TiO2结构对光催化性能的影响及其提高的途径

文中介绍了TiO2的晶体结构与表面态性质对其光催化活性的影响，综述了近年来有关贵金属沉积、金属离子掺杂、表面光敏化、复合半导体、表面酸化和无机模板合成纳米粒子等改性技术的研究现状，还简单地介绍了电化学、微波场和超声波等外加场辅助光催化的进展。     

纳米TiO2改性可见光催化降解有机物研究进展

光催化降解水中有机污染物是一项颇有发展前途的废水处理技术.目前主要的研究工作由紫外光逐步向可见光催化方向发展,使这项技术向实用性又迈进了一步.系统介绍了纳米TiO2的光催化降解有机污染物的原理,光催化处理水的现状,并从离子掺杂、表面光敏化和分子筛负载几个方面综述了可见光化的研究现状和发展方向.     

纳米TiO2改性可见光催化降解有机物研究进展

光催化降解水中有机污染物是一项颇有发展前途的废水处理技术.目前主要的研究工作由紫外光逐步向可见光催化方向发展,使这项技术向实用性又迈进了一步.系统介绍了纳米TiO2的光催化降解有机污染物的原理,光催化处理水的现状,并从离子掺杂、表面光敏化和分子筛负载几个方面综述了可见光化的研究现状和发展方向.     

BiOBr可见光催化剂的研究进展

BiOBr光催化剂具有特殊的层状结构与适宜的禁带宽度,在可见光条件下表现出优越的光催化活性及稳定性。介绍了BiOBr在国内外的研究现状,包括BiOBr的性质、稳定性、结构、提高光催化活性的途径等。微结构调控、半导体复合、贵金属沉积、离子掺杂和表面敏化等改性手段可改变BiOBr的禁带宽度,促进光生电子与空穴的分离,从而提高BiOBr光催化性能。最后,展望了BiOBr光催化剂的研究前景与发展趋势。     

纳米二氧化钛的改性及光催化氧化烷烃研究

催化剂的表面结构是影响催化反应的重要因素之一.利用原位红外(In-situ FT-IR)、X射线衍射(XRD)和紫外-可见漫反射(UV-Vis DRS)等现代物理技术考察了热处理改性对纳米 TiO2的表面结构、晶相结构、粒子大小、比表面积和吸光性能的影响,采用In-situ FT-IR光谱着重研究了纳米TiO2催化剂上环己烷光催化降解机制及催化剂的结构特性与催化反应之间的相关性.研究表明,400 ℃条件下热处理纳米TiO2具有最佳光催化活性,适宜的表面结构、晶相结构、吸光能力及晶化度是纳米TiO2光催化剂高催化活性的主要原因.借助In-situ FT-IR光谱,观察到环己烷氧化的主要产物是CO2和H2O,同时捕捉到了中间产物CO以及乙酸,提出了环己烷光催化降解的可能机理.     

负载型纳米TiO2光催化剂的研究进展

ＴｉＯ２光催化剂固载化具有重要的实用价值，介绍了载体种类和性能以及两种固载化方法，这了负载型光催化剂的晶型、膜厚和表面状态、载体对二氧化钛光催化活性的影响，指出了该领域的发展方向。     

中央空调净化系统的改进措施

介绍了室内空气净化技术及其特点.针对中央空调系统的特点,提出了将活性炭吸附技术、TiO2光催化技术与静电除尘技术结合的静电活性炭-TiO2光催化复合技术,这一组合技术可能成为今后空调系统空气净化系统重要的改进措施.     

TiO2薄膜气相光催化氧化低浓度三氯甲烷和三氯乙烯的研究

自行设计了气固相光催化实验系统,以铝材为担载体,TCM和TCE为模拟污染物,在常温、常压下,对辐射光源、气体相对湿度、污染物反应浓度等因素对TCM和TCE的光催化降解反应的影响进行了研究.结果表明,在研究所采用的实验条件下,辐射光源采用254 nm时的降解效率要比采用365 nm时高10%左右;气体相对湿度为40%时光催化降解效率最高;随着污染物反应浓度的增加,TCM的降解效率降低,而TCE的降解效率增加.初步的反应动力学研究结果表明,TCM和TCE在二氧化钛表面的光催化降解反应可采用Langmuir-Hinshelwood动力学方程来表征.     

