了分析.结果表明,TPHP在UV-H₂ O₂、UV-TiO₂和UV-PS体系下均能得到有效降解,其光降解半衰期分别为74、150和89 min.其中,UV-H₂ O₂体系对TPHP的降解效果最好.TPHP在3种体系下的降解反应均符合一级动力学.当H₂ O₂浓度为0~0.097 mol ·L^-1时,H₂ O₂浓度升高会促进TPHP降解;当TiO₂浓度为0~0.013 mol ·L^-1时,TiO₂浓度升高会促进TPHP降解.TPHP的光降解路径主要是P—O—C键断裂、苯环结构的C—H键断裂和水解反应.利用UV-H₂ O₂体系对成都市环境水体中OPEs进行降解实验,发现对公园景观水体的水样进行降解反应60 min时,TPHP的去除率为66%.     

水中无机阴离子对UV/H2O2降解LAS的影响及机理

研究了UV/H₂O₂工艺对直链烷基苯磺酸钠（LAS）的去除效果以及水中常见无机阴离子对LAS降解的影响和机理.结果表明,UV/H₂O₂工艺可以有效的去除水中LAS,光降解过程符合一级反应动力学模型.在H₂O₂投加量为8 mg·L^-1,14 W低压汞灯照射下,LAS在蒸馏水和自来水中光降解速率常数分别为0.018 0 min^-1和0.012 2 min^-1;NO^-₃、Cl^-、SO^２－₄和HCO^-_３对LAS光降解有抑制作用,4种离子在浓度分别为5、10、15　mmol·L^-1时,对LAS光降解的抑制程度均为HCO^-_３>NO^-₃>Cl^->SO^２－₄;随着离子浓度增大,抑制作用增强;自来水中的光降解速率常数低于蒸馏水中的光降解速率常数是由于水中多种离子影响的结果.     

水质对UV/H2O2降解17α-乙炔基雌二醇（EE2）的影响

采用UV/H₂O₂间歇式光氧化反应器,研究了溶液pH值、腐殖酸及水中常见阴离子HCO₃^-、NO₃^-、CO₃^2-、Cl^-和SO₄^2-对UV/H₂O₂工艺降解17α-乙炔基雌二醇(EE2)的影响.结果表明,UV/H₂O₂工艺可以有效地去除水中的EE2,光降解过程符合一级反应动力学模型.双氧水投加量为5 mg/L时,在14W低压汞灯照射下,EE2在自来水和蒸馏水中的光降解一级反应速率常数为0.063 0min^-1和0.132 4min^-1.溶液中的腐殖酸和阴离子HCO₃^-、NO₃^-、Cl^-、SO₄^2-对EE2的光降解反应有抑制作用,4种阴离子浓度为5 mmol/L时,抑制作用依次为HCO₃^->SO₄^2->Cl^->NO₃^-,HCO₃^-可使光降解速率常数降低到50%.自来水中的光降解速率常数低于蒸馏水中的光降解速率常数是水中多种离子影响的结果.     

高含固餐厨垃圾有机组成对其流变特征的影响

餐厨垃圾在厌氧消化过程中的流变特征直接关系到搅拌传质和产甲烷效率,而餐厨垃圾的有机物组成差异可能导致其表现出不同的流变特征.本研究以碳水化合物、蛋白质、脂肪和纤维素等不同有机组成比例的餐厨垃圾为对象,通过单因素实验,研究单一组分对餐厨垃圾流变特征的影响.结果表明,在TS 15%的条件下,淀粉类碳水化合物比例的增加将增大餐厨垃圾的粘度,使屈服应力和宾汉粘度分别呈指数（τ_B=6.098x^0.14）和线性关系（μ_B=0.795x+0.0971）增长;热加工后的豆制品蛋白质比例增加反而降低餐厨垃圾粘度,使屈服应力和宾汉粘度分别呈线性（τ_B=6.976x+12.043）降低和指数（μ_B=0.668e^-1.584x）降低的变化趋势;粮油类脂肪因其为牛顿流体特征,其比例的增加不仅降低了餐厨垃圾粘度,屈服应力和宾汉粘度均呈对数降低（τ_B=8.459lnx+37.184和μ_B=0.373lnx+1.676）的变化趋势;而蔬菜类纤维素比例的增加将增大餐厨垃圾粘度,屈服应力和宾汉粘度均呈指数关系（τ_B=4.938e^14.138x和μ_B=0.263e^11.76x）增加.因此,未来需依据不同有机组分组成差异下餐厨垃圾的不同流变特征变化规律,合理考虑不同组成餐厨垃圾搅拌控制策略和物料含固率.     

