臭氧化法在高分子生物材料表面改性中的应用

综述了臭氧化法在高分子生物材料表面改性中的应用及研究，介绍了臭氧化法的特点，过氧化物浓度的测定及臭氧化反应和过氧化物引发接枝共聚的反应机理。     

玻璃纤维表面的乙烯基单体接枝聚合

用玻璃纤维表面处理剂ＭＡＣ处理玻璃纤维后，再进行臭氧处理，使玻璃纤维的表面产生活性中心，引发苯乙烯、甲基丙烯酸甲酯、及丙烯酸等乙烯基单体在玻璃纤维表面上接枝聚合。接枝纤维的密度减小，对水的浸润性下降，红外光谱及扫描电镜观察证明玻璃纤维表面上接枝聚合物的存在。     

非均相催化臭氧氧化反应机制

臭氧催化氧化作为高级氧化技术是目前水处理领域研究的热点,其中非均相臭氧催化氧化技术因其氧化能力强、降低臭氧投加量特别是能显著提高有机物矿化率等优点而备受关注。非均相催化臭氧氧化领域不断研究新的催化剂,但是其反应过程及机制更加复杂。催化臭氧氧化的性能很大程度上取决于催化剂及其表面性质。污染物在催化剂表面形成络合物,或者臭氧在催化剂表面分解产生不同的含氧物种如表面氧原子、过氧化物和羟基自由基等。本文评述了非均相臭氧催化氧化反应中存在的多种机理,主要是自由基理论、氧空位理论、表面原子氧理论、表面络合物理论和臭氧直接氧化理论。催化剂表面的羟基基团是主要的催化活性中心,本文探讨了表面羟基基团催化反应机制,得出催化剂表面性质决定其表面活性位点的特性及含量,对诱导臭氧分解产生含氧活性物种起了关键作用;概述了催化剂改性后的结构形态、比表面积及其性能和作用机制;并讨论了非均相臭氧催化氧化反应催化剂未来的发展趋势,为催化臭氧氧化污水处理技术提供了理论参考。     

臭氧的应用及产生技术

主要阐述了臭氧的性质、用途及产生技术,并重点介绍了臭氧的用途和臭氧产生技术的现状。     

SnO2的制备及催化臭氧氧化活性

采用沉淀法制备了SnO2催化剂,以SnO2催化臭氧氧化降解糖蜜酒精废水脱色为探针反应,对催化剂的活性进行了评价.采用X射线衍射、红外光谱及热分析(TG-DSC)等技术对催化剂进行表征,研究了沉淀剂及焙烧温度等制备参数对SnO2催化臭氧氧化活性的影响.结果表明,SnO2催化剂对臭氧氧化降解糖蜜酒精废水脱色具有较高的催化活性,反应60 min后,糖蜜酒精废水的脱色率从单独臭氧氧化的43.04%提高到60.24%.沉淀剂对SnO2催化剂的活性影响很大,其中以氨水为沉淀剂制备的SnO2催化剂去羟基化反应程度高,所制得的催化剂活性最大.催化剂适宜的焙烧温度为723 K.SnO2吸附吡啶的红外光谱表明,催化剂表面存在L酸中心.臭氧在SnO2表面吸附的红外光谱表明,通过臭氧的末端氧原子与表面羟基及L酸中心成键,生成的活性氧可氧化降解糖蜜酒精废水.     

北京地区臭氧污染的来源分析

光化学烟雾污染是影响北京地区夏季空气质量的一个重要环境问题．利用区域空气质量模（CAMx）对2000年6月底至7月初发生在北京地区的臭氧污染过程进行模拟,运用臭氧源识别技术（OSAT）和地区臭氧评估技术（GOAT）,量化了不同地区的污染源排放对北京市城近郊区臭氧污染的贡献,探讨了周边地区排放的臭氧贡献方式问题,分析了北京地区臭氧污染的化学机制特征．研究表明,北京地区臭氧污染分布存在显著差异,并且具有明显的区域性特征,定陵地区的超标臭氧主要受到城近郊区烟羽的严重影响（占55％）,城近郊区则除了受到北京市的前体物排放影响外（占46％）,来自天津市、河北省南部地区的贡献往往也占有重要份额;周边地区对北京市城近郊区的贡献中,直接输入的臭氧约占七层,其余部分以输入前体物的方式贡献臭氧;北京城近郊区的臭氧生成主要受挥发性有机物控制,而在远郊区县和农村地区臭氧生成对氮氧化物变得更为敏感．对北京地区臭氧污染的源排放控制,需要综合考虑各种臭氧来源和不同贡献方式的重要性,以及臭氧生成机制的变化规律．     

