Photodegradation of a herbicide derivative, 2,4-dichlorophenoxy acetic acid in aqueous suspensions of titanium dioxide

The photocatalytic degradation of a herbicide derivative, 2,4-dichlorophenoxy acetic acid (2,4-D, 1), has been investigated in aqueous suspensions of titanium dioxide. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic analysis and decrease in Total Organic Carbon (TOC) content as a function of irradiation time in the presence of UV light source. The degradation kinetics was investigated under a variety of conditions, such as different types of TiO₂, pH, catalyst and substrate concentrations. Higher photonic efficiencies were observed with Degussa P25 as compared with other photocatalysts. The degradation products were analysed by GC-MS and probable pathways for the formation of different products were proposed.     

氯分子束与钛表面激光化学反应动力学

本文采用飞行时间质谱技术测定了在紫外(355nm), 可见(560nm)和近代红外(1064nm)脉冲激光作用下, 氯分子束与Ti表面反应产物的质量分布和速度分布。所得结果表明, 不同波长激光诱导反应的主要产物相同, 有Ti, TiCl, TiCl3和TiCl4。在高能量密度的紫外激光作用下, 首次测得具有很高动能的原生Ti+。各种含Ti氯化物的飞行时间谱, 能满意地用单组分或多组分Maxwell-Boltzmann公式拟合和分析。上述激光诱导气-固表面反应的机理主要由氯分子在Ti表面上的解离吸附,吸附态氯原子在表面上生成TiClx(X=1～4)的连串反应以及激光诱导脱附所组成。近红外激光主要引起热脱附, 而紫外激光的作用还原可能有非热脱附过程。     

1,1'-(六甲基三硅撑)双环戊二烯基二(对氯苯氧基)钛的合成及晶体结构

以1,3-二氯六甲基三硅烷相继与环戊二烯基钠、正丁基锂和四氯化钛作用合成了1,1'-(六甲基三硅撑)双环戊二烯基二氯化钛(1),1在氨基钠的存在下与对氯苯酚作用制得题目化合物(2)。通过元素分析、^1HNMR和MS鉴定了1与2的结构,并对2进行X射线结构分析确证了其结构。2的晶体属单斜晶系的P21/c空间群。晶胞参数:a=1.0746(3),b=2.4865(7),c=1.2568(2)nm; β=113.42(2)°;V=3.08137nm^3;Z=4,D0=1.305g·cm^-3。化合物中三个硅原子的桥链发生明显扭曲。通过氧原子中心原钛与苯环发生共轭,使整个分子形成共轭体系。     

TiO2/PtO-Pt复合膜和SnO2/PtO-Pt复合膜氢敏性能的研究

将PtO-Pt纳米粒子膜与TiO2，SnO2纳米粒子膜复合，利用PtO-Pt纳米粒子膜作 为插入电极和催化剂，设计并研制出一类新型双层结构复合膜气体传感器。采用 TEM和SEM对薄膜的显微结构进行了表征，对空气中4.0H2的氢敏性能研究表明： 200℃时，TiO2/PtO-Pt复合膜对氢气的灵敏度为70％，而TiO2纳米粒子膜无响应。 100℃时，SnO2/PtO-Pt复合膜的灵敏度为92％，同样条件下，SnO2纳米粒子膜的灵 敏度仅为4％。说明PtO-Pt纳米粒子膜的催化作用能够显著提高TiO2和SnO2的膜氢 敏性能。另外，TiO2/PtO-Pt复合膜和SnO2/PtO-Pt复合膜均对空气中H2有很高的选 择性。     

[TPPFe(III)]~2O的合成及其对细胞色素P-450的模拟

TPPFe(III)Cl通过中性Al~2O~3色谱柱得到一个新化合物, 它在HPLC中的保留时间比TPPFe(III)Cl大得多, IR、UV-Vis和元素分析表明, 这个新化合物是[TPPFe(III)]~2O. 同TPPFe(III)Cl一样, 它具有在常温常压下催化碳氢化合物单充氧化的性质。[TPPFe(III)]~2O催化下PhIO氧化环己烷的反应, 在CH~2Cl~2和环己烷介质中, 氧化产率分别为14.97和62.6%, 高于TPPFe(III)Cl作催化剂时的产率。在环己烷溶剂中, 反应产率与反应时间呈线性关系, 且反应有大约3小时诱导期。但在CH~2Cl~2溶剂中不存在反应产物与时间的线性关系, 也不存在诱导期。与TPPFe(III)Cl比较,[TPPFe(III)]~2O对氧化剂更稳定。上述事实表明, [TPPFe(III)]~2O能够作为细胞色素P-450的模型化合物。     

全氟和多氟烷基磺酸的研究 XVI.以二氟甲磺酸作为二氟卡宾前体合成全氟或多氟烷基磺酸二氟甲酯

二氟甲磺酸(1)在室温下即可和五氧化二磷作用,但和全氟烷烃磺酸不同,它并不生成相应的磺酸酐。脱水后进一步消除二氧化硫产生二氟卡宾,二氟卡宾再插入二氟甲磺酸得到二氟甲磺酸二氟甲酯(2)。若有其它全氟烷基磺酸或全氟烷基羧酸存在时,也可得到相应的全氟烷基磺酸二氟甲酯(4)或全氟烷基羧酸二氟甲酯(6)。用三氯氧磷或二氯亚砜代替五氧化二磷和1作用,也得到类似的结果。对二氟卡宾生成的可能机理进行了讨论。     

甲氧基代多个氧化乙烯结构交联型酚醛聚合物的合成

采用对甲氧基苯酚、多缩乙二醇二氯化物为原料, 合成了五个4,4'-二甲氧基多缩乙二醇二苯醚新单体; 分别经甲醛、2,6-二羟甲基对甲氧基苯酚聚合, 得到二个系列甲氧基代多个氧化乙烯结构交联型酚醛聚合物。这些聚合物含有假冠醚结构单元, 配合容量在0.9-3.0mmol/g之间, 可作为配合树脂使用, 富集分离多种金属离子。     

Experimental study of photocatalytic oxidation of formaldehyde and its by-products

Formaldehyde is one of the most harmful pollutants that endanger occupants' health and the way of its effective removal has become a focus in the field of air quality. This paper studies the static photocatalytic removal of formaldehyde experimentally and finds out that carbon monoxide, which is more harmful to occupants' health than the formaldehyde itself, is one of the by-products in the process of photocatalytic oxidation of formaldehyde. The increase of carbon monoxide concentration should be taken into consideration in the photocatalytic application. The photocatalyst surface at room temperature can weakly adsorb CO and CO₂, which can deactivate the photocatalysts.     

Changes in surface composition of Fe-Si-Cr-K oxide alkylation catalyst: the marked role of potassium ferrites

The influence of gas-phase methylation of phenol on the state of the Fe-Si-Cr-K oxide catalyst surface was investigated by thermodesorption of K atoms and ions. Changes in potassium desorption energies, as determined from Arrhenius-like plots, varied from 3.07 eV to 1.21 eV for the atoms and from 2.59 eV to 2.89 eV for ion desorption from the active and deactivated samples, respectively. The results were discussed in terms of transformation of the catalyst surface and formation of β-ferrite.