A comparative study on the activity of TiO2 in pulsed plasma under different discharge conditions

In the present study,a combination of pulsed discharge plasma and TiO_2(plasma/TiO_2)has been developed in order to study the activity of TiO_2by varying the discharge conditions of pulsed voltage,discharge mode,air flow rate and solution conductivity.Phenol was used as the chemical probe to characterize the activity of TiO_2in a pulsed discharge system.The experimental results showed that the phenol removal efficiency could be improved by about 10%by increasing the applied voltage.The phenol removal efficiency for three discharge modes in the plasma-discharge-alone system was found to be highest in the spark mode,followed by the spark–streamer mode and finally the streamer mode.In the plasma/TiO_2system,the highest catalytic effect of TiO_2was observed in the spark–streamer discharge mode,which may be attributed to the favorable chemical and physical effects from the spark–streamer discharge mode,such as ultraviolet light,O_3,H_2O_2,pyrolysis,shockwaves and high-energy electrons.Meanwhile,the optimal flow rate and conductivity were 0.05 m~3l~(-1)and 10μS cm~(-1),respectively.The main phenolic intermediates were hydroquinone,catechol,and p-benzoquinone during the discharge treatment process.A different phenol degradation pathway was observed in the plasma/TiO_2system as compared to plasma alone.Analysis of the reaction intermediates demonstrated that p-benzoquinone reduction was selectively catalyzed on the TiO_2surface.The effective decomposition of phenol constant(D_e)increased from 74.11%to 79.16%when TiO_2was added,indicating that higher phenol mineralization was achieved in the plasma/TiO_2system.     

Plasma-assisted Co/Zr-metal organic framework catalysis of CO_2 hydrogenation:influence of Co precursors

In this study, Co/Zr-metal organic framework(MOF) precursors were obtained by a roomtemperature liquid-phase precipitation method and the equivalent-volume impregnation method,respectively, using a Zr-MOF as the support, and Co/Zr-MOF-M and Co/Zr-MOF-N catalysts were prepared after calcination in a hydrogen–argon mixture gases(V_(Ar):V_(H_2)= 9: 1) at 350 °C for 2 h. The catalytic activities of the prepared samples for CO_2 methanation under atmosphericpressure cold plasma were studied. The results showed that Co/Zr-MOF-M had a good synergistic effect with cold plasma. At a discharge power of 13.0 W, V_(H_2):V_(CO_2)= 4: 1 and a gas flow rate of 30 ml·min~(-1), the CO_2 conversion was 58.9% and the CH_4 selectivity reached 94.7%,which was higher than for Co/Zr-MOF-N under plasma(CO_2 conversion 24.8%, CH_4 selectivity 9.8%). X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N_2 adsorption and desorption(Brunauer–Emmett–Teller) and x-ray photoelectron spectroscopy analysis results showed that Co/Zr-MOF-M and Co/Zr-MOF-N retained a good Zr-MOF framework structure, and the Co oxide was uniformly dispersed on the surface of the Zr-MOF. Compared with Co/Zr-MOF-N, the Co/Zr-MOF-M catalyst has a larger specific surface area and higher Co~(2+)/Cototaland Co/Zr ratios. Additionally, the Co oxide in Co/ZrMOF-M is distributed on the surface of the Zr-MOF in the form of porous particles, which may be the main reason why the catalytic activity of Co/Zr-MOF-M is higher than that of Co/ZrMOF-N.     

Generation of reactive species in atmospheric pressure dielectric barrier discharge with liquid water

Atmospheric pressure helium/water dielectric barrier discharge(DBD) plasma is used to investigate the generation of reactive species in a gas–liquid interface and in a liquid. The emission intensity of the reactive species is measured by optical emission spectroscopy(OES)with different discharge powers at the gas–liquid interface. Spectrophotometry is used to analyze the reactive species induced by the plasma in the liquid. The concentration of OH radicals reaches 2.2 μm after 3 min of discharge treatment. In addition, the concentration of primary longlived reactive species such as H_2O_2, NO_3~- and O_3 are measured based on plasma treatment time.After 5 min of discharge treatment, the concentration of H_2O_2, NO_3~-, and O_3 increased from 0 mg?·?L~(-1) to 96 mg?·?L~(-1), 19.5 mg?·?L~(-1), and 3.5 mg?·?L~(-1), respectively. The water treated by plasma still contained a considerable concentration of reactive species after 6 h of storage. The results will contribute to optimizing the DBD plasma system for biological decontamination.     

