Gas-phase degradation of CCl<Subscript>4</Subscript>, CHCl<Subscript>3</Subscript> and CH<Subscript>2</Subscript>Cl<Subscript>2</Subscript> over metallic Fe

We studied the hydrolysis of gas-phase carbon tetrachloride (CCl₄), chloroform (CHCl₃), and dichloromethane (CH₂Cl₂) over a metallic Fe surface for its application in combination with air stripping and soil vapour extraction. The effects of chlorocarbon concentration, type and preparation of the iron-containing material, humidity, and temperature on process performance are reported. The hydrolysis of chlorinated methane derivatives is catalysed by metallic iron resulting in a noticeable decrease of the reaction temperature. The reaction kinetics were found to be consistent with the Langmuir-Hinshelwood model.     

Preparation of effective TiO<Subscript>2</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> photocatalysts for water treatment

Photocatalytic oxidation using semiconductors is one of the advanced oxidation processes for degradation of organic pollutants in water and air. TiO₂ is an excellent photocatalyst that can mineralize a large range of organic pollutants such as pesticides and dyes. The main challenge is to improve the efficiency of the TiO₂ photocatalyst and to extend TiO₂ light absorption spectra to the visible region. A potential solution is to couple TiO₂ with a narrow band gap semiconductor possessing a higher conduction band such as bismuth oxide. Therefore, here we prepared Bi₂O₃/TiO₂ heterojunctions by the impregnation method with different Bi/Ti ratio. The prepared composites have been characterized by UV–Vis diffused reflectance spectra and X-ray diffraction. The photocatalytic activity of the heterojunction has been determined from the degradation of orange II under visible and UV light. Results show that Bi₂O₃/TiO₂ heterojunctions are more effective than pure TiO₂-anatase under UV-A irradiation, with an optimum for the Bi/Ti ratio of 5 %, for the photocatalytic degradation of Orange II. However, the photocatalytic activity under irradiation at λ higher than 420 nm is not much improved. Under UV–visible radiation, the two semiconductors are activated. We propose a mechanism explaining why our products are more effective under UV–visible irradiation. In this case the charge separation is enhanced because a part of photogenerated electrons from the conduction band of TiO₂ will go to the conduction band of bismuth oxide. In this composite, titanium dioxide is the main photocatalyst, while bismuth oxide acts as adsorbent photosensitizer under visible light.     

Metal-free oxidation of aldehydes to acids using the 4Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O<Subscript>2</Subscript>·NaCl adduct

Oxidation of aldehydes to carboxylic acids is a major reaction. Conventionally, this reaction is carried out with oxidants and metal catalysts, thus producing unwanted metal waste. Recently, aqueous media have been used as an alternative for toxic organic solvents. Here, we tested the clathrate-structured, neutral hydrogen peroxide adduct 4Na₂SO₄·2H₂O₂·NaCl for the oxidation of aldehydes to acids in aqueous solution. We found that various aromatic, heteroaromatic and aliphatic aldehydes were selectively oxidized to corresponding acids in 70–98% yields. This simple acid–base treatment allows to separate easily the acid product in high purity without any organic solvent. Moreover, the adduct is produced using 25% H₂O₂, with inexpensive sodium sulphate, Na₂SO₄, and sodium chloride, NaCl. The adduct is a non-toxic white crystalline solid, readily soluble in water, and easy to handle.     

Spectroscopic tools for remote sensing of greenhouse gases CH<Subscript>4</Subscript>, CF<Subscript>4</Subscript> and SF<Subscript>6</Subscript>

Highly symmetrical molecules such as CH₄, CF₄ or SF₆ are known to be atmospheric pollutants and greenhouse gases. High-resolution spectroscopy in the infrared is particularly suitable for the monitoring of gas concentration and radiative transfers in the earth's atmosphere. This technique requires extensive theoretical studies for the modeling of the spectra of such molecules (positions, intensities and shapes of absorption lines). Here, we have developed powerful tools for the analysis and the simulation of absorption spectra of highly symmetrical molecules. These tools have been implemented in the spherical top data system (STDS) and highly-spherical top data system (HTDS) software available at http://www.u-bourgogne.fr/LPUB/shTDS.html. They include a compilation of modeled data obtained during the last 20 years. An overview of our latest results in this domain will be presented. Electronic Publication     

Promotion of transition metal oxides on the NH<Subscript>3</Subscript>-SCR performance of ZrO<Subscript>2</Subscript>-CeO<Subscript>2</Subscript> catalyst

Chromium oxide and manganese oxide promoted ZrO₂-CeO₂ catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NO _x with NH₃. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H₂ temperatureprogrammed reduction (H₂-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH₃-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO₂-CeO₂ binary oxide for the low temperature NH₃-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO₂ and H₂O. Cr-Zr-Ce mixed oxide exhibited>80% NO _x conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr^{6 +}. The present mixed oxide can be a candidate for the low temperature abatement of NO _x .

