A Novel Photocatalytic Functional Coating Applied to the Degradation of Xylene in Coating Solvents under Solar Irradiation.

A novel photocatalytic functional coating was prepared with g-C3N4/TiO2 composites as the photocatalytic active component modified by dielectric barrier discharge (DBD), and it showed an efficient catalytic performance under solar light irradiation. The degradation of xylene released from fluorocarbon coating solvents by the g-C3N4/TiO2 composite coatings was investigated under simulated solar irradiation. The degradation efficiency of the coating mixed with DBD-modified 10%-g-C3N4/TiO2 showed a stable, long-lasting, and significantly higher activity compared to the coatings mixed with the unmodified catalyst. Ninety-eight percent of the xylene released from fluorocarbon coating solvents was successfully removed under solar light irradiation in 2 h. The properties of the catalyst samples before and after modification were evaluated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible (UV-vis) spectroscopy, X-ray photoelectron spectroscopy (XPS), and other characterization techniques. The results suggested that DBD-modified g-C3N4/TiO2 showed an improved capture ability and utilization efficiency of solar light with reduced band gap and lower complexation rate of electron-hole pairs. The prepared photocatalytic coating offers an environmentally friendly approach to purify the volatile organic compounds (VOCs) released from solvent-based coatings.

Nonthermal air plasma dehydration of hydrochar improves its carbon sequestration potential and dissolved organic matter molecular characteristics.

Labile organic compounds are associated with high environmental risk and are common on hydrochar surfaces. However, a comprehensive re-evaluation of hydrochar properties after the removal of labile compounds has long been overlooked. This study confirms that air-based nonthermal plasma can successfully modify hydrochar properties and change hydrochar's environmental benefits. NMR and FTIR results indicate that, aliphatic and alkyl structures are more reactive, while aromatic structures are highly resistant to the hydrochar modification process, leading to increased carbon sequestration potential and decreased dissolved organic matter (DOM). Van Krevelen diagram results indicate that dehydration controls the hydrochar modification process and leads to a decrease in oxygen content and O/C atomic ratio in the hydrochar; this weakens the ability of the hydrochar to immobilize hydrophobic organic pollutants (such as triclosan) due to the decrease in O­alkyl C species within the hydrochar. Most importantly, air-based nonthermal plasma changes the structures of hydrochar associated DOM, and high molecular weight (>351 Da), and high degree of unsaturation and oxidation in the modified-hydrochar DOM compounds is observed. This study is therefore considered to have important implications for the carbon cycle and sustainable application of hydrochar.

Decomposition of gaseous toluene using a continuous flow discharge plasma reactor with new configurations.

The destruction of gaseous toluene was carried out in a tubular multilayer dielectric barrier discharge reactor which can yield a steady state of low-temperature plasma with an array structure. The research was investigated under different relative humidities, input voltages, energy densities, energy consumption and the reactor processing capacities. The results showed that the highest removal efficiency and processing capacity (γ) were acquired using an additional dielectric with the width of 2 mm between adjacent discharge quartz tubes, and the removal efficiency of toluene reached 86.5% and γ increased to 6272 kg/s m³ at a voltage of 6 kV. The gas-phase by-products (O3, NOx, COx and intermediate organics) were also presented and the reaction mechanism was described according to the decomposition reaction tunnels.

Decomposition of dimethylamine gas with dielectric barrier discharge.

The decomposition of dimethylamine (DMA) with gas under high flow rate was investigated with dielectric barrier discharge (DBD) technology. Different parameters including removal efficiency, energy yield, carbon balance and CO2 selectivity, secondary products, as well as pathways and mechanisms of DMA degradation were studied. The experimental results showed that removal efficiency of DMA depended on applied voltage and gas flow rate, but had no obvious correlation with initial concentration. Excellent energy performance was obtained using present DBD technology for DMA abatement. When experiment conditions were controlled at: gas flow rate of 14.9 m(3)/h, initial concentration of 2104 mg/m(3), applied voltage of 4.8 kV, removal efficiency of DMA and energy yield can reach 85.2% and 953.9 g/kWh, respectively. However, carbon balance (around 40%) was not ideal due to shorter residence time (about 0.1s), implying that some additional conditions should be considered to improve the total oxidation of DMA. Moreover, secondary products in outlet gas stream were detected via gas chromatogram-mass spectrum and the amounts of NO3(-) and NO2(-) were analyzed by ion chromatogram. The obtained data demonstrated that NOx might be suppressed due to reductive NH radical form DMA dissociation. The likely reaction pathways and mechanisms for the removal of DMA were suggested based on products analysis. Experimental results demonstrated the application potential of DBD as a clean technology for organic nitrogen-containing gas elimination from gas streams.