Excellent dye degradation performance of FeSiBP amorphous alloys by Fenton-like process

Amorphous alloys are being newly applied in wastewater treatment because of their unique atomic packing structure. They possess excellent degradation efficiency, stability and reusability. In this work, Fe₈₀Si₁₀B₁₀ and Fe₈₃Si₅B₈P₄ amorphous ribbons exhibited advanced catalytic performance for the degradation of Methyl Blue (MB) and Rhodamine B (RhB) dyes, and the color removal reach nearly 100% within 11 min for both the dyes. Compared with the Fe₈₀Si₁₀B₁₀ amorphous ribbon, the Fe₈₃Si₅B₈P₄ ribbon showed higher degradation efficiency due to its lower reaction activation energy, higher electron transfer ability and higher Fe content, and the formation of the galvanic cell between the strong Fe–P bonds and the weak Fe–B bonds. It also exhibited high stability and reusability. The degradation efficiency was improved when the appropriate concentration of H₂O₂ is added. As regards the pH, high degradation efficiency was observed in acidic MB solution, but it decreased as the pH increased up to pH 7. The application of the electro–Fenton–like process is discussed, which can effectively improve the degradation performance in a nearly natural solution. This study presents a high efficiency low-cost catalyst for synthetic dye degradation and expands the functional applications of Fe-based amorphous alloys.     

Preparation of MgO/B2O3 coatings by plasma spraying on SUS304 surface and effects of heat-resistant

This study mainly deals with the preparation of MgO/B₂O₃ coatings by plasma spraying on the SUS304 surface and the effects of heatresistant. The power materials of low thermal conductivity were selected to control the heat divergent performance of high temperature parts. The reticular micro-structure between the cover thermal layer and the substrate was prepared by using the plasma spraying method. The powder mixture of MgO and B₂O₃ were selected as spraying materials and the SUS304 was used as the substrate material. The MgO/B₂O₃ coating was prepared on the surface of the SUS304 to provide better cover thermal performance. The properties of the microstructures and the morphologies were studied by Optical Microscope, Scanning Electron Microscope, Electron Probe Microanalyzer, and X-ray Diffraction. The results showed that the cover thermal performance has been improved.     

基于g-C3 N4研究环境中甲氧苄啶的光降解行为及其毒性

为研究残留抗生素在不同环境介质中的可见光降解行为特征,借助非金属和生物相容的石墨相氮化碳（g-C₃N₄）构建恒温恒湿和快速模拟可见光降解的实验环境,考察甲氧苄啶（TMP）进入不同环境（水、大气颗粒物和土壤）中的光降解过程与机制,并深入探讨TMP降解前后毒性变化规律.结果表明,用氙灯模拟太阳光和g-C₃N₄共存下,水、大气颗粒物和土壤中TMP经光照3 h后降解率分别为89.2%、35.8%和16.9%,同时发现参与水体TMP光降解的主要活性物质是·OH,而在大气颗粒物和土壤介质中光降解过程主要受·O₂^-控制.与大气颗粒物、土壤相比,水中TMP光解后可生成较为稳定的羰基化中间产物（m/z,305）,水生毒性试验结果表明TMP光解产物对斜生栅藻表现出较原药更强的毒性,可显著抑制藻细胞生长率、叶绿素a和b的含量,并引起细胞氧化应激.     

水和正已烷中痕量四氯联苯光降解研究

多氯联苯(PCBs)已成为全球性污染物,在人类生存的各种环境因素中,包括空气、水体、土壤、生物体,甚至远离大陆的海洋中已都发现PCBs的存在.自从发现PCBs能吸收190—240nm和280—310nm紫外光以来,人们推断PCBs吸收阳光中的紫外线后的光降解可能是从环境中除去PCBs的一种有效途径.因此对PCBs的光降解     

