纳米复合ZnO-TiO2晶体的制备及其光电催化性能研究

采用溶胶-凝胶法制备了纳米复合半导体ZnO-TiO2薄膜,并进行了结构和光电催化性能的测试.TiO2薄膜对五氯酚溶液的光电催化降解结果表明当输入正向偏压后,其光催化性能有较大提高.由于ZnO的掺入,半导体薄膜电极的光吸收能力增强;同时,Zn2+可能作为光生载流子的浅俘获中心,导致表面界面电荷转移加速,从而延长光生电子/空穴对的寿命并抑制其复合,有效地提高了TiO2薄膜光电催化活性.     

The preparation of Zn2+-doped TiO(2) nanoparticles by sol-gel and solid phase reaction methods respectively and their photocatalytic activities

The photocatalytic oxidation of the organic pollutants with TiO(2) as photocatalyst has been widely studied in the world, and many achievements have been made. The degradation of pollutants is highly related to the photocatalytic activity of TiO(2). It is demonstrated that doping ions to TiO(2) is one way to enhance the photocatalytic activity of TiO(2). In this paper, Zn(2+)-doped TiO(2) nanoparticles were prepared through sol-gel and solid phase reaction methods, characterized by means of X-ray diffraction (XRD) and transmission electron microscopy (TEM). The photocatalytic activity of the elaborated powders was studied following the degradation of Rhodamine B. The results showed that the photocatalytic activity of Zn(2+)-doped TiO(2) prepared by sol-gel method is close to that of pure TiO(2) particles, however, the photocatalytic activity of Zn(2+)-doped TiO(2) prepared by solid phase reaction method is much higher than that of pure TiO(2) particles. The most efficient degradation of Rhodamine B was found with TiO(2) particles doped with 0.5% Zn(2+) in mole and calcined at 500 degrees C. Also the reason for the enhancement of the photocatalytic activity of TiO(2) by Zn(2+) doping through solid phase reaction method was discussed.     

Photoelectrocatalytic degradation of 4,4'-dibromobiphenyl in aqueous solution on TiO₂ and doped TiO₂ nanotube arrays

Polybrominated biphenyls have been widely used as flameretardants in textile and electronic industries, and additives in plastics. Over the past few decades, much attention has been given to polybrominated biphenyls in the environment and their effects on humans. In this paper, we studied on the degradation of 4,4′-dibromobiphenyl, a typical one of polybrominated biphenyls, through photoelectrocatalytic process with TiO₂, Zr/TiO₂ and Zr, N/TiO₂ nanotube arrays. The results showed that the photoelectrocatalytic process was more efficient than photocatalytic and electrolytic process alone. The results exhibited that the photoelectrocatalytic efficiency was significantly affected by the properties of the catalysts and bias potential, and the highest photoelectrocatalytic degradation rate was achieved with Zr, N/TiO₂ at 1 V and the order was Zr, N/TiO₂ > Zr/TiO₂ > TiO₂. The mechanism was also discussed by detecting the changes of pH value, bromine anion, total organic carbon and intermediates during the process.     

溶胶-凝胶法制备复合光催化剂（MWNTs/TiO_2）工艺条件的研究

以多壁碳纳米管（MWNTs）为载体,在煅烧温度200~900℃、煅烧时间1~7 h、溶胶体系pH值为2~10的工艺条件下,采用溶胶-凝胶法制备复合光催化剂（MWNTs/TiO2）。通过其对甲基橙的光催化降解效果对比,评价各种复合光催化剂催化活性之间的差异,结果表明,随着煅烧温度的升高,复合光催化剂中纳米TiO2的晶型由锐钛型逐渐向金红石型转变,500℃时为2种晶型的混合相;pH值为2的强酸性条件有利于形成金红石晶型,pH值为5的中性及弱酸性条件则有利于形成锐钛型,而pH值为3时为2种晶型的混合相;在煅烧温度500℃、煅烧时间3 h、溶胶凝胶体系pH值为3的最佳制备工艺条件下,复合光催化剂催化活性最高,借助扫描电镜发现其TiO2均匀地包覆在多壁碳纳米管管壁上。     

