Detection of Oxidants Such as Hydroxyl Radicals and Chlorine Electrogenerated on a BDD Electrode by Simple Methods

The aim of this work is to detect electrogenerated hydroxyl radicals and chlorine by simple and less expensive methods. Preparative electrolyses of perchloric acid (HClO4) and sodium chloride (NaCl) were performed on a boron-doped diamond (BDD) electrode. The hydroxyl radicals were quantified indirectly by assaying the samples from the HClO4 (0.1 M) electrolysis with a 10−4 M potassium permanganate solution. The investigations showed that the amount of hydroxyl radicals depends on the concentration of HClO4 and the current density. As for chlorine, a qualitative determination was carried out. A mixture of the electrolyte solution of HClO4 (0.1 M) + NaI (0.2 M) + 2 mL of hexane, taken in this order, leads to a purplish-pink coloration attesting to the presence of Cl2. The same test was carried out with NaBr and NaI giving pale and very pale pink colourations, respectively, showing that the intensity of the colouration depends on the strength of the oxidant present. In addition, oxidants were detected during the electrooxidation of metronidazole (MNZ). The results showed the participation of electrogenerated hydroxyl radicals. The generation of chlorine has also been proven. Furthermore, the degradation leads to a chemical oxygen demand (COD) removal rate of 83.48% and the process is diffusion-controlled.

掺杂BN-OH纳米片的P/PEG@BN-OH同轴纳米纤维的制备及其热性能

为制备高效稳定的相变储热材料,采用同轴静电纺丝技术制备了以聚丙烯腈(PAN)为鞘、聚乙二醇(PEG)与羟基化氮化硼纳米片(BN-OH)为芯的同轴纳米纤维(P/PEG@x BN-OH),并分别通过场发射扫描电子显微镜、透射电子显微镜、差示扫描量热仪、红外热成像仪等手段分析了掺杂不同质量BN-OH纳米片对纤维形貌、热性能、循环稳定性、热能效率及热导率的影响。结果表明:纤维形成了稳定且连续的鞘-芯同轴结构,平均直径介于279~335 nm,而且PEG和BN-OH被包裹在PAN纤维内部,内径大小范围为107~188 nm;P/PEG@x BN-OH纳米纤维显示了优异的相变储热焓值(75~78 J/g)和热稳定性,经100次热循环后PEG无相变渗漏现象;掺杂质量分数为10.0%的BN-OH纳米片可将纤维的热导率提高95%,而且其相变储热和释放率分别提高了67%和154%。

Quantitative measurement of hydroxyl radical(OH) concentration in premixed flat flame by combining laser-induced fluorescence and direct absorption spectroscopy

An accurate and reasonable technique combining direct absorption spectroscopy and laser-induced fluorescence（LIF）methods is developed to quantitatively measure the concentrations of hydroxyl in CH;/air flat laminar flame. In our approach, particular attention is paid to the linear laser-induced fluorescence and absorption processes, and experimental details as well. Through measuring the temperature, LIF signal distribution and integrated absorption, spatially absolute OH concentrations profiles are successfully resolved. These experimental results are then compared with the numerical simulation. It is proved that the good quality of the results implies that this method is suitable for calibrating the OH-PLIF measurement in a practical combustor.

Singlet oxygen synergistic surface-adsorbed hydroxyl radicals for phenol degradation in CoP catalytic photo-Fenton

In recent years,there have been numerous studies on Fenton or Fenton-like reactions mediated by nonfree radicals such as singlet oxygen(1O_(2));however,there are few studies on the synergistic effect of 1O_(2) and free radicals on the degradation of organic molecules,such as phenol in Fenton reaction.In this study,a cocatalyst,CoP,commonly used in photocatalysis was synthesized using a simple two-step method,and a CoP/Fe^(2+)/AM1.5 system was constructed by introducing Fe^(2+)and simulated sunlight(AM1.5)irradiation.The newly constructed CoP/Fe^(2+)/AM1.5 system could effectively degrade various organic pollutants,including dyes,phenols,and antibiotics.Radical quenching experiments and electron paramagnetic resonance detection confirmed that there were three reactive oxygen species(ROS)in the CoP/Fe^(2+)/AM1.5 system,including·OH_(ads),·O_(2)^(-),and 1O_(2).Further,combined with the liquid chromatogram of phenol,its intermediate products,and the fluorescence diagram of o-hydroxybenzoic acid,it can be concluded that a synergistic effect exists between 1O_(2) and the surface-adsorbed·OH_(ads) in the CoP/Fe^(2+)/AM1.5 system.The controllable formation of surface 1O_(2) and·OH_(ads) was achieved through the oxidation(Co^(3+))and reduction(Pδ−)centers exposed on the CoP surface,and the synergistic effect between them results in phenol’s hydroxylation,ring-opening,and degradation.The study of this new mechanism provides a new perspective for revealing the surface interface reaction between ROS and organic pollutants.