固体聚合物电解质电解臭氧发生器中不同晶型PbO2阳极催化剂的特性

固体聚合物电解质电解臭氧发生器中不同晶型ＰｂＯ_２阳极催化剂的特性周元全，吴秉亮，高荣，张红，江巍（武汉大学化学系武汉４３００７２）关键词臭氧，阳极催化剂，二氧化铅，固体聚合物电解质臭氧（Ｏ３）是一种强氧化剂，它具有强烈的杀菌消毒作用和氧化降解有机污?..     

珠江三角洲夏季臭氧区域污染及其控制因素分析

2006年夏季,在珠江三角洲(简称珠三角)开展了一次大型野外综合空气质量观测实验.实验包括了珠三角现有的环境监测网络和两个额外设置的超级观测站.本文基于环境监测网络的观测结果对区域臭氧污染状况和污染过程进行了分析,对各站点所记录的气团光化学属性进行了诊断.结果发现,两个超级站点分别对应着污染城市地区和下风向远郊区的光化学条件,它们较好地覆盖了区域尺度上主要的臭氧高值区.使用基于观测的模型对超级站上臭氧的光化学产生过程及臭氧控制区进行了分析.结果显示,第一,模式中的醛类化学和缺失的HONO化学对于臭氧光化学产生具有重要影响;第二,在城市地区,臭氧的光化学产生速率主要受人为源排放碳氢化合物控制;而在城市远郊区,臭氧的光化学产生速率主要受NO控制;第三,重要的人为源排放的碳氢化合物是烯烃和芳香烃.使用O′x和NOz的回归结果对臭氧产生效率进行了估算,发现城市和郊区的数值存在显著差异(分别为2.1和7.8),这从侧面支持了模型对于城市和郊区臭氧控制区属性的判断.     

臭氧氧化法及其联合技术在废水处理中的应用

臭氧具有极强的氧化能力,其反应产生的物质一般对环境污染很小。综述了臭氧处理单元的几种方式、臭氧联合技术及其在处理城市污水及工业污水中的应用,并概述了臭氧氧化技术的发展现状及趋势。     

烟雾箱模拟丙烯-NOx的大气光化学反应

利用自制烟雾箱对丙烯-NO_x的光化学反应进行了一系列模拟实验, 研究了相对湿度及丙烯与NO_x的初始浓度比值对丙烯-NO_x光化学反应产物如O₃和CO的影响. 实验得到了臭氧最大值、CO最大值及反应掉的C₃H₆均随相对湿度的增加而减少, 丙烯的臭氧生成活性最大值(IR_max)也随着相对湿度的增加而减小, 且两者间存在显著的线性关系. 丙烯与NO_x的比值对反应生成臭氧最大值的影响出现两种情况: 当初始浓度比值在1.0～3.4之间时, 臭氧最大值随着该比值的增加而有大幅度提高|而当该比值分别在3.7～7.4之间时, 臭氧最大值随比值的增加而有小幅度的下降. 此外, 本研究还利用丙烯MCMv3.1机理对反应进行了数值模拟.     

Personal and atmospheric concentrations of ozone in southeastern hyogo prefecture, Japan

Twenty-one data sets composed of readings collected by atmospheric ozone monitors worn by individuals on their clothing and installed outside their home or office were collected using Ogawa passive ozone samplers in southeastern Hyogo prefecture, Japan from September 12 to 13, 2011. The concentrations of personal and outdoor ozone ranged from not detectable to 23.2?ppb and from 4.7 to 38.3?ppb, respectively. The mean concentration of personal exposure to ozone was 3.7?ppb and was significantly lower than that of outdoor ozone (18.5?ppb). This suggests that the concentrations of outdoor ozone affect personal ozone exposure. However, in this study, we found no correlation between the concentrations of personal ozone and the total time spent outdoors or the time of day the individual was outside. In contrast, the mean concentrations of outdoor ozone were similar to those of ozone measured at the 12 nearest Ambient Monitoring Stations (AMSs). However, when the AMS was situated near a main road, the regional ozone levels were underestimated.     

