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1.
A series of cobalt doped TiO_2(Co-TiO_2) and Co Oxloaded TiO_2(Co/TiO_2) catalysts prepared by sol–gel and impregnation methods respectively were investigated on selective catalytic reduction with NH_3(NH_3-SCR) of NO. It was found that Co-TiO_2 catalyst showed more preferable catalytic activity at low temperature range. From characterization results of XRD,TEM, Raman and FT-IR, Co species were proved to be doped into TiO_2 lattice by replaced Ti atoms. After being characterized and analyzed by NH_3-TPD, PL, XPS, EPR and DRIFTS, it was found that the better NH_3-SCR activities of Co-TiO_2 catalysts, compared with Co/TiO_2 catalyst, were ascribed to the formation of more oxygen vacancies which further promoted the production of more superoxide ions(O-2). The superoxide ions were crucial for the formation of low temperature SCR reaction intermediates(NO-3) by reacting with adsorbed NO molecule. Therefore, these aspects were responsible for the higher low temperature NH_3-SCR activity of Co-TiO_2 catalysts.  相似文献   

2.
The solid acid catalyst, N–F codoped TiO2/SiO2 composite oxide was prepared by a sol–gel method using NH4F as nitrogen and fluorine source. The prepared materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV–Visible diffuse reflectance spectroscopy (UV–Vis), ammonia adsorption and temperature-programmed desorption (NH3-TPD), in situ Fourier transform infrared spectroscopy (FT-IR) and N2 physical adsorption isotherm. The photocatalytic activity of the catalyst for acrylonitrile degradation was investigated under simulant solar irradiation. The results showed that strong Lewis and Brønsted acid sites appear on the surface of the sample after N–F doping. Systematic investigation showed that the highest photocatalytic activity for acrylonitrile degradation was obtained for samples calcined at 450°C with molar ratio (NH4F to Ti) of 0.8. The degradation ratio of 71.5% was achieved with the prepared catalyst after 6-min irradiation, demonstrating the effectiveness of photocatalytic degradation of acrylonitrile with N–F codoped TiO2/SiO2 composite oxide. The photocatalyst is promising for application under solar light irradiation. Moreover, the intermediates generated after irradiation were verified by gas chromatography–mass spectrometry (GC–MS) analysis and UV–Vis spectroscopy to be simple organic acids with lower toxicity, and the degradation pathway was also proposed for acrylonitrile degradation with the prepared catalyst.  相似文献   

3.
A series of CeO_2–ZrO_2–WO_3(CZW)catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction(SCR)of NO with NH_3 over a wide temperature of 150–550°C.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H_2O.The fresh catalyst showed above 90% NO_x conversion at 201–459°C,which is applicable to diesel exhaust NO_x purification(200–440°C).The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures(below 300°C),while the activity was notably enhanced at high temperature(above 450°C).The aged CZW catalyst(hydrothermal aging at 700°C for 8 hr)showed almost 80% NO_x conversion at 229–550°C,while the V_2O_5–WO_3/TiO_2 catalyst presented above 80% NO_x conversion at 308–370°C.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO_2–ZrO_2 solid solution,amorphous WO_3 phase and optimal acidity.In addition,the formation of WO_3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.  相似文献   

4.
A series of WO3/CeO2 (WOx/CeO2) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO2 support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH3-TPD, H2 temperature-programmed reduction (H2-TPR), NH3/NO oxidation and activity measurements for NOx reduction by NH3 (NH3-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO2 and WOx. As a result, the N2 selectivity of NH3 oxidation and NH3-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO2 catalyst. A tentative model of the NH3-SCR reaction route on WOx/CeO2 catalysts is presented.  相似文献   

5.
Nitrogen oxides(NO_x:NO,NO_2)are a concern due to their adverse health effects.Diesel engine transport sector is the major emitter of NO_x.The regulations have been strengthened and to comply with them,one of the two methods commonly used is the selective catalytic reduction of NO_xby NH_3(NH_3-SCR),NH_3being supplied by the in-situ hydrolysis of urea.Efficiency and durability of the catalyst for this process are highly required.Durability is evaluated by hydrothermal treatment of the catalysts at temperature above 800°C.In this study,very active catalysts for the NH_3-SCR of NO_xwere prepared by using a silicoaluminophosphate commercial zeolite as copper host structure.Characterizations by X-ray diffraction(XRD),scanning electron microscopy(SEM)and temperature programmed desorption of ammonia(NH_3-TPD)showed that this commercial zeolite was hydrothermally stable up to 850°C and,was able to retain some structural properties up to950°C.After hydrothermal treatment at 850°C,the NO_xreduction efficiency into NH_3-SCR depends on the copper content.The catalyst with a copper content of 1.25 wt.%was the most active.The difference in activity was much more important when using NO than the fast NO/NO_2reaction mixture.  相似文献   