Modifying sorbents in controlled release formulations to prevent herbicides pollution

The herbicides chloridazon and metribuzin, identified as groundwater pollutants, were incorporated in alginate-based granules to obtain controlled release properties. In this research the effect of incorporation of sorbents such as bentonite, anthracite and activated carbon in alginate basic formulation were not only studied on encapsulation efficiency but also on the release rate of herbicides which was studied using water release kinetic tests. In addition, sorption studies of herbicides with bentonite, anthracite and activated carbon were made. The kinetic experiments of chloridazon and metribuzin release in water have shown that the release rate is higher in metribuzin systems than in those prepared with chloridazon, which has lower water solubility. Besides, it can be deduced that the use of sorbents reduces the release rate of the chloridazon and metribuzin in comparison to the technical product and to the alginate formulation without sorbents. The highest decrease in release rate corresponds to the formulations prepared with activated carbon as a sorbent. The water uptake, permeability, and time taken for 50% of the active ingredient to be released into water, T(50), were calculated to compare the formulations. On the basis of a parameter of an empirical equation used to fit the herbicide release data, the release of chloridazon and metribuzin from the various formulations into water is controlled by a diffusion mechanism. Sorption capacity of the sorbents for chloridazon and metribuzin, ranging from 0.53mgkg(-1) for the metribuzin sorption on bentonite to 2.03x10(5)mgkg(-1) for the sorption of chloridazon on the activated carbon, was the most important factor modulating the herbicide release.     

Evaluation of bactericidal efficacy of silver ions on Escherichia coli for drinking water disinfection

Purpose

The purpose of this study is the development of a suitable process for the disinfection of drinking water by evaluating bactericidal efficacy of silver ions from silver electrodes.

Methods

A prototype of a silver ioniser with silver electrodes and control unit has been fabricated. Silver ions from silver electrodes in water samples were estimated with an atomic absorption spectrophotometer. A fresh culture of Escherichia coli (1.75?×?10³ c.f.u./ml) was exposed to 1, 2, 5, 10 and 20?ppb of silver ions in 100?ml of autoclaved tap water for 60?min. The effect of different pH and temperatures on bactericidal efficacy was observed at constant silver ion concentration (5?ppb) and contact time of 30?min.

Results

The maximum bactericidal activity (100%) was observed at 20?ppb of silver ion concentration indicating total disinfection after 20?min while minimum bactericidal activity (25%) was observed after 10?min at 01?ppb of silver ions. Likewise, 100% bactericidal activity was noticed with 2, 5 and 10?ppb of silver ions after 60, 50 and 40?min, respectively. Bactericidal activity at pH?5, 6, 7, 8 and 9 was observed at 79.9%, 79.8%, 80.5%, 100% and 100%, respectively, whereas it was 80.4%, 88.3%, 100%, 100% and 100% at 10°C, 20°C, 30°C, 40°C and 50°C, respectively.

Conclusion

The findings of this study revealed that very low concentrations of silver ions at pH?8?C9 and temperature >20°C have bactericidal efficacy for total disinfection of drinking water. Silver ionisation is suitable for water disinfection and an appropriate alternative to chlorination which forms carcinogenic disinfection by-products.     

不同电极降解2-氯苯酚

采用电沉积法制备了4种钛基二氧化铅电极,并与商业化的钛基RuO2电极进行了对比。分别用XRD和阳极极化曲线对电极性能进行了表征,并以2-氯苯酚为目标污染物,考察了6种电极的电催化氧化性能。研究结果表明,以钛板为基体的系列电极的综合性能优于以钛网为基体的相应电极。以β-PbO2为活性外层的二氧化铅电极的综合性能优于以RuO2为活性外层的电极。6种电极对2-氯苯酚降解反应均遵循一级反应动力学规律。其中Ti/α-PbO2/β-PbO2电极析氧电位最高,电催化性能最好,对2-氯苯酚的去除率可达99.3%。     

Electrocatalytic reduction of nitrate in water with a palladium-modified copper electrode.