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Unexpected release of HNO<Subscript>3</Subscript> and related species from UV-illuminated TiO<Subscript>2</Subscript> surface into air in photocatalytic oxidation of NO<Subscript>2</Subscript>

We have discovered that HNO₃ and related species are released from the TiO₂ surface into air in the TiO₂ photocatalytic oxidation of NO₂ (1 ppm) under continuous UV light illumination (1 mW cm⁻²) by dehumidifying the outlet gas of the reaction and analyzing the recovered condensate liquid by ion chromatography. The origin of the HNO₃ recovered in the dehumidifier could not be explained by a simple desorption of HNO₃ overproduced on the TiO₂ surface. The produced HNO₃ must be activated on the TiO₂ surface and causing the unidentified reaction.     

Decolorisation of Acid Blue 74 by ultraviolet/H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The photodegradation of Acid blue 74 in aqueous solution employing a H₂O₂/ultraviolet system in a photochemical reactor was investigated. The kinetics of decolorization were studied by application of a kinetic model. The results show that the reaction of decolorization followed pseudo-first order kinetics. We demonstrate that there is an optimum H₂O₂ concentration, at which the rate of the decolorization reaction is maximum. Irradiation at 253.7 nm of the dye solution in the presence of H₂O₂ results in complete discoloration after ten minutes of treatment.     

Effects of Pd doping on N<Subscript>2</Subscript>O formation over Pt/BaO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> during NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> storage and reduction process

N₂O is a powerful greenhouse gas and plays an important role in destructing the ozone layer. This present work investigated the effects of Pd doping on N₂O formation over Pt/BaO/Al₂O₃ catalyst. Three types of catalysts, Pt/BaO/Al₂O₃, Pt/Pd mechanical mixing catalyst (Pt/BaO/Al₂O₃ + Pd/Al₂O₃) and Pt-Pd co-impregnation catalyst (Pt-Pd/BaO/Al₂O₃) were prepared by incipient wetness impregnation method. These catalysts were first evaluated in NSR activity tests using H₂/CO as reductants and then carefully characterized by BET, CO chemisorption, CO-DRIFTs and H2-TPR techniques. In addition, temperature programmed reactions of NO with H2/CO were conducted to obtain further information about N₂O formation mechanism. Compared with Pt/BaO/Al₂O₃, (Pt/BaO/ Al₂O₃ + Pd/Al₂O₃) produced less N₂O and more NH3 during NO _x storage and reduction process, while an opposite trend was found over (Pt-Pd/BaO/Al₂O₃ + Al₂O₃). Temperature programmed reactions of NO with H₂/CO results showed that Pd/Al₂O₃ component in (Pt/BaO/Al₂O₃ + Pd/Al₂O₃) played an important role in NO reduction to NH₃, and the formed NH3 could reduce NO _x to N₂ leading to a decrease in N₂O formation. Most of N₂O formed over (Pt-Pd/BaO/Al₂O₃ + Al₂O₃) was originated from Pd/BaO/Al₂O₃ component. H₂-TPR results indicated Pd-Ba interaction resulted in more difficultto- reduce PdOx species over Pd/BaO/Al₂O₃, which inhibits the NO dissociation and thus drives the selectivity to N₂O in NO reduction.

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Effects of SO<Subscript>2</Subscript> contamination on rising CO<Subscript>2</Subscript> drops under high pressure

Although the flow dynamics of pure liquid drops in other liquids has been well researched, little attention has been paid to the impacts of impurities. Hence, most of research is not directly applicable to the real world. To address this gap, we conducted numerical experiments simulating the rise of pure and contaminated drops. It was selected to study liquid CO₂ drops contaminated with SO₂ under high pressure because such mixtures mimic potential scenarios in which drops may leak from carbon capture and storage (CCS) facilities or pipelines. First, numerical simulation experiments were performed to validate our method by comparing our results with previous research on pure drops. Second, the validated numerical approach was applied to simulations of contaminated drops to investigate how contaminants affect rising drops. The results show that the SO₂ contamination caused changes in deformation, breakup phenomena, rising velocities, surrounding flow fields and drag coefficients. Most importantly, the contamination resulted in the formation of smaller “child drops”; such breakup is not observed in pure CO₂ drops. The formation of child drops in turn affects the streamlines, patterns and areas of wakes behind the contaminated drops. The addition of contaminants also enhances the dissolution rate, which is affected by the contaminant concentration and by the flow dynamics of the rising drop. Our results would improve understanding the rise of impure CO₂ drops, such as drops potentially leaked by future CCS operations.     

