TiO2光催化降解胸腺嘧啶的动力学和机理

考察了用于降解来自嘧啶家族的一种核酸—胸腺嘧啶(C5H6N2O2)的高级氧化过程。结果发现,在光催化剂TiO2作用下,胸腺嘧啶的光降解进行得很快,且在紫外光照射和水溶液中时更为明显。研究了胸腺嘧啶在TiO2催化剂上的吸附、降解动力学、以及pH值对光催化降解胸腺嘧啶性能的影响。另外,考察了胸腺嘧啶降解产物的矿化;比较和讨论了在光催化过程中胸腺嘧啶的消失和矿化速率。同时还研究了氮的矿化,确立了中间产物的识别方法。最后,采用电子密度计算提出了在紫外光照射下TiO2催化剂上胸腺嘧啶降解的可能化学途径。     

UV/Fe(Ⅲ)-富马酸盐体系降解对硝基苯酚

研究了在紫外光(UV)照射下,Fe(Ⅲ)-富马酸盐体系对p-硝基苯酚(PNP)的光降解反应,考察了溶液pH、Fe(Ⅲ)、富马酸盐和PNP的初始浓度对PNP降解率的影响。结果表明,UV/Fe(Ⅲ)-富马酸盐体系对PNP有光降解作用,相比于只含Fe(Ⅲ)或者富马酸盐体系,同时加入Fe(Ⅲ)与富马酸盐构成的体系在降解PNP方面有协同作用。在pH 3.0~6.0范围内,PNP的降解率随着pH和PNP初始浓度的增大而降低,而随着Fe(Ⅲ)和富马酸盐的初始浓度的增大而增大。氯仿猝灭法证实,该体系在降解PNP反应过程中产生了超氧负离子自由基;采用荧光法和异丙醇猝灭法证实了该体系在反应过程中产生了羟基自由基,同时证实了羟基自由基为PNP光降解反应的主要反应物质。     

Intermediate free radicals in the oxidation of wastewaters

The cleaning action on wastewater as obtained through oxidation methods has been investigated by means of EPR spectroscopy to achieve qualitative and quantitative information on the radicals produced upon utilising peracetic acid and hydrogen peroxide with and without UV irradiation. The DEPMPO spin trap was employed to detect hydroxyl and carbon-centred short living radicals during water disinfection, either in the absence or in the presence of UV-C irradiation. Moreover, three different kinds of water (wastewater, demineralized water, distilled water) were analysed in order to assess the contribution of Fenton reactions to the radical production. The spectroscopic results are discussed in relation to the efficiency of the different oxidising agents and UV irradiation in wastewater disinfection evaluated as Escherichia coli, faecal and total coliforms inactivation.     

EPR analysis of the interacting properties and the degradation over time and irradiation of mastic resin used for painting protection

Mastic resin used as a covering film for painting protection was analyzed by electron paramagnetic resonance (EPR) spectroscopy, both as received and upon aging in sun-light. The effect of prolonged exposure to sun-light was mimicked by UV and, more so, by xenon lamp irradiation. Solid mastic presented EPR signals due to radicals trapped by PBN in solution. Data in the literature indicated the formation of acyl radicals (RCO·). These radicals preferentially dissolved in medium polarity solvents. The radical concentration in the solid mastic increased over time more than 50 times upon UV irradiation for 96 h and, even more, by xenon irradiation for 800 h. Also the PBN-trapped radicals in solution increased in concentration by irradiation. Small nitroxide radicals (TEMPO) interacted with a polar fraction of mastic dissolved in methanol, but mainly interacted with low polar mastic molecules in hydrophobic solvents. It was suggested, on the basis of both the PBN-spin trapping data and the TEMPO mobility variation in the solvents at different polarities, that terpenoid molecules partially polymerize by a radical mechanism to form low molecular weight products. A polyaromatic-radical (pyrene-TEMPO) and a biomolecule-radical (doxylcholestane) both interact weakly with mastic molecules in cyclohexane solutions. A positively charged surfactant radical (dimethylammonium-TEMPO bromide) was easily adsorbed onto the solid mastic surface suggesting that detergents are responsible for mastic degradation. In conclusion, this study provided information on the degradation mechanism of mastic resin and on its interacting ability towards external molecules and pollutants.     