Ozone Degradation by Fluoride onto Plasma-Treated Activated Carbon in CF4

The ozone degradation of fluorine was investigated using the tetrafluoromethane plasma-treated activated carbon (PT-AC). The ozone in the stratosphere has been degraded by the chloride and bromide radicals which are produced from chlorofluorocarbons and bromofluorocarbons, respectively. However, we believe that fluorine also was related to the ozone degradation. The fluoride was introduced onto the activated carbon surface by tetrafluoromethane plasma treatment. The breakthrough curve of ozone onto PT-AC was measured to elucidate the relationship between the ozone and the fluoride. The amount of ozone adsorbed/degraded onto the PT-AC was larger than the amount that was adsorbed/degraded onto the untreated activated carbon. The amount of fluoride ion eluted from the PT-AC before the adsorption/degradation of ozone was larger than that which eluted after the adsorption/degradation of ozone. These results indicated that the ozone was degraded by the fluoride on the PT-AC surface.     

大气臭氧化学研究进展

臭氧是大气化学中的核心物种。在平流层中,臭氧层可以吸收对生物有害的紫外辐射,对地球生命起保护伞作用。在对流层大气中,适量臭氧对清洁大气是有益的。但是,由于对流层中臭氧前体物排放量的增加,特别是在大城市,产生的高浓度臭氧会对大气环境造成严重污染,对人类、动植物和生态环境具有极大危害。臭氧的研究一般结合外场观测、实验室烟雾箱模拟和计算机数值模拟进行。深入开展大气臭氧化学研究,不仅有助于全面深入理解大气氧化过程以及全面掌握区域乃至全球大气自净能力,而且能为对流层污染控制提供科学依据和方案。本文总结了近年来有关臭氧化学的研究进展,论述了臭氧问题与人类当前面临的一些主要环境问题间的相互关系;重点综述了近年来有关南极臭氧空洞、中纬度地区臭氧低值和北极地区臭氧的损耗机理及其发展趋势;综述了臭氧与大气光化学和气溶胶间的耦合关系,并结合我国实际情况,提出了大气臭氧化学尚待深入开展研究的一些重要科学问题。     

Detection of ozone gas using gold nanoislands and surface plasmon resonance

Gold nanoislands interact with gaseous ozone to produce a surface plasmon resonance shift, similarly to the interaction of ozone and gold nanoparticles in water. Gold nanoislands are produced by sputtering, which significantly simplifies the synthesis and produces controlled size for the gold nanoislands. The shift of surface plasmon resonance peak was monitored while gold nanoislands were exposed to variable concentration of gaseous ozone. The shift was then correlated with ozone concentration. Our current results indicate sensing gaseous ozone at concentration of as low as 20 μg/L is achievable. Gold nanoislands were reversed to their original wavelength and were able to cycle between the wavelengths as ozone was introduced and removed. Potentially, this system can be useful as a sensor that identifies the presence of ozone at low part-per-billion concentrations of ozone in gaseous media.     

Mass-dependent and non-mass-dependent isotope effects in ozone photolysis: resolving theory and experiments

In addition to the anomalous (17)O and (18)O isotope effects in the three-body ozone formation reaction O+O(2)+M, isotope effects in the destruction of ozone by photolysis may also play a role in determining the isotopic composition of ozone and other trace gases in the atmosphere. While previous experiments on ozone photolysis at 254 nm were interpreted as evidence for preferential loss of light ozone that is anomalous (or "non-mass-dependent"), recent semiempirical theoretical calculations predicted a preferential loss of heavy ozone at that wavelength that is mass dependent. Through photochemical modeling results presented here, we resolve this apparent contradiction between experiment and theory. Specifically, we show that the formation of ozone during the UV photolysis experiments is not negligible, as had been assumed, and that the well-known non-mass-dependent isotope effects in ozone formation can account for the non-mass-dependent enrichment of the heavy isotopologs of ozone observed in the experiment. Thus, no unusual non-mass-dependent fractionation in ozone photolysis must be invoked to explain the experimental results. Furthermore, we show that theoretical predictions of a mass-dependent preferential loss of the heavy isotopologs of ozone during UV photolysis are not inconsistent with the experimental data, particularly if mass-dependent isotope effects in the chemical loss reactions of ozone during the photolysis experiments or experimental artifacts enrich the remaining ozone in (17)O and (18)O. Before the calculated fractionation factors can be quantitatively evaluated, however, further investigation of possible mass-dependent isotope effects in the reactions of ozone with O((1)D), O((3)P), O(2)((1)Delta), and O(2)((1)Sigma) is needed through experiments we suggest here.     

