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1.
Refractory antibiotics in domestic wastewater are hard to be completely eliminated by conventional methods, and then lead to severe environmental contamination and adverse effects on public health. In present work, advanced oxidation processes (AOPs) are adopted to remove the antibiotic of sulfachloropyridazine (SCP). Nanosized Mn2O3 was fabricated on the SBA-15 material to catalytically activate potassium peroxydisulfate (PDS) to generate reactive oxygen radicals of ?OH and SO4- for SCP degradation. The effects of location and size of Mn2O3 were explored through choosing either the as-made or template-free SBA-15 as the precursor of substrate. Great influences from the site and size of Mn2O3 on the oxidation activity were discovered. It was found that Mn2O3 with a large size at the exterior of SBA-15 (Mn-tfSBA) was slightly easier to degrade SCP at a low manganese loading of 1.0–2.0?mmol?g?1; however, complete SCP removal could only be achieved on the catalyst of Mn2O3 with a refined size at the interior of SBA-15 (Mn-asSBA). Moreover, the SO4- species were revealed to be the decisive radicals in the SCP degradation processes. Exploring the as-made mesoporous silica as a support provides a new idea for the further development of environmentally friendly catalysts.  相似文献   

2.
H2O2 used in the photo-Fenton reaction with iron catalyst can accelerate the oxidation of Fe2+ to Fe3+ under UV irradiation and in the dark (in the so called dark Fenton process). It was proved that conversion of phenol under UV irradiation in the presence of H2O2 predominantly produces highly hydrophilic products and catechol, which can accelerate the rate of phenol decomposition. However, while H2O2 under UV irradiation could decompose phenol to highly hydrophilic products and dihydroxybenzenes in a very short time, complete mineralization proceeded rather slowly. When H2O2 is used for phenol decomposition in the presence of TiO2 and Fe–TiO2, decrease of OH radicals formed on the surface of TiO2 and Fe–TiO2 has been observed and photodecomposition of phenol is slowed down. In case of phenol decomposition under UV irradiation on Fe–C–TiO2 photocatalyst in the presence of H2O2, marked acceleration of the decomposition rate is observed due to the photo-Fenton reactions: Fe2+ is likely oxidized to Fe3+, which is then efficiently recycled to Fe2+ by the intermediate products formed during phenol decomposition, such as hydroquinone (HQ) and catechol.  相似文献   

3.
The inhibition effect of H2O on V2O5/AC catalyst for NO reduction with NH3 is studied at temperatures up to 250 °C through TPD, elemental analyses, temperature-programmed surface reaction (TPSR) and FT-IR analyses. The results show that H2O does not reduce NO and NH3 adsorption on V2O5/AC catalyst surface, but promotes NH3 adsorption due to increases in Brønsted acid sites. Many kinds of NH3 forms present on the catalyst surface, but only NH4+ on Brønsted acid sites and a small portion of NH3 on Lewis acid sites are reactive with NO at 250 °C or below, and most of the NH3 on Lewis acid sites does not react with NO, regardless the presence of H2O in the feed gas. H2O inhibits the SCR reaction between the NH3 on the Lewis acid sites and NO, and the inhibition effect increases with increasing H2O content. The inhibition effect is reversible and H2O does not poison the V2O5/AC catalyst.  相似文献   

4.
Combined effect of H2O and SO2 on V2O5/AC the activity of catalyst for selective catalytic reduction (SCR) of NO with NH3 at lower temperatures was studied. In the absence of SO2, H2O inhibits the catalytic activity, which may be attributed to competitive adsorption of H2O and reactants (NO and/or NH3). Although SO2 promotes the SCR activity of the V2O5/AC catalyst in the absence of H2O, it speeds the deactivation of the catalyst in the presence of H2O. The dual effect of SO2 is attributed to the SO42− formed on the catalyst surface, which stays as ammonium-sulfate salts on the catalyst surface. In the absence of H2O, a small amount of ammonium-sulfate salts deposits on the surface of the catalyst, which promote the SCR activity; in the presence of H2O, however, the deposition rate of ammonium-sulfate salts is much greater, which results in blocking of the catalyst pores and deactivates the catalyst. Decreasing V2O5 loading decreases the deactivation rate of the catalyst. The catalyst can be used stably at a space velocity of 9000 h−1 and temperature of 250 °C.  相似文献   