SO2的气相光催化氧化及催化剂的失活和再生研究

在模拟大气环境中,紫外光照射以及纳米TiO2光催化剂的作用下,气相无机污染物SO2被完全氧化为SO3或H2SO4.本文提出了SO2的非均相光催化氧化机理,并得出光催化反应速率符合一级动力学过程;经过连续使用之后,TiO2的光催化活性降低,最后活性消失;经过水洗之后,失活的TiO2可以得到再生.失活的TiO2和新鲜的TiO2的IR和XPS光谱差异表明,失活的TiO2表面存在H2SO4,其被认为是使催化剂失活的成分.     

一种新型铋基光催化剂的合成及其可见光催化性能

采用水热法合成铋基光催化剂Bi4VO8Br,通过X-射线粉末衍射、扫描电镜等手段对其进行表征.选择甲基橙为目标降解物来评价不同条件下合成的Bi4VO8Br在可见光下的光催化活性,发现pH 3、反应时间15 h、反应温度160℃为材料水热合成的最佳条件.考察了Bi4VO8Br在可见光及紫外光下对几种农药和增塑剂的光催化降解性能,显示了Bi4VO8Br对不易光解的含苯环有机物的可见光高活性.五氯酚的光催化过程影响因素优化结果表明,可见光和紫外光分别照射120 min和20 min,其降解率分别达到97％和99％,Bi4VO8Br表面上活性基团的捕获即空穴的氧化作用是主要反应原理.     

Relationship of surface changes to metal leaching from tungsten composite shot exposed to three different soil types

Physical changes that occur on the surface of fired shots due to firing and impact with soil may increase the dissolution of muniton metals. Increased metal dissolution could potentially increase metal transport and leaching, affecting metal concentrations in surface and groundwater. This research describes the relationship between the surface changes on fired tungsten-nickel-iron (94% W:2% Ni:4% Fe) composite shots and metals leaching from those shots. Tungsten composite shot was fired into, and aged in, three soil types (Silty Sand, Sandy Clay, and Silt) in mesoscale rainfall lysimeters to simulate live-fire conditions and subsequent interactions between the metals of the composite and soil. Leachate, runoff, and soil samples were collected from the lysimeters and analyzed for metal content. The shots were analyzed using scanning electron microscopy (SEM) to evaluate surface changes. SEM results indicated that a soil’s particle size distribution initially affected the amount of metal that was sheared from the surface of the fired W-composite shots. Shearing was greatest in soils with larger soil particles (sand and gravel); shearing was least in soils composed of small soil particles (fines). Increased metallic shearing from the shot’s surface was associated with increased W dissolution, compared to controls, following a simulated 1 year soil aging.     

Adsorption/desorption properties of copper ions on the surface of iron-coated sand using BET and EDAX analyses

This study was conducted to develop a heating process for coating hydrated iron oxide on the sand surface to utilise the adsorbent properties of the coating and the filtration properties of the sand. BET and scanning electron microscope (SEM) analyses were used to investigate the surface properties of the coated layer. An energy dispersive X-ray (EDAX) technique of analysis was used for characterising metal adsorption sites on the iron-coated sand surface. The results indicated that the iron-coated sand had more micropores and higher specific surface area because of the attachment of iron oxide. Copper ions could penetrate into the micropores and mesopores of iron oxide on sand surface, and the regeneration of the iron-coated sand could be achieved by soaking with pH = 3.0 acid solution. Besides, the results of EDAX analysis showed that copper ions were chemisorbed on the surface of iron-coated sand. Results of the study developed an innovative technology for coating iron oxide on sand surface for the treatment of heavy metal in water.     

Heavy metal removal by activated sludge: influence of Nocardia amarae.

The goal of this research was to examine the metal binding capacity of Nocardia amarae cells and to assess the influence of Nocardia cells on the overall metal binding capacity of activated sludge. Metal sorption capacities of the pure Nocardia cells and activated sludge biomass containing various levels of added Nocardia pure cultures were determined by a series of batch experiments. Batch sorption isotherms for nickel (Ni), copper (Cu), and cadmium (Cd) showed that the pure culture of N. amarae exhibited significantly higher metal sorption capacity than the activated sludge biomass obtained from Wilmington Wastewater Treatment Plant (Wilmington, DE). Surface area of biomass estimated by a dye technique showed that pure N. amarae cells growing at stationary phase have substantially more specific surface area than that of activated sludge from Wilmington Treatment Plant. A two-fold difference in specific surface area indicated that the higher metal sorption capacity of Nocardia cells may be due to the higher specific surface area. The metal sorption capacity of activated sludge increased proportionally with the amount of Nocardia cells present in the mixed liquor. This increase was attributed to the greater specific surface area of the mixed liquor samples containing greater amounts of Nocardia cells.     