Degradation of carbendazim by UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> investigated by kinetic modelling

The transformation of the fungicide carbendazim (methyl-2 benzimidazole carbamate) induced by hydroxyl radical generated by the UV photolysis of H₂O₂ has been studied in dilute aqueous solution. The efficient reaction of hydroxyl radicals with carbendazim led to the rapid degradation of carbendazim. The study of reaction kinetics yielded a second order rate constant of 2.2±0.3 10⁹ M⁻¹ s⁻¹ for HO^· radicals with carbendazim. This value is in agreement with a high reactivity of HO^· radicals with carbendazim. Most degradation products were identified by high performance liquid chromatography mass spectrometry (HPLC-MS). In the presence of hydrogenocarbonate and carbonate ions, hydroxyl radicals were quenched and in turn carbonate radicals CO₃ ^·− were formed. Carbonate radicals are indeed known to react efficiently with compounds containing electron-rich sites such as nitrogen or sulfur atoms. The use of a kinetic modelling software gave evidence for the occurrence of such reactions with carbendazim. The second order rate constant of carbonate radical with carbendazim was equal to 6±2 10⁶ M⁻¹ s⁻¹. Electronic Publication     

Effective degradation of tetracycline by mesoporous Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> under visible light irradiation

Bi₂WO₆ was synthesized with a hydrothermal method at different pHs and used for the degradation of tetracycline (TC) in water. The mesoporous Bi₂WO₆ prepared at pH 1 (BWO-1) displayed the highest adsorption and degradation capacity to TC due to its large surface area and more efficient capacity to separate photogenerated electrons and holes. 97% of TC at 20 mg·L^?1 was removed by BWO-1 at 0.5 g·L^?1 after 120 min irradiation under simulated solar light. Only 31% of the total organic carbon (TOC) was removed after 360 min irradiation although the TC removal reached 100%, suggesting that TC was mainly transformed to intermediate products rather than completely mineralized. The intermediates were identified by high-performance liquid chromatography-time of flight-mass spectrometry (HPLC-TOF-MS) and possible photodegradation pathways were proposed.     

Pt/Mg-Ce-O catalyst for NO/H<Subscript>2</Subscript>/O<Subscript>2</Subscript> lean de-No<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reaction

The NO/H₂/O₂ reaction was studied under oxidizing conditions in the 100-400 °C range over 0.1 wt% Pt supported on various metal oxides such as MgO, CeO₂, SiO₂, La₂O₃, CaO, Y₂O₃ and TiO₂. The Pt/MgO and Pt/CeO₂ catalysts showed good catalytic behaviours. Here, we find that the Pt/Mg-Ce-O catalyst, prepared from MgO and CeO₂ by the sol-gel method, is a very active and selective catalyst towards N₂ formation in the whole 100–400 °C range. This catalyst appears to be the most active, selective and stable one ever reported in the literature for the NO/H₂/O₂ reaction, even in the presence of 5%v H₂O or 20 ppmv of SO₂ in the feed stream.Selected article from the Regional Symposium on Chemistry and Environment, Krusevac, Serbia, June 2003, organised by Dr. Branimir Jovancicevic.     

Static and dynamic characteristics of SO<Subscript>2</Subscript>-O<Subscript>2</Subscript> aqueous solution in the microstructure of porous carbon materials

Porous carbon material facilitates the reaction SO₂ + O₂ + H₂O → H₂SO₄ in coal-burned flue gas for sulfur resources recovery at mild conditions. It draws a long-term mystery on its heterogeneous catalysis due to the complicated synergic effect between its microstructure and chemical components. To decouple the effects of geometric structure from chemical components, classical molecular dynamics method was used to investigate the static and dynamic characteristics of the reactants (H₂O, SO₂ and O₂) in the confined space truncated by double-layer graphene (DLG). Strong adsorption of SO₂ and O₂ by the DLG was observed, which results in the filling of the solute molecules into the interior of the DLG and the depletion of H₂O. This effect mainly results from the different affinity of the DLG to the species and can be tuned by the separation of the two graphene layers. Such dimension dependence of the static and dynamic properties like distribution profile, molecular cluster, hydrogen bond and diffusion coefficient were also studied. The conclusions drawn in this work could be helpful to the further understanding of the underlying reaction mechanism of desulfurization process in porous carbon materials and other applications of carbon-based catalysts.