Effects of hydroxyl radicals and oxygen species on the 4-chlorophenol degradation by photoelectrocatalytic reactions with TiO2-film electrodes

The supported nano-TiO₂ electrode was prepared by sol–gel and hydrothermal method, and the photoelectrocatalytic degradation of 4-chlorophenol (4-CP) under UV irradiation has been investigated to reveal the roles of hydroxyl radicals and dissolved oxygen species for TiO₂-assisted photocatalytic reactions. The degradation kinetics, the formation and decay of intermediates, the isotopic tracer experiments with H₂O¹⁸, the removal yield of total organic carbon and the formation of active radical species in the presence of oxygen or not were examined by HPLC, GC–MS, TOC and spin-trap ESR spectrometry. It was found that most of OH radicals in the primary hydroxylated intermediates derived from the oxidation of adsorbed H₂O or HO⁻ by photo-holes in the electrochemically assisted TiO₂ photocatalytic system. It also indicates that the enhancement in the separation efficiency of photogenerated charges by applying a positive bias (+0.5 V vs SCE) has little role in the following decomposition and mineralization of these hydroxylated intermediates in the absence of oxygen. According to above experimental results, the pathway of 4-CP photocatalytic degradation was deduced initially. Due to the combined effect of OH radicals and dissolved oxygen species, the hydroxylated 4-chlorphenol, via cis, cis-3-chloromuconic acid, was decomposed into low molecular weight acid and CO₂.     

Oxidative degradation of phenols in sono-Fenton-like systems upon high-frequency ultrasound irradiation

The kinetics of oxidative degradation of phenol and chlorophenols upon acoustic cavitation in the megahertz range (1.7 MHz) is studied experimentally in model systems, and the involvement of in situ generated reactive oxygen species (ROSs) is demonstrated. The phenols subjected to high frequency ultrasound (HFUS) are ranked in terms of their rate of conversion: 2,4,6-trichlorophenol > 2,4-dichlorophenol ~ 2-chlorophenol > 4-chlorophenol ~ phenol. Oxidative degradation upon HFUS irradiation is most efficient at low concentrations of pollutants, due to the low steady-state concentrations of the in situ generated ROSs. A dramatic increase is observed in the efficiency of oxidation in several sonochemical oxidative systems (HFUS in combination with other chemical oxidative factors). The system with added Fe²⁺ (a sono-Fenton system) derives its efficiency from hydrogen peroxide generated in situ as a result of the recombination of OH radicals. The S₂O₈^2-/Fe²⁺/HFUS system has a synergetic effect on substrate oxidation that is attributed to a radical chain mechanism. In terms of the oxidation rates, degrees of conversion, and specific energy efficiencies of 4-chlorophenol oxidation based on the amount of oxidized substance per unit of expended energy the considered sonochemical oxidative systems form the series HFUS < S₂O₈^2-/HFUS < S₂O₈^2-/Fe²⁺/HFUS.     

A Novel Electrocatalysis Method for Organic Pollutants Degradation

As typical contaminants, phenolic pollutants are wide spread and are toxic to aquatic life. Thus the demand for new technology to remove or detoxify such organics should be widely recognized. Recently, electrochemical method has attracted a great deal of attention for treating such kinds of wastewater, mainly because of its amenability to automation, high efficiency and environmental compatibility1. Various electrochemical processes have been developed and anodic oxidation might be the most w…     

TiO<Subscript>2</Subscript> photocatalytic oxidation: I. Photocatalysts for liquid-phase and gas-phase processes and the photocatalytic degradation of chemical warfare agent simulants in a liquid phase