电镀污泥的热处理特性以及对金属回收的影响

焙烧-酸浸法可有效回收电镀污泥中的有价金属,而污泥的热处理特性是决定能否采用焙烧预处理的重要因素。研究了氧化焙烧和还原焙烧对污泥成分和金属浸出性的影响,并对焙烧前后的污泥进行了金属形态分析和X射线衍射(XRD)分析。结果表明,焙烧预处理实现了污泥减量和金属富集;ES1经氧化焙烧后金属浸出率接近原泥,Cu的浸出率达99%;ES2的还原焙烧效果优于氧化焙烧,特别是Cu的浸出率超过97%,XRD分析发现,还原焙烧过程中金属Cu被还原为铁铜合金;2种焙烧均造成了ES3中目标金属Ni的浸出率的降低;金属浸出性的下降与残渣态的形成有关。     

Degradability of ethylenediaminedisuccinic acid (EDDS) in metal contaminated soils: implications for its use soil remediation

Previous research has identified ethylenediaminedisuccinate (EDDS) as a promising biodegradable alternative for persistent compounds such as EDTA for application in soil washing or enhanced phytoextraction of heavy metals. This study examines heavy metal mobilization in three polluted soils varying in soil composition, with specific attention for competitive behaviour for complexation between the various metals and major elements, such as Al, Fe, Mn, Ca and Mg. In addition, amendment biodegradability was compared between the different soil types. The selected soils included a moderately contaminated calcareous clayey soil, a dredged sediment derived surface soil with similar soil characteristics yet more heavily polluted with Cd, Cr and Zn, and a sandy soil moderately contaminated by historical smelter activity (atmospheric deposition). Biodegradability of EDDS in the three soils varied distinctly. This was mainly expressed in the duration of the lag phase prior to metal complex degradation, and not so much in the half life when degradation effectively did set in. Differences in the lag phase were attributed to differences in soil pollution. However, EDDS was fully degraded within a period of 54 d in all soils regardless of initial delay. Assessment of the cation mobilisation patterns in the three soils under study revealed that mainly Ca, Fe and Al can reduce effectiveness of heavy metal mobilisation by competition for complexation.     

Biosorption of Cr3+, Cd2+ and Cu2+ ions by blue-green algae Spirulina sp.: kinetics, equilibrium and the mechanism of the process

The process of biosorption of heavy metal ions (Cr3+, Cd2+, Cu2+) by blue-green algae Spirulina sp. is discussed in this paper. Spirulina sp. was found to be a very efficient biosorbent. The aim of the present study was to investigate quantitatively the potential binding sites present at the surface of Spirulina sp., using both potentiometric titrations and adsorption isotherms. The kinetic experiments showed that the process equilibrium was reached quickly, in less than 5-10 min. It was found that the equilibrium dependence between biosorption capacity and bulk metal ion concentration could be described with Langmuir equation. This suggests that the mechanism of biosorption is rather chemisorption than physical adsorption and was further confirmed by the low surface area associated with physical adsorption and by the presence of cations that appeared in the solution after biosorption. The maximum contribution of physical adsorption in the overall biosorption process was evaluated as 3.7%. It was proposed that functional groups on the cell surface contributed to the binding of metal ions by a biosorbent via equilibrium reaction. Three functional groups capable of cation exchange were identified on the cell surface. The biomass was described as weakly acidic ion exchanger. Since deprotonation of each functional group depends on pH, the process of biosorption is strongly pH-dependent. This was confirmed in the biosorption experiments carried out at different pH. The contribution of functional groups in the biosorption process was confirmed by chemical modification of the groups. Chemically blocked groups did not show neither biosorption nor ion-exchange capabilities. It has been shown that growth conditions can affect the metal adsorption properties of microalgae. The paper also discusses desorption characteristics of the biosorbent. The criteria for desorption were high elution efficiency and preservation of biosorptive properties. Desorbent that possessed these characteristics was nitric acid.     

