DC corona ozone generation enhanced by TiO<Subscript>2</Subscript> photocatalyst

Non-thermal electrical discharges, such as corona discharge are apart of the source of ozone, charged, and excited species and acoustic noise also the source of electromagnetic radiation of different wavelengths. The important component of this radiation from the standpoint of photocatalyst activation is the ultraviolet radiation. We studied the role of UV radiation on corona discharge ozone production by placing the titanium dioxide photocatalyst into the discharge region. We used hollow needle to mesh DC corona discharge at atmospheric pressure with TiO₂ globules on the mesh. The discharge was enhanced by the flow of air through the needle. We found that for the needle biased negatively addition of TiO₂ photocatalyst on the mesh electrode drastically increases discharge ozone production as well as the ozone production yield. These quantities are also influenced by the mass of the used photocatalyst and its distribution in the discharge chamber.     

Non-thermal plasma generation by using back corona discharge on catalyst

This paper discusses a novel plasma catalysis generation method based on back-corona discharge along porous catalyst bed reactor. The reactor consists of a high-voltage needle electrode, one floated mesh electrode, one catalyst bed and one grounded mesh electrode. Typical plasma current density is 11.88 μA/cm². It can be used for ozone generation and volatile organic compounds decomposition. By using a home-made AgMnOx/Al₂O₃-1 catalyst, 90% of toluene is removed at the specific plasma energy density of 123 J/L. At the same time, aerosol byproducts are collected and then decomposed on the catalyst bed. Moreover, the catalyst is regenerated because of the back-corona discharge.     

Investigation of the ozone formation process in a nanosecond microwave discharge in air and oxygen

Results are presented from an investigation of the dynamics of ozone formation in a freely localized discharge generated by a periodic train of 3-cm nanostructured microwave pulses in oxygen and air at a pressure p=3–30 Torr. Conditions for the efficient generation of ozone in air with the minimum production of nitrogen oxides are demonstrated experimentally. It is shown that when the microwave pulse repetition frequency is high, heating of the gas and the buildup of nitrogen oxides in the discharge in air reduce the ozone formation efficiency while under prolonged exposure the ozone formed initially is destroyed. The energy cost of forming ozone in oxygen and air is determined as a function of the microwave pulse length and repetition frequency and the gas pressure. The lowest energy cost of forming a single ozone molecule in these experiments is 16 eV per molecule for a discharge in air and 4 eV per molecule in oxygen. It was observed that circulating the gas through the discharge zone enhances th ozone formation efficiency. It is shown that there are optimal conditions for ozone formation as a function of the reduced electric field in the plasma. Zh. Tekh. Fiz. 67, 9–18 (March 1997)     

Experimental investigations and modelling studies of ozone producing corona discharges

The ozone generation by negative corona discharge in coaxial cylindrical system of electrodes have been studied experimentally in Ar+O₂ and N₂+O₂ mixtures. Both in argon and nitrogen mixtures with oxygen the monotonous decrease in ozone concentration [O₃] was observed at decreasing oxygen content in mixtures and the constant input energy density η. The rate coefficients for the ozone generation and ozone decomposition were obtained by fitting experimentally measured data [O₃]=f(η) with Vasiljev-Eremin formula. The calculated rate coefficient for ozone generation in N₂+O₂ mixtures at low content of oxygen (below 20%) was found considerably higher than that in Ar+O₂ mixtures. Increase in the rate coefficients for ozone generation and decomposition was observed with decreasing content of oxygen in both mixtures. The experimental results are in qualitative agreement with the simple model incorporating five main chemical processes in mechanism of ozone generation. The research was partially supported by Slovak Grant Agency under project 1/765920 The UK EPSRC (Grant GM/98944) and NATO Joint Project PST CLG 976544.     

The dependence of ozone generation efficiency in silent discharge on a width of a discharge gap

The generation of ozone was studied experimentally in silent discharge on oxygen and air under the atmospheric pressure. The concentration of ozone was detected by means of UV absorption. It is shown that we must recount the charge (Q _T) transferred in outer circuit to the charge (Q _s) transferred in the discharge gap to establish the energetic load of ozone generation w[gO₃/Wh]. The width 0.8–1.1 mm of discharge gap was determined as optimal for ozone generation.     