Photooxidation of hydrochlorofluocarbons and hydrofluorocarbons initiated by OH radicals

Under simulated atmospheric condition, photoomdation for HCFC-22 + H2O2, HCFC-22 + H2O2+O2, HFC-134A + H2O2 and HFC-134A + H2O2+ O2 systems were studied.H2O2 was irradiated by low pressure mercury lamp and produced OH radicals. The OH radicals can initiate photooxidation of HCFC-22 and 134A. The products of photooxidation were determined by a Fourier Transform infrared Spectroscopy with a 20ml long path cell. The products were COF2,CO2, HCI, H2O and HF for HCFC-22 + H2O2 system, HO, CO2, HCI and HF for HCFC-22 +H2O2 +O2 system, HCOF, CF3OOCF3,CO2, H2O and HF for HFC-134A +H2O2 system, HCOF, CO2, H2O, and HF for HFC-134A + H2O2+ O2 system. Based on those results, the mechanisms of photooxidation were suggested.

Hydroxyl radicals-mediated oxidative cleavage of the glycosidic bond in cellobiose by copper catalysts and its application to low-temperature depolymerization of cellulose

As the most abundant source of biomass in nature for sustainable production of fuels and chemicals,efficient depolymerization of cellulose under mild conditions,due to the difficulty in selective cleavage of itsβ-1,4-glycosidic bonds,still remains challenging.Here,we report a novel method for oxidative cleavage of the glycosidic bonds by free radicals.Probed by the cellobiose reaction,it was found that·OH radicals,generated from the decomposition of H2O2 catalyzed by CuSO4 or CuO/SiO2,were efficient for selective conversion of cellobiose to glucose and gluconic acid at a low temperature of 333 K,and their selectivities reached 30.0%and 34.6%,respectively,at 23.4%cellobiose conversion.Other radicals,such as·SO4?,also exhibited high efficacy in the cellobiose reaction.Mechanistic studies suggest that the oxidative cleavage of theβ-1,4-glycosidic bond by the free radicals involve formation of the carbon radical intermediate via abstraction of the H atom dominantly at the C1 position.Following this oxidative mechanism,treatment of microcrystalline cellulose with·OH by impregnation with H2O2 and CuSO4 catalyst at 343 K led to significant enhancement in its hydrolysis efficiency.These results demonstrate the effectiveness of this new method in the oxidative cleavage of glycosidic bonds,and its viability for the efficient depolymerization of cellulose at low temperatures,which can be further improved,for example,by exploring new free radicals and optimizing their reactivity and selectivity.

Degradation of Phenol by Hydroxyl Radicals on Different Coating Lead Dioxide Electrodes

Lead dioxide electrodes on Ti substrates were prepared by thermal-deposition or electro-deposition. The amount of hydroxyl radicals generated at the electrodes prepared by the above-mentioned two methods was compared with that at the electrodes mingled with Bi or La prepared by electro-deposition. The experimental results indicate that the highest concentration of hydroxyl radicals generated by thermal-deposition, electro-deposition mingled with nothing, electro-deposition mingled with Bi or La was 0.781, 1.048, 1.838 or 2.044 μmol/L, respectively. When phenol was electrolyzed on the four electrodes at a current density of 30 mA/cm2, the removal efficiency of phenol after electrolysis for 1.5 h was 87.30%, 93.55%, 97.95% or 98.70%, TOC removal efficiency after electrolysis for 5 h was 86.76%, 94.26%, 98.53% or 99.60%, respectively. Through the degradation experiments of phenol, the amount of hydroxyl radicals was responsible for the removal efficiency of phenol. The electro-catalytic characteristics were investigated by SEM, the generation amount of hydroxyl radicals, the degradation degree of phenol and the stability and conductivity of the electrodes were also investigated. The experimental results indicate that the four electrodes all show good electro-catalytic characteristics; the electro-catalytic characteristics of the electrode mingled with La were superior to those of the other three ones, and the electrochemical degradation of phenol followed one-step reaction dynamics.