Research on the degradation mechanism of dimethyl phthalate in drinking water by strong ionization discharge

The degradation mechanism of dimethyl phthalate(DMP) in the drinking water was investigated using strong ionization discharge technology in this study. Under the optimized condition, the degradation efficiency of DMP in drinking water was up to 93% in 60 min. A series of analytical techniques including high-performance liquid chromatography, liquid chromatography mass spectrometry, total organic carbon analyzer and ultraviolet–visible spectroscopy were used in the study. It was found that a high concentration of ozone(O_3) produced by dielectric barrier discharge reactor was up to 74.4 mg l~(-1) within 60 min. Tert-butanol, isopropyl alcohol,carbonate ions(CO_3~(2-)) and bicarbonate ions (HCO_3~-) was added to the sample solution to indirectly prove the presence and effect of hydroxyl radicals(·OH). These analytical findings indicate that mono-methyl phthalate, phthalic acid(PA) and methyl ester PA were detected as the major intermediates in the process of DMP degradation. Finally, DMP and all products were mineralized into carbon dioxide(CO_2) and water(H_2O) ultimately. Based on these analysis results, the degradation pathway of DMP by strong ionization discharge technology were proposed.     

Surface treatment of titanium dioxide nanopowder using rotary electrode dielectric barrier discharge reactor

Titanium dioxide (TiO2) nanopowder (P-25;Degussa AG) was treated using dielectric barrier discharge (DBD) in a rotary electrode DBD (RE-DBD) reactor.Its electrical and optical characteristics were investigated during RE-DBD generation.The treated TiO2 nanopowder properties and structures were analyzed using x-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR).After RE-DBD treatment,XRD measurements indicated that the anatase peak theta positions shifted from 25.3° to 25.1°,which can be attributed to the substitution of new functional groups in the TiO2 lattice.The FTIR results show that hydroxyl groups (OH) at 3400 cm-1 increased considerably.The mechanism used to modify the TiO2 nanopowder surface by air DBD treatment was confirmed from optical emission spectrum measurements.Reactive species,such as OH radical,ozone and atomic oxygen can play key roles in hydroxyl formation on the TiO2 nanopowder surface.     

易水湖水下天然中子测量

使用研制的以球形3 He正比计数器为中子灵敏元件的水下中子测量装置对易水湖水下1~25m范围内不同深度处的天然中子进行了测量,并结合相应的蒙特卡罗模拟,获得了易水湖水下不同深度处的低能天然中子产生速率和注量率随湖水深度的变化规律。结果表明:在易水湖水面下方1~10m范围内,低能天然中子产生速率c(cm~(-3)·s~(-1))随深度h(cm)呈指数规律下降,关系式为c=2.7×10~(-5)e~(-0.005 7h),10m以下的变化较为平缓。根据测量结果外推,在易水湖水面附近,水中低能天然中子的产生速率约为2.7×10~(-5) cm~(-3)·s~(-1)(或2.7×10~(-5) g~(-1)·s~(-1))。     

Degradation of phenol using a combination of granular activated carbon adsorption and bipolar pulse dielectric barrier discharge plasma regeneration

A combined method of granular activated carbon (GAC) adsorption and bipolar pulse dielectric barrier discharge (DBD) plasma regeneration was employed to degrade phenol in water. After being saturated with phenol, the GAC was filled into the DBD reactor driven by bipolar pulse power for regeneration under various operating parameters. The results showed that different peak voltages, air flow rates, and GAC content can affect phenol decomposition and its major degradation intermediates, such as catechol, hydroquinone, and benzoquinone. The higher voltage and air support were conducive to the removal of phenol, and the proper water moisture of the GAC was 20％. The amount of H2O2 on the GAC was quantitatively determined, and its laws of production were similar to phenol elimination. Under the optimized conditions, the elimination of phenol on the GAC was confirmed by Fourier transform infrared spectroscopy,and the total removal of organic carbons achieved 50.4％. Also, a possible degradation mechanism was proposed based on the HPLC analysis. Meanwhile, the regeneration efficiency of the GAC was improved with the discharge treatment time, which attained 88.5％ after 100 min of DBD processing.     