A highly active electrocatalytic electrode for nitrate reduction was prepared by the electro-deposition of palladium onto a copper electrode. The capacity of nitrate reduction by a palladium-modified copper electrode has been studied using cyclic voltammetry (CV). The existence of a reduction peak at -0.605 V versus saturated calomel electrode in 0.1-M sodium nitrate + 0.1-M perchloric acid solution (pH = 0.86) can be found in the CV measurement. The influence of solution properties, such as pH, nitrate concentration, and other anions in solution, on nitrate reduction was determined in detail. Results showed that nitrate reduction was suppressed in alkaline solution, while it was beneficial to nitrate reduction in acid or neutral solution. At low nitrate concentrations (0.01 to 0.5 M), nitrate reduction current increased with increasing nitrate concentration, but was hindered by sulfate. At high nitrate concentrations (1 to 5 M), no significant difference on nitrate reduction was observed. Compared with other different electrodes prepared in our work (copper, titanium, and palladium-modified titanium electrodes), the palladium-modified copper electrode showed the highest electrocatalytic capacity and stability in the nitrate-reduction process.     

Catalytic performance of Ag/Al2O3-C2H5OH-Cu/Al2O3 system for the removal of NOx from diesel engine exhaust

The selective catalytic reduction (SCR) of NOx by C(2)H(5)OH was studied in excess oxygen over Ag/Al(2)O(3) catalysts with different Ag loadings at lab conditions. The 4% Ag/Al(2)O(3) has the highest activity for the C(2)H(5)OH-SCR of NOx with a drawback of simultaneously producing CO and unburned THC in effluent gases. An oxidation catalyst 10% Cu/Al(2)O(3) was directly placed after the Ag/Al(2)O(3) to remove CO and unburned THC. Washcoated honeycomb catalysts were prepared based on the 4% Ag/Al(2)O(3) and 10% Cu/Al(2)O(3) powders and tested for the C(2)H(5)OH-SCR of NOx on a diesel engine at the practical operating conditions. Compared with the Ag/Al(2)O(3) powder, the Ag/Al(2)O(3) washcoated honeycomb catalyst (SCR catalyst) has a similar activity for NOx reduction by C(2)H(5)OH and the drawback of increasing the CO and unburned THC emissions. Using the SCR+Oxi composite catalyst with the optimization of C(2)H(5)OH addition, the diesel engine completely meets EURO III emission standards.     

化学活化法制备羊骨基活性炭工艺的优化及其孔结构的表征

以氯化锌为活化剂,用羊骨为原料,利用化学活化法制备羊骨基活性炭。通过正交实验和单因素实验相结合得出最优工艺条件为:氯化锌溶液浓度0.05 g/100 mL、活化温度350℃、活化时间10 min、浸渍时间为36 h。在此最佳工艺条件下羊骨基活性炭的碘吸附量为407.35 mg/g,得率为62%;用此工艺制备的羊骨基活性炭等温曲线类型属于多层吸附;BET比表面积为59 m2/g,总孔容为0.1945 cm3/g,孔径分布落在1.31～20 nm之间,为中孔结构;羊骨基活性炭SEM图可看出,颗粒呈不规则状,结构疏松。     

Performance of Gd-doped Ti-based Sb-SnO2 anodes for electrochemical destruction of phenol

The performance of electrodes for the electro-catalytic decomposition of a model pollutant (phenol) was enhanced using Gd-doped Ti/SnO(2)-Sb electrodes prepared by a thermal deposition method. Phenol degradation followed first-order rate kinetics, with the maximum rate achieved using a 2% Gd doping level (molar ratio based on Gd:Sn) for tests conducted over a doping range of 1-10%. The first-order rate constant with 2% Gd was 0.044 min(-1), versus 0.026 min(-1) obtained with the control (plain Ti/SnO(2)-Sb). TOC removal and UV scans revealed that different intermediates were produced for different Gd contents, and that destruction efficiencies of these intermediates also varied with Gd doping levels of 1-5%. Electrodes were characterized by scanning electron microscopy, X-ray diffraction, electron dispersive spectrometry, and X-ray photon-electron spectroscopy. It is suggested that the state of specific active sites on the electrode surface and the oxygen transfer activity at the electrode/electrolyte interface affect the performance of anodes with different compositions.     