Physicochemical process of non-thermal plasma at gas-liquid interface and synergistic effect of plasma with catalyst

An atmospheric-pressure plasma jet (APPJ) was directly irradiated at a gas-liquid interface under ambient conditions. The reactive oxygen species (ROS) like hydroxyl radicals (•OH), hydrogen peroxide (H₂O₂) and ozone (O₃) and also reactive nitrogen species (RNS) such as nitrogen oxides (NO_x) and nitric acid (HNO₃) formed during the plasma discharge were quantified under various experimental parameters. In a chemical dosimetry method, terephthalic acid (TA) was employed for the quantification of •OH and titanium sulfate was used to quantify the H₂O₂. Quantitative determination of NO₃⁻ was carried out by using Ion chromatography (IC). The changes in the solution pH were studied during the plasma treatment. Strong acidification along with the production of dominant reactive nitrogen species and ozone formation were observed with air. The effect of various gases, gas flow rate, various applied voltage and catalyst were studied to optimize the experimental conditions for the best performance. The influence of catalyst Fe²⁺ salt, TiO₂ on the formation of reactive species were studied. The efficiency of the plasma device for the degradation of crystal violet (CV) was also investigated with TiO₂ and Fe²⁺ salt.     

Ozone generation in oxygen-fed wire-to-cylinder ozonizer: effect of CH2Cl2, CHCl3 and CCl4 diluents

The inhibition effect of methylene chloride CH₂Cl₂, chloroform CHCl₃ and carbon tetrachloride CCl₄ on the ozone generation process from oxygen by negative corona discharge was experimentally investigated. The experiments were performed in a system of coaxial cylindrical electrodes at total gas pressure of 900 mbar and ambient temperature of gaseous mixtures. The rate of ozone generation as well as ozone concentration apparently decreases with a rising number of substituted chlorine atoms in the methane molecule at constant specific energy consumption dissipated in the discharge and at constant concentration of gaseous impurities in oxygen. In addition to experimental results, the paper presents theoretical considerations aimed at identifying the main process responsible for inhibition of ozone generation. The consumption of considerable fraction of oxygen atoms by CH _x Cl _y–1 radicals formed in discharge, is likely the most important mechanism responsible for the deleterious effect of such compounds on the efficiency of ozone production.     

LDA approximation based analysis of the adsorption of O<Subscript>3</Subscript> by boron nitride sheet

Based on the density functional theory whitin the local density aproximation, we investigated the adsorption of the ozone molecule by the boron nitride sheet. To model the sheet we used a planar C _n H _m cluster; four high symmetry sites in the mesh were considered. A total energy calculation indicates that the boron nitride sheet remains planar and the ozone is adsorbed with an energy of 0.41 eV; the ozone reacts with the sheet forming an epoxy group and an oxygen molecule in an unstable configuration.     

Relaxing Phenomena in Negative Corona Discharge: New Aspects

Two theories, explaining the time dependence of the negative corona discharge current in air, are confronted with new experimental results. The influence of the ozone concentration on the discharge current was experimentally confirmed in dry air and in mixtures of nitrogen with oxygen. Assuming that only the dissociative electron attachment to ozone molecule is a process being responsible for a reduction of the electron component in the total mean discharge current, the mean value of the electron attachment rate constant k = (3 - 5.5) × 10^?9 cm^?3 s^?1 was derived from the measured dependence of the discharge current on the ozone concentration. The calculated value of the rate constant k corresponds to the dissociative attachment of electron to ozone molecule via process e + O₃ → products (O^? or O^?₂ negative ions).     

Ultrasonic resonator with electrical discharge cell for ozone generation

The effect of ultrasound waves in an ultrasonic resonator cell on ozone generation by a hollow needle to plate electrical discharge enhanced by the airflow through the needle is experimentally investigated. It was found that the application of ultrasound waves increases ozone generation for discharge when the needle is negatively biased, and has no effect on ozone generation for the discharge when the needle is biased positively. We try to explain the influence of ultrasound on the discharge mechanisms.     

DC corona discharge ozone production enhanced by magnetic field

We have studied the effect of a stationary magnetic field on the production of ozone from air at atmospheric pressure by a negative corona discharge in a cylindrical electrode configuration. We used a stainless steel hollow needle placed at the axis of the cylindrical discharge chamber as a cathode. The outer wall of the cylinder was used as an anode. The vector of magnetic induction was perpendicular to the vector of current density. We found that: (a) the magnetic field extends the current voltage range of the discharge; (b) for the discharge in the Trichel pulses regime and in the pulseless glow regime, the magnetic field has no substantial effect on the discharge voltage or on the concentration of ozone that is produced; (c) for the discharge in the filamentary streamer regime for a particular current, the magnetic field increases the discharge voltage and consequently an approximately 30% higher ozone concentration can be obtained; (d) the magnetic field does not substantially increase the maximum ozone production yield. A major advantage of using a magnetic field is that the increase in ozone concentration produced by the discharge can be obtained without additional energy requirements.     