硼掺杂CeO2/TiO2光催化剂的制备及其活性研究

在三氯化钛和钛酸丁酯水解过程中引入硼酸、硝酸铈,制备了具有可见光活性的硼(B)掺杂CeO₂/TiO₂复合氧化物光催化剂,采用XRD、DRS、XPS等手段进行表征,以偶氮染料酸性红B为模型污染物评估了催化活性.结果表明,硝酸铈加入量影响催化剂的吸收带边,随用量增加,吸收带边红移至481nm(Ce/Ti=1.0,摩尔比),继续增加用量,吸收带边轻微蓝移.催化剂晶相组成与焙烧温度有关,500℃时焙烧样品主要由立方晶型CeO₂和锐钛矿TiO₂组成,焙烧温度高于700℃时,TiO₂转化为金红石型,CeO₂则无显著变化.随焙烧温度升高,催化剂吸收带边明显蓝移,综合考虑催化剂稳定性和太阳能利用,认为500℃焙烧较为合适.B1s XPS显示仅有少量B原子进入复合氧化物晶格取代了氧原子,主要以B₂O₃形式存在.酸性红B降解试验显示B掺杂CeO₂/TiO₂可以提高TiO₂的催化活性,紫外光辐射10min最高可使96.0%的酸性红B分解,且反应彻底,表现出较强的氧化能力,但Ce/Ti>0.5(摩尔比)时催化活性显著下降.     

游离羟基及表面活性剂对乙草胺光解的影响

以高压汞灯为光源,以p-亚硝基-N,N-二甲基苯胺(PNDA)作为·OH自由基的探针,研究了H2O2及表面活性剂0206-B(苯乙烯苯酚聚氧乙烯醚和十二烷基苯磺酸钙混剂)对除草剂乙草胺在水中间接光解作用的影响.结果表明,H2O2对水中乙草胺具有光敏化降解作用,其敏化作用效应与·OH有关;而0206-B对乙草胺具有光猝灭降解作用,光猝灭降解作用效应与0206-B减少水溶液中的·OH自由基含量有关.乙草胺直接光解与H2O2作用的乙草胺间接光解相同的产物有Rf(比移值)为0.12、0.52、0.61、0.72的化合物;H2O2敏化降解抑制了乙草胺直接光解产物Rf为0.04、0.10、0.18、0.21、0.79的化合物产生,但促进乙草胺间接光解Rf为0.45、0.66的新光解产物生成.     

可见光激发下模拟海水中四环素光降解的机制和路径

为了探明海水体系中多相光催化降解污染物的机制和路径,研究了在可见光激发下不同介孔TiO₂光催化降解纯水和模拟海水中四环素(TC)的过程,明确了不同盐离子对光催化降解过程的影响.结合自由基捕获实验,电子自旋共振(ESR)光谱和中间产物分析研究了光降解污染物的主要活性物种和模拟海水中TC降解途径.结果表明,模拟海水中TC光催化过程会受到显著抑制,手性介孔TiO₂催化剂对TC光降解反应速率相比其在纯水体系降低了70%左右,而非手性TiO₂光催化剂在海水体系中几乎不能降解TC.模拟海水中阴离子对光降解过程影响较小,但Mg²⁺和Ca²⁺存在会显著抑制光催化过程.无论在纯水还是模拟海水中,可见光激发后催化剂产生的活性物种都是空穴为主,因此模拟海水中降解路径与纯水体系中相同.盐离子不会抑制活性物种的产生,但Mg²⁺和Ca²⁺会富集在TC分子中电负性强的原子周边,阻碍空穴等对TC分子中电负性强原子的攻击,从而抑制了光催化降解效率.     

水环境中不同形态氮对甲芬那酸光降解影响机制的研究

研究了紫外光照射下水环境中不同形态的无机氮(NO-3、NO-2和NH+4)对甲芬那酸(MEF)光解的影响.NO-3与NO-2均促进MEF的光解,NH+4对MEF的光解基本无影响;在NO-3、NO-2存在下添加适量异丙醇,显著抑制MEF的降解,实验表明NO-3、NO-2在光照下产生了·OH并参与对MEF的氧化降解.同时模拟研究了水体处于不同p E值下,水中存在的不同形态的无机氮对MEF光解的复合影响,其对MEF光解促进作用不是简单的叠加关系,增大p E值,MEF的光解速率先增大后减小.当NO-2和NH+4共存时,对MEF的光解主要表现为NO-2的影响;当NO-2和NO-3共存时,两者对MEF的光解存在拮抗作用.     