Effects of Hydroxyl Radicals on Introduced Organisms of Ship's Ballast Water Based Micro-Gap Discharge

With the physical method of micro-gap gas discharge, OH. radicals were produced by the ionization of O2 in air and H2O in the gaseous state, in order to explore more effective method totreat the ship＇s ballast water. The surface morphology of Al2O3 dielectric layer was analysed using Atomic Force Microscopy （AFM）, where the size of Al2O3 particles was in the range of 2 μm to 5 μm. At the same time, the biochemical effect of hydroxyl radicals on the introduced organisms and the quality of ship＇s ballast water were studied. The results indicate that the main reasons of cell death are lipid peroxide and damage of the antioxidant enzyme system in Catalase （CAT）, Peroxidase （POD） and Superoxide dismutase （SOD）. In addition, the quality of the ballast water was greatly improved.

绿脱石结构Fe(Ⅲ)还原程度对氧化过程·OH形成及有机质矿化的影响

土壤和沉积物有氧-无氧界面黏土矿物结构Fe(Ⅱ)氧化产生的羟自由基(·OH)在有机物质转化过程中具有重要作用。土壤和沉积物黏土矿物结构Fe(Ⅲ)的还原程度会随环境条件变化而不同,然而,关于含铁黏土矿物还原程度[Fe(Ⅱ)/Fe总]对氧化过程中·OH的形成及有机质矿化的影响尚不明确。本研究以富铁绿脱石为黏土矿代表,研究了不同还原程度绿脱石[Fe(Ⅱ)/Fe总:15%、22%、39%和56%]有氧氧化产生·OH的机制及该过程对溶解性有机质(DOM)转化的差异。结果表明,当不同还原程度绿脱石的悬浊液体系中结构Fe(Ⅱ)浓度为2.2 mmol·L^(-1)时,随着还原程度从15%增加到56%,其氧化120 min后·OH的累积浓度从13.6μmol·L^(-1)增加到27.1μmol·L^(-1),单位O_(2)转化为·OH的效率从3.3%提高到5.9%。傅里叶变换红外光谱(FTIR)、氮蓝四唑(NBT)猝灭实验和2,2′-联吡啶(BPY)钝化边缘反应位点的结果证明了还原程度为15%的绿脱石主要存在二八面体Fe(Ⅱ)[Al-Fe(Ⅱ)],并在边缘位点活化O2产生·OH;而还原程度为56%的绿脱石除二八面体Fe(Ⅱ)外,还存在高活性三八面体[Fe(Ⅱ)-Fe(Ⅱ)-Fe(Ⅱ)],底面位点和边缘位点均可活化O_(2)产生·OH,并且O2在底面位点还原形成·OH效率更高。氧化过程中·OH矿化溶解性有机质(DOM)形成CO_(2)的含量随绿脱石的还原程度的升高而升高。因此,与低还原程度绿脱石(15%)相比,高还原程度的绿脱石(56%)存在高活性三八面体并能从底面位点形成·OH从而提高了·OH生成的效率并进一步促进了DOM的矿化。

Determination of hydroxyl radicals with salicylic acid in aqueous nitrate and nitrite solutions

The qualitative and quantitative analyses of reactive oxygen species are essential to determine their steady-state concentration and related reaction mechanisms in environmental aquatic systems. In this study, salicylic acid was employed as an innovative molecular probe of hydroxyl radical(OH) generated in aqueous nitrate and nitrite solutions through photochemical reactions. Kinetic studies showed that the steady-state concentrations of OH in aqueous NO- 3(10 mmol/L, pH=5) and NO- 2(10 mmol/L, pH=5) solutions under ultraviolet irradiation were at a same magnitude, 10 -15 mol/L. Apparent quantum yields of OH at 313 nm were measured as 0.011 and 0.07 for NO- 3 and NO- 2 respectively, all comparable to the results of previous studies.