[Investigation of the oxidation reaction of O3 with bromide ion in aqueous solution].

The reaction mechanism of O3 with bromide ion in aqueous solution was studied by ion chromatography and UV-Vis spectrometry instruments. Ion chromatography analysis showed that only 10% of Br- which was oxidized by ozone was formed into bromate ion. The results demonstrated that the final products of the oxidation reaction were identified as Br2 and Br3- except for BrO3-. The formation of Br3- which was yielded from the reaction of Br2 with Br- was the major process in the reaction of Br attacked by O3. The characteristic absorption spectrum of Br3- with an absorption peak at 260 nm was also investigated. The results may provide helpful information about the mechanism of the oxidation reaction of Br- with O3 and fate of Br- or its derivatives in the environment by the oxidation processes.

[New-type electrodeless excilamp for advanced treatment on nitrogen-heterocyclic compounds (NHCs) in aqueous solution].

A novel 206 nm excilamp generated by microwave-driven Kr/I2 mixtures was employed for nitrogen-heterocyclic compounds (NHCs) degradation in aqueous solution. The photodissociation efficiencies of indole and quinoline with 206 nm excilamp were estimated on the basis of removal efficiency of targeted compounds and the loss of total organic carbon (TOC). The results indicated that removal efficiency of 20 mg x L(-1) indole was as high as 62.0% after 80 min and TOC loss efficiency of 50.7% for 150 min. The irradiation time, initial concentration and pH value had some influences on quinoline degradation. Indole removal efficiency and TOC loss was markedly higher than that of quinoline under the same condition. The intermediates were identified qualitatively by gas chromatography/mass spectrum (GC/MS) with headspace sampling after they were extracted by rotary evaporator. GC/MS analysis indicated that indole and quinoline underwent ring-open dissociation under 206 nm irradiation, as a result, benzene, xylene, acetate, aldehyde, as well as ester compounds were formed, while indole aggregation reaction occurred during indole photodegradation. At last, degradation mechanisms of quinoline and indole in aqueous media with 206 nm excilamp were proposed on the basis of intermediates.

Photodegradation of SF6 on polyisoprene surface: implication on elimination of toxic byproducts.

Photodegradation of SF(6) was performed on the surface of polyisoprene (PI) based on a brand new mechanism of "controlled release of radicals". Effective decomposition of SF(6) (60% of SF(6) was degraded in 4h) was achieved due to the highly reductive radicals (mainly allylic radicals and excited CC bond) which were generated from the photolysis of PI. No toxic fluoride was detected by FT-IR. The PI irradiated for 200 h in SF(6) circumstance was examined by XPS to be doped with fluorine and sulfur. Fouling due to photoinitiated polymerization on UV lamp was avoided because the radicals were released slowly. Photolysis of SF(6) in pure argon with the presence of irradiated PI showed kinetics of pseudo-first-order reaction and the degradation rate constant was 5.16 x 10(-5)s(-1). Factors which may affect the photolysis process such as introduction of O(2) and H(2)O were also examined.

Photoreductive degradation of sulfur hexafluoride in the presence of styrene.

Sulfur hexafluoride (SF6) is known as one of the most powerful greenhouse gases in the atmosphere. Reductive photodegradation of SF6 by styrene has been studied with the purpose of developing a novel remediation for sulfur hexafluoride pollution. Effects of reaction conditions on the destruction and removal efficiency (DRE) of SF6 are examined in this study. Both initial styrene-to-SF6 ratio and initial oxygen concentration exert a significant influence on DRE. SF6 removal efficiency reaches a maximum value at the initial styrene-to-SF6 ratio of 0.2. It is found that DRE increases with oxygen concentration over the range of 0 to 0.09 mol/m3 and then decreases with increasing oxygen concentration. When water vapor is fed into the gas mixture, DRE is slightly enhanced over the whole studied time scale. The X-ray Photoelectron Spectroscopy (XPS) analysis, together with gas chromatography-mass spectrometry (GC-MS) and Fourier Transform Infrared spectroscopy (FT-IR) analysis, prove that nearly all the initial fluorine residing in the gas phase is in the form of SiF4, whereas, the initial sulfur is deposited in the form of elemental sulfur, after photodegradation. Free from toxic byproducts, photodegradation in the presence of styrene may serve as a promising technique for SF6 abatement.