不同形态无机氮对水中微量药物安替比林光降解效能影响

在300 W氙灯光照条件下,研究了消炎镇痛类药物安替比林(ANT)在纯水中的光降解效能与机制,重点考察了水中不同形态无机氮及pE值对ANT光降解效能的影响.结果表明,ANT在不同条件下的光降解均符合假一级反应动力学;ANT在纯水中的光降解包括直接光解以及由羟基自由基(.OH)和单线态氧(1O2)参与的自敏化光解,贡献率分别为55.27%、22.19%和22.54%.不同形态无机氮(NH4+、NO2-和NO3-)单独存在条件下对ANT光降解效能的影响差异较大.在pE值较低时,即无机氮主要以NH4+形式存在,对ANT的光降解几乎没有影响;随着pE值的升高(由4.82～6.85),NH4+向NO2-转化,由于NO2-不仅能与ANT竞争吸收光子,同时还对.OH具有较强的淬灭作用,使得其对ANT光降解的抑制作用逐渐增强,当pE值达到6.85,即无机氮主要以NO2-形式存在时,ANT光降解的抑制率达到最高为35.31%;随着pE值的继续升高(由6.85～8.15),NO2-向NO3-转化,对ANT光降解的抑制作用逐渐减弱.     

Effects of environmental factors on sulfamethoxazole photodegradation under simulated sunlight irradiation: Kinetics and mechanism

To advance the knowledge of the environmental fate of sulfamethoxazole (SMX), we systematically investigated the effects of natural water constituents and synthetic substances (i.e., TiO₂ nanoparticles (nTiO₂) and Ti-doped β-Bi₂O₃ (NTB)) on the photodegradation kinetics of SMX under xenon lamp irradiation. The photolysis of SMX in aqueous solution followed first-order kinetics. Our results showed that higher concentrations of SMX, fulvic acid, suspended sediments, NTB and higher pH value decreased the photodegradation rates of SMX, whereas H₂O₂ improved the SMX photodegradation. TiO₂ nanoparticles had a dual effect on photodegradation due to their photocatalytic activity and photoabsorption of photons. No intermediates more toxic toward Vibrio fischeri than SMX were produced after direct photolysis and photocatalytic degradation for 3 hr. The photolysis of SMX involved three pathways: hydroxylation, cleavage of the sulfonamide bond, and fragmentation of the isoxazole ring. This study lays the groundwork for a better understanding of the environmental fate of SMX.     

低频无极灯降解偶氮染料酸性橙7

以40 W的新型低频感应无极灯(LFEL)作为反应光源,研究了其对于水中难生化降解偶氮染料酸性橙7(AO7)的降解效果.通过专用浸没式反应器研究了这种新型光源降解AO7的有效实验参数,并与传统汞灯光源做了降解AO7的实验对比,用GC-MS检测了主要降解产物小分子,探讨了LEEL对AO7的降解机制及反应活性物质(ROS).结果表明,LFEL对于水中的AO7染料具有较好的降解效果和较高的矿化率,在浸没式反应器中曝气量2 m3·min-1,AO7浓度为20 mg·L-1(7 L)在4 h的反应后能达到94.1%的降解率,而其降解能耗远低于传统汞灯光源.降解贡献来自于两个方面:直接吸收降解和间接通过活性物质(ROS)氧化作用.氧气是ROS的重要来源,加大曝气量会提高降解效率,反应过程中有臭氧的生成.添加淬灭剂显示,·OH对降解反应几乎无贡献,1O2和O2·-则是反应的主要活性物质.     

Photocatalytic degradation of 4-tert-octylphenol in a spiral photoreactor system

A spiral photoreactor system (SPS) was developed for the degradation of 4-tert-octylphenol (4-t-OP) in aqueous phase. 4-t-OP was previously considered as a endocrine disrupting compound frequently present in water. The direct photodegradation reaction caused by the SPS was found to accord with the characteristic of apparent first-order reaction with reaction rate constantk= 4.8 × 10^-2 min^-1. However, the direct photodegradation reaction could not make the 4-t-OP mineralized. The photodegradation efficiency increased from 88% to 91.2% in 45 min irradiation period after the internal surface of SPS was sintered with TiO₂ thin film as catalyst. Catalyst concentration, number of catalyst coating layers and initial concentration of 4-t-OP were proven to be the factors affecting the photocatalytic degradation performance of the SPS on aqueous 4-t-OP. The degradation mechanism was investigated and the byproducts were analyzed using total organic carbon analyzer (TOC) and LC-MS. The possible chemical structures of the products were suggested. SPS with single layer of TiO₂ prepared by sintering 13.6% of TiO₂ precursor was proven to be more efficient than most of previous systems for removal of 4-t-OP from aqueous phase. 28.3% of the 4-t-OP was mineralized in 45 min according to the decreased amount of TOC value.