Effects of Ce on catalytic combustion of methane over Pd-Pt/Al2O3 catalyst

Activity and stability of 1%Pd-0.2%Pt/Al₂O₃ and 1%Pd-0.2%Pt/0.6%Ce/Al₂O₃ catalysts prepared by impregnation method for catalytic combustion of methane in air were investigated. The catalysts before and after reaction were characterized by BET, CO chemisorption, XRD and XPS techniques. Results showed that the presence of Ce significantly increased the activity and thermal stability of the Pd-Pt/Al₂O₃ catalyst towards methane combustion, which could be attributed to more highly-dispersed active PdO particles over the Pd-Pt/Ce/Al₂O₃ catalyst surface as well as the retarded sintering of PdO and the maintained oxidized state of surface Pd during the combustion process in the presence of Ce.     

Photocatalytic degradation of C. I. Reactive Red 24 solution with K6SiW11O39SnⅡ

Environmental friendly materials, K₆SiW₁₁O₃₉Sn (SiWSn), was synthesized. SiWSn photocatalytic decomposition of C. I. Reactive Red 24 (RR24) with the UV-lamp (253.7 nm, 20 W), Xenon lamp filtered less than 390 nm light (500 W) and sun light was investigated. The results showed that RR24 solution could be effectively decolorized with the SiWSn photocatalyst. The photocatalytic degradation efficiency of RR24 with SiWSn was affected by the initial concentration of RR2 solution, the amount of SiWSn and the photolysis time. It is demonstrated that the process of photodegradation of RR24 with SiWSn is a pesudo first-order reaction, which can be described by Langmuir-Hinshelwood equation. Hydroxyl radicals and holes are both the main oxidants in the photocatalytic reaction of RR24 with SiWSn.     

Self-catalytic degradation of ortho-chlorophenol with Fenton's reagent studied by chemiluminescence

The degradation of ortho-chlorophenol using Fenton's reagent was studied by chemiluminescence (CL). Without a special CL reagent, a weak CL emission from the mixture of ferrous ion and hydrogen peroxide was observed at room temperature. The CL intensity was increased by the addition of ortho-chlorophenol into the mixed solution. When the temperature was raised to 65℃, the CL intensity was enhanced strongly. The CL mechanisms for the system H₂O₂-Fe²⁺ with and without ortho-chlorophenol were studied by examining the CL spectrum, gas chromatography-mass spectrometry and electron spin resonance spectrum. The effects of various free radical scavengers, surfactants and fluorescence compounds on the CL intensity were also investigated. A self-catalytic oxidation mechanism was proposed. The results showed that singlet oxygen was the main emitter for the system H₂O₂-Fe²⁺. The strong CL from the system H₂O₂-Fe²⁺-ortho-chlorophenol was due to singlet oxygen and electronically excited quinone. The benzenediol-like intermediate product formed during the phenol oxidation process greatly promoted the Fenton's reaction and led to higher CL intensity. Chemiluninescence is a novel approach for the investigation of the oxidation of some organic pollutants by Fenton's reagent.     

Kinetics of photoelectrocatalytic degradation of humic acid using B2O3·TiO2/Ti photoelectrode

An innovative photoelectrode, B₂O₃·TiO₂/Ti electrode, was prepared by galvanostaticanodisation. The morphology and crystalline texture of the B₂O₃·TiO₂ film on electrode were examined by acomic force microscopy (AFM) and X-ray diffraction respectively. The examination results indicated that the anatase was the dominant component. The kinetics of photoelectrocatalytic(PEC) degradation of humic acid(HA) was investigated; the results demonstrated that effects from strongness to weakness on the photoelectrocatalytic degraded rate of humic acid: power of UV-lamp, area of TiO₂ film, bias, original concentration of humic acid solution. The optimum conditions were power of UV-lamp 125 W, area of TiO2 film 42.0 cm² , bias 1.4 V, original concentration of humic acid solution 5 mg/L in this PEC reaction system.     

TiO2/Ag modified penta-bismuth hepta-oxide nitrate and its adsorption performance for azo dye removal

A modified hydrophilic penta-bismuth hepta-oxide nitrate (Bi₅O₇NO₃) surface was synthesized via a precipitation method using TiO₂ and Ag as modified agents. The synthesized product was characterized by different analytical techniques. The removal efficiency was evaluated using mono-and di-sulphonated azo dyes as model pollutants. Different kinetic, isotherm and diffusion models were chosen to describe the adsorption process. X-ray photoelectron spectroscopy (XPS) results revealed no noticeable differences in the chemical states of modified adsorbent when compared to pure Bi₅O₇NO₃;however, the presence of hydrophilic centres such as TiO₂ and Ag developed positively charged surface groups and improved its adsorption performance to a wide range of azo dyes. Dyes removal was found to be a function of adsorbent dosage, initial dye concentration, solution pH and temperature. The reduction of Langmuir 1,2-mixed order kinetics to the second or first-order kinetics could be successfully used to describe the adsorption of dyes onto the modified adsorbent. Mass transfer can be described by intra-particle diffusion at a certain stage, but it was not the rate limiting step that controlled the adsorption process. Homogenous behavior of adsorbent surface can be explored by applying Langmuir isotherm to fit the adsorption data.     