Feasibility of destruction of gaseous benzene with dielectric barrier discharge.

Destruction of gaseous benzene (C(6)H(6)) by dielectric barrier discharge (DBD) was studied in both laboratory-scale and scale-up DBD systems. The effects of input power, gas flow rate as well as initial concentration on benzene decomposition and energy yield were investigated. In addition, qualitative analysis on byproducts and relatively detailed discussion on mechanisms were also presented in this paper. At last, we systematically illustrated the feasibility of benzene removal with DBD on basis of three aspects: estimation of treatment cost per unit volume, comparison with other plasmas, and problems existed in DBD system. The results will help impel actual application of DBD on waste gas containing benzene.

Different reaction mechanisms of diphenylether and 4-bromodiphenylether with nitrous acid in the 355 nm laser flash photolysis of mixed aqueous solution.

The microscopic reaction mechanisms of diphenylether (DPE) and 4-bromodiphenylether (4-BrDPE) with nitrous acid (HNO(2)) in the absence of O(2) have been explored by the 355nm laser flash photolysis. It was proposed that OH radical, from the photolysis of HNO(2), added to DPE forms the C(12)H(10)O-OH adduct while added to 4-BrDPE forms the 4-BrDPE-OH and 4-BrOH-DPE adducts. The first-order decay rate constants of the C(12)H(10)O-OH adduct, 4-BrDPE-OH adduct and 4-BrOH-DPE adduct were measured to be (1.86+/-0.14)x10(5)s(-1), (2.19+/-0.04)x10(5)s(-1) and (1.56+/-0.03)x10(5)s(-1), respectively. The final photolysis products of DPE and HNO(2) identified by GC/MS analysis were phenol, o-hydroxydiphenylether, p-hydroxydiphenylether and p-nitrodiphenylether, while the final photolysis product of 4-BrDPE and HNO(2) identified by LC/MS analysis was mainly the dimer.

Removal of ammonia from gas streams with dielectric barrier discharge plasmas.

We reported on the experimental study of gas-phase removal of ammonia (NH3) via dielectric barrier discharge (DBD) at atmospheric pressure, in which we mainly concentrated on three aspects--influence of initial NH3 concentration, peak voltage, and gas residence time on NH3 removal efficiency. Effectiveness, e.g. the removal efficiency, specific energy density, absolute removal amount and energy yield, of the self-made DBD reactor had also been studied. Basic analysis on DBD physical parameters and its performance was made in comparison with previous investigation. Moreover, products were detected via ion exchange chromatography (IEC). Experimental results demonstrated the application potential of DBD as an alternative technology for odor-causing gases elimination from gas streams.

A novel method to decompose two potent greenhouse gases: photoreduction of SF6 and SF5CF3 in the presence of propene.

SF5CF3 and SF6 are the most effective greenhouse gases on a per molecule basis in the atmosphere. Original laboratory trial for photoreduction of them by use of propene as a reactant was performed to develop a novel technique to destroy them. The highly reductive radicals produced during the photolysis of propene at 184.9 nm, such as .CH3, .C2H3, and .C3H5, could efficiently decompose SF6 and SF5CF3 to CH4, elemental sulfur and trace amounts of fluorinated organic compounds. It was further demonstrated that the destruction and removal efficiency (DRE) of SF5X (X represented F or CF3) was highly dependent on the initial propene-to-SF5X ratio. The addition of certain amounts of oxygen and water vapor not only enhanced the DRE but avoided the generation of deposits. In both systems, employment nitrogen as dilution gas lessened the DRE slightly. Given the advantage of less toxic products, the technique might contribute to SF5X remediation.

[Photolysis of simulating CS2 malodorous gas using microwave electrodeless lamps].