氮铁共掺锐钛矿相TiO2电子结构和光学性质的第一性原理研究

本文采用基于密度泛函理论的平面波超软赝势方法研究了N,Fe共掺杂TiO₂的晶体结构、电子结构和光学性质.研究表明,N,Fe共掺杂TiO₂的晶格体积、原子间的键长及原子的电荷量发生变化,导致晶体中产生八面体偶极矩,并因此光生电子-空穴对有效分离,提高TiO₂的光催化活性;N,Fe共掺杂同时在导带底和价带顶形成了杂质能级,使TiO₂的禁带宽度变窄,光吸收带边红移到可见光区,这些杂质能级可以降低光生载流子的复合概率,提高Ti     

约化场强对氮-氧混合气放电等离子体演化特性的影响

采用零维等离子体动力学模型,计算了不同约化场强条件下N₂/O₂放电等离子体的演化特性.结果表明,平均电子能量与约化场强有着近似的线性关系,在约化场强为100 Td时,平均电子能量约为2.6 eV、最大电子能量达35 eV;约化场强是影响电子能量函数分布的主要因素.气体放电过程结束后,振动激发态氮分子的粒子数浓度不再变化,电子激发态的氮分子、原子和氧原子的粒子数浓度达到一峰值后开始降低;放电结束后的氧原子通过复合反应生成臭氧.约化场强升高,由于低能电子减少的影响,振动激发态氮分子的粒子数浓度降低,当约化场强由50 Td增加75 Td,100 Td时,粒子数浓度由3.83×10¹¹ cm^-3降至1.98×10¹¹ cm^-3和1.77×10¹¹ cm^-3,其他粒子浓度则相应增大. 关键词： 等离子体 约化场强 粒子演化 数值模拟     

Effect of Ag doping on the crystallization and phase transition of TiO2 nanoparticles

TiO₂ nanoparticles doped with different Ag contents were prepared by a modified sol–gel method, using titanium tetraisopropoxide and silver nitrate as precursors and 2-propanol as solvent. Silver was incorporated into the TiO₂ matrix via decomposition of AgNO₃ during thermal treatment in different atmospheres. Effects of Ag doping on the crystallization and phase transition of the TiO₂ nanoparticles were studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and Raman spectroscopy techniques. While air annealing incorporates silver into TiO₂ matrix in silver oxide form, annealing in nitrogen incorporates metallic silver into TiO₂. Formation of silver oxide increases the thermal stability of the TiO₂ particles. Silver oxide affects the crystallization process of TiO₂ particles and the temperature of transition form anatase to rutile. On the other hand, presence of metallic silver in the samples annealed in nitrogen atmosphere decreases the temperature of phase transition of TiO₂ nanoparticles.     

Combination of spontaneous polarization plasma and photocatalyst for toluene oxidation

In this paper, we report toluene destruction using a spontaneous polarization plasma and photocatalyst reactor in air at atmospheric pressure and room temperature. A spontaneous polarization material (BaTiO₃) and photocatalyst (TiO₂) were added to the plasma system simultaneously. Three types of catalyst, i.e., TiO₂, BaTiO₃, or TiO₂/BaTiO₃, were used for toluene removal. The catalyst carrier, type, and amount were important factors in the toluene removal efficiency. The specific energy density and energy yield during the discharge process were investigated. The toluene removal efficiency increased when a spontaneous polarization plasma was combined with the photocatalyst. In terms of toluene removal efficiency, the activity order was TiO₂/BaTiO₃ > BaTiO₃ > TiO₂ > none. Large amounts of BaTiO₃ in the TiO₂/BaTiO₃ catalyst gave slightly better conversion. The TiO₂/BaTiO₃ catalyst not only enhanced the toluene removal efficiency, but also saved energy, making it useful for industrial applications.     

The potential use of nanosilver-decorated titanium dioxide nanofibers for toxin decomposition with antimicrobial and self-cleaning properties

While chemical and biological attacks pose risk to human health, clean air is of scientific, environmental and physiological concerns. In the present contribution, the potential use of nanosilver-decorated titanium dioxide (TiO₂) nanofibers for toxin decomposition with antimicrobial activity and self-cleaning properties was investigated. Titanium dioxide nanofibers were prepared through sol-gel reaction followed by an electrospinning process. Following the Japan Industrial Standard (JIS) protocol, decompositions of nitrogen oxide (NOx) and volatile organic compound (VOC) by the TiO₂ nanofibers suggested that these materials were capable of air treatment. To further enhance their anti-microbial activity, silver nanoparticles were decorated onto the TiO₂ nanofibers’ surfaces via photoreduction of silver ion in the presence of the nanofibers suspension. Furthermore, tests of photocatalytic activity of the samples were performed by photodegrading methylene blue in water. The nanofibrous membranes prepared from these nanofibers showed superhydrophilicity under UV. Finally, the possibility of using these hybrid nanofibers in environmental and hygienic nanofiltration was proposed, where the self-cleaning characteristics was expected to be valuable in maintenance processes.     

