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1.
    
The reaction of Cl atoms with two C5 aldehydes (3-methyl-2-butenal and 3-methylbutanal) were investigated by proton-transfer-reaction mass spectrum (PTR-MS) using smog chamber at 298 ± 1 K and 760 Torr. A relative rate method was used to determine the rate constants of the title reactions with m-xylene and trans-2-butene as reference compounds: (3.04 ± 0.18)  ×  10−10 and (2.07 ± 0.14)  ×  10−10 cm3/(molecule⋅sec) for 3-methyl-2-butenal and 3-methylbutanal, respectively. Additionally, the gas-phase products were also identified by PTR-MS, and the possible reaction mechanisms were proposed basing on the identified products. The detected gas-phase products are similar for two C5 aldehydes reactions, mainly including small molecules of aldehydes, ketones and chlorinated aldehyde compounds. The atmospheric lifetimes (τ) calculated for 3-methyl-2-butenal (τ = 7.0 hr, marine boundary layer (MBL)) and 3-methylbutanal (τ = 10.3 hr, MBL) according to the obtained rate constants. The results indicate that Cl atoms at MBL are competitive with OH radicals for the degradation contribution of C5 aldehyde compounds.  相似文献   

2.
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The construction and application of novel highly efficient photocatalysts have been the focus in the field of environmental pollutant removal. In this work, a novel CuFe2O4/Bi12O17Cl2 photocatalysts were synthesized by simple hydrothermal and chemical precipitation method. The fabricated CuFe2O4/Bi12O17Cl2 composite exhibited much higher photocatalytic activity than pristine CuFe2O4 and Bi12O17Cl2 in the removal of bisphenol A (BPA) under visible-light illumination, which ascribed to the intrinsic p-n junction of CuFe2O4 and Bi12O17Cl2. The photocatalytic degradation rate of BPA on CuFe2O4/Bi12O17Cl2 with an optimized CuFe2O4 content (1.0 wt.%) reached 93.0% within 30 min. The capture experiments of active species confirmed that the hydroxyl radicals (•OH) and superoxide radicals (•O2) played crucial roles in photocatalytic BPA degradation process. Furthermore, the possible degradation mechanism and pathways of BPA was proposed according to the detected intermediates in photocatalytic reaction process.  相似文献   

3.
With increasing concerns on the environment and human health, the degradation of glyphosate through the formation of less toxic intermediates is of great importance. Among the developed methods for the degradation of glyphosate, photodegradation is a clean and efficient strategy. In this work, we report a new photocatalyst by doping F ion on BiVO4 that can efficiently degrade glyphosate and reduce the toxic emissions of aminomethylphosphonic acid (AMPA) through the selective (P)−C−N cleavage in comparison of BiVO4 catalyst. The results demonstrate that the best suppression of AMPA formation was achieved by the catalyst of 0.3F@BiVO4 at pH = 9 (AMPA formation below 10%). In situ attenuated total reflectance Fourier transforms infrared (ATR-FTIR) spectroscopy indicates that the adsorption sites of glyphosate on BiVO4 and 0.3F@BiVO4 are altered due to the difference in electrostatic interactions. Such an absorption alteration leads to the preferential cleavage of the C−N bond on the N−C−P skeleton, thereby inhibiting the formation of toxic AMPA. These results improve our understanding of the photodegradation process of glyphosate catalyzed by BiVO4-based catalysts and pave a safe way for abiotic degradation of glyphosate.  相似文献   

4.
    
A new state-of-the-art indoor smog chamber facility(CAPS-ZJU) has been constructed and characterized at Zhejiang University,which is designed for chemical mechanism evaluation under well-controlled conditions.A series of characterization experiments were performed to validate the well-established experimental protocols,including temperature variation pattern,light spectrum and equivalent intensity(JNO2),injection and mixing performance,as well as gases and particle wall loss.In additi...  相似文献   