The photolysis of simulating carbon disulfide malodorous gas was studied under UV irradiation emitted by microwave electrodeless lamps. Experiments results show that the photolysis of carbon disulfide is determined by the initial concentration, residence time and gas humidity. When air velocity is 0.2 m/s, initial concentration is about 100 mg/m3, and gas humidity is about 40%, the conversion ratio of carbon disulfide can reach to 75% with microwave electrodeless mercury lamp and 50% with microwave electrodeless iodine lamp. The mechanism of carbon disulfide photolysis was further studied. It is concluded that the photolysis of carbon disulfide is probably a collective action of direct photolysis and *OH radical oxidation.

Investigation of a new approach to decompose two potent greenhouse gases: photoreduction of SF(6) and SF(5)CF(3) in the presence of acetone.

In this paper, we addressed the utilization of photochemical method as an innovative technology for the destruction and removal of two potent greenhouse gases, SF(6) and SF(5)CF(3). The destruction and removal efficiency (DRE) of the process was determined as a function of excitation wavelength, irradiation time, initial ratio of acetone to SF(5)X (X represented F or CF(3)), initial SF(5)X concentration, additive oxygen and water vapor concentration. A complete removal was achieved by a radiation period of 55min and 120min for SF(6)-CH(3)COCH(3) system and SF(5)CF(3)-CH(3)COCH(3) system respectively under 184.9nm irradiation. Extra addition of water vapor can enhance DRE by approximately 6% points in both systems. Further studies with GC/MS and FT-IR proved that no hazardous products such as S(2)F(10), SO(2)F(2), SOF(2), SOF(4) were generated in this process.

[Photocatalytic degradation of hexafluorobenzene by tungstophosphoric acid].

We verified that C6F6, a typical perfluorine compound, could be photocatalytic degraded by H3PW12O40. The defluorination of C6F6 was determined as a function of irradiation time, pH, initial concentration of H3PW12O40, and additives as well. The defluorination of C6F6 increased with the irradiation time. Acid condition, especially pH = 1.0 is preferred. 3 mL solution of 2.0 x 10(-4) mol/L C6F6 and 5.0 x 10(-6) mol/L H3PW12O40 was irradiated for 20 min and the defluorination of C6F6 was equal to 208.1%. O2, KMnO4 and K2S2O8 added in the solution were able to increase the defluorination of C6F6 via oxidating [PW12O40](4-). The defluorination of C6F6 would decline in the presence of alcohol and aromatic compounds.

[Differentiated thyroid carcinoma in children and adolescents: clinical characteristics and treatment].

OBJECTIVE: To explore the clinicopathologic characteristics, treatment and prognosis of differentiated thyroid carcinoma (DTC) in adolescents. METHODS: The data of 46 patients with DTC under the age of 18 years were retrospectively reviewed. RESULTS: Twenty patients were misdiagnosed in this group (43.5%). All patients received operation, including 39 unilateral neck dissection and 6 bilateral neck dissection, followed by postoperative thyrotropin suppressive therapy. There were 42 cases of papillary carcinoma (91.3%) and 4 cases of follicular carcinoma (8.7%). Cervical lymph node metastasis was found in 39 cases (84.8%). In the follow-up period of 1 to 25 years (mean 10 years), no death of thyroid carcinoma occurred. CONCLUSIONS: The most common DTC in adolescents is papillary carcinoma with better prognosis regardless of the higher incidence of cervical lymph node metastasis. The optimal extent of primary thyroidectomy and neck dissection followed by postoperative thyrotropin suppressive therapy in adolescents with DTC may improve the quality of life and decrease the incidence of complications.

[Dissociation of SF5CF3 under discharge].

SF5CF3 was identified recently as a potent greenhouse gas with strong radiative force and long atmosphere residential life. Spark discharge method was used to take simulative investigation on the elimination of SF5CF3 from atmosphere under discharge here. The results show that SF5CF3 was dissociated under discharge and formed some compounds containing S, F, O and C. The dissociation of SF5CF3 was reduced if the system existed H2O, but it was independent of the amount of H2O. The rate coefficients were estimated to be 0.011s(-1) under moisture circumstance when the system total pressure was about 31 kPa. And the increase of the system pressure would cause exponential decrease of SF5CF3 dissociation. The reactive mechanism was argued based on the experiment results and the sinks of SF5CF3 under lightning (one of the discharge in the atmosphere) was estimated to be 53.6 kg x a(-1).