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.     

Chemical poison and regeneration of SCR catalysts for NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> removal from stationary sources

Selective catalytic reduction (SCR) of NO _x with NH₃ is an effective technique to remove NO _x from stationary sources, such as coal-fired power plant and industrial boilers. Some of elements in the fly ash deactivate the catalyst due to strong chemisorptions on the active sites. The poisons may act by simply blocking active sites or alter the adsorption behaviors of reactants and products by an electronic interaction. This review is mainly focused on the chemical poisoning on V₂O₅-based catalysts, environmental-benign catalysts and low temperature catalysts. Several common poisons including alkali/alkaline earth metals, SO₂ and heavy metals etc. are referred and their poisoning mechanisms on catalysts are discussed. The regeneration methods of poisoned catalysts and the development of poison-resistance catalysts are also compared and analyzed. Finally, future research directions in developing poisoning resistance catalysts and facile efficient regeneration methods for SCR catalysts are proposed.     

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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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.     

NO oxidation over Co-La catalysts and NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reduction in compact SCR

A series of Co-La catalysts were prepared using the wet impregnation method and the synthesis of catalysts were modified by controlling pH with the addition of ammonium hydroxide or oxalic solution. All the catalysts were systematically investigated for NO oxidation and SO₂ resistance in a fixed bed reactor and were characterized by Brunanuer–Emmett–Teller (BET) method, Fourier Transform infrared spectroscopy (FTIR), X–ray diffraction (XRD), Thermogravimetric (TG) and Ion Chromatography (IC). Among the catalysts, the one synthesized at pH = 1 exhibited the maximum NO conversion of 43% at 180°C. The activity of the catalyst was significantly suppressed by the existence of SO₂ (300 ppm) at 220°C. Deactivation may have been associated with the generation of cobalt sulfate, and the SO₂ adsorption quantity of the catalyst might also have effected sulfur resistance. In the case of the compact selective catalytic reduction (SCR), the activity increased from 74% to 91% at the highest gas hourly space velocity (GHSV) of 300000 h^–1 when the NO catalyst maintained the highest activity, in excess of 50% more than that of the standard SCR.

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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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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.     

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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Effect of biochar addition on short-term N<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> emissions during repeated drying and wetting of an anthropogenic alluvial soil

Agricultural soils are an important source of greenhouse gases (GHG). Biochar application to such soils has the potential of mitigating global anthropogenic GHG emissions. Under irrigation, the topsoils in arid regions experience repeated drying and wetting during the crop growing season. Biochar incorporation into these soils would change the soil microbial environment and hence affect GHG emissions. Little information, however, is available regarding the effect of biochar addition on carbon dioxide (CO₂) and nitrous oxide (N₂O) emissions from agricultural soils undergoing repeated drying and wetting. Here, we report the results of a 49-day aerobic incubation experiment, incorporating biochar into an anthropogenic alluvial soil in an arid region of Xinjiang Province, China, and measuring CO₂ and N₂O emissions. Under both drying–wetting and constantly moist conditions, biochar amendment significantly increased cumulative CO₂ emission. At the same time, there was a significant reduction (up to ~20 %) in cumulative N₂O emission, indicating that the addition of biochar to irrigated agricultural soils may effectively slow down global warming in arid regions of China.     

Photocatalytic degradation of the herbicide cinosulfuron in aqueous TiO<Subscript>2</Subscript> suspension

The photocatalytic degradation of a sulfonylurea herbicide, cinosulfuron, has been studied in TiO₂ aqueous suspensions. A first order kinetic law was found. The influence of the initial concentration of cinosulfuron and of the initial radiant flux on the kinetics were evaluated. The identification of the intermediate products was based on high performance liquid chromatography coupled with mass spectrometry analyses (HPLC-MS). The mineralization of cinosulfuron was traced using ion chromatography and total organic carbon (TOC) measurements. These results indicate that the photocatalytic degradation of cinosulfuron leads to CO₂, NO₃ ⁻ and SO₄ ²⁻ as final products, and in addition cyanuric acid (C₃H₃O₃N₃), confirming previous results on triazinic ring-containing compounds. Electronic Publication     

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.     