二氧化钛/碳纳米管/壳聚糖薄膜的制备及对苯的降解性能

研究了光催化降解挥发性有机化合物过程中催化剂二氧化钛/碳纳米管/壳聚糖薄膜的制备以及该催化剂对苯的光催化性能。首先采用溶胶-凝胶法制备纳米复合材料二氧化钛/碳纳米管,然后利用壳聚糖作为交联剂,制得二氧化钛/碳纳米管/壳聚糖复合材料催化薄膜。通过傅立叶红外光谱(FT-IR)、X射线衍射(XRD)透射电镜扫描(TEM)和紫外-可见光漫反射(UV-Vis)等技术分析了复合材料薄膜的组成、结构、形貌和对光的吸收性能,然后使用该催化剂对室内常见的污染物苯进行降解,并在同样的实验条件下,使用催化剂二氧化钛(P25)/壳聚糖对苯进行降解,对两者催化性能进行对比,结果表明,二氧化钛/碳纳米管/壳聚糖对苯有更强的吸附能力和更高的催化活性。     

Preparation of the Mn/Co mixed oxide catalysts for low-temperature CO oxidation reaction

The Mn/Co mixed powders with various Mn/Co molar ratios were prepared by the coprecipitation method and used in low-temperature CO oxidation. The physicochemical characteristics of these powders were characterized using the Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM) analyses. The results demonstrated that the Mn/Co molar ratio significantly affected both the textural and catalytic properties and the sample with a Mn/Co = 1:1 possessed a BET area of 123.7 m²g⁻¹ with a small mean pore size of 6.44 nm. The catalytic results revealed that the pure cobalt and manganese catalysts possessed the low catalytic activity and the pure Co catalyst is not active at temperatures lower than 140 °C. The highest catalytic activity was observed for the catalyst with a Mn/Co = 1. The obtained results showed that the incorporation of Pd into the Mn/Co catalyst significantly enhanced the catalytic activity for oxidation of carbon monoxide and the highest CO conversion was observed for the catalyst with 1 wt.% Pd and this catalyst exhibited a CO conversion of 100% at 80 ^°C.

     

活性炭吸附化学战剂--沙林染毒水的试验研究

研究了 5种国产活性炭吸附水中沙林的性能及影响因素。果壳质活性炭的吸附性能优于煤质活性炭。果壳活性炭WP 2 0 2的吸附等温线方程为 qe=11 45C0 39e ,其粉状炭在 10min时能达到吸附容量的 98%。活性炭颗粒小则吸附速度快 ,温度升高不利于吸附。活性炭与水中的氯反应后 ,吸附性能下降 3 0 % ,在含盐量 2 0 0 0mg/L的苦咸水中吸附量降低 5 %。处理化学战剂 -沙林染毒水宜多种水处理技术相结合 ,并采用活性炭吸附作为最后一级处理单元     

Photoelectrocatalytic degradation of 4-chlorophenol and oxalic acid on titanium dioxide electrodes

Photocatalytically active thin TiO(2) films were produced by spin-coating or dip-coating an alkoxy precursor onto a transparent conducting electrode substrate and by thermal oxidation of titanium metal. The thin films were used to study the photoelectrocatalytic or photoelectrochemical degradation of oxalic acid and 4-chlorophenol (4-CP) under near UV (monochromatic, 365 nm) light irradiation. Degradation was monitored by a variety of methods. In the course of oxalic acid degradation, CO(2) formation accounted for up to 100% of the total organic carbon degradation for medium starting concentrations; for the degradation of 4-CP, less CO(2) was detected due to the higher number of oxidation steps, i.e. intermediates. Incident-photon-to-current conversion efficiency, educt degradation and product formation as well as Faradaic efficiencies were calculated for the degradation experiments. Quantum yields and Faradaic efficiencies were found to be strongly dependent on concentration, with maximum values (quantum yield) around 1 for the highest concentrations of oxalic acid.     