5.
Wastewater containing an azo dye Orange G (OG) causes massive environmental pollution, thus it is critical to develop a highly effective, environmental-friendly, and reusable catalyst in peroxymonosulfate (PMS) activation for OG degradation. In this work, we successfully applied a magnetic MnFe2O4/α-MnO2 hybrid fabricated by a simple hydrothermal method for OG removal in water. The characteristics of the hybrid were investigated by X-ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller method, vibrating sample magnetometry, electron paramagnetic resonance, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The effects of operational parameters (i.e., catalytic system, catalytic dose, solution pH, and temperature) were investigated. The results exhibited that 96.8% of OG degradation was obtained with MnFe2O4/α-MnO2(1:9)/PMS system in 30 min regardless of solution pH changes. Furthermore, the possible reaction mechanism of the coupling system was proposed, and the degradation intermediates of OG were identified by mass spectroscopy. The radical quenching experiments and EPR tests demonstrated that SO4 ̶, O2 ̶, and 1O2 were the primary reactive oxygen species responsible for the OG degradation. The hybrid also displayed unusual stability with less than 30% loss in the OG removal after four sequential cycles. Overall, magnetic MnFe2O4/α-MnO2 hybrid could be used as a high potential activator of PMS to remove orange G and maybe other dyes from wastewater.  相似文献   

6.
    
Achieving an efficient and stable heterogeneous Fenton reaction over a wide pH range is of great significance for wastewater treatment. Here, a pollen-derived biochar catalyst with a unique honeycomb-like structure, coupled with the dispersion of magnetic Fe3O4/FeS (Fe/S) nanoparticles, was synthesized by simple impregnation precursor, followed by pyrolysis. The prepared Fe/S-biochar catalyst demonstrated outstanding phenol degradation efficiency across a wide pH range, with 98% of which eliminated even under neutral conditions (pH 7.0). The high catalytic activity was due to the multilevel porous structure of pollen-derived biochar provided enough active sites and allowed for better electron transfer, then increases oxidation ability to promote the reaction. Moreover, the acid microenvironment formed by SO42− group from Fe/S composite extended the pH range for Fenton reaction, and S2− facilitated the conversion of Fe3+ to Fe2+, resulting in remarkable degradation efficiency. Further, biochar can effectively promote cycling stability by limiting Fe leaching. This work may provide a general strategy for designing 3D framework biochar-based Fe/S catalysts with excellent performance for heterogeneous Fenton reactions.  相似文献   

7.
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Crystal defect is well-known to have a significant effect on the photocatalytic performance of semiconductors. Herein, defect-rich and -poor BaSn(OH)6 (BSOH-Sn and BSOH-Ba) photocatalysts were synthesized by exchanging the addition order of Ba and Sn. Results show that the defect-poor BSOH-Ba exhibited more efficient toluene degradation under ultraviolet (UV) light, which could attribute to the great suppression of photogenerated electron-hole (e-h+) pairs recombination by tuning the defect concentration. The low defect concentration in BSOH-Ba finally promotes the charge separation efficiency, the generation of reactive oxygen species (ROS), and the photocatalytic toluene degradation reactions. This work not only provides an effective way to inhibit the recombination of photogenerated carriers and improve the photocatalytic performance, but also promotes the understanding of defective perovskite-type hydroxide for more photoreactions.  相似文献   

8.
Mineralization of benzene, toluene, and xylene (BTX) with high efficiency at room temperature is still a challenge for the purification of indoor air. In this work, a foam Ti/Sb-SnO2/β-PbO2 anode catalyst was prepared for electrocatalytically oxidizing gaseous toluene in an all-solid cell at ambient temperature. The complex Ti/Sb-SnO2/β-PbO2 anode, which was prepared by sequentially deposing Sb-SnO2 and β-PbO2 on a foam Ti substrate, shows high electrocatalytic oxidation efficiency of toluene (80%) at 7 hr of reaction and high CO2 selectivity (94.9%) under an optimized condition, i.e., a cell voltage of 2.0 V, relative humidity of 60% and a flow rate of 100 mL/min. The better catalytic performance can be ascribed to the high production rate of ⋅OH radicals from discharging adsorbed water and the inhibition of oxygen evolution on the surface of foam Ti/Sb-SnO2/β-PbO2 anode when compared with the foam Ti/Sb-SnO2 anode. Our results demonstrate that prepared complex electrodes can be potentially used for electrocatalytic removal of gaseous toluene at room temperature with a good performance.  相似文献   

9.
    