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Interaction between cadmium,lead and potassium fertilizer (K<Subscript>2</Subscript>SO<Subscript>4</Subscript>) in a soil-plant system

A pot experiment was conducted to examine the influence of potassium (K) fertilizer (K₂SO₄) application on the phytoavailability and speciation distribution of cadmium (Cd) and lead (Pb) in soil. Spring wheat (Triticum aestivum L.) was selected as the test plant. There were seven treatments including single and combined contamination of Cd and Pb. CdCl₂·2.5 H₂O and Pb(NO₃)₂ were added to the soil at the following dosages: Cd + Pb = 0.00 + 0.00, 5.00 + 0.00, 25.0 + 0.00, 0.00 + 500, 0.00 + 1000, 5.00 + 500 and 25.0 + 1000 mg kg⁻¹, denoted by CK, T1, T2, T3, T4, T5 and T6, respectively. The K fertilizer had five levels: 0.00, 50.0, 100, 200 and 400 mg K₂O kg⁻¹ soil, denoted by K0, K1, K2, K3 and K4, respectively. The results showed that the K fertilizer promoted the dry weight (DW) of wheat in all treatments and alleviated the contamination by Cd and Pb. The application of K₂SO₄ reduced the uptake of Cd in different parts including roots, haulms and grains of wheat; the optimum dosage was the K2 level. K supply resulted in a significant (P < 0.05) decrease in the soluble plus exchangeable (SE) fraction of Cd and there was a negative correlation (not significant, P > 0.05) between the levels of K and the SE fraction of Cd in soil. The application of the K fertilizer could obviously restrain the uptake of Pb by wheat and there were significant (P < 0.05) negative correlations between the concentrations of Pb in grains and the levels of K in soil. K supply resulted in a decrease in the SE fraction of Pb (except the K1 level) from the K0 to K4 levels. At the same time, the application of the K fertilizer induced a significant (P < 0.05) decrease in the weakly specifically adsorbed (WSA) fraction of Pb and a significant (P < 0.05) increase in the bound to Fe–Mn oxides (OX) fraction of Pb. At different K levels, the concentration of Pb in the roots, haulms and grains had a positive correlation with the SE (not significant, P > 0.05) and WSA (significant, P < 0.05) fractions of Pb in the soil. All the K application levels in this experiment reduced the phytoavailability of Cd and Pb. Thus, it is feasible to apply K fertilizer (K₂SO₄) to alleviate contamination by Cd and/or Pb in soil. Moreover, the level of K application should be considered to obtain an optimal effect with the minimum dosage.     

Covering α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> protection layer on the surface of p-Si micropillar array for enhanced photoelectrochemical performance

The spontaneous oxidation process of pristine silicon (Si) limits its application as photocatalyst or electrode in aqueous solution or moist air. Covering a protection layer on Si surface is an effective approach to overcome this disadvantage. In this paper, α-Fe₂O₃ is demonstrated to be an excellent alternative as a protection material. α-Fe₂O₃ layer was deposited around each p-type Si micropillar (SiMP) in well-ordered array by chemical bath deposition method. The diameter of SiMP was 5 mm and the thickness of α-Fe₂O₃ layer was about 20 nm. The photoeletrochemical stability of SiMP/α-Fe₂O₃ was proved by 10 circles cyclic voltammetry testing. Compared with SiMP, its optical absorption and photocurrent density improved 2 times and 4 times, respectively, and its onset potential for hydrogen evolution moved positively about 0.4 V. These improved performances could be ascribed to the enhanced photogenerated-charge-separation efficiency deriving from built-in electric field at the interface between Si and α-Fe₂O₃. The above results show an effective strategy to utilize Si material as photocatalyst or electrode in aqueous solution or moist air.