5.
WO_3负载量对V_2O_5/WO_3-TiO_2催化剂脱硝性能的影响   总被引:1,自引:0,他引:1  
采用V_2O_5/WO_3-TiO_2作为脱硝催化剂,考察活性组分V_2O_5和助剂WO_3负载量对催化剂脱硝活性和抗硫抗水性能的影响。结果表明,3%V_2O_5/x WO_3-TiO_2催化剂(x=3%、4%、5%、6%、7%、8%、9%、10%)上NOx转化率随着WO_3负载量增加而升高,催化剂反应温度窗口不断拓宽。单独通水蒸汽及同时通SO2和水蒸汽对催化剂的毒害作用均较强,表明H2O和NH3的竞争吸附是催化剂抗硫抗水性能较差的重要原因。SO_2与H_2O和NH_3反应生成亚硫酸铵盐和硫酸铵盐,导致催化剂孔隙堵塞,催化活性降低。  相似文献   

6.
CH4/CO2 reforming over La2NiO4 and 10%NiO/CeO2–La2O3 catalysts under the condition of supersonic jet expansion was studied via direct monitoring of the reactants and products using the sensitive technique of cavity ring-down spectroscopy. Vibration–rotational absorption lines of CH4, H2O, CO2 and CO molecules were recorded in the near infrared spectral region. Our results indicated that La2NiO4 is superior to 10%NiO/CeO2–La2O3 in performance. In addition, we observed enhanced reverse-water-gas-shift reaction at augmented reaction temperature. The formation of reaction intermediates was also investigated by means of time-of-flight mass spectrometry and there was the detection of CHx+, OH+ and H+ species.  相似文献   

7.
A novel heterogeneous catalyst has been used for the oxidation of aqueous solutions of phenol by catalytic wet peroxide oxidation assisted by ultrasound irradiation. This composite catalyst material that contains crystalline hematite particles embedded into a mesostructured SBA-15 matrix was used successfully in the oxidation of phenol by heterogeneous Fenton and photo-Fenton processes. Ultrasound is found to enhance the activity of the catalyst in the process, without prejudice to the stability of the iron supported species. The influence of different variables, such as hydrogen peroxide concentration or catalyst loadings in the reaction was studied by factorial design of experiments. Catalyst loadings of 0.6 g L−1 and a concentration of hydrogen peroxide close to twice the stoichiometric amount yield a remarkable organic mineralization, accompanied by excellent catalyst stability. The coupled US/Fe-SBA-15/H2O2 process at room temperature is revealed as a promising technique for wastewater treatment.  相似文献   

8.
The mixed oxide catalyst (Mn2O3 + SnO2) prepared by the coprecipitation method has been impregnated with Pd metal and it's catalytic behaviour for CO oxidation reaction has been investigated. In the coprecipitated material, Mn2O3 and SnO2 were found to crystallise at 875 K and 1175 K, respectively, which are significantly higher than the crystallisation temperatures of individual oxides prepared under similar conditions. Results of catalytic oxidation of CO, carried out using the pulse method for the mixed oxide system and the individual oxides, suggest significant synergistic effects between these two oxides. The impregnation of palladium metal facilitated CO oxidation and the catalyst Pd/(Mn2O3 + SnO2) was found to be quite effective for CO oxidation even at room temperature. Further, the CO disproportionation has been observed on palladium sites in the temperature range 350 to 400 K for the individual oxide systems.  相似文献   

9.
Combustion of CO, ethyl acetate and ethanol was studied over CuOx/Al2O3, CuOx–CeO2/Al2O3, CuMn2O4/Al2O3 and Mn2O3/Al2O3 catalysts. It was found that modification of the alumina with ceria before subsequent copper oxide deposition increases the activity for combustion of CO substantially, but the effect of ceria was small on the combustion of ethyl acetate and ethanol. The activity increases with the CuOx loading until crystalline CuO particles are formed, which contribute little to the total active surface. The CuOx–CeO2/Al2O3 catalyst is more active than the CuMn2O4/Al2O3 catalyst for the oxidation of CO but the CuMn2O4/Al2O3 catalyst is more active for the combustion of ethyl acetate and ethanol.

Thermal ageing and water vapour in the feed caused a modest decrease in activity and did not affect the CuOx–CeO2/Al2O3 and CuMn2O4/Al2O3 catalysts differently. In addition, no difference in intermediates formed over the two catalysts was observed.

