Green Efficient One-Pot Synthesis and Separation of Nitrones in Water Assisted by a Self-Assembled Nanoreactor.

This article reports an alternative method for preparing nitrones using a tetrahedral capsule as a nanoreactor in water. Using the hydrophobic cavity of the capsule allowed us to reduce the reaction times and easily separate the nitrones from the reaction mixture, obtaining reaction yields equal or comparable to those obtained with the methods already reported. Furthermore, at the basis of this methodology, there is an eco-friendly approach carried out that can certainly be extended to other synthesis methods for the preparation of other substrates by exploiting various types of macrocyclic hosts, suitably designed and widely used in supramolecular chemistry.

A DFT study on the effect of oxygen vacancies and H2O in Mn-MOF-74 on SCR reactions.

As one of the main air pollutants, nitrogen oxides (NOx) have serious effects on human health and the environment. In our previous study, we found that Mn-MOF-74 shows excellent catalytic performance for the selective catalytic reduction (SCR) reaction with NH3 being the reductant (NH3-SCR) at low temperature. To obtain a further understanding of the NH3-SCR mechanism in Mn-MOF-74, in this paper, we investigated two important parts of the NH3-SCR process in Mn-MOF-74 using the density functional theory (DFT) method. On the one hand, the structural characteristics of two types of oxygen vacancies of Mn-MOF-74, namely carboxyl oxygen vacancies and hydroxyl oxygen vacancies, and their adsorption properties to reaction species were calculated. It was found that the oxygen vacancies not only activate the reaction species, but also promote the desorption of NO2 molecules from metal sites for the subsequent rapid SCR reactions. On the other hand, we studied the effect of H2O on the structural stability and catalytic performance of Mn-MOF-74. It was found that the interaction of Mn-O bonds was weakened by H2O. Therefore, the influence of H2O should be considered for the future design of MOF-based catalysts for the SCR process.

Dihydroxy-Substituted Coumarins as Fluorescent Probes for Nanomolar-Level Detection of the 4-Amino-TEMPO Spin Label.

This paper reports on dihydroxycoumarins as fluorescent probes suitable for the detection and determination of the nitroxide radical, namely 4-amino-TEMPO. Since 4-amino-TEMPO is used as a spin label for the detection of various radicals and damage caused by these species, its determination under physiological conditions might help us to understand the mechanism of the oxidative stress. Among different coumarins studied, only dihydroxy-substituted derivatives show high sensitivity, specificity, and selectivity for the nitroxide radical. In this assay, dihydroxy-substituted coumarins under the action of 4-amino-TEMPO show a very fast and significant increase in fluorescence intensity and lifetime. Among them 6,7-dihydroxycoumarin (esculetin) exhibits the strongest fluorescence enhancement (up to 40 times), with an estimated limit of detection equal to 16.7 nM-a significantly lower value when compared with UV-Vis or electron paramagnetic resonance (EPR) spectroscopy. The method is characterized by an easy procedure of sample preparation and very short time of analysis. The mechanism of the interaction between 6,7-dihydroxycoumarin and 4-amino-TEMPO has been examined with the use of a series of complementary techniques, such as steady-state and time-resolved fluorescence spectroscopy, UV-Vis spectroscopy, electron paramagnetic resonance spectroscopy, potentiometric titration, and high-performance liquid chromatography. It has been proven that the only route of the reaction in the system studied is a proton transfer from the molecule of esculetin to the amino group of the nitroxide. Biological studies performed on prostate cancer cells, breast cancer cells, and normal skin fibroblasts revealed significant anticancer properties of 6,7-dihydroxycoumarin, which caused a considerable decrease in the viability and number of cancer cells, and affected their morphology, contrary to normal fibroblasts. Furthermore, the experiment performed on prostate cancer cells showed that fluorescence emission of esculetin is closely related to intracellular pH-the higher pH, the higher observed fluorescence intensity (in accordance with a chemical experiment). On the other hand, the studies performed in different pH levels revealed that when pH of the solution increases, the observed fluorescence intensity enhancement under the action of 4-amino-TEMPO decreases (better sensing properties of esculetin towards the nitroxide in lower pH).