Environmental impact of CO<Subscript>2</Subscript>, Rn,Hg degassing from the rupture zones produced by Wenchuan <Emphasis Type="Italic">M</Emphasis><Subscript>s</Subscript> 8.0 earthquake in western Sichuan,China

The concentrations and flux of CO₂, ²²²Radon (Rn), and gaseous elemental mercury (Hg) in soil gas were investigated based on the field measurements in June 2010 at ten sites along the seismic rupture zones produced by the May 12, 2008, Wenchuan M _s 8.0 earthquake in order to assess the environmental impact of degassing of CO₂, Rn and Hg. Soil gas concentrations of 344 sampling points were obtained. Seventy measurements of CO₂, Rn and Hg flux by the static accumulation chamber method were performed. The results of risk assessment of CO₂, Rn and Hg concentration in soil gas showed that (1) the concentration of CO₂ in the epicenter of Wenchuan M _s 8.0 earthquake and north end of seismic ruptures had low risk of asphyxia; (2) the concentrations of Rn in the north segment of seismic ruptures had high levels of radon, Maximum was up to level 4, according to Chinese code (GB 50325-2001); (3) the average geoaccumulation index I _geo of soil Hg denoted the lack of soil contamination, and maximum values classified the soil gas as moderately to strongly polluted in the epicenter. The investigation of soil gas CO₂, Rn and Hg degassing rate indicated that (1) the CO₂ in soil gas was characterized by a mean \(\updelta^{13}C_{CO2}\) of ?20.4 ‰ and by a mean CO₂ flux of 88.1 g m^?2 day^?1, which were in the range of the typical values for biologic CO₂ degassing. The maximum of soil CO₂ flux reached values of 399 g m^?2 day^?1 in the epicenter; (2) the soil Rn had higher exhalation in the north segment of seismic ruptures, the maximum reached value of 1976 m Bq m^?2 s^?1; (3) the soil Hg flux was lower, ranging from ?2.5 to 18.7 n g m^?2 h^?1 and increased from south to north. The mean flux over the all profiles was 4.2 n g m^?2 h^?1. The total output of CO₂ and Hg degassing estimated along seismic ruptures for a survey area of 18.17 km² were approximately 0.57 Mt year^?1 and 688.19 g year^?1. It is recommended that land-use planners should incorporate soil gas and/or gas flux measurements in the environmental assessment of areas of possible risk. A survey of all houses along seismic ruptures is advised as structural measures to prevent the ingress of soil gases, including CO₂ and Rn, were needed in some houses.     

Ambient photolysis frequency of NO<Subscript>2</Subscript> determined using chemical actinometer and spectroradiometer at an urban site in Beijing

The photolysis frequency of NO₂, j(NO₂), is an important analytical parameter in the study of tropospheric chemistry. A chemical actinometer (CA) was built to measure the ambient j(NO₂) based on a high precision NO _x instrument with 1 min time resolution. Parallel measurements of the ambient j(NO₂) by using the CA and a commercial spectroradiometer (SR) were conducted at a typical urban site (Peking University Urban Environmental Monitoring Station) in Beijing. In general, good agreement was achieved between the CA and SR data with a high linear correlation coefficient (R ² = 0.977) and a regression slope of 1.12. The regression offset was negligible compared to the measured signal level. The j(NO₂) data were calculated using the tropospheric ultraviolet visible radiation (TUV) model, which was constrained to observe aerosol optical properties. The calculated j(NO₂) was intermediate between the results obtained with CA and SR, demonstrating the consistency of all the parameters observed at this site. The good agreement between the CA and SR data, and the consistency with the TUV model results, demonstrate the good performance of the installed SR instrument. Since a drift of the SR sensitivity is expected by the manufacturer, we propose a regular check of the data acquired via SR against those obtained by CA for long-term delivery of a high quality series of j(NO₂) data. Establishing such a time series will be invaluable for analyzing the long-term atmospheric oxidation capacity trends as well as O₃ pollution for urban Beijing.