Radioactive tracer of the photochemical reaction of 14CS2 with OH in the presence of O2

The photochemical reaction of¹⁴CS ₂ with OH has been studied．The results indicated that the main products of the reaction were¹⁴COS and ¹⁴CO with a small amount of ¹⁴CO₂ in the reaction system(¹⁴CS₂-H₂O₂-C₃H₈-N₂-O₂>)．The reaction was promoted by oxygen．¹⁴COS and ¹⁴CO had the similar kinetic curves while ¹⁴CO₂ got a different kind of Curve．The overall rate constant increased with the increasing of oxygen partial pressure．The rate constant for the removal of ¹⁴CS₂ was K=3.4×10^-12cm³/(mO1.s) at 33330 Pa 0₂．The conversion of ¹⁴CS₂ to ¹⁴CO₂ at room temperature was observed and the possible mechanism of the photochemical reaction was disscussed．     

Effect of SO2 on performance of the turnip moth,Agrotis segetum Schiff

Effect of SO₂-enriched air on the turnip moth, Agrotis segetum Schiff.was investigated by rearing the larvae on rape leaves that had been exposed to 40 or 80 ppb of the air pollutant in field fumigation chambers. An examination on the 11th day showed that the larvae in both treatments survived more, developed markedly faster, their fresh v/eig'ht and mean relative growth rate were significantly greater than those of control insect. Improvement of their growth and development resulted in decrease of total larval duration by 0.5 - 1.0 day. Pupal and adult performances were little affected by SO₂ level to which larval food plant was exposed. Possible reason responsible for enhanced growth and development of the insect species was discussed.     

Preparation of MgO/B2O3 coatings by plasma spraying on SUS304 surface and effects of heat-resistant

This study mainly deals with the preparation of MgO/B₂O₃ coatings by plasma spraying on the SUS304 surface and the effects of heatresistant. The power materials of low thermal conductivity were selected to control the heat divergent performance of high temperature parts. The reticular micro-structure between the cover thermal layer and the substrate was prepared by using the plasma spraying method. The powder mixture of MgO and B₂O₃ were selected as spraying materials and the SUS304 was used as the substrate material. The MgO/B₂O₃ coating was prepared on the surface of the SUS304 to provide better cover thermal performance. The properties of the microstructures and the morphologies were studied by Optical Microscope, Scanning Electron Microscope, Electron Probe Microanalyzer, and X-ray Diffraction. The results showed that the cover thermal performance has been improved.     

Photocatalytic degradation of organochlorine compounds using TiO2 supported on fiberglass cloth

The feasibility of photocatalytic degradation of organochlorine compounds using TiO₂ supported on fiberglass cloth as a photocatalyst was studied. The results showed that 2.0×10^-4 mol/dm³ of dichloroethylene, trichloroethylene and tetrachloroethylene can be completely photocatalytically degraded within a short time under illumination with a 375W medium pressure mercury lamp. The effects of parameters such as illumination time, initial concentration of organochlorine compounds, amount of air flow and concentration of H₂O₂ on the photocatalytic degradation were investigated. The TiO₂ supported on the fiberglass was not easily detached and after 500h illumination there was no significant loss of photocatalytic activity of TiO₂. The passible mechanisms of photocatalytic degradation were discussed.     

Simulated-sunlight-activated photocatalysis of Methylene Blue using cerium-doped SiO2/TiO2 nanostructured fibers

Cerium-doped SiO₂/TiO₂ nanostructured fibers were fabricated by electrospinning technology. The prepared fibers were characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Using the fibers as catalysts, photocatalytic degradation of Methylene Blue (MB) aqueous solution was carried out under simulated sunlight. The 0.2% Ce doping proved to be the optimal concentration for the doping of TiO₂/SiO₂, compared to other Ce-doped molar concentrations. The 0.2% Ce-doped SiO₂/TiO₂ fibers exhibited higher photocatalytic activity than industrial Degussa P25 and the samples doped with only Ce or SiO₂. The reasons for improving the photocatalytic activity were also discussed. Several operational parameters were studied, which showed that the photocatalytic efficiency of MB was influenced by parameters such as the initial dye concentration, the initial pH, inorganic anions, and so on. In addition, the influences of an electron acceptor and a radical scavenger suggested that OH was the dominant photooxidant during the photocatalytic process. The reuse evaluation of the fibers indicated that their photocatalytic activity had good stability.     

