Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

Plasmonic silver/silver oxide nanoparticles anchored bismuth vanadate as a novel visible-light ternary photocatalyst for degrading pharmaceutical micropollutants

The degradation of pharmaceutical micropollutants is an intensifying environmental problem and synthesis of efficient photocatalysts for this purpose is one of the foremost challenges worldwide. Therefore, this study was conducted to develop novel plasmonic Ag/Ag₂O/BiVO₄ nanocomposite photocatalysts by simple precipitation and thermal decomposition methods, which could exhibit higher photocatalytic activity for mineralized pharmaceutical micropollutants. Among the different treatments, the best performance was observed for the Ag/Ag₂O/BiVO₄ nanocomposites (5 wt.%; 10 min's visible light irradiation) which exhibited 6.57 times higher photodegradation rate than the pure BiVO₄. Further, the effects of different influencing factors on the photodegradation system of tetracycline hydrochloride (TC-HCl) were investigated and the feasibility for its practical application was explored through the specific light sources, water source and cycle experiments. The mechanistic study demonstrated that the photogenerated holes (h⁺), superoxide radicals (?O₂^?) and hydroxyl radicals (?OH) participated in TC-HCl removal process, which is different from the pure BiVO₄ reaction system. Hence, the present work can provide a new approach for the formation of novel plasmonic photocatalysts with high photoactivity and can act as effective practical application for environmental remediation.     

有机物分子结构与光催化氧化反应活性的关系

从正辛醇－水分配系数与Ｈａｍｍｅｔｔ常数，光催化氧化过程中的光解作用，表面活性剂的微环境效应及取代基的诱导效应等方面，探讨了有机物分子结构与其光催化氧化反应性之间的关系。     

Efficient degradation of organic pollutants by S-NaTaO3/biochar under visible light and the photocatalytic performance of a permonosulfate-based dual-effect catalytic system

Removing large concentrations of organic pollutants from water efficiently and quickly under visible light is essential to developing photocatalytic technology and improving solar energy efficiency. This study used a simple hydrothermal method to prepare a non-metallic, S-doped NaTaO₃ (S-NTO) photocatalyst, which was then loaded onto biochar (BC) to form a S-NTO/BC composite photocatalyst. After uniform loading onto BC, the S-NTO particles transformed from cubic to spherical. The photogenerated electron-hole pair recombination probability of the composite photocatalyst was significantly lower than those of the NTO particles. The light absorption range of the catalyst was effectively widened from 310 nm UV region to visible region. In addition, a dual-effect catalytic system was constructed by introducing peroxymonosulfate (PMS) into the environment of the pollution to be degraded. The Rhodamine B, Methyl Orange, Acid Orange 7, tetracycline, and ciprofloxacin degradation efficiency at 40 mg/L reached 99.6%, 99.2%, 84.5%, 67.1%, and 70.7%, respectively, after irradiation by a 40 W lamps for 90 min. The high-efficiency visible-light catalytic activity of the dual-effect catalytic system was attributed to doping with non-metallic sulfur and loading of catalysts onto BC. The development of this dual-effect catalytic system provides new ideas for quickly and efficiently solving the problem of high-concentration organic pollution in aqueous environments, rationally and fully utilizing solar energy, and expanding the application of photocatalytic technology to practice.     

TiO2光催化剂载体及提高其光催化活性的研究进展

光催化技术是一种新型的绿色环保技术,TiO2是光催化反应中的一种研究较为广泛的光催化剂,其在污水处理以及空气净化等领域具有广泛的应用前景。文章综述了TiO2作为光催化剂的研究现状,着重介绍了TiO2光催化剂载体的研究及TiO2的改性研究。并结合我们在TiO2载体以及提高其催化活性方面所作的一些研究工作,提出一些看法。     

In-situ-reduced synthesis of cyano group modified g-C3N4/CaCO3 composite with highly enhanced photocatalytic activity for nicotine elimination

Graphite carbon nitride has many excellent properties as a two-dimensional semiconductor material so that it has a wide application prospect in the field of photocatalysis. However, the traditional problems such as high recombination rate of photogenerated carriers limit its application. In this work, we introduce nitrogen deficiency into g-C₃N₄ to solve this problem a simple and safe in-situ reduction method. g-C₃N₄/CaCO₃ was obtained by a simple and safe one-step calcination method with industrial-grade micron particles CaCO₃. Cyano group modification was in-situ reduced during the thermal polymerization process, which would change the internal electronic structure of g-C₃N₄. The successful combination of g-C₃N₄ and CaCO₃ and the introduction of cyanide have been proved by Fourier transform infrared spectroscopy and X-ray photoelectron spectrometer. The formation of the cyano group, an electron-absorbing group, promotes the effective separation of photogenic electron hole pairs and inhibits the recombination of photogenic carriers. These advantages result in the generation of more •O₂⁻ and ¹O₂ in the catalytic system, which increases the photocatalytic efficiency of nicotine degradation by ten times. Furthermore, the degradation process of nicotine has been studied in this work to provide a basis for the degradation of nicotine organic pollutants in the air.     

活性炭吸附-光催化氧化深度净水工艺实验研究

以光催化氧化作为活性炭吸附工艺出水通常存在的亚硝酸盐、余氯与细菌总数超标等问题,并能去除铁穿透炭层的极性短链有机污染物,使出水达到《饮用净水水质标准》（CJ94－1999）。与目前常用的活性炭－反渗透组合工艺相比,该工艺具有可保留水中有益的矿物成分的特点,具有良好的应用前景。     

TiO2膜固载型多孔催化剂的光催化分解试验

以多孔基质为载体,用溶胶-凝胶法制备出载ＴｉＯ２薄膜的多孔型光催化剂。用Ｘ射线衍射和扫描电镜对催化剂的物相和形貌进行了表征，此催化剂能在光照下分解水溶液中四环素抗菌素。经１ｈ光照，四环素的分解率可达８５％左右。     

4—氯苯甲酸钠的光催化氧化降解及其影响因素

本试验采用P－25TiO2，光催化剂，对4－氯苯甲酸钠的光催化氧化降解及污染物初始浓度，催化剂投加量和入射光强等因素的影响进行了研究，研究发现污染物初始降解速率与其初始浓度的关系遵循Langmuir-Hinshelwood模式，其中半饱和浓度常数Ks不仅是催化剂和污染物种类的函数，而且也是入射光强的函数，催化剂投加量存在一限值，当低于此限值时，污染物降解速率由于催化剂浓度的不足受到影响而下降，当高于此限值时，污染物降解速率受催化剂投加量的影响变小，在本试验4－CBA－Na浓度为0.15-0.6mmol／L时该催化剂限值浓度大约为0.4g/L，在入射光强为1-7mW/cm^2和催化剂浓度为0.4g／L下，污染物降解速率与光强成0.67次幂关系，经估算其量子效率为6．3％。