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Characteristics of PM<Subscript>2.5</Subscript>, CO<Subscript>2</Subscript> and particle-number concentration in mass transit railway carriages in Hong Kong

Fine particulate matter (PM_2.5) levels, carbon dioxide (CO₂) levels and particle-number concentrations (PNC) were monitored in train carriages on seven routes of the mass transit railway in Hong Kong between March and May 2014, using real-time monitoring instruments. The 8-h average PM_2.5 levels in carriages on the seven routes ranged from 24.1 to 49.8 µg/m³, higher than levels in Finland and similar to those in New York, and in most cases exceeding the standard set by the World Health Organisation (25 µg/m³). The CO₂ concentration ranged from 714 to 1801 ppm on four of the routes, generally exceeding indoor air quality guidelines (1000 ppm over 8 h) and reaching levels as high as those in Beijing. PNC ranged from 1506 to 11,570 particles/cm³, lower than readings in Sydney and higher than readings in Taipei. Correlation analysis indicated that the number of passengers in a given carriage did not affect the PM_2.5 concentration or PNC in the carriage. However, a significant positive correlation (p < 0.001, R ² = 0.834) was observed between passenger numbers and CO₂ levels, with each passenger contributing approximately 7.7–9.8 ppm of CO₂. The real-time measurements of PM_2.5 and PNC varied considerably, rising when carriage doors opened on arrival at a station and when passengers inside the carriage were more active. This suggests that air pollutants outside the train and passenger movements may contribute to PM_2.5 levels and PNC. Assessment of the risk associated with PM_2.5 exposure revealed that children are most severely affected by PM_2.5 pollution, followed in order by juveniles, adults and the elderly. In addition, females were found to be more vulnerable to PM_2.5 pollution than males (p < 0.001), and different subway lines were associated with different levels of risk.     

Efficient photocatalytic degradation of Rhodamine B dye using ZnO/graphitic C<Subscript>3</Subscript>N<Subscript>4</Subscript> nanocomposites synthesized by microwave

Semiconductor photocatalysis is a solution to issues of environmental pollution and energy shortage because photocatalysis can use solar energy to degrade pollutants. The photocatalytic activity can be improved by using composites of ZnO and other semiconductors. Here, composites of ZnO and polymeric graphite-like C₃N₄ (g-C₃N₄) with high photocatalytic activities were prepared by microwave synthesis. Products were characterized by X-ray diffraction, transmission electron microscopy, ultraviolet–visible and Fourier transform infrared spectroscopy. The photocatalytic degradation of Rhodamine B was tested under irradiation from a Xe lamp. Results show that adding graphite-like C₃N₄ promotes the photocatalytic activity of ZnO. Composites with 1.0 wt% g-C₃N₄ showed the best photodegradation efficiency, and the reaction average energy was approximately 33.71 kJ mol^?1.     

PM<Subscript>10</Subscript> emissions from industrial coal-fired chain-grate boilers

Industrial coal-fired boiler is an important air pollutant emission source in China. The chain-grate boiler is the most extensively used type of industrial coal-fired boiler. An electrical low-pressure impactor, and a Dekati® Low Pressure Impactor were applied to determine mass and number size distributions of PM₁₀ at the inlet and the outlet of the particulate emission control devices at six coalfired chain-grate boilers. The mass size distribution of PM₁₀ generated from coal-fired chain-grate boilers generally displays a bimodal distribution that contains a submicron mode and a coarse mode. The PM in the submicron mode for burning with raw coal contributes to 33% ± 10 % of PM₁₀ emissions, much higher than those for pulverized boilers. And the PM in the submicron mode for burning with briquette contributes up to 86 % of PM₁₀ emissions. Multiclones and scrubbers are not efficient for controlling PM10 emission. Their average collection efficiencies for sub-micron particle and super-micron particle are 34% and 78%, respectively. Operating conditions of industrial steam boilers have influence on PM generation. Peak of the submicron mode during normal operation period is larger than the start-up period.

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Investigation of the effects of humic acid and H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s^?1, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Photocatalytic degradation of organic dyes by Er<Superscript>3+</Superscript>:YAlO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> composite under solar light

In this work, Er³⁺:YAlO₃/TiO₂ composite was synthesized by a ultrasonic dispersion and liquid boil method. The Er³⁺:YAlO₃/TiO₂ composite and pure TiO₂ powder were characterized by XRD. The degradation of different organic dyes was used to evaluate the photocatalytic activity of the Er³⁺:YAlO₃/TiO₂ composite. It is found that the photocatalytic activity of Er³⁺:YAlO₃/TiO₂ composite is much higher than that for the similar system with only TiO₂. Moreover, this Er³⁺:YAlO₃/TiO₂ composite provides a new way to take advantage of TiO₂ in sewage treatment aspects using solar light.