Optical Emission Spectroscopic Measurement of Hydroxyl Radicals in Air Discharge with Atomized Water

Effects of discharge mode, voltage applied, size of the nozzle discharge electrode and flow rate of water on the generation of hydroxyl radical were investigated in air discharge with atomized water, by using optical emission spectroscopy （OES）. Water was injected into the discharge region through the discharge nozzle electrode, and a large amount of fine water drops, formed and distributed in the discharge region, corona discharge was more effective to generate were observed. It was found that negative DC the hydroxyl radicals in comparison to positive DC corona discharge or negative pulsed discharge. A larger outer diameter of the nozzle electrode or a stronger electric field is beneficial for hydroxyl-radical generation. Moreover, there is a critical value in the flow rate of atomized water against the discharge voltage. Below this critical value, hydroxyl-radical generation increases with the increase in flow rate of the water, while above this value, it decreases. In addition, it is observed that OES from the discharge is mainly in the ultraviolet domain. The results are helpful in the study of the mechanism and application of plasma in pollution-control in either air or water.

Determination of hydroxyl radicals in TiO2/Ti photoelectrocatalytic oxidation system using Fe（phen）3^2＋ spectrophotometry

A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic（PEC） oxidation system was established by o-phenanthroline-Fe（Ⅱ）（Fe（phen）3^2＋） spectrophotometry and using anion exchange membrane. Fe （phen）3^2＋ can be oxidized to o-phenanthroline-Fe（Ⅲ）（Fe（phen）3^3＋） by strong oxidization of hydroxyl radicals（·OH）. Then the cumulate concentration of hydroxyl radicals can be calculated through determining the change of the Fe（phen）3^3＋ absorbency at 509 nm. In addition, the research results showed the production rate of hydroxyl radicals was affected obviously by pH of solution, the cumulate concentration of hydroxyl radicals was the largest at nearby the initial pH 6.3 （isoelectric point）, and the change direction of pH after illumination tended to nearby isoelectric point.

Key Role of Some Specific Occupied Molecular Orbitals of Short Chain n-Alkanes in Their Surface Tension and Reaction Rate Constants with Hydroxyl Radicals: DFT Study

Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH• (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH• radicals are determined by the energies Eorb of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |Eorb|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.

Experimental Studies on Elimination of Microbial Contamination by Hydroxyl Radicals Produced by Strong Ionization Discharge

Using fogdrops of OH^· radicals to eliminate microbial contamination is an effective way to solve the current domestic and international problem. The results show that the threshold of OH solution used in the experiment is 0.6 mg/L, the lethal time is 1 s, and the spray density of OH solution is 21 μL/m^2. The experimental results show that the OH radical possesses the following advantages： celerity, low lethal concentration and spray density, short lethal time, and absence of secondary pollution.

The investigation of OH radicals produced in a DC glow discharge by laser-induced fluorescence spectrometry

In this paper the OH radicals produced by a needle-plate negative DC discharge in water vapor,N_(2)+H_(2)O mixture gas and He+H_(2)O mixture gas are investigated by a laser-induced fluorescence(LIF)system.With a ballast resistor in the circuit,the discharge current is limited and the discharges remain in glow.The OH rotation temperature is obtained from fluorescence rotational branch fitting,and is about 350 K in pure water vapor.The effects of the discharge current and gas pressure on the production and quenching processes of OH radicals are investigated.The results show that in water vapor and He+H_(2)O mixture gas the fluorescence intensity of OH stays nearly constant with increasing discharge current,and in N_(2)+H_(2)O mixture gas the fluorescence intensity of OH increases with increasing discharge current.In water vapor and N_(2)+H_(2)O mixture gas the fluorescence intensity of OH decreases with increasing gas pressure in the studied pressure range,and in He+H_(2)O mixture gas the fluorescence intensity of OH shows a maximum value within the studied gas pressure range.The physicochemical reactions between electrons,radicals,ground and metastable molecules are discussed.The results in this work contribute to the optimization of plasma reactivity and the establishment of a molecule reaction dynamics model.