Nanomaterials to Combat NO(x) Pollution.

The presence of NO9x) gases (NO+NO2) in the atmosphere is a major concern of society because of their associated adverse and harmful effects. In order to remove the NO(x) gases from the air, photocatalysis arises as an innovative and promising technique. Through the use of photochemical oxidation processes the NO and NO2 gases are oxidised to NO3- form and thus removed from the air. In recent years new nanomaterials are being developed by researchers with the aim to enhance their photocatalytic activity to combat the NO(x) pollution. The main focus is devoted to preparing new TiO2 based compounds with the highest specific surface area (SSA), different morphology and chemical modifications. In order to increase the SSA, different substrates were used to disperse the TiO2 nanoparticles: organic and carbon fibres, mesoporous materials, clays composites and nanoporous microparticles. In the other hand, high photocatalytic performances were obtained with nanotubes, self-orderer nano-tubular films and nanoparticles with the lowest size. Conversely, when TiO2 is doped with ions the oxide exhibited a better photocatalytic performance under visible light, which is related to the creation of intermediate energy states between the conduction band and the valence band. Alternatively, visible light photocatalysts different from titanium oxide have been studied, which exhibit a good De-NO(x) efficiency working under λ > 400 nm visible light irradiation.

Adsorption of SOx and NOx in activated viscose fibers.

SOx and NOx are emissions resulting from combustion processes and are the main agents that contribute to the formation of acid rain, which causes harm to humans and the environment. Several techniques for removing these pollutants are applied in i.e. oil refineries, thermoelectric that use petroleum oils and vehicular pollution. Among these, highlight the adsorption of contaminants by the usage of activated carbon fibers and activated carbon, which are characterized by high surface area and uniform distribution of pores, providing appropriate conditions for application in processes of removing environmental contaminants. In the present work, activated viscose fibers (AVF) were prepared and applied in adsorption experiments of NO and SO2. The materials produced showed high values of surface area, with a predominance of micro pores with diameters in the range of 1.0 nm. The AVF had satisfactory performance in the removal of contaminants and are compatible with other synthetic fibers. Thus, the formation of active sites of carbon provides contaminants adsorption, demonstrating that carbon fibers cloth can be applied for the removal of pollutants.

Evaluation of an oil-producing green alga Chlorella sp. C2 for biological DeNOx of industrial flue gases.

NOx, a significant portion of fossil fuel flue gases, are among the most serious environmental issues in the world and must be removed in an additional costly gas treatment step. This study evaluated the growth of the green alga Chlorella sp. C2 under a nitrite-simulated NOx environment and the removal rates of actual flue gas fixed salts (FGFSs) from Sinopec's Shijiazhuang refinery along with lipid production. The results showed that nitrite levels lower than 176.5 mM had no significant adverse effects on the cell growth and photosynthesis of Chlorella sp. C2, demonstrating that this green alga could utilize nitrite and NOx as a nitrogen source. High concentrations of nitrite (88.25-176.5 mM) also resulted in the accumulation of neutral lipids. A 60% nitrite removal efficiency was obtained together with the production of 33% algae lipids when cultured with FGFS. Notably, the presence of nitrate in the FGFS medium significantly enhanced the nitrite removal capability, biomass and lipid production. Thus, this study may provide a new insight into the economically viable application of microalgae in the synergistic combination of biological DeNOx of industrial flue gases and biodiesel production.

Biological NOx removal by denitrification process in a jet-loop bioreactor: system performance and model development.