Characterisation with XRD, FT-Raman and TPR indicates that the copper oxide is present as a copper aluminate surface phase on alumina at low loading. At high loading, bulk CuO crystallites are present as well. Modification of the alumina with ceria before the copper oxide deposition gives well dispersed copper oxide species and bulk CuO crystallites associated to the ceria, in addition to the two copper oxide species on the bare alumina. The distribution of copper species depends on the ceria and copper oxide loading. The alumina supported copper manganese oxide and manganese oxide catalysts consist mainly of crystalline CuMn2O4 and Mn2O3, respectively, on Al2O3.  相似文献   


10.
Chunli Zhao  Israel E. Wachs   《Catalysis Today》2006,118(3-4):332-343
The vapor-phase selective oxidation of propylene (H2CCHCH3) to acrolein (H2CCHCHO) was investigated over supported V2O5/Nb2O5 catalysts. The catalysts were synthesized by incipient wetness impregnation of V-isopropoxide/isopropanol solutions and calcination at 450 °C. The catalytic active vanadia component was shown by in situ Raman spectroscopy to be 100% dispersed as surface VOx species on the Nb2O5 support in the sub-monolayer region (<8.4 V/nm2). Surface allyl species (H2CCHCH2*) were observed with in situ FT-IR to be the most abundant reaction intermediates. The acrolein formation kinetics and selectivity were strongly dependent on the surface VOx coverage. Two surface VOx sites were found to participate in the selective oxidation of propylene to acrolein. The reaction kinetics followed a Langmuir–Hinshelwood mechanism with first-order in propylene and half-order in O2 partial pressures. C3H6-TPSR spectroscopy studies also revealed that the lattice oxygen from the catalyst was not capable of selectively oxidizing propylene to acrolein and that the presence of gas phase molecular O2 was critical for maintaining the surface VOx species in the fully oxidized state. The catalytic active site for this selective oxidation reaction involves the bridging VONb support bond.  相似文献   

11.
A series of CeO2 promoted cobalt spinel catalysts were prepared by the co-precipitation method and tested for the decomposition of nitrous oxide (N2O). Addition of CeO2 to Co3O4 led to an improvement in the catalytic activity for N2O decomposition. The catalyst was most active when the molar ratio of Ce/Co was around 0.05. Complete N2O conversion could be attained over the CoCe0.05 catalyst below 400 °C even in the presence of O2, H2O or NO. Methods of XRD, FE-SEM, BET, XPS, H2-TPR and O2-TPD were used to characterize these catalysts. The analytical results indicated that the addition of CeO2 could increase the surface area of Co3O4, and then improve the reduction of Co3+ to Co2+ by facilitating the desorption of adsorbed oxygen species, which is the rate-determining step of the N2O decomposition over cobalt spinel catalyst. We conclude that these effects, caused by the addition of CeO2, are responsible for the enhancement of catalytic activity of Co3O4.  相似文献   

12.
A commercial Co---Mo/Al2O3 catalyst was labeled with the radioisotope 35S in hydrodesulfurization (HDS) of 35S-labeled dibenzothiophene (35S-DBT) in a high-pressure flow reactor at 50 kg/cm2. Then, HDS of 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) or sulfur exchange of H2S were carried out on the labeled catalyst at 50 kg/cm2 and 260–360°C. The amounts of labile sulfur participating in the reaction were determined from the radioactivity of 35S---H2S released from the 35S-labeled catalyst. In the HDS reactions, the amount of labile sulfur participating in the reaction decreased in the order: DBT> 4-MDBT> 4,6-DMDBT. In the sulfur exchange reaction with H2S, the adsorption of H2S on the catalyst reached saturation above a H2S partial pressure of 0.36 kg/cm2. It was suggested that the release of H2S from the labile sulfur may be the rate determining step of the HDS reaction.  相似文献   