The results of studies on the effect of the preparation procedure on the properties of TiO₂-based photocatalysts and the kinetics and mechanism of the photocatalytic oxidation of organic water pollutants are surveyed. The effects of calcination temperature, surface modification with platinum, and acid-base treatment of the surface of titanium dioxide on its activity in model gas-phase and liquid-phase reactions are considered. Optimal catalyst preparation conditions were found in order to achieve maximum activity, and conceivable reasons for the effects of the above factors on the activity were revealed. The intermediate products and mechanisms of the photocatalytic and dark reactions of solutes that simulated chemical warfare agents in water are considered. All of the test simulants can undergo complete oxidation to form inorganic products in an aqueous TiO₂ suspension under irradiation with UV light. It was found that, in addition to oxidation, the dark steps of hydrolysis also play an important role in the degradation of these substances. The low-frequency ultrasonic treatment (20 kHz) of a photocatalyst suspension in the course of the photocatalytic oxidation of dimethyl methylphosphonate can accelerate the reaction because of the facilitated transport of reactants to the surface of photocatalyst particles.__________Translated from Kinetika i Kataliz, Vol. 46, No. 2, 2005, pp. 203–218.Original Russian Text Copyright © 2005 by Vorontsov, Kozlov, Smirniotis, Parmon.     

Type I Photosensitized Oxidation of Methionine†

Methionine (Met) is an essential sulfur‐containing amino acid, sensitive to oxidation. The oxidation of Met can occur by numerous pathways, including enzymatic modifications and oxidative stress, being able to cause relevant alterations in protein functionality. Under UV radiation, Met may be oxidized by direct absorption (below 250 nm) or by photosensitized reactions. Herein, kinetics of the reaction and identification of products during photosensitized oxidation were analyzed to elucidate the mechanism for the degradation of Met under UV‐A irradiation using pterins, pterin (Ptr) and 6‐methylpterin (Mep), as sensitizers. The process begins with an electron transfer from Met to the triplet‐excited state of the photosensitizer (Ptr or Mep), to yield the corresponding pair of radicals, Met radical cation (Met^?+) and the radical anion of the sensitizer (Sens^??). In air‐equilibrated solutions, Met^?+ incorporates one or two atoms of oxygen to yield methionine sulfoxide (MetO) and methionine sulfone (MetO₂), whereas Sens^?? reacts with O₂ to recover the photosensitizer and generate superoxide anion (O₂^??). In anaerobic conditions, further free‐radical reactions lead to the formation of the corresponding dihydropterin derivatives (H₂Ptr or H₂Mep).     

Oxygen as a promoter for efficient degradation of organic pollutants by high-temperature and high-pressure electrochemistry

The introduction of oxygen in electrochemical oxidation at relatively high temperature and pressure as a promoter resulting in synergetic effects, greatly improves the mineralization of high-concentrated organic pollutants.     

菲在TiO2催化下的光降解研究

以汞灯为光源,TiO₂为催化剂,对菲的光催化降解途径进行了研究.将水溶性极小的菲预先吸附到TiO₂上之后,菲可以在紫外线的照射下发生快速、完全的矿化.通过GC-MS手段检测到一些中间产物,给出了菲光催化降解的详细途径.另外,研究了菲在表面活性剂十六烷基三甲基溴化铵(HTAB)的助溶下TiO₂催化的光降解过程,探讨了表面活性剂的浓度和溶液pH值对反应速率的影响.     