Nitrogen monoxide (NO) and nitrogen dioxide referred as NOx are one of the most important air pollutants in the atmosphere. Biological NOx removal technologies have been developing to reach a cost-effective control method for upcoming stringent NOx emission standards. The BioDeNOx system was seen as a promising biological NOx control technology which is composed of two reactors, one for absorbing of NO in an aqueous Fe(II)EDTA2- solution and the other for subsequent reduction to N2 gas in a biological reactor by the denitrification process. In this study, instead of two discrete reactors, only one jet-loop bioreactor (JLBR) was utilized as both absorption and denitrification unit and no chelate-forming chemicals were added. In other words, the advantage of better mass transfer conditions of jet bioreactor was used instead of Fe(II)EDTA2-. The process was named as Jet-BioDeNOx. The JLBR was operated for the removal of NOx from air streams containing 500-3000 ppm NOx and the results showed that the removal efficiency was between 81% and 94%. The air to liquid flow ratio (Q(G)/Q(RAS)) varied in the range of 0.07-0.12. Mathematical modelling of the system demonstrated that the removal efficiency strongly depends on this ratio. The high mass transfer conditions prevailed in the reactor provided a competitive advantage on removing NO gas without any requirement of chelating chemicals.

Spray absorption and electrochemical reduction of nitrogen oxides from flue gas.

This work developed an electrochemical reduction system which can effectively scrub NO× from flue gas by using aqueous solution of Fe(II)(EDTA) (ethylenediaminetetraacetate) as absorbent and electrolyte. This new system features (a) complete decomposition of NOX to harmless N2; and (b) fast regeneration of Fe(II)(EDTA) through electrochemical reaction. The Fe(II)(EDTA) solution was recycled and reused continuously during entire process, and no harmful waste was generated. The reaction mechanism was thoroughly investigated by using voltammetric, chromatographic and spectroscopic approaches. The operating conditions of the system were optimized based on NOX removal efficiency. Approximately 98% NO removal was obtained at the optimal condition. The interference of SO2 in flue gas and the system operating stability was also evaluated.

Combination of photocatalysis and HC/SCR for improved activity and durability of DeNOx catalysts.

A photocatalytic HC/SCR system has been developed and its high deNOx performance (54.0-98.6% NOx conversion) at low temperatures (150-250 °C) demonstrated by using a representative diesel fuel hydrocarbon (dodecane) as the reductant over a hybrid SCR system of a photocatalytic reactor (PCR) and a dual-bed HC/SCR reactor. The PCR generates highly active oxidants such as O3 and NO2 from O2 and NO in the feed stream, followed by the subsequent formation of highly efficient reductants such as oxygenated hydrocarbon (OHC), NH3, and organo-nitrogen compounds. These reductants are the key components for enhancing the low temperature deNOx performance of the dual-bed HC/SCR system containing Ag/Al2O3 and CuCoY in the front and rear bed of the reactor, respectively. The OHCs are particularly effective for both NOx reduction and NH3 formation over the Ag/Al2O3 catalyst, while NH3 and organo-nitrogen compounds are effective for NOx reduction over the CuCoY catalyst. The hybrid HC/SCR system assisted by photocatalysis has shown an overall deNOx performance comparable to that of the NH3/SCR, demonstrating its potential as a promising alternative to the current urea/SCR and LNT technologies. Superior durability of HC/SCR catalysts against coking by HCs has also been demonstrated by a PCR-assisted regeneration scheme for deactivating catalysts.

Effect of solution pH on SO2, NO(x), and Hg removal from simulated coal combustion flue gas in an oxidant-enhanced wet scrubber.

This paper presents a study on the simultaneous removal of SO2, NO(x) and Hg (both Hg0 and Hg2+) from a simulated flue gas by oxidant injection in a bench-simulated wet limestone scrubber for a wide range of slurry pH. The slurry pH strongly influenced the chemical mechanism in the scrubber and, therefore, affected pollutant removal. This paper also examines the potential ClO2(gas) reemission from a developed multipollutant scrubber at different slurry pHs. To better understand the chemical mechanisms at each slurry pH and to apply a mass balance to the process, detailed product ion analyses were performed for all experiments. Ion analysis covered three different chlorine species (chlorite, chloride, chlorate), sulfate, nitrite and nitrate. Different NO(x) removal efficiencies and mechanisms were found in acidic and alkaline pHs in the multipollutant scrubber. The acidic solution was favorable for NO and Hg0 oxidation, but increasing the slurry pH above 7.0 was disadvantageous for NO and Hg oxidation/removal. However the rate of NO(x) absorption (by percentage) was higher for the alkaline solution.