Graphite carbon nitride has many excellent properties as a two-dimensional semiconductor material so that it has a wide application prospect in the field of photocatalysis. However, the traditional problems such as high recombination rate of photogenerated carriers limit its application. In this work, we introduce nitrogen deficiency into g-C3N4 to solve this problem a simple and safe in-situ reduction method. g-C3N4/CaCO3 was obtained by a simple and safe one-step calcination method with industrial-grade micron particles CaCO3. Cyano group modification was in-situ reduced during the thermal polymerization process, which would change the internal electronic structure of g-C3N4. The successful combination of g-C3N4 and CaCO3 and the introduction of cyanide have been proved by Fourier transform infrared spectroscopy and X-ray photoelectron spectrometer. The formation of the cyano group, an electron-absorbing group, promotes the effective separation of photogenic electron hole pairs and inhibits the recombination of photogenic carriers. These advantages result in the generation of more •O2 and 1O2 in the catalytic system, which increases the photocatalytic efficiency of nicotine degradation by ten times. Furthermore, the degradation process of nicotine has been studied in this work to provide a basis for the degradation of nicotine organic pollutants in the air.  相似文献   

10.
To improve the removal capacity of NO + O2 effectively, the alkaline earth metal-doped order mesoporous carbon (A-C-FDU-15(0.001) (A = Mg, Ca, Sr and Ba)) and Mg-C-FDU-15(x) (x = 0.001?0.003) samples were prepared, and their physicochemical and NO + O2 adsorption properties were determined by means of various techniques. The results show that the sequence in (NO + O2) adsorption performance was as follows: Mg-C-FDU-15(0.001) (93.2 mg/g) > Ca-C-FDU-15(0.001) (82.2 mg/g) > Sr-C-FDU-15(0.001) (76.1 mg/g) > Ba-C-FDU-15(0.001) (72.9 mg/g) > C-FDU-15 (67.1 mg/g). Among all of the A-C-FDU-15(0.001) samples, Mg-C-FDU-15(0.001) possessed the highest (NO + O2) adsorption capacity (106.2 mg/g). The species of alkaline earth metals and basic sites were important factors determining the adsorption of NO + O2 on the A-C-FDU-15(x) samples, and (NO + O2) adsorption on the samples was mainly chemical adsorption. Combined with the results of (NO + O2)-temperature-programmed desorption ((NO + O2)-TPD) and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization, we deduced that there were two main pathways of (NO + O2) adsorption: one was first the conversion of NO and O2 to NO2 and then part of NO2 was converted to NO2? and NO3?; and the other was the direct oxidation of NO to NO2? and NO3?.  相似文献   

11.
    
Mass level of fine particles(PM2.5) in main cities in China has decreased significantly in recent years due to implementation of Chinese Clean Air Action Plan since 2013,however,03 pollution is getting worse than before,especially in megacities such as in Shanghai.In this work,O3 and PM2.5 were continuously monitored from May 27,2018 to March 31,2019.Our data showed that the annual average concentration of PM2.5 and O3(O3-8 hr,max...  相似文献   

12.
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Fenthion and parathion are two representative kinds of organophosphorus pesticides and widely used in agriculture. They are directly or indirectly released into the atmosphere by spraying or volatilization processes. However, their heterogeneous reactivity toward OH radicals has not yet been well understood. Therefore, this work investigated the heterogeneous kinetics of the OH-initiated degradation of surface-bound fenthion and parathion using a flow reactor. The results showed that OH radicals played an important role in the atmospheric degradation of fenthion and parathion. Their average rate constants were (7.20 ± 0.77) × 10−12 and (10.40 ± 0.60) × 10−12 cm3/(mol· sec) at a relative humidity (RH) and temperature of 35% and 20 °C, respectively, suggesting that they have relatively short lifetimes in the atmosphere. In addition, a negative RH dependence and a positive temperature dependence of the rate constants were observed. The Arrhenius expressions of fenthion and parathion were k2 = (1.34 ± 0.48) × 10−9exp[−(1432.59 ± 105.29)/T] and k2 = (1.96 ± 1.38) × 10−9exp[−(1619.98 ± 222.02)/T], respectively, and their overall activation energy was estimated to be (11.88 ± 0.87) and (13.48 ± 1.83) kJ/mol. The experimental results will update the kinetic data of fenthion and parathion in the atmosphere and be helpful to further understand their atmospheric transportation processes.  相似文献   