UV and H2O2/UV degradation of a pharmaceutical intermediate in aqueous solution

The degradation of 5-methyl-1,3,4-thiadiazole-2-thiol (MMTD), a pharmaceutical intermediate found in some aquifers of Northern Italy, has been investigated by means of UV and UV/H2O2 treatments. The study has been carried out with a 17 W low pressure mercury lamp at room temperature, using a (100)/(1) (H2O2)/(MMTD) molar ratio. The results have demonstrated that: (i) with an initial MMTD concentration of 1 mg/l, 90% MMTD removal can be achieved within 1 hour or less than 5 minutes by UV or UV/H2O2 respectively; (ii) the sole UV irradiation does not cause any MMTD mineralization; (iii) with an initial MMTD concentration of 50 mg/l, 4 hours of UV/H2O2 treatment lead to an almost complete mineralization of the MMTD organic sulfur and to a partial mineralization of carbon (59%) and nitrogen (14%). The identification of degradation by-products, performed by HPLC-UV-MS analysis, revealed that the sole UV irradiation gives rise to the MMTD transformation into a single by-product that continuously accumulates in the solution. Conversely, the UV/H2O2 treatment forms seven intermediates that undergo further degradation through the breakdown of the thiadiazole ring. On the basis of the obtained results a degradation pathway has been proposed.     

Efficient photocatalytic degradation of Acid Red 57 using synthesized ZnO nanowires

Zinc oxide photocatalyst was synthesized through a low‐temperature co‐precipitation process using zinc sulfate as precursor for the degradation of Acid Red 57 (AR57) under UV irradiation. The activities of the prepared photocatalyst at different calcination temperatures (400, 500, and 600 °C) were investigated. The synthesized zinc oxides were characterized by different techniques such as X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, N₂ adsorption–desorption, and pH titration for the determination of the zero‐point charge (pH_ZPC). The efficiency of photocatalytic degradation of ZnO prepared at the calcination temperatures of 400, 500, and 600 °C was 90.03, 77.67, and 72.71%, respectively, after 190 min. The kinetics and scavengers of the reactive species during the degradation were also investigated. It was found that the degradation of AR57 fitted first‐order kinetics and the OH^? radicals were the main species. During irradiation, the formation of OH^? free radicals was ascertained by photoluminescence studies using terephthalic acid as the probe molecule.     

Pt/TiO2上苯和乙烯光催化氧化过程的磁场效应

以Pt/TiO₂为催化剂和365 nm紫外光为光源, 在低于0.2 T的磁场强度范围考察了磁场对苯和乙烯光催化氧化反应的影响. 实验发现, 当用紫外灯管作光源并靠近磁场磁极或者置于磁场磁极间隙内照射反应器时, 磁场可显著提高气相苯和乙烯的光催化转化率和矿化率; 而当光源远离磁场磁极而通过光导纤维传导照射到反应器上时, 磁场对这两个反应没有促进作用. 在前一种情况下, 紫外灯管的发光强度随磁场的增强而提高, 磁场对这两个光催化降解反应的促进作用被证实是由于磁场提高了紫外灯管的发光强度, 进而为反应提供了更多的光能和使反应温度升高所致；在后一种光照方式下, 由于光源不受磁场影响, 磁场对这两个光催化反应不产生影响. 这一研究结果表明, 在所研究磁场强度范围, 磁场对气-固相光催化反应没有任何本征影响.     

The electrochemical advanced oxidation processes coupling of oxidants for organic pollutants degradation: A mini-review

In this mini-review, the homogeneous and heterogeneous EAOPs-oxidant processes were summarized. The reaction mechanisms of different EAOPs combined with different oxidants are elucidated in detail, as well as the synergistic effect for improving the treatment efficiency.     

Effects of exogenic chloride on oxidative degradation of chlorinated azo dye by UV-activated peroxodisulfate