Experimental study on removals of SO2 and NO(x) using adsorption of activated carbon/microwave desorption.

UNLABELLED: Experimental studies on desulfurization and denitrification were carried out using activated carbon irradiated by microwave. The influences of the concentrations of nitric oxide (NO) and sulfur dioxide (SO2), the flue gas coexisting compositions, on adsorption properties of activated carbon and efficiencies of desulfurization and denitrification were investigated. The results show that adsorption capacity and removal efficiency of NO decrease with the increasing of SO2 concentrations in flue gas; adsorption capacity of NO increases slightly first and drops to 12.79 mg/g, and desulfurization efficiency descends with the increasing SO2 concentrations. Adsorption capacity of SO2 declines with the increasing of O2 content in flue gas, but adsorption capacity of NO increases, and removal efficiencies of NO and SO2 could be larger than 99%. Adsorption capacity of NO declines with the increase of moisture in the flue gas, but adsorption capacity of SO2 increases and removal efficiencies of NO and SO2 would be relatively stable. Adsorption capacities of both NO and SO2 decrease with the increasing of CO2 content; efficiencies of desulfurization and denitrification augment at the beginning stage, then start to fall when CO2 content exceeds 12.4%. The mechanisms of this process are also discussed. IMPLICATIONS: The prominent SO2 and NOx treatment techniques in power plants are wet flue gas desulfurization (FGD) and the catalytic decomposition method like selective catalytic reduction (SCR) or nonselective catalytic reduction (NSCR). However, these processes would have some difficulties in commercial application due to their high investment, requirement of expensive catalysts and large-scale equipment, and so on. A simple SO2 and NOx reduction utilizing decomposition by microwave energy method can be used. The pollutants control of flue gas in the power plants by the method of microwave-induced decomposition using adsorption of activated carbon/microwave desorption can meet the requirements of environmental protection, which will be stricter in the future.

Experimental study on removal of NO using adsorption of activated carbon/reduction decomposition of microwave heating.

Experimental studies were carried out on flue gas denitrification using activated carbon irradiated by microwave. The effects of microwave irradiation power (reaction temperature), the flow rate of flue gas, the concentration of NO and the flue gas coexisting compositions on the adsorption property of activated carbon and denitrification efficiency were investigated. The results show that: the higher of microwave power, the higher of denitrification efficiency; denitrification efficiency would be greater than 99% and adsorption capacity of NO is relatively stable after seven times regeneration if the microwave power is more than 420 W; adsorption capacity of NO in activated carbon bed is 33.24 mg/g when the space velocity reaches 980 per hour; adsorption capacity declines with increasing of the flow rate of flue gas; the change in denitrification efficiency is not obvious with increasing oxygen content in the flue gas; and the maximum adsorption capacity of NO was observed when moisture in flue gas was about 5.88%. However, the removal efficiency of NO reduces with increasing moisture, and adsorption capacity and removal efficiency of NO reduce with increasing of SO2 concentration in the flue gas.

Simultaneous desulfurization and denitrification from flue gas by Ferrate(VI).

An innovative semidry process has been developed to simultaneously remove NO and SO2 from flue gas. According to the conditions of the flue gas circulating fluidized bed (CFB) system, ferrate(VI) absorbent was prepared and added to humidified water, and the effects of the various influencing factors, such as ferrate(VI) concentration, humidified water pH, inlet flue gas temperature, residence time, molar ratio of Ca/(S+N), and concentrations of SO2 and NO on removal efficiencies of SO2 and NO were studied experimentally. Removal efficiencies of 96.1% for SO2 and 67.2% for NO were obtained, respectively, under the optimal experimental conditions, in which the concentration of ferrate(VI) was 0.03 M, the humidified water pH was 9.32, the inlet flue gas temperature was 130 °C, the residence time was 2.2 s, and the molar ratio of Ca/(S+N) was 1.2. In addition, the reaction mechanism of simultaneous desulfurization and denitrification using ferrate(VI) was proposed.

Photochemical modeling in California with two chemical mechanisms: model intercomparison and response to emission reductions.