Roles of SO2 oxidation in new particle formation events

The oxidation of SO₂ is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO₂ and observed long-term (duration > 3 hr) and short-term (duration <1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J₃₀) showed a moderate correlation with the concentration of sulfuric acid ([H₂SO₄]) calculated from the measured mixing ratio of SO₂ in long-term NPF events and some short-term NPF events (Category I) (R² = 0.66). The exponent in the fitting line of J₃₀ ~ [H₂SO₄]ⁿ in these events was 1.6. It was also found that SO₂ mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO₂-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO₂ probably made a negligible contribution to the growth of >10 nm new particles.     

Synthesis, crystal structure, photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c= 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^-1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2- and NO₃^-, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography- mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.     

Photocatalytic degradation of 4-chlorophenol under P-modified TiO2/UV system:Kinetics, intermediates, phytotoxicity and acute toxicity

A series of phosphorus-modified titanium dioxide samples with varying P/Ti atomic ratio were conveniently prepared via a conventional solgel route. The effects of phosphorus content and calcination temperature on the crystalline structure, grain growth, surface area, and the photocatalytic activity of P-modified TiO₂ were investigated. The XRD results showed that P species slow down the particle growth of anatase and increase the anatase-to-rutile phase transformation temperature to more than 900℃. Kinetic studies on the P-modified TiO₂ to degraded 4-chlorophenol had found that the TP5₅₀₀ prepared by adopting a P/Ti atomic ratio equal to 0.05 and calcined at 500℃ had an apparent rate constant equal to 0.0075 min^-1, which is superior to the performance of a commercial photocatalyst Degussa P25 K_app = 0.0045 min^-1 and of unmodified TiO₂ (TP0₅₀₀) K_app = 0.0022 min^-1. From HPLC analyses, various hydroxylated intermediates formed during oxidation had been identified, including hydroquinone (HQ), benzoquinone (BQ) and (4CC) 4-chlorocatechol as main products. Phytotoxicity was assessed before and after irradiation against seed germination of tomato (Lycopersicon esculentum) whereas acute toxicity was assessed by using Folsomia candida as the test organism. Intermediates products were all less toxic than 4-chlorophenol and a significant removal of the overall toxicity was accomplished     

In situ preparation of g-C3N4/polyaniline hybrid composites with enhanced visible-light photocatalytic performance

The graphic carbon nitride/polyaniline (g-C₃N₄/PANI) hybrid composites were successfully synthesized by a facile in situ polymerization process under ice water bath. The photocatalytic activities of the g-C₃N₄/PANI composites were evaluated by using oxytetracycline (OTC) as model pollutants. The optimal g-C₃N₄/PANI composite (5%PANI: the g-C₃N₄/PANI hybrid with 5 wt.% of PANI) showed an enhancement degradation rate of 5-fold compared to that of conventional g-C₃N₄ under simulated-sunlight irradiation. In addition, the 5%PANI demonstrate significantly photocatalytic evolution H₂ rate (163.2 μmol/(g?hr)) under the visible light irradiation. Furthermore, based on the results of optical performance and electrochemical testing, a possible mechanism was proposed, indicating that the incorporation of PANI into the traditional g-C₃N₄ can effectively tune the electronic structures, improve the photo-generated electrons-holes separation and enhance extensive absorption of visible light. Such a g-C₃N₄/PANI hybrid nanocomposites could be envisaged to possess great potentials in practical wastewater treatment and water splitting.     

Optimization of H2O2 dosage in microwave-H2O2 process for sludge pretreatment with uniform design method

A microwave-H₂O₂ process for sludge pretreatment exhibited high efficiencies of releasing organics, nitrogen, and phosphorus, but large quantities of H₂O₂ residues were detected. A uniform design method was thus employed in this study to further optimize H₂O₂ dosage by investigating effects of pH and H₂O₂ dosage on the amount of H₂O₂ residue and releases of organics, nitrogen, and phosphorus. A regression model was established with pH and H₂O₂ dosage as the independent variables, and H₂O₂ residue and releases of organics, nitrogen, and phosphorus as the dependent variables. In the optimized microwave-H₂O₂ process, the pH value of the sludge was firstly adjusted to 11.0, then the sludge was heated to 80℃ and H₂O₂ was dosed at a H₂O₂:mixed liquor suspended solids (MLSS) ratio of 0.2, and the sludge was finally heated to 100℃ by microwave irradiation. Compared to the microwave-H₂O₂ process without optimization, the H₂O₂ dosage and the utilization rate of H₂O₂ in the optimized microwave-H₂O₂ process were reduced by 80% and greatly improved by 3.87 times, respectively, when the H₂O₂:MLSS dosage ratio was decreased from 1.0 to 0.2, resulting in nearly the same release rate of soluble chemical oxygen demand in the microwave-H₂O₂ process without optimization at H₂O₂:MLSS ratio of 0.5.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O³ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ >> NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