Air sampling of aromatic hydrocarbons in the presence of ozone by solid-phase microextraction

Effects of ozone on air sampling of standard gas mixtures of aromatic hydrocarbons were tested using solid-phase microextraction (SPME). Standard concentrations of ozone ranging from 10 ppb (v/v) to 6400 ppm (v/v) were generated using an in-house built ozone generator based on corona discharge. Effects of temperature, discharge voltage, and oxygen flow on the ozone generation were tested. The working dc voltage had the greatest effect on generated ozone concentration and was proportional to the ozone concentration. Generation temperature and oxygen flow rate were inversely proportional to ozone concentrations. Produced ozone was mixed with standard benzene, toluene, ethylbenzene, and xylenes (BTEX) gas at less than 100 ppb (v/v). Air samples were collected with poly(dimethylsiloxane) (PDMS) 100 microm SPME fibers and analyzed by gas chromatography (GC)-flame ionization detection (FID) and GC-MS. Significant reductions of BTEX concentrations were observed. In addition, some products of BTEX-ozone-oxygen reactions were identified. SPME worked well as a rapid sampler for BTEX and BTEX-ozone-oxygen reaction products. No significant deterioration of the PDMS coating and no significant reduction of absorption capacity were observed after repeated exposure to ozone.     

臭氧层的化学破坏及其对策

臭氧层的化学破坏是人类的重大环境问题。本文对臭氧层的形成，作用，臭氧层破坏的后果，破坏臭氧层的物质及作用机制和保护臭氧层的对策作了探讨。     

Physicochemical patterns of ozone absorption by wood

Results from studying aspen and pine wood ozonation are presented. The effect the concentration of ozone, the reagent residence time, and the content of water in a sample of wood has on ozone consumption rate and ozone demand are analyzed. The residence time is shown to determine the degree of ozone conversion degree and the depth of substrate destruction. The main patterns of ozone absorption by wood with different moisture content are found. Ways of optimizing the ozonation of plant biomass are outlined.     

Formation of hydroxyl radicals by collapsing ozone microbubbles under strongly acidic conditions

Hydroxyl radicals are strong oxidants in aqueous solution, reacting rapidly with a wide range of dissolved compounds. In contrast, ozone is a highly selective oxidant. Understanding the process by which ozone is transformed into hydroxyl radicals is important in the treatment of wastewater and drinking water. We use electron spin-resonance spectroscopy to demonstrate that when microbubbles of ozone in strongly acidic aqueous solution collapse, the ozone progressively decomposes and large quantities of hydroxyl radicals are generated. Moreover, the degradation of polyvinyl alcohol, which is ozone resistant, was also observed during the collapse of the microbubbles. These findings indicate that ozone microbubbles are potentially useful in future water-treatment applications.     

Synthesis of Ozone at Atmospheric Pressure by a Quenched Induction-Coupled Plasma Torch

The technical feasibility of using an induction-coupled plasma (ICP) torch to synthesize ozone at atmospheric pressure is explored. Ozone concentrations up to ~250 ppm were achieved using a thermal plasma reactor system based on an ICP torch operating at 2.5 MHz and ~11 kVA with an argon/oxygen mixture as the plasma-forming gas. The corresponding production rate and yield were ~20 g ozone/hr and ~2g ozone/kWh, respectively. A gaseous oxygen quench formed ozone by rapid mixing of molecular oxygen with atomic oxygen produced by the torch. The ozone concentration in the reaction chamber was measured by Fourier Transform infrared (FTIR) spectroscopy over a wide range of experimental conditions and configurations. The geometry of the quench gas flow, the quench flow velocity, and the quench flow rate played important roles in determining the ozone concentration. The ozone concentration was sensitive to the torch RF power, but was insensitive to the torch gas flow rates. These observations are interpreted within the framework of a simple model of ozone synthesis.