载银TiO2光催化降解2,4-二氯苯酚水溶液的研究

以新型载银TiO₂为催化剂,太阳光为光源,对2,4-二氯苯酚水溶液进行了光降解。结果表明,载银TiO₂催化剂的光解效率是单纯TiO₂的1.9倍;经回归分析,由Langmiur-HinsheiWood方程计算出的反应速率R值与实验值的最大偏差不超过6.5%。证明该光解反应是非均相催化动力学反应。      

Effects of fulvic acid concentration and origin on photodegradation of polycyclic aromatic hydrocarbons in aqueous solution: Importance of active oxygen

With an Xe arc lamp house as simulated sunlight, the influences of fulvic acid (FA) concentration and origins on photodegradation of acenaphthene, fluorine, phenanthrene, fluoranthene and pyrene in aqueous solution have been studied. Similar effects of FAs, collected from five places around China, on polycyclic aromatic hydrocarbon (PAH) photodegradation have been observed. Active oxygen was of significance in PAH photodegradation with the presence of FAs. For systems with 1.25 mg L⁻¹ FAs, the contributions of OH to PAH photodegradation rates were from 33% to 69%. FAs had two opposite effects, i.e., stimulating the generation of active oxygen and advancing PAH photodegradation; competing with PAHs for energy and photons and restraining PAH photodegradation. Generally, photodegradation rates of the 5 PAHs decreased with the increase of FAs concentration; except fluoranthene and pyrene were advanced in solutions with low FA concentration. The influences of FA concentration on PAH photodegradation were more significant than FA origin.     

Photolysis of Enrofloxacin in aqueous systems under simulated sunlight irradiation: Kinetics, mechanism and toxicity of photolysis products

Photolysis of Enro in water was investigated under simulated sunlight irradiation using a Xenon lamp. The results showed that Enro photolysis followed apparent first-order kinetics. Increasing Enro concentration from 5.0 to 40.0 mg L⁻¹ led to the decrease of the photolysis rate constant from 1.6 × 10⁻² to 3.0 × 10⁻³ min⁻¹. Compared with the acidic and basic conditions, the photolysis rate was faster at neutral condition. Both of nitrate and humic acid can markedly decrease the photolysis rate of Enro because they can competitively absorb photons with Enro. The electron spin resonance and reactive oxygen species scavenging experiments indicated that Enro underwent self-sensitized photooxidation via OH and ¹O₂. After irradiation for 90 min, only 13.1% reduction of TOC occurred in spite of fast photolysis of 58.9% of Enro, indicating that Enro was transformed into intermediates without complete mineralization. The photolysis of Enro involved three main pathways: decarboxylation, defluorination, and piperazinyl N⁴-dealkylation. The bioluminescence inhibition rate using Vibrio fischeri increased to 67.2% at 60 min and then decreased to 56.9% at 90 min, indicative of the generation of some more toxic intermediates than Enro and then the degradation of the intermediates. The results will help us understand fundamental mechanisms of Enro photolysis and provide insight into the potential fate and transformation of Enro in surface waters.     

Direct and indirect photolysis of two quinolinecarboxylic herbicides in aqueous systems

The photodegradation of two quinolinecarboxylic herbicides, 7-chloro-3-methylquinoline-8-carboxylic acid (QMe) and 3,7-dichloroquinoline-8-carboxylic acid (QCl), was studied in aqueous solution at different irradiation wavelengths. The effect of sunlight irradiation was investigated also in the presence of titanium dioxide (TiO₂). UV irradiation degraded rapidly QMe affording 7-chloro-3-methylquinoline (MeQ) through a decarboxylation reaction. The reaction rate was lower in the presence of dissolved organic carbon (DOC) because of the adsorption of the herbicide on the organic components. Instead, QCl was stable under both UV light and sunlight irradiation. The irradiation of QMe or QCl solutions with simulated sunlight in the presence of TiO₂ produced the complete mineralization of the two herbicides.     

Photodegradation of perfluorooctanoic acid by synthesized TiO2-MWCNT composites under 365nm UV irradiation

Degradation of perfluorooctanoic acid (PFOA) is of great importance due to its global distribution, persistence and toxicity to bioorganisms. In present study, a composite TiO₂ with multiple wall carbon nano-tubes (MWCNTs) was synthesized using sol-gel method and it was used as photocatalyst to degrade PFOA in water. The prepared composite catalyst displayed significant absorption in UV to visible light region. The loading content of TiO₂ on MWCNTs could be adjusted by changing the ratio of precursor to MWCNTs. Due to the combined effect of the adsorption ability and e⁻ transport capacity of MWCNT, the composites displayed much higher photocatalytic ability to PFOA as compared to pure TiO₂ under UV irradiation. The photocatalyst prepared with 10:1 of tetrabutyl titanate/MWCNT was the most effective. With the optimal dosage at 1.6 g L⁻¹, almost 100% of PFOA was degraded in acid medium after irradiation for 8 h. It was proposed that PFOA were mainly degraded by stepwise losing a moiety of CF₂.