Enhanced photocatalytic activity of fish scale loaded TiO2 composites under solar light irradiation

Fish scale (FS) loaded TiO₂ composites were investigated as photocatalysts in degradation of Methyl Orange under solar light irradiation. Composites were prepared through sol-gel method by varying mass ratio of TiO₂/FS at 90:10, 70:30 and 50:50, respectively. The catalysts prepared in this study were characterized by using XRD, SEM, FT-IR and nitrogen sorption. The effects of solar irradiation, mass ratio of TiO₂/FS composites, irradiation time and catalyst loadings were studied. Synergistic effect was found in TiO₂/FS of 90:10 composite which performed higher photocatalytic degradation than synthesized TiO₂ under solar light irradiation. However, further increasing fish scale content in the composites reduced the photocatalytic activity drastically. Under solar light irradiation, all the catalysts in this study exhibited photocatalytic activity, except TiO₂/FS of 50:50 composite that only acted as a weak biosorbent without performing any photocatalytic property. Photocatalytic degradation increased with increasing catalyst loading and irradiation time but decreased with increased of initial dye concentration.     

Soil warming effect on net ecosystem exchange of carbon dioxide during the transition from winter carbon source to spring carbon sink in a temperate urban lawn

The significant warming in urban environment caused by the combined effects of global warming and heat island has stimulated widely development of urban vegetations. However, it is less known of the climate feedback of urban lawn in warmed environment. Soil warming effect on net ecosystem exchange (NEE) of carbon dioxide during the transition period from winter to spring was investigated in a temperate urban lawn in Beijing, China. The NEE (negative for uptake) under soil warming treatment (temperature was about 5℃ higher than the ambient treatment as a control) was -0.71 μmol/(m².sec), the ecosytem was a CO₂ sink under soil warming treatment, the lawn ecosystem under the control was a CO₂ source (0.13 μmol/(m².sec)), indicating that the lawn ecosystem would provide a negative feedback to global warming. There was no significant effect of soil warming on nocturnal NEE (i.e., ecosystem respiration), although the soil temperature sensitivity (Q₁₀) of ecosystem respiration under soil warming treatment was 3.86, much lower than that in the control (7.03). The CO₂ uptake was significantly increased by soil warming treatment that was attributed to about 100% increase of α (apparent quantum yield) and A_max (maximum rate of photosynthesis). Our results indicated that the response of photosynthesis in urban lawn is much more sensitive to global warming than respiration in the transition period.     

Applying a new method for direct collection, volume quantification and determination of N2 emission from water

The emission of N₂ is important to remove excess N from lakes, ponds, and wetlands. To investigate the gas emission from water, Gao et al. (2013) developed a new method using a bubble trap device to collect gas samples from waters. However, the determination accuracy of sampling volume and gas component concentration was still debatable. In this study, the method was optimized for in situ sampling, accurate volume measurement and direct injection to a gas chromatograph for the analysis of N₂ and other gases. By the optimized new method, the recovery rate for N₂ was 100.28% on average; the mean coefficient of determination (R²) was 0.9997; the limit of detection was 0.02%. We further assessed the effects of the new method, bottle full of water, vs. vacuum bag and vacuum vial methods, on variations of N₂ concentration as influenced by sample storage times of 1, 2, 3, 5, and 7 days at constant temperature of 15°C, using indices of averaged relative peak area (%) in comparison with the averaged relative peak area of each method at 0 day. The indices of the bottle full of water method were the lowest (99.5%-108.5%) compared to the indices of vacuum bag and vacuum vial methods (119%-217%). Meanwhile, the gas chromatograph determination of other gas components (O₂, CH₄, and N₂O) was also accurate. The new method was an alternative way to investigate N₂ released from various kinds of aquatic ecosystems.     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO₂ on the properties of Pd/Co₃O₄/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O₂ and CO + NO) and total hexane oxidation (C₆H₁₄ + O₂). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO₂ addition promotes the SO₂ resistance of Pd/Co₃O₄/cordierite. The second support decreases the activity of Pd/Co₃O₄/cordierite catalyst in the reactions of CO and C₆H₁₄ with oxygen because of CoAl₂O₄ formation.