Recently, the degradation of organic compounds in saline dye wastewater by sulfate radicals (SO₄⁻)-based advanced oxidation processes (AOPs) have attracted much attention. However, previous studies on these systems have selected non-chlorinated dyes as model compounds, and little is known about the transformation of chlorinated dyes in such systems. In this study, acid yellow 17 (AY-17) was selected as a model of chlorinated contaminants, and the degradation kinetics and evolution of oxidation byproducts were investigated in the UV/PDS system. AY-17 can be efficiently degraded (over 98% decolorization) under 90 min irradiation at pH 2.0–3.0, and the reaction follows pseudo-first order kinetics. Cl^‒ accelerated the degradation of AY-17, but simultaneously led to an undesirable increase of absorbable organic halogen (AOX). Several chlorinated byproducts were identified by liquid chromatography-mass spectrometry (LC–MS/MS) in the UV/PDS system. It indicates that endogenic chlorine and exogenic Cl^– reacted with SO₄⁻ to form chloride radicals, which are involved in the dechlorination and rechlorination of AY-17 and intermediates. The possible degradation mechanisms of AY-17 photooxidative degradation are proposed. This work provides valuable information for further studies on the role of exogenic chloride in the degradation of chlorinated azo dyes and the kinetic parameters in the PDS-based oxidation process.     

Green light radiation effects on free radicals inhibition in cellular and chemical systems

Free radicals generation is inhibited through green light (GL) irradiation in cellular systems and in chemical reactions. Standard melanocyte cultures were UV-irradiated and the induced cellular reactive oxygen species (ROS) were quantified by the fluorescence technique. The same cell cultures, previously protected by a 24h GL exposure, displayed a significantly lower ROS production. A simple chemical reaction is subsequently chosen, in which the production of free radicals is well defined. Paraffin wax and mineral oil were GL irradiated during thermal degradation and the oxidation products checked by chemiluminescence [CL] and Fourier transform infrared spectra [FT-IR]. The same clear inhibition of the radical oxidation of alkanes is recorded. A quantum chemistry modeling of these results is performed and a mechanism involving a new type of Rydberg macromolecular systems with implications for biology and medicine is suggested.     

二氧化钛纳米管阵列的构建及其光电催化性能

利用阳极氧化法制备了TiO2纳米管阵列, 研究了其光电化学性能, 并且应用该电极对偶氮染料催化降解进行了初步研究.     

掺硼金刚石电极电催化氧化酚类有机物的取代基效应

本文主要以当前水环境中存在酚类有机污染物为研究对象,探讨酚类有机污染物在掺硼金刚石(BDD)电极上的取代基效应,具体研究具有不同位置及种类官能团的取代酚类有机污染物在BDD电极上的电催化氧化过程,通过化学需氧量和浓度变化考察有机污染物在电催化降解过程中的降解趋势,深入分析电极种类、官能团位置与种类与电催化氧化活性之间的联系的同时,研究阳极材料电催化氧化有机污染物的机理及动力学。结果表明,有机物在电极表面的电催化过程以电产生羟基自由基为媒介,对苯二酚在不同电极上的电催化活性与电极析氧电位及表面产生羟基自由基量有着重要的联系,BDD电极拥有最强的电催化氧化活性;不同取代基团的对位取代酚在BDD电极上的电化学降解实验显示电催化反应速率受取代官能团自身的电子效应制约,有机物矿化过程中羟基自由基首先进攻苯环的对位发生取代反应,同时取代基脱离苯环过程成为整个取代酚类电化学降解过程的决速步骤,且有机物的电催化反应速率与取代基特征Hammett常数σ呈近似线性关系。     

Photochemical reduction of cytochrome c by a 1,4,5,8-naphthalenediimide radical anion

Steady-state UV irradiation of aqueous solutions containing cytochrome c (cyt c) and N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (BPNDI), a water-soluble aromatic imide, resulted in the reduction of the heme iron from the Fe(III) to the Fe(II) oxidation state. The reaction kinetics were followed by the increase of the ferrocytochrome c absorbance band at 549 nm. The rate of the photochemical reaction was pH dependent, reaching its maximum values over the pH range 4-7. Addition of electrolyte (NaCl) at pH 5 resulted in a decrease in the reaction rate, as expected for reactions between oppositely charged species. Flash photolysis studies revealed that the actual reductant in the reaction was a photogenerated BPNDI radical anion, which transferred an electron to the cyt c heme iron. The participation of imide radicals in the process was confirmed by the ready reduction of cyt c by BPNDI radicals chemically generated with sodium dithionite.