Photosensitized Oxidation of Cyanide in Aqueous Solutions of Photoactive Modified Hydroxyethylcellulose

Novel water-soluble polymeric photosensitizers based on a natural polymer, naphthalene-modified hydroxyethylcellulose (HENC), were obtained and used for the photooxidation of cyanide. The reaction leads to the formation of cyanate. The process occurs via photoinduced electron transfer from CN⁻ to the naphthalene or naphthoquinone polymeric chromophores. The kinetics of the reaction depend on the degree of substitution of HENC, its concentration, and pH of the solution. The polymers can be easily removed after reaction as prolonged irradiation leads to their photodegradation.     

TiO2光电催化中光生电子降解对苯醌的行为研究

通过施加外加偏压把TiO2/Ti薄膜阳极产生的光生电子转移到阴极,并对其在阴极的电化学行为进行了研究.用水杨酸探针法对阴极溶液中产生的活性氧自由基进行了检测,探讨了pH值、恒电流值和连接类型等因素对阴极室溶液中对苯醌降解效果的影响.实验结果表明,在酸性条件下,转移至阴极的光生电子可将溶液中的溶解氧还原生成H2O2,再进而生成·OH;在pH值为2.0、恒电流为3.5mA和阳离子膜作为反应器双室连接类型的条件下,在60min内,阴极溶液中对苯醌的降解率可达到82.3%.     

Photocatalytic degradation of perfluorooctanoic acid with β-Ga2O3 in anoxic aqueous solution

Perfluorooctanoic acid (PFOA) is a new-found hazardous persistent organic pollutant, and it is resistant to decomposition by hydroxyl radical (HO·) due to its stable chemical structure and the high electronegativity of fluorine. Photocatalytic reduction of PFOA with β-Ga₂O₃ in anoxic aqueous solution was investigated for the first time, and the results showed that the photoinduced electron (e_cb^-) coming from the β-Ga₂O₃ conduction band was the major degradation substance for PFOA, and shorter-chain perfluorinated carboxylic acids (PFCAs, C_nF_2n+1COOH, 1 ≤ n ≤ 6) were the dominant products. Furthermore, the concentration of F^- was measured by the IC technique and defluorination efficiency was calculated. After 3 hr, the photocatalytic degradation efficiency was 98.8% and defluorination efficiency was 31.6% in the presence of thiosulfate and bubbling N₂. The degradation reaction followed first-order kinetics (k = 0.0239 min^-1, t_1/2 = 0.48 hr). PFCAs (C_nF_2n+1COOH, 1 ≤ n ≤ 7) were detected and measured by LC-MS and LC-MS/MS methods. It was deduced that the probable photocatalytic degradation mechanism involves e_cb^- attacking the carboxyl of C_nF_2n+1COOH, resulting in decarboxylation and the generation of C_nF_2n+1·. The produced C_nF_2n+1· reacted with H2O, forming C_nF_2n+1OH, then C_nF_2n+1OH underwent HF loss and hydrolysis to form C_nF_2n+1COOH.     

精□唑禾草灵和1-氨基-2,4-二溴蒽醌光致毒性演变过程与机理

研究了除草剂精□唑禾草灵和染料中间体1-氨基-2,4-二溴蒽醌对大型□(Daphnia magna)的光致急性毒性作用机制. 精□唑禾草灵(EC₅₀ 95%置信区间为4.62～6.63 mg/L)光解生成光稳定性以及急性毒性更大的产物□唑酚(EC₅₀ 95%置信区间为1.49～1.64 mg/L),推测精□唑禾草灵通过光修饰作用机制对大型□发挥光致毒性作用. 1-氨基-2,4-二溴蒽醌通过光化学转化生成二聚体,光修饰作用降低了其母体化合物的光致毒性. 在1-氨基-2,4-二溴蒽醌和模拟日光单独存在的条件下,大型□体内的活性氧物种(ROS)没有明显变化;在1-氨基-2,4-二溴蒽醌和模拟日光共同存在的条件下,生物体内的ROS呈先增加后降低的趋势. 另外,添加抗氧化剂可以减弱1-氨基-2,4-二溴蒽醌对大型□的光致毒性. 结果表明,光敏化作用是1-氨基-2,4-二溴蒽醌对大型□产生光致毒性的主要作用机制. 含时-密度泛函理论(TD-DFT)的计算结果表明,1-氨基-2,4-二溴蒽醌在水溶液中能够通过能量传递和电子转移2种方式发生光敏化反应.