Yield of OH radicals in water under heavy ion irradiation.Dependence on mass,specific energy,and elapsed time

Dependence of yields of OH (hydroxyl) radicals on the mass and specific energy of heavy ions and elapsed time after irradiation was investigated,to understand chemical reactions of aqueous solutions.The yields of irradiation products of phenol,super-linearly increased with the incident energy of He,C,and Ne ions ranging from 2 to 18 MeV/u.The yields of the OH radicals were estimated by analyzing the yields of the irradiation products of phenol. The yields of the OH radicals increased with the specific energy for each ion,but decreased both with the mass of each ion at the same specific energy and elapsed time after irradiation.

Effect of gas components on the postdischarge temporal behavior of OH and O of a non-equilibrium atmospheric pressure plasma driven by nanosecond voltage pulses

OH radicals and O atoms are two of the most important reactive species of non-equilibrium atmospheric pressure plasma(NAPP),which plays an important role in applications such as plasma medicine.However,experimental studies on how the gas content affects the postdischarge temporal evolutions of OH and O in the noble gas ns-NAPP are very limited.In this work,the effect of the percentages of O_(2),N_(2),and H_(2)O on the amounts of OH and O productions and their post-discharge temporal behaviors in ns-NAPP is investigated by laser-induced fluorescence(LIF)method.The results show that the productions of OH and O increase and then decrease with the increase of O_(2)percentage.Both OH and O densities reach their maximum when about 0.8%O_(2)is added.Further increase of the O_(2)concentration results in a decrease of the initial densities of both OH and O,and leads to their faster decay.The increase of N_(2)percentage also results in the increase and then decrease of the OH and O densities,but the change is smaller.Furthermore,when the H_(2)O concentration is increased from 100 to 3000 ppm,the initial OH density increases slightly,but the OH density decays much faster,while the initial density of O decreases with the increase of the H_(2)O concentration.After analysis,it is found that OH and O are mainly produced through electron collisional dissociation.O(^(1)D)is critical for OH generation.O_(3)accelerates the consumption processes of OH and O at high O_(2)percentage.The addition of H_(2)O in the NAPP considerably enhances the electronegativity,while it decreases the overall plasma reactivity,accelerates the decay of OH,and reduces the O atom density.

Rate constants for the reaction of hydroxyl radicals with HFC-134a

Rate constants for the reaction of hydroxyl radicals with HFC 134a (CH 2FCF 3) have been measured by the discharge flow resonance fluorescence (DF RF) technique over the temperature range 288—370 K. The derived Arrhenius equation is: k″ =(1.27±0.16)×10 -12 exp(-(1662±41)/ T )cm 3/(mol·s). The tropospheric lifetime of HFC 134a is estimated to be 10.5 years, which is in excellent agreement with the most recent results.

Kinetics for the reaction of hydroxyl radicals with CH_3Br and its implications in the atmosphere

ＫｉｎｅｔｉｃｓｆｏｒｔｈｅｒｅａｃｔｉｏｎｏｆｈｙｄｒｏｘｙｌｒａｄｉｃａｌｓｗｉｔｈＣＨ３ＢｒａｎｄｉｔｓｉｍｐｌｉｃａｔｉｏｎｓｉｎｔｈｅａｔｍｏｓｐｈｅｒｅＺｈａｎｇＤｅｑｉａｎｇ，ＺｈｏｎｇＪｉｎｘｉａｎＲｅｓｅａｒｃｈＣｅｎｔｅｒｆｏ...

Photolysis and Rate Constant of 2,3-butanedione with OH Radicals in the Aqueous Phase under Tropospheric Conditions

Photolysis rate （J1） and reaction rate constants （kl） for the biacetyl （butane-2,3-dione） were evaluated in aqueous phase using a continuous photolysis system with a conventional Xe-Hg arc lamp as a light source. The OH radicals was generated by H2OE/UV process and biacetyl （CH3C（O）C（O）CH3） concentrations were monitored using 2,4-DNPH derivatization method. 2,3-butanedione molecule is widely present in the atmosphere, it have been detected in hydrometeors （fogs, rain, and clouds） and at a significant yield （up to 10μmolar）. The measurements were performed at 294 K and with free pH values. Our results lead to the following obtained values： J1= 3×10^-4 S^-1 and k1 = （6.17±0.95）×10^8 M^-1·s^-1.The uncertainty listed above is ±15%.