An updated version of the Statewide Air Pollution Research Center (SAPRC) chemical mechanism (SAPRC07C) was implemented into the Community Multiscale Air Quality (CMAQ) version 4.6. CMAQ simulations using SAPRC07C and the previously released version, SAPRC99, were performed and compared for an episode during July-August, 2000. Ozone (O3) predictions of the SAPRC07C simulation are generally lower than those of the SAPRC99 simulation in the key areas of central and southern California, especially in areas where modeled concentrations are greater than the federal 8-hr O3 standard of 75 parts per billion (ppb) and/or when the volatile organic compound (VOC)/nitrogen oxides (NOx) ratio is less than 13. The relative changes of ozone production efficiency (OPE) against the VOC/NOx ratio at 46 sites indicate that the OPE is reduced in SAPRC07C compared with SAPRC99 at most sites by as much as approximately 22%. The SAPRC99 and SAPRC07C mechanisms respond similarly to 20% reductions in anthropogenic VOC emissions. The response of the mechanisms to 20% NOx emissions reductions can be grouped into three cases. In case 1, in which both mechanisms show a decrease in daily maximum 8-hr O3 concentration with decreasing NOx emissions, the O3 decrease in SAPRC07C is smaller. In case 2, in which both mechanisms show an increase in O3 with decreasing NOx emissions, the O3 increase is larger in SAPRC07C. In case 3, SAPRC07C simulates an increase in O3 in response to reduced NOx emissions whereas SAPRC99 simulates a decrease in O3 for the same region. As a result, the areas where NOx controls would be disbeneficial are spatially expanded in SAPRC07C. Although the results presented here are valuable for understanding differences in predictions and model response for SAPRC99 and SAPRC07C, the study did not evaluate the impact of mechanism differences in the context of the U.S. Environmental Protection Agency's guidance for using numerical models in demonstrating air quality attainment. Therefore, additional study is required to evaluate the full regulatory implications of upgrading air quality models to SAPRC07.

Application for a newly developed high-capacity NOx denuder: low-NOx diesel transformation experiments.

To conduct low oxides of nitrogen (NOx) chamber experiments with modern diesel emissions (DE), a high-capacity NO, denuder was developed and used at the European Photoreactor (EUPHORE) outdoor simulation chamber. The denuder displayed a sufficient NOx storage capacity for use with DE, and efficient removal of NO, during injections of DE was achieved (>98%). Degradation of the denuder performance after repeated regeneration by heating (400 degrees C) and flushing with an air/oxygen ratio of 2:1 was not observed for a total of nine experiments. Evaluation of dark (with chamber cover closed) experiments (four in total) with and without the denuder in-line revealed some reduction (22%) of diesel particulate matter (DPM) with use of the denuder, most likely a result of impaction or settling of DPM during DE transit. However, DPM reduction may have also been a result of reductions in effective load of the engine-dyno system during the DE injections. Extensive chemical characterization of DPM revealed no significant perturbation of major compound groups associated with denuder use, except for nitrated polyaromatic hydrocarbon (NPAH) concentrations. The implications of high-NOx experiments without the use of a NOx denuder are discussed.

Field validation of the Ogawa diffusive sampler for NO2 and NOx in a cold climate.

A small-scale field trial in Umeå, Sweden with Ogawa samplers and a chemiluminescence instrument indicated that the NO(2) concentration was underestimated with respect to the reference monitor, if calculated according to the manufacturer's Ogawa sampling protocol. By co-locating Ogawa samplers and reference monitors at six sites in two Swedish cities, uptake rates were determined for NO(2) and NO(x) better applicable to the Swedish conditions and climate. The concentrations of NO(2) and NO(x) calculated according to the instruction manual of the sampler and using the field-determined uptake rates were compared with values derived from chemiluminescence monitors for each week over which samples were taken. When calculated according to the manufacturer's suggested protocol, the Ogawa sampler underestimated the NO(2) concentrations by 9.1% on average for all samples (N = 53), with respect to the reference monitor. In contrast, NO(x) concentrations were overestimated by a mean value of 15% for all samples (N = 45). By using the field determined uptake rates for the calculation of NO(2) and NO(x) a better estimation of the concentrations was obtained. The ratio between concentrations determined with the Ogawa samplers and chemiluminescence monitors was then 1.02 for all measurements of NO(2) and 1.00 for NO(x). Precision, expressed as the mean coefficient of variation, was 6.4% for six, 6-replicate measurements of NO(2) and 3.7% for five, 6-replicate measurements of NO(x).