Key factor affecting the structural and textural properties of ZSM-5/MCM-41 composite

ZSM-5/MCM-41 micro/mesoporous composite materials were synthesized by the hydrothermal technique with alkali-treated ZSM-5 zeolite as source of silica and aluminum and characterized by various physico-chemical techniques such as X-ray diffraction (XRD), nitrogen sorption at 77 K, transmission electronic microscopy (TEM), FTIR spectroscopy and NH₃ temperature programmed desorption (TPD) techniques. The effect of concentration of CTAB in the synthesis of these solids has been investigated, the mesopore volume, surface area and surface acidity decrease with increasing the concentration of CTAB. Increasing the CTAB concentration causes the recrystallization of zeolite ZSM-5 and it disadvantage the formation of mesoporous materials MCM-41. The catalytic activity of ZSM-5/MCM-41 materials has been evaluated in the Friedel–Crafts acylation of anisole with benzoyl chloride as alkylating agent. The results revealed the reaction to be influenced by surface area, pore volume and surface acidity.     

Mo-X(B, C, N, O, F)共掺杂TiO2体系的光催化协同效应研究

采用密度泛函理论平面波超软赝势方法, 计算并分析了Mo/X(B, C, N, O, F)共掺杂TiO₂体系的形成能、电子结构和光学性质, 研究了共掺杂协同效应对于计算体系光催化性能的影响机制. 首先计算出不同掺杂体系的态密度及能带结构, 利用能带理论分析了共掺杂效应对于禁带宽度的调控作用, 进而分析了共掺杂对TiO₂光催化能力和稳定性的协同作用. 结合电荷密度图, 分析原子间的电荷转移情况, 得到计算体系中各原子成键状态. 最后, 结合光吸收谱线分析得出Mo/C共掺杂类型在调制TiO₂体系中可见光波段的光催化性能上优势明显, 在催化作用上表现出协同效应. 本文的理论研究对共掺杂方法在TiO₂光催化领域有着一定的指导意义.     

Numerical modeling of ozone production in a pulsed homogeneousdischarge: a parameter study

The pulsed volume discharge is an alternative for the efficient generation of ozone in compact systems. This paper presents a parameter study of the reactions in this kind of homogeneous discharge by using a numerical model which solves plasma chemical kinetic rate and energy equations. Simulations are performed for 10^-9-10^-5 s single pulses and oxygen gas density in the range 10<300 K and normalized electric field of 1000 decreased. The maximum concentration is 3% at 10 amagat and 100 K. The results on ozone accumulation in multiple pulse discharges are presented. In contrast to the single pulse case, higher efficiency is achieved at lower gas density. This scaling can be explained by losses due to ion currents     

Preparation and mechanism investigation of highly sensitive humidity sensor based on Ag/TiO2

In this paper, a high-performance silver-doped titanium dioxide (Ag/TiO₂) humidity sensor was synthesized using a hydrothermal synthesis method for respiratory monitoring. The sensing mechanism was studied by the first principles of density functional theory (DFT). Calculations show that the doping of Ag⁺ ions increases the adsorption energy of TiO₂ to water molecules. Furthermore, the Ti–O bond in TiO₂ is broken due to the doping of Ag⁺ ions, which promotes the generation of Ti³⁺ defects. Experiments show that the doping of Ag⁺ ions can increase the hydroxide groups, Ti³⁺ defects and oxygen vacancies on the surface of TiO₂, thus effectively improving the responsivity, linearity and hysteresis of the TiO₂ humidity sensor. Compared to TiO₂, the resistance of the Ag/TiO₂ (0.5 mM) humidity sensor reaches 4.5 orders of magnitude with a high response of 39707.1, maximum hysteresis rate of 4.6%, response/recovery time of 31 s/15 s and the best linearity in a range of 11%–95% RH. In addition, the Ag/TiO₂ humidity sensor has been successfully used to detect different modes of respiration and determine the respiratory rate under different respiratory states. Significantly, this work demonstrates potential application value in human healthcare and activities monitoring.