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1.
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.  相似文献   

2.
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.  相似文献   

3.
Fine particulate matter (PM2.5) 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 PM2.5 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 PM2.5 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 PM2.5 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 PM2.5 levels and PNC. Assessment of the risk associated with PM2.5 exposure revealed that children are most severely affected by PM2.5 pollution, followed in order by juveniles, adults and the elderly. In addition, females were found to be more vulnerable to PM2.5 pollution than males (p < 0.001), and different subway lines were associated with different levels of risk.  相似文献   

4.
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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5.
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.  相似文献   

6.
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.  相似文献   

7.
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  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
The explosive growth in anthropogenic energy consumption, coupled with the consequent environmental pollution, have been acknowledged as two impending challenges confronting humanity. Photocatalytic CO2 reduction to produce value-added hydrocarbon fuels, by using abundant solar energy and redundant atmospheric CO2, is an innovative way to satisfy global energy requirements whilst simultaneously reducing atmospheric CO2 levels. Although this notion is several decades old, it has unfortunately been lingering in a state of infancy due to inherently poor CO2-to-fuel conversion efficiencies, and the generation of low-value products (e.g., CO, HCHO). These pitfalls hamper this process from any potential commercial breakthrough and are primarily fuelled by the lack of progress in developing high-performance photocatalytic materials. Fortunately, the advent of nanotechnology has recently introduced many promising novel materials for this purpose. Here, we review photocatalysts with proven potential for converting CO2 into methanol, a high-value, energy-dense hydrocarbon fuel that is easily transported using existing pipeline infrastructure. Methanol possesses multifarious applications in the automobile, industrial and petrochemical sector. In addition, the development of direct methanol fuel cells (DMFCs) has introduced the tantalizing prospect of using methanol as a medium for storing solar energy that is easily converted to electricity via DMFCs. As such, methanol is an ideal fuel, with numerous advantages over its counterparts. This article reviews several photocatalysts that have been reported for this environmentally sustainable process of converting CO2 into methanol by photocatalysis. Specifically, the performance enhancement effected by adding dopant atoms, forming heterostructured composites and nanostructures, is investigated in terms of four key areas: (1) enhanced visible light sensitivity, (2) improved adsorption of reactants on the catalytic surface, (3) lowered electron–hole recombination and (4) increased CO2 reduction kinetics. The trends deduced therein are invaluable for researchers developing novel photocatalytic materials, which will utilize sunlight to convert CO2 into methanol with enhanced efficiency, thus ushering in the era of a green methanol-based economy.  相似文献   

11.
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 Cr6 +. The present mixed oxide can be a candidate for the low temperature abatement of NO x .
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12.
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.  相似文献   

13.
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.  相似文献   

14.
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  相似文献   

15.
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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16.
Climate change has become increasingly serious due to the greenhouse effect. It is therefore necessary to control the content of greenhouse gases such as carbon dioxide in the atmosphere, using, for instance, CO2-adsorbing materials. Here, we synthesized ultra-lightweight and spherical cellulose nanofibres aerogels by a suspension titration method using an efficient amination process. These functional materials with high porosity, higher than 96.54%, and three-dimensional network structure, were prepared by freeze-drying spherical cellulose nanofibres hydrogel. Their maximum CO2 adsorption capacity reaches 1.78 mmol/g, and they show excellent regeneration, of more than 10 cycles. This synthesis of bioaerogels represents a new method for the preparation of bio-CO2 adsorbents.  相似文献   

17.
Cordgrasses of the genus Spartina form dense monospecific stands worldwide, profoundly influencing the ecology of estuaries. One species, Spartina anglica, originated by allopolyploidy in the 1800s and has been particularly prolific as an invasive species worldwide. S. anglica tolerates low-lying estuarine mudflats that its progenitor species and other coastal halophytes cannot. However, very little is known of the physiology of S. anglica. In the present study, an automated flow-through respirometry system was used to quantify metabolic gas fluxes (O2, H2S, CO2, and NH3) of S. anglica rhizomes. Enhanced physiological mechanisms to transport O2 and H2S in both directions between the rhizosphere and the atmosphere were exhibited by S. anglica, but not by the native North American species S. alterniflora. These results suggest that tolerance of anoxia and H2S may assist S. anglica in colonizing extensively flooded environments. Enhanced sediment oxygenation by S. anglica may be potentially useful for phytoremediation of contaminated sediments, since microbial degradation of organic pollutants is often limited by O2 availability.  相似文献   

18.
Future atmospheric CO2 levels will most likely have complex consequences for marine organisms, particulary photosynthetic calcifying organisms. Corallina officinalis L. is an erect calcifying macroalga found in the inter- and subtidal regions of temperate rocky coastlines and provides important substrate and refugia for marine meiofauna. The main goal of the current study was to determine the physiological responses of C. officinalis to increased CO2 concentrations expected to occur within the next century and beyond. Our results show that growth and production of inorganic material decreased under high CO2 levels, while carbonic anhydrase activity was stimulated and negatively correlated to algal inorganic content. Photosynthetic efficiency based on oxygen evolution was also negatively affected by increased CO2. The results of this study indicate that C. officinalis may become less competitive under future CO2 levels, which could result in structural changes in future temperate intertidal communities.  相似文献   

19.
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.  相似文献   

20.
Radon (222Rn) and carbon dioxide were monitored simultaneously in soil air under a cool-temperate deciduous stand on the campus of Hokkaido University, Sapporo, Japan. Both 222Rn and CO2 concentrations in soil air varied with atmospheric (soil) temperature in three seasons, except for winter when the temperature in soil air remained constant at 2–3°C at depth of 80 cm. In winter, the gaseous components were influenced by low-pressure region passing through the observation site when the ground surface was covered with snow of ~1 m thickness. Carbon isotopic analyses of CO2 suggested that CO2 in soil air may result from mixing of atmospheric air and soil components of different origins, i.e. CO2 from contemporary soil organic matter and old carbon from deeper source, to varying degrees, depending on seasonal meteorological and thus biological conditions.  相似文献   

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