Ru-TiO2光电极对亚甲基蓝的光电催化降解

采用阳极氧化法制备Ru—TiO2光电极,以该电极为工作电极,石墨作对电极,饱和甘汞电极为参比电极,对亚甲基蓝溶液的光电催化降解进行了研究。结果表明：煅烧温度600oC,掺杂1％Ru的Ru-TiO2光电极催化活性最好;以紫外灯（125W）为光源,当外加偏压0．2V,pH为5时,Ru-TiO2光电催化亚甲基蓝120min可使其完全脱色;亚甲基蓝的光电催化降解遵从Langmuir—Hinshelwood动力学模型,测得其反应速率常数k：0．781mmol／（L·min）,吸附常数K=0．225L／mmol。     

Ru-TiO_2光电极对亚甲基蓝的光电催化降解

采用阳极氧化法制备Ru-TiO2光电极,以该电极为工作电极,石墨作对电极,饱和甘汞电极为参比电极,对亚甲基蓝溶液的光电催化降解进行了研究。结果表明:煅烧温度600℃,掺杂1%Ru的Ru-TiO2光电极催化活性最好;以紫外灯(125 W)为光源,当外加偏压0.2 V,pH为5时,Ru-TiO2光电催化亚甲基蓝120 min可使其完全脱色;亚甲基蓝的光电催化降解遵从Langmuir-Hinshelwood动力学模型,测得其反应速率常数k=0.781 mmol/(L.min),吸附常数K=0.225 L/mmol。     

Effect of soil compaction on organic carbon amounts and distribution, South-Central Iowa

Soils on the Mormon Trail have been compacted for over 150 years. Bulk density, carbon, and nitrogen samples were taken in 5-cm increments to 20 cm. Bulk density was determined using rings of known volume; total carbon and nitrogen with a LECO CHN-600. Total above ground biomass (AGB) samples were collected by clipping vegetation within a 0.25 m2 frame and were analyzed for carbon. Statistical comparisons were made using a t-test (alpha = 0.05). Bulk density was higher in the on-trail soils from 5 to 20 cm; soil carbon and C/N ratios were higher in the off-trail soils from 10 to 20 cm. AGB and AGB carbon is significantly less on the trail. Results indicate the compacted layer on the trail alters the soil carbon pool by limiting additions of fresh organic matter to the soil, limiting vegetative production, and by "pooling" carbon additions in the upper 10 cm of the soil.     

氧化锰矿渣改性制备SCR脱硝催化剂

以锰酸钾生产过程中产生的氧化锰矿渣为原料,制备了一系列Mn基SCR脱硝催化剂。研究了活性炭、二氧化钛、以及含锰量的变化对催化剂的脱硝活性的影响。结果表明,直接由矿渣制备的催化剂和添加活性炭、二氧化钛制备的催化剂,其最大脱硝率分别为40%和78%。XPS表征发现催化剂中的锰元素存在多种氧化价态,活性炭的加入在一定程度上改变了不同价态之间的相对含量;在矿渣中加入硫酸锰后,发现总锰含量达到10%时,催化剂的最大脱硝率从78%降低至57%,XRD测试发现硫酸锰的加入导致S2O27-物种的生成,可能是引起催化剂活性下降的原因之一;而加入醋酸锰至总锰含量达到10%时,增大了催化剂的活性温度窗口,当总锰含量达到20%时,在空速10 000 h-1条件下,催化剂的最大脱硝率达到86.7%。     

低温净化氮氧化物的改性活性炭材料

针对活性炭室温净化NO₂过程中生成NO的问题,分别用还原性物质和强氧化性物质对活性炭进行了改性研究,并分析了NO的生成原因和各种改性材料处理氮氧化物的作用机理。金属氧化物改性活性炭性能最好,室温条件下,对NO₂的净化效率在20 h内保持在98%以上,NO生成量为活性炭处理时的1/2弱。