Properties of the acrylic acid polymers obtained by atmospheric pressure plasma polymerization

Plasma polymers of acrylic acid were obtained using an atmospheric pressure discharge system. The plasma polymerization reactor uses a dielectric barrier discharge, with the polyethylene terephthalate dielectric acting as substrate for deposition. The plasma was characterized by specific electrical measurements, monitoring the applied voltage and the discharge current. Based on the spatially resolved optical emission spectroscopy, we analyzed the distribution of the excited species in the discharge gap, specific plasma temperatures (vibrational and gas temperatures) being calculated with the Boltzmann plot method. The properties of the plasma polymer films were investigated by contact angle measurements, infrared and UV-Vis spectroscopy, scanning electron microscopy. The films produced by plasma polymerization at atmospheric pressure showed a hydrophilic character, in correlation with the strong absorbance of OH groups in the FTIR spectrum. Moreover, the surface of the plasma polymers at micrometric scale is smooth and free of defects without particular features.     

Catalytic technology for water treatment by micro arc oxidation on Ti-Al alloy

The feasibility of the formation of a liquid plasma catalysis system through micro arc oxidation (MAO) under AC power with titanium-aluminum alloy electrodes was investigated.In the decolorization of organic dyeing wastewater simulated with Rhodamine B,Ti-Al alloy electrodes were superior over Ti electrodes and A1 electrodes.The optimal molar percentage of Ti in alloy electrodes was 70％ and the optimal decolorization rate was up to 88.9％ if the additive suitable for Al was added into the solution to be treated.The decolorization rates were the same in the case of the alloy-alloy electrodes and alloy-A1 electrodes.The proportion of the effects of plasma,TiO2 catalyzer during MAO and H2O2 after MAO in decolorization has been obtained.With the catalysis of TiO2 formed on the electrodes,the reaction rate was improved by a maximum of 95％ and the decolorization rate was improved by a maximum of 71.6％.Based on the spectral analysis,the plasma catalysis mechanism has been studied.     

Preparation of Zn/TiO2 powder and its photocatalytic performance for oxidation of P-nitrophenol

Zn-doped TiO2 catalysts were prepared using a sol-gel method and characterized by XPS,UV-Vis, BET, XRD in this study. Under the irradiation of simulant sunlight, the photocatalytic activity for the degradation of p-nitrophenol was studied too. After irradiation for 2.5 h, the degradation percentage of p-nitrophenol could rise to more than 80 %. The results showed that the spectrum absorption band edge of Zn/TiO2 powder does not broaden obviously comparing with pure TiO2 powder. Zinc exists as Zn （11）. When calcined at 973 K, there is a new phase as ZnTiO3 in Zn/TiO2 catalyst. The order of photocatalytic activity of Zn/TiO2 catalysts calcined at different temperatures for p-nitrophenol is 773 K 〉 673 K 〉 873 K 〉 573 K 〉 973 K and the photocatalytic activity of Zn/TiO2 catalyst calcined at 773 K is better than TiO2 catalysts heated at the same temperature, and outclasses that of commercial TiO2 catalyst. It also showed that the photocatalytic degradation of p-nitrophenol follows first-order kinetics under the irradiation of simulant sunlight.     

~(99m)Tc标记生长抑素类似物KE108的制备及生物学评价

为了探讨生长抑素类似物~(99m)Tc-HYNIC-KE108用于生长抑素受体阳性肿瘤显像的可行性,本研究设计合成了新型的生长抑素类似物HYNIC-KE108,并进行~(99m)Tc标记,优化标记条件,测定标记物的脂水分配系数和体外稳定性,研究其在正常小鼠及荷瘤鼠体内的生物分布。在优化条件下,~(99m)TcHYNIC-KE108的标记率90%,经Waters Oasis HLB小柱纯化后,放化纯度98%,标记物的脂水分配系数logP为0.43±0.02(n=3),体外稳定性良好。标记物在正常小鼠体内血液清除快,主要通过肾脏代谢,在胃、肺和肝脏中放射性摄取相对较高。荷瘤鼠体内分布结果表明,标记物注入体内4h时在肿瘤中的放射性摄取为(1.14±0.91)%ID·g-1,肿瘤与血、肌肉、心脏的放射性摄取比(T/NT)为1.78、8.14、3.35。本工作为进一步研究~(99m)Tc标记的KE108作为生长抑素受体阳性肿瘤显像剂提供了实验依据。     

Characteristics of gas-liquid diaphragm discharge and its application on decolorization of brilliant red B in aqueous solution

A simple gas-liquid diaphragm discharge reactor was designed and characteristics of the discharge and its application on decolorization of brilliant red B in an aqueous solution were investigated. The results showed that strong oxidizing agents such as ·OH and ·O radicals were generated. Average electron temperature of the discharge was 0.72 eV, 1.15 eV and 0.83 eV with air, oxygen and argon as the discharge gas, respectively. Solution p H and conductivity changed little when oxygen or argon was used as the discharge gas; however, these two parameters changed significantly when the discharge was performed in air. During the discharge treatment,the characteristic absorption peaks of brilliant red B gradually decreased where the decolorization followed the first-order kinetics. With 10 min of discharge, the decolorization of brilliant red B(30 mg L~(-1)) can reach 96%, 81% and 62% in the cases of oxygen, argon and air,respectively. The analysis of by-products showed that the brilliant red B molecule can be effectively destroyed in this discharge mode.     