13.
The processing of molybdenum-uranium ore in a sulfuric acid solution using hydrogen peroxide as an oxidant has been investigated. The leaching temperature, hydrogen peroxide concentration, sulfuric acid concentration, leaching time, particle size, liquid-to-solid ratio and agitation speed all have significant effects on the process. The optimum process operating parameters were: temperature: 95°C; H2O2 concentration: 0.5 M; sulfuric acid concentration: 2.5 M; time: 2 h; particle size: 74 μm, liquid-to-solid ratio: 14 ∶ 1 and agitation speed: 600 rpm. Under these experimental conditions, the extraction efficiency of molybdenum was about 98.4%, and the uranium extraction efficiency was about 98.7%. The leaching kinetics of molybdenum showed that the reaction rate of the leaching process is controlled by the chemical reaction at the particle surface. The leaching process follows the kinetic model 1 ? (1?X)1/3 = kt with an apparent activation energy of 40.40 kJ/mole. The temperature, concentrations of H2O2 and H2SO4 and the mesh size are the main factors that influence the leaching rate. The reaction order in H2SO4 was 1.0012 and in H2O2 it was 1.2544.  相似文献   

14.
采用水热和沉淀两步合成法制备AgBr/Zn3(OH)2V2O7·2H2O催化剂,研究其在可见光下降解亚甲基蓝溶液的性能,并考察催化剂用量、亚甲基蓝溶液初始浓度、pH值以及盐浓度对光催化性能的影响,评价AgBr/Zn3(OH)2V2O7·2H2O催化剂的重复使用性能。结果表明,在前驱液pH为10、120 ℃水热10 h、Ag与Br物质的量比为0.20条件下制备的复合催化剂在可见光下反应120 min后,1.0 g·L-1的催化剂对10 mg·L-1的亚甲基蓝溶液脱色率达到85.2%。NaCl对亚甲基蓝的降解起抑制作用,Na2SO4对亚甲基蓝的降解起促进作用。催化剂重复使用4次后,光照120 min后的亚甲基蓝溶液脱色率可达66.4%。催化剂对不同初始浓度亚甲基蓝溶液的光催化降解符合一级动力学模型。  相似文献   

15.
A multi-component NOx-trap catalyst consisting of Pt and K supported on γ-Al2O3 was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H2O and CO2 on NOx storage. The Al2O3 support was shown to have NOx trapping capability with and without Pt present (at 250 °C Pt/Al2O3 adsorbs 2.3 μmols NOx/m2). NOx is primarily trapped on Al2O3 in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NOx/m2, and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al2O3 catalyst are coordinated on the Al2O3 support at saturation.

When 5% CO2 was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H2O was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al2O3-based nitrates decreased by 92%. Interestingly, with both 5% CO2 and 5% H2O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al2O3 destabilized the K–CO2 bond; specifically, H2O mitigates the NOx storage capacity losses associated with carboxylate competition.  相似文献   


16.
以γ-Al_2O_3为载体,负载Zr OCl_2和H_2SO_4制备Zr OCl_2-H_2SO_4/γ-Al_2O_3催化剂,并用于1-丁烯齐聚反应。采用气相色谱在线分析,确定产物组成,考察制备条件对催化剂催化活性的影响,通过1-丁烯转化率和主产物选择性确定适宜的反应条件。结果表明,在Zr OCl_2和H_2SO_4负载质量分数为4.5%和焙烧温度500℃条件下制备的催化剂,在反应温度140℃、1-丁烯液时空速2 h-1和N2分压1.4 MPa条件下,表现出较好的催化活性,1-丁烯转化率96.77%,产物以二聚体(C8)为主,选择性85.99%。该催化剂失活后容易再生,且催化活性良好,1-丁烯转化率92.73%,C8选择性86.73%。  相似文献   

17.
Both NO decomposition and NO reduction by CH4 over 4%Sr/La2O3 in the absence and presence of O2 were examined between 773 and 973 K, and N2O decomposition was also studied. The presence of CH4 greatly increased the conversion of NO to N2 and this activity was further enhanced by co-fed O2. For example, at 773 K and 15 Torr NO the specific activities of NO decomposition, reduction by CH4 in the absence of O2, and reduction with 1% O2 in the feed were 8.3·10−4, 4.6·10−3, and 1.3·10−2 μmol N2/s m2, respectively. This oxygen-enhanced activity for NO reduction is attributed to the formation of methyl (and/or methylene) species on the oxide surface. NO decomposition on this catalyst occurred with an activation energy of 28 kcal/mol and the reaction order at 923 K with respect to NO was 1.1. The rate of N2 formation by decomposition was inhibited by O2 in the feed even though the reaction order in NO remained the same. The rate of NO reduction by CH4 continuously increased with temperature to 973 K with no bend-over in either the absence or the presence of O2 with equal activation energies of 26 kcal/mol. The addition of O2 increased the reaction order in CH4 at 923 K from 0.19 to 0.87, while it decreased the reaction order in NO from 0.73 to 0.55. The reaction order in O2 was 0.26 up to 0.5% O2 during which time the CH4 concentration was not decreased significantly. N2O decomposition occurs rapidly on this catalyst with a specific activity of 1.6·10−4 μmol N2/s m2 at 623 K and 1220 ppm N2O and an activation energy of 24 kcal/mol. The addition of CH4 inhibits this decomposition reaction. Finally, the use of either CO or H2 as the reductant (no O2) produced specific activities at 773 K that were almost 5 times greater than that with CH4 and gave activation energies of 21–26 kcal/mol, thus demonstrating the potential of using CO/H2 to reduce NO to N2 over these REO catalysts.  相似文献   