Trace metal and metalloid levels in surface water of Marcal River before and after the Ajka red mud spill, Hungary

The aim of this study was to compare and assess the dissolved concentrations of trace elements (As, Zn, Hg, Cd, Cr, Ni, Pb and Cu) in surface water of Marcal River before and after the red mud spill that occurred in Ajka, western Hungary, in October 2010. The caustic sludge flooded the surrounding settlements and polluted the nearby Torna Creek, which flows through the Marcal and Raba rivers into the Danube. A total of 92 surface water samples were collected from the Marcal River in the period of 2007–2012 and analysed for dissolved trace metal(loid)s by atomic absorption spectroscopy method. After the spill, the water management authority initially focused on acid dosing of surface waters to lower pH and was effective in lowering both pH and metal(loid) concentrations. Among the dissolved trace metal(loid)s, arsenic and nickel levels were moderately higher in the Marcal River 2 years since the spill compared to that observed in the pre-disaster period. The concentrations of dissolved trace metal(loid)s did not exceed the European water quality standards and the US Environmental Protection Agency aquatic life criteria values (excluding one sample for cadmium).     

The relation between Acid Volatile Sulfides (AVS) and metal accumulation in aquatic invertebrates: Implications of feeding behavior and ecology

The present study evaluates the relationship between Acid Volatile Sulfides (AVS) and metal accumulation in invertebrates with different feeding behavior and ecological preferences. Natural sediments, pore water and surface water, together with benthic and epibenthic invertebrates were sampled at 28 Flemish lowland rivers. Different metals as well as metal binding sediment characteristics including AVS were measured and multiple regression was used to study their relationship with accumulated metals in the invertebrates taxa.Bioaccumulation in the benthic taxa was primarily influenced by total metal concentrations in the sediment. Regarding the epibenthic taxa metal accumulation was mostly explained by the more bioavailable metal fractions in both the sediment and the water. AVS concentrations were generally better correlated with metal accumulation in the epibenthic invertebrates, rather than with the benthic taxa. Our results indicated that the relation between AVS and metal accumulation in aquatic invertebrates is highly dependent on feeding behavior and ecology.     

微量金属元素及其配合物对厨余垃圾甲烷发酵的影响

生物可利用的微量金属元素不仅能够保证污染物以最大的速率转化，而且还可以使某些特殊的转化得以发生，并提高微生物对有毒污染物质的耐受能力。在研究厨余垃圾总固体浓度(total solid, TS)、接种量和C/N比对厨余垃圾厌氧发酵影响的基础上，重点探讨微量金属元素钴及其配合物丝氨酸对厨余垃圾厌氧发酵甲烷产量及关键酶含量的影响。结果表明，当TS为0.5%、接种污泥量为100 mL/L和C/N比为20∶1时，厨余垃圾厌氧发酵的甲烷产率较高，为367 mL/g COD；添加2 μmol/L的微量金属元素钴-配合物丝氨酸时，甲烷产率则提高到432 mL/g COD，相应地，辅酶M的含量由空白实验的41.21 μmol/g VSS提高到54.64 μmol/g VSS，辅酶F₄₂₀的含量由0.31 μmol/g VSS提高到0.48 μmol/g VSS。     

Relation between extracellular polymers' composition and its ability to complex Cd,Cu and Pb

Activated sludges originated from wastewater treatment plants (WWTPs) play an important role in heavy metal removal from effluents. Extracellular polymers (ECP) form a major part of the activated sludge and are heavily involved in biosorption of heavy metals. The complexation of three heavy metals (Cd, Cu and Pb) with ECP extracted from six activated sludges, originated from different WWTPs, was investigated at pH 7.

ECP in the study were shown to be mainly composed of proteins, humic acids, uronic acids and polysaccharides along with smaller amounts of lipids and nucleic acids. IR spectra confirmed the presence of the functional groups usually found in the ECP and the content in each fraction was determined using colorimetric methods. The determination of surface charge was carried out on each ECP sample and allowed two pK_a values characteristic of two distinctive functional groups to be determined. At the pH used in the study, the value of these constants indicates that only one functional group is under protonated form.

A polarographic method was used to determine the complexation parameters (number of binding sites and complexation constant) of ECP solutions towards metals. The following orders were established for the number of binding sites: Cu > Pb  Cd and for the stability of the ECP–metal complex: Cd > Pb  Cu.

A matrix of correlation between the composition of the polymers and the complexation parameters showed that the number of binding sites and the complexation constant were strongly linked to proteins, polysaccharides and humic substances content.