P25半导体矿物光催化还原U(Ⅵ)

采用直流电压法将P25型TiO2粉末负载于FTO导电玻璃制成半导体矿物电极,研究其在不同小分子有机物(甲酸、甲醇、乙酸、乙醇)、不同浓度(0、20、40、60、80、100mmol/L)甲酸作为空穴捕获剂下对U(Ⅵ)的光催化还原。研究结果表明,由于电离能力的强弱不同,酸类小分子有机物对空穴的捕获能力强于醇类小分子有机物,添加的小分子有机物均能提高U(Ⅵ)的还原率且甲酸效果最好,添加60mmol甲酸光催化反应4h后,U(Ⅵ)的还原率能达到90.26%。扫描电镜(SEM)及能谱(EDS)分析表明,反应后电极表面有大颗粒方块状U(Ⅳ)的矿物生成,占据反应活性位点。电化学阻抗分析显示,反应后电极传递电子的阻力增大,电子传输能力减弱,催化活性降低。     

Interaction of hydrogen plasma with carbon-tungsten composite layer

Interaction of neutral hydrogen atoms with the layer of hydrogenated carbon-tungsten composite was studied. A 1 μm thick layer was prepared by sputter deposition from C and WC-targets in Ar/C₂-H₂ gas mixture. After deposition the samples were treated in weakly ionized highly dissociated hydrogen plasma created in a microwave discharge at a power of 1 kW. The gas flow was 13 l/h and pressure was 90 Pa. Temperature of the samples during treatment was about 850 K. After plasma treatment the samples were analyzed by AES (Auger electron spectroscopy) depth profiling, XPS (X-ray photoelectron spectroscopy) and SEM (scanning electron microscopy). It was found that during hydrogen plasma treatment selective etching of the C-W layer occurred. Carbon was preferentially removed from the C-W layer, and after about 10 min of treatment practically only tungsten with a huge porosity was detected.     

Fabrication of stable MWCNT bucky paper for solar-driven interfacial evaporation by coupling y-ray irradiation with borate crosslinking

Herein,we report a facile solution process for preparing multi-walled carbon nanotube(MWCNT)bucky paper for solar-driven interfacial water evaporation.This process involves vacuum filtrating a dispersion of MWCNTs that was modified by polyvinyl alcohol(PVA)under γ-ray irradiation on a cellulose acetate microporous membrane,followed by borate crosslinking.Fourier transform infrared spectroscopy,Raman spectroscopy,and thermogravimetry confirmed the success of PVA grafting onto MWCNTs and borate crosslinking between modified MWCNT nanoyarns.The as-prepared crosslinked MWCNT bucky papers(BBP membranes)were used as a solar absorber,by placing them on a paper-wrapped float-ing platform,for interfacial water evaporation under simulated solar irradiation.The BBP membranes showed good water tolerance and mechanical stability,with an evaporation rate of 0.79 kg m-2 h-1 and an evaporation efficiency of 56％under 1 sun illumination in deionized water.Additionally,the BBP membranes achieved an evaporation rate of 0.76 kg m-2 h-1 in both NaCl solution(3.5 wt％)and sulfuric acid solution(1 mol L-1),demon-strating their impressive applicability for water reclamation from brine and acidic conditions.An evaporation rate of 0.70 kg m-2 h-1(very close to that from deionized water)was obtained from the solar evaporation of saturated NaCl solution,and the BBP membrane exhibited unexpected stability without the inference of salt accumulation on the membrane surface during long-term continuous solar evaporation.     