13.
以气相甲苯为对象,研究其在波长为254 nm紫外光下的光氧化降解反应.同时,考察了甲苯初始浓度、光强和相对湿度对甲苯转化率的影响,分析了甲苯降解中间产物的生成机理.结果表明,随着甲苯初始浓度的增加,甲苯转化率缓慢下降;随着光照强度的增强,甲苯转化率逐渐增加;而提高相对湿度,甲苯转化率则为先升高后降低.在甲苯降解动力学分析中发现其光氧化降解过程符合伪一级反应动力学,且表观速率常数与光照强度成正比.通过对甲苯降解中间产物的分析,发现随着光照强度的增加,含苯环物质的降解更为充分,乙醇、乙酸等的相对含量逐渐增加,苯甲醇、苯甲醛缩二甲醇等的含量逐渐降低,在此基础上提出了甲苯生成含苯环产物及开环生成2-戊酮等的降解机理.  相似文献   

14.
    
Over the recent past, fluoroquinolone antibiotics (FQs) have raised extensive attention due to their potential to induce the formation of resistance genes and “superbugs”, thus various advanced oxidation techniques have been developed to eliminate their release into the environment. In the present study, the prototype tetraamido macrocyclic ligand (FeIII-TAML)/hydrogen peroxide (H2O2) system is employed to degrade FQs (i.e., norfloxacin and ciprofloxacin) over a wide pH range (i.e., pH 6-10), and the reaction rate increases with the increase in pH level. The effect of dosage of FeIII-TAML and H2O2 on the degradation of FQs is evaluated, and the reaction rate is linearly correlated with the added amount of chemicals. Moreover, the impact of natural organic matters (NOM) on the removal of FQs is investigated, and the degradation kinetics show that both NOM type and experimental concentration exhibit negligible influence on the oxidative degradation of selected antibiotics. Based on the results of liquid chromatography-high resolution mass spectrometry and theoretical calculations, the reaction sites and pathways of FQs by FeIII-TAML/H2O2 system are further predicted and elucidated.  相似文献   

15.
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The graphic carbon nitride/polyaniline (g-C3N4/PANI) hybrid composites were successfully synthesized by a facile in situ polymerization process under ice water bath. The photocatalytic activities of the g-C3N4/PANI composites were evaluated by using oxytetracycline (OTC) as model pollutants. The optimal g-C3N4/PANI composite (5%PANI: the g-C3N4/PANI hybrid with 5 wt.% of PANI) showed an enhancement degradation rate of 5-fold compared to that of conventional g-C3N4 under simulated-sunlight irradiation. In addition, the 5%PANI demonstrate significantly photocatalytic evolution H2 rate (163.2 μmol/(g?hr)) under the visible light irradiation. Furthermore, based on the results of optical performance and electrochemical testing, a possible mechanism was proposed, indicating that the incorporation of PANI into the traditional g-C3N4 can effectively tune the electronic structures, improve the photo-generated electrons-holes separation and enhance extensive absorption of visible light. Such a g-C3N4/PANI hybrid nanocomposites could be envisaged to possess great potentials in practical wastewater treatment and water splitting.  相似文献   

16.
    
With the rapid expansion of livestock production, the amount of livestock wastewater accumulated rapidly. Lack of biodegradable organic matter makes denitrification of livestock wastewater after anaerobic digestion more difficult. In this study, Myriophyllum aquaticum constructed wetlands(CWs) with efficient nitrogen removal performance were established under different carbon/nitrogen(C/N) ratios. Analysis of community composition reveals the change of M. aquaticum CWs in microbial community str...  相似文献   

17.
    