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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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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.     

Improving simulations of sulfate aerosols during winter haze over Northern China: the impacts of heterogeneous oxidation by NO<Subscript>2</Subscript>

We implemented the online coupled WRF-Chem model to reproduce the 2013 January haze event in North China, and evaluated simulated meteorological and chemical fields using multiple observations. The comparisons suggest that temperature and relative humidity (RH) were simulated well (mean biases are–0.2K and 2.7%, respectively), but wind speeds were overestimated (mean bias is 0.5 m?s^–1). At the Beijing station, sulfur dioxide (SO₂) concentrations were overpredicted and sulfate concentrations were largely underpredicted, which may result from uncertainties in SO₂ emissions and missing heterogeneous oxidation in current model. We conducted three parallel experiments to examine the impacts of doubling SO₂ emissions and incorporating heterogeneous oxidation of dissolved SO₂ by nitrogen dioxide (NO₂) on sulfate formation during winter haze. The results suggest that doubling SO₂ emissions do not significantly affect sulfate concentrations, but adding heterogeneous oxidation of dissolved SO₂ by NO₂ substantially improve simulations of sulfate and other inorganic aerosols. Although the enhanced SO₂ to sulfate conversion in the HetS (heterogeneous oxidation by NO₂) case reduces SO₂ concentrations, it is still largely overestimated by the model, indicating the overestimations of SO₂ concentrations in the North China Plain (NCP) are mostly due to errors in SO₂ emission inventory.

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New insights into mercury removal mechanism on CeO<Subscript>2</Subscript>-based catalysts: A first-principles study

First-principles calculations were performed to investigate the mechanism of Hg⁰ adsorption and oxidation on CeO₂(111). Surface oxygen activated by the reduction of Ce⁴⁺ to Ce³⁺ was vital to Hg⁰ adsorption and oxidation processes. Hg0 was fully oxidized by the surface lattice oxygen on CeO₂(111), without using any other oxidizing agents. HCl could dissociate and react with the Hg adatom on CeO₂(111) to form adsorbed Hg–Cl or Cl–Hg–Cl groups, which promoted the desorption of oxidized Hg and prevented CeO₂ catalyst deactivation. In contrast, O–H and H–O–H groups formed during HCl adsorption consumed the active surface oxygen and prohibited Hg oxidation. The consumed surface oxygen was replenished by adding O₂ into the flue gas. We proposed that oxidized Hg desorption and maintenance of sufficient active surface oxygen were the rate-determining steps of Hg⁰ removal on CeO₂-based catalysts. We believe that our thorough understanding and new insights into the mechanism of the Hg⁰ removal process will help provide guidelines for developing novel CeO₂-based catalysts and enhance the Hg⁰ removal efficiency.

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High CO<Subscript>2</Subscript> absorption of <Emphasis Type="Italic">O</Emphasis>-carboxymethylchitosan synthesised from chitosan

CO₂ absorption by liquid-containing amines to form carbamate and bicarbonates is an effective method of CO₂ mitigation from industrial exhausts, but this process is expensive and requires large quantities of amines. Here we modified chitosan, a naturally occurring biopolymer containing NH₂ functions, to use it for CO₂ absorption in aqueous media. Chitosan was dispersed in 40% aqueous NaOH solution then treated with monochloroacetic acid dissolved in isopropanol, to yield O-carboxymethylchitosan. Results show that the CO₂ absorption capacity of O-carboxymethylchitosan is 0.508 g/g, which is higher than the capacity of conventional amines such as 1-aminoamine, 2-methylpropanolamine and methyldiethanol amine, but lower than the capacity of monoethanolamine. A cyclic study showed that O-carboxymethylchitosan is a stable component for CO₂ absorption and regeneration.