Research on quinoline degradation in drinking water by a large volume strong ionization dielectric barrier discharge reaction system

Quinoline is widely used in the production of drugs as a highly effective insecticide, and its derivatives can also be used to produce dyes. It has a teratogenic carcinogen to wildlife and humans once entering into the aquatic environment. In this study, the degradation mechanism of quinoline in drinking water by a strong ionization dielectric barrier discharge(DBD) lowtemperature plasma with large volume was explored. High concentration of hydroxyl radical(·OH)(0.74 mmol l-1) and ozone(O3)(58.2 mg l-1) produced by strongly ionized discharge DBD system were quantitatively analyzed based on the results of electron spin resonance and O3 measurements. The influencing reaction conditions of input voltages, initial p H value, ·OH inhibitors, initial concentration and inorganic ions on the removal efficiency of quinoline were systematically studied. The obtained results showed that the removal efficiency and TOC removal of quinoline achieved 94.8% and 32.2%, degradation kinetic constant was 0.050 min-1 at 3.8 k V and in a neutral p H(7.2). The proposed pathways of quinoline were suggested based on identified intermediates as hydroxy pyridine, fumaric acid, oxalic acid, and other small molecular acids by high-performance liquid chromatography/tandem mass spectrometry analysis. Moreover, the toxicity analysis on the intermediates demonstrated that its acute toxicity, bioaccumulation factor and mutagenicity were reduced. The overall findings provided theoretical and experimental basis for the application of a high capacity strong ionization DBD water treatment system in the removal of quinoline from drinking water.     

Study of tetracycline removal and saturated resin regenerated by dielectric barrier discharge plasma

The wastewater produced by the large-scale usage of antibiotics worldwide was more harmful to the ecological environment and human health.In the research,the coupling technology of'adsorption-plasma regeneration'was taken to treat tetracycline in aqueous solution.The pollutants were adsorbed by the resins firstly and then regenerated ectopically by dielectric barrier discharge plasma.The discharge parameters,such as discharge voltage and frequency were researched to achieve the optimal regeneration efficiency and energy efficiency.Meanwhile,the analyses of the surface functional groups and microstructure were also investigated.After the five'adsorption-regeneration'processes,the results showed that the optimal discharge parameters of voltage and frequency were 20 kV and 1 kHz,respectively.The regeneration efficiency and energy efficiency were above 80％and 115 g kW-1·h-1,respectively.The tetracycline adsorption by virgin resin and regenerated resin nearly followed pseudo-second order kinetics,and there was no fatal damage to the surface characteristics and physicochemical properties of the resins through the multiple plasma regeneration processes.Finally,according to the intra-particle diffusion model and the degradation products detected by GC-MS,the adsorption and degradation mechanisms of tetracycline were deduced.     

脂质体介导的^99Tc^m标记c—mycmRNA反认寡核苷酸的初步研究

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Effect of low-temperature plasma on the degradation of omethoate residue and quality of apple and spinach

Dielectric barrier corona discharge was developed to generate low-temperature plasma(LTP) to treat apple and spinach samples contaminated with omethoate. Experimental results showed that,after 20 min exposure, the degradation rate of omethoate residue in apple and spinach was(94.55± 0.01)% and(95.55 ± 0.01)%, respectively. When the treatment time was shorter than 20 min,the contents of moisture, vitamin C and beta-carotene were not affected by LTP. Exploration of related mechanisms suggested that LTP might destroy unsaturated double bonds of omethoate and produce phosphate ion, eventually leading to omethoate destruction. It is concluded that appropriate dosage of LTP can effectively degrade omethoate residue in fruits and vegetables without affecting their quality.     

Analysis of the microstructure and elemental occurrence state of residual ash-PM following DPF regeneration by injecting oxygen into non-thermal plasma

Particulate matter (PM) capture tests were carried out on clean diesel particulate filters (DPFs)under different loads (25％,50％,75％ and 100％).DPFs were regenerated by a non-thermal plasma (NTP) injection device.Raman spectroscopy and x-ray photoelectron spectroscopy were used to investigate changes in the microstructure and element occurrence state of the sediment in DPF channel before and after regeneration.The order of the PM samples decreased before NTP treatment as the load increased;the amorphous carbon content was high,and the oxidation activity was higher.After NTP treatment,the carbon atoms at the edge of the microcrystalline structure in the ash-PM samples were oxidized,and the structure was reorganized;in addition,the amorphous carbon content decreased,and the structure was more diversified.Before NTP,the C element of PM samples was the main component,and the content of the O element was relatively low.The C element occurred in the form of C-C,C-OH,and O-C=O functional groups,and O atoms were mainly combined with C-O.After NTP,the content of Na,P,S,Ca,and other inorganic elements in ash-PM samples was prominent because C atoms were removed by NTP active substances.There were two forms of S element occurrence (SO42-and SO32-);the proportion of SO42-was approximately 40％,and the proportion of SO32-was approximately 60％.Study of the microstructure and element occurrence of the residues in the DPF channels improved our understanding of the mechanism of the low-temperature regeneration of DPF from NTP.