18.
Dispersing La2O3 on δ- or γ-Al2O3 significantly enhances the rate of NO reduction by CH4 in 1% O2, compared to unsupported La2O3. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La2O3 precursor used, the pretreatment, and the La2O3 loading. The most active family of catalysts consisted of La2O3 on γ-Al2O3 prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m2) occurred between the addition of one and two theoretical monolayers of La2O3 on the γ-Al2O3 surface. The best catalyst, 40% La2O3/γ-Al2O3, had a turnover frequency at 700°C of 0.05 s−1, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La2O3/Al2O3 catalysts exhibited stable activity under high conversion conditions as well as high CH4 selectivity (CH4 + NO vs. CH4 + O2). The addition of Sr to a 20% La2O3/γ-Al2O3 sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO=4 to the latter Sr-promoted La2O3/Al2O3 catalyst decreased activity although sulfate increased the activity of Sr-promoted La2O3. Dispersing La2O3 on SiO2 produced catalysts with extremely low specific activities, and rates were even lower than with pure La2O3. This is presumably due to water sensitivity and silicate formation. The La2O3/Al2O3 catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.  相似文献   

19.
For high performance supercapacitors, novel hierarchical yolk-shell a-Ni(OH)2/Mn2O3 microspheres were controllably synthesized using a facile two-step method based on the solvothermal treatment. The unique a-Ni(OH)2 based yolk-shell microstructures decorated with numerous interconnected nanosheets and the hetero-composition features can synergistically enhance reactive site exposure and electron conduction within the microspheres, facilitate charge transfer between electrolyte and electrode materials, and release structural stress during OH chemisorption/desorption. Moreover, the Mn2O3 sediments distributed over the a-Ni(OH)2 microspheres can serve as an effective protective layer for electrochemical reactions. Consequently, when tested in 1 mol·L−1 KOH aqueous electrolyte for supercapacitors, the yolk-shell a-Ni(OH)2/Mn2O3 microspheres exhibited a considerably high specific capacitance of 2228.6 F·g−1 at 1 A·g−1 and an impressive capacitance retention of 77.7% after 3000 cycles at 10 A·g−1. The proposed a-Ni(OH)2/Mn2O3 microspheres with hetero-composition and unique hierarchical yolk-shell microstructures are highly promising to be used as electrode materials in supercapacitors and other energy storage devices.  相似文献   

20.
Ta3N5 was synthesized by nitridation of Ta2O5 under NH3 flow at 700 °C. The catalyst was pure Ta3N5 according to X-ray diffraction (XRD), and was about 5 nm in size with a BET specific surface area 52.8 m2/g. When Ta3N5 was added to Fe3+/H2O2 solution (known as Fenton-like system), most Fe3+ were adsorbed on the Ta3N5 surface and could not react with H2O2 in the dark, which is different from the general Fenton reaction. Under visible light irradiation, adsorbed Fe3+ ions were reduced to Fe2+ rapidly and Fe2+ were reoxidized by H2O2 on the Ta3N5 surface, thus a fast Fe3+/Fe2+ cycling was established. Kinetics and ESR measurements supported this mechanism. The Ta3N5/Fe3+/H2O2 system could efficiently decompose H2O2 to generate hydroxyl radicals driven by visible light, which could accelerate significantly the degradation of organic molecules such as N,N-dimethylaniline (DMA), and 2,4-dichlorophenol (DCP). A mechanism was proposed for iron cycling on the basis of experimental results.  相似文献   

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