Simultaneous removal of NO(x) and SO2 in exhausted gas through landfill leachate.

Simultaneous removal of NO(x) and SO2 from exhausted gas were investigated by studying co-culture of sulfate reducing bacteria and anaerobic denitrifying bacteria, separated from landfill leachate. When H2S, generated by sulfate reducing bacteria was chosen as the sole electron donor for anaerobic denitrifying bacteria, the co-culture system demonstrated a faster NO removal rate, higher stability and better permanence. When the feed gas flow rates of N2 and SO2 were maintained constant at 0.1 m3/h and 16 ml/min respectively, the maximum NO-removal rate could be achieved at over 92% with NO feed gas kept between 2-6 ml/min, while the SO2 removal rate was always above 95%. Long-term continuous removal of NO exhibited an evident periodicity of five days, however, the fluctuation range of NO-removal was decreasing. Moreover, the decrease of the gas flow rate and the increase in NO inlet concentration could contribute to a higher NO- removal rate.

Photo-assisted SCR removal of NO by upconversion CeO2/Pr3+/attapulgite nanocatalyst.

The emission of nitrogen oxides has caused severe harm to the ecosystem; thus, the development of low-cost and high-efficiency denitrification catalysts and new methods are of great significance. In this work, a co-precipitation method was employed to prepare Pr-doped CeO2/attapulgite (CeO2/Pr3+/ATP) nanocomposites. X-ray diffraction (XRD), photoluminance spectroscopy (PL), ultraviolet-visible diffuse reflectance (UV-Vis), Fourier transform infrared (FT-IR), and high-resolution transmission electron microscopy (HRTEM) were utilized to characterize the products. Results showed that the CeO2/Pr3+ nanoparticles were uniformly coated on the surface of ATP and demonstrated outstanding upconversion effect which converted the visible light to ultraviolet light. The upconversion luminescence of CeO2/Pr3+/ATP was strongest when the molar doping amount of Pr was 1 mol%, and the photo-SCR denitrification achieved the highest of 90% conversion and 95% selectivity when the loading amount of CeO2/Pr3+ was 40 wt%. The ATP and CeO2/Pr3+ constructed an indirect Z-type heterojunction structure mediated by oxygen vacancy which benefited the separation of charge carriers and enhanced the reduction-oxidation potentials, both are responsible for the remarkable denitrification performance.

Evaluation of constructed wetlands by wastewater purification ability and greenhouse gas emissions.

Domestic wastewater is a significant source of nitrogen and phosphorus, which cause lake eutrophication. Among the wastewater treatment technologies, constructed wetlands are a promising low-cost means of treating point and diffuse sources of domestic wastewater in rural areas. However, the sustainable operation of constructed wetland treatment systems depends upon a high rate conversion of organic and nitrogenous loading into their metabolic gaseous end products, such as N2O and CH4. In this study, we examined and compared the performance of three typical types of constructed wetlands: Free Water Surface (FWS), Subsurface Flow (SF) and Vertical Flow (VF) wetlands. Pollutant removal efficiency and N2O and CH4 emissions were assessed as measures of performance. We found that the pollutant removal rates and gas emissions measured in the wetlands exhibited clear seasonal changes, and these changes were closely associated with plant growth. VF wetlands exhibited stable removal of organic pollutants and NH3-N throughout the experiment regardless of season and showed great potential for CH4 adsorption. SF wetlands showed preferable T-N removal performance and a lower risk of greenhouse gas emissions than FWS wetlands. Soil oxidation reduction potential (ORP) analysis revealed that water flow structure and plant growth influenced constructed wetland oxygen transfer, and these variations resulted in seasonal changes of ORP distribution inside wetlands that were accompanied by fluctuations in pollutant removal and greenhouse gas emissions.