The tetC gene has been found to be one of the most widely distributed tetracycline resistance (tet) genes in various environmental niches, but the detailed dissemination mechanisms are still largely unknown. In the present study, 11 tetC-containing Aeromonas media strains were isolated from an aerobic biofilm reactor under oxytetracycline stresses, and the genome of one strain was sequenced using the PacBio RSII sequencing approach to reveal the genetic environment of tetC. The tetC gene was carried by an IS26 composite transposon, named Tn6434. The tetC-carrying Tn6434 structure was detected in all of the A. media strains either in a novel plasmid pAeme2 (n=9) or other DNA molecules (n=2) by PCR screening. The NCBI database searching result shows that this structure was also present in the plasmids or chromosomes of other 13 genera, indicating the transferability of Tn6434. Inverse PCR and sequencing confirmed that Tn6434 can form a circular intermediate and is able to incorporate into a preexisting IS26 element, suggesting that Tn6434 might be responsible for the dissemination of tetC between different DNA molecules. This study will be helpful in uncovering the spread mechanism of tet genes in water environments.  相似文献   

18.
生物膜填料塔净化有机废气研究   总被引:38,自引:1,他引:38  
为在国内开展生物化学法净化低浓度有机废气的研究工作,采用国内现有微生物菌种挂膜接种的生物膜填料塔净化低浓度甲苯废气,结果表明,在入口气体甲苯浓度0.183~1.803mg/L及气体流量86.4~190.8L/h(停留时间6.2~13.6s)的实验范围内,增加入口气体甲苯浓度和气体流量,可使甲苯的生化去除量增大,每升体积的生物膜填料对甲苯的生化去除量最大可达157.13mg/h。由实验结果推断,生物膜填料塔对废气中甲苯的净化去除过程属于传质控制过程。对比结果表明,本研究建立的动力学模式对实际过程有很好的适用性,计算值与实验值之间的相关系数R=0.98。  相似文献   

19.
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Designing high-efficiency photocatalysts responsive to visible light is important for the degradation of antibiotics in water. Heterojunction engineering is undoubtedly an effective strategy to improve the photocatalytic performance. In this work, spinel-type metal oxides (NiAl2O4, NAO) are synthesized by a simple sol-gel and calcination process. After compounding graphitic carbon nitride (g-C3N4), NAO/g-C3N4 heterojunction is obtained, which then is used as the photocatalyst for tetracycline hydrochloride (TC). The effects of photocatalyst dosage, the initial concentration of TC, and solution pH on photodegradation performance are systematically studied. The removal rate of TC on NAO/g-C3N4 reach up to ∼90% after visible light irradiation for 2 hr and the degradation rate constant is ∼7 times, and ∼32 times higher than that of pure NAO and g-C3N4. The significantly improved photocatalytic activity can be attributed to the synergistic effect between well matched energy levels in NAO/g-C3N4 heterojunctions, improvement of interfacial charge transfer, and enhancement of visible light absorption. This study provides a way for the synthesis of efficient photocatalysts and an economic strategy for removing antibiotics contamination in water.  相似文献   

20.
    
Dichloromethane (DCM) has been listed as a toxic and harmful water pollutant, and its removal needs attention. Microbial electrolysis cells (MECs) are viewed as a promising alternative for pollutant removal, which can be strengthened from two aspects: microbial inoculation and acclimation. In this study, the MEC for DCM degradation was inoculated with the active sludge enhanced by Methylobacterium rhodesianum H13 (strain H13) and then acclimated in the form of a microbial fuel cell (MFC). Both the introduction of strain H13 and the initiation in MFC form significantly promoted DCM degradation. The degradation kinetics were fitted by the Haldane model, with Vmax, Kh, Ki and vmax values of 103.2 mg/L/hr, 97.8 mg/L, 268.3 mg/L and 44.7 mg/L/hr/cm2, respectively. The cyclic voltammogram implies that DCM redox reactions became easier with the setup of MEC, and the electrochemical impedance spectrogram shows that the acclimated and enriched microbes reduced the charge transfer resistance from the electrode to the electrolyte. In the biofilm, the dominant genera shifted from Geobacter to Hyphomicrobium in acclimation stages. Moreover, Methylobacterium played an increasingly important role. DCM metabolism mainly occurred through the hydrolytic glutathione S-transferase pathway, given that the gene dcmA was identified rather than the dhlA and P450/MO. The exogenous electrons facilitated the reduction of GSSG, directly or indirectly accelerating the GSH-catalyzed dehalogenation. This study provides support for the construction of an efficient and stable MEC for DCM removal in water environment.  相似文献   

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