6.
Compressed natural gas(CNG)is most appropriate an alternative of conventional fuel for automobiles.However,emissions of carbon-monoxide and methane from such vehicles adversely affect human health and environment.Consequently,to abate emissions from CNG vehicles,development of highly efficient and inexpensive catalysts is necessary.Thus,the present work attempts to scan the effects of precipitants(Na_2CO_3,KOH and urea)for nickel cobaltite(Ni Co_2O_4)catalysts prepared by co-precipitation from nitrate solutions and calcined in a lean CO-air mixture at 400°C.The catalysts were used for oxidation of a mixture of CO and CH_4(1:1).The catalysts were characterized by X-ray diffractometer,Brunauer–Emmett–Teller surface-area,X-ray photoelectron spectroscopy;temperature programmedreductionandScanningelectronmicroscopycoupledwith Energy-Dispersive X-Ray Spectroscopy.The Na_2CO_3was adjudged as the best precipitant for production of catalyst,which completely oxidized CO-CH_4mixture at the lowest temperature(T_(100)=350°C).Whereas,for catalyst prepared using urea,T_(100)=362°C.On the other hand the conversion of CO-CH_4mixture over the catalyst synthesized by KOH limited to 97%even beyond 400°C.Further,the effect of higher calcination temperatures of 500 and600°C was examined for the best catalyst.The total oxidation of the mixture was attained at higher temperatures of 375 and 410°C over catalysts calcined at 500 and 600°C respectively.Thus,the best precipitant established was Na_2CO_3and the optimum calcination temperature of 400°C was found to synthesize the Ni Co_2O_4catalyst for the best performance in CO-CH_4oxidation.  相似文献   

7.
ZnBiYO4 was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO4 were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–Vis diffuse reflectance. ZnBiYO4 crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO4 were a = b = 11.176479 Å and c = 10.014323 Å. The band gap of ZnBiYO4 was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO4 was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO4 had higher catalytic activity compared with N-doped TiO2 under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO4 or N-doped TiO2 as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min− 1 for ZnBiYO4 and N-doped TiO2, respectively. After visible light irradiation for 220 min with ZnBiYO4 as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO42 − and NO3, and evolution of CO2 revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography–mass spectrometry. The ZnBiYO4/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.  相似文献   

8.
The selective catalytic reduction(SCR) activities of the MoO_3 doped V/WTi catalysts prepared by the incipient wetness impregnation method at low temperature were investigated.The results showed that the addition of MoO_3 could enhance the NO_ xconversion at low temperature and the best SCR activity was obtained when the dosage of MoO_3 reached5 wt.%. The NH3-TPD and DRIFTS experiments indicated that the addition of MoO_3 changed the type and number of acid sites on the surface of catalysts and reaction activities of acid sites were altered at the same time. The redox capacity and amount of active oxygen species got improved for V3Mo5/WTi catalyst, which could be confirmed by the H_2-TPR and transient response experiments. Water vapor inhibited the NO_xconversion at low temperature. Deposition of ammonium sulfate or bisulfate might be main reason for the loss of catalytic activity in the presence of SO_2 at low temperature. Choosing the suitable NH_3/NO ratio and elevation of reaction temperature both could weaken the influence of SO_2 on the SCR activity of the V3Mo5/WTi catalyst. Thermal treatment of the deactivated catalyst at350°C could get the low temperature activity recovered. The decrease of GHSV improved the de NO_x efficiency at low temperature and we speculated that the rational technological process and operation parameters could contribute to the application of this kind of catalysts in real industrial environment.  相似文献   

9.
A series of meso-microporous Cu-SAPO-34 catalysts were successfully synthesized by a one-pot hydrothermal crystallization method, and these catalysts exhibited excellent NH_3-SCR performance at low temperature. Their structure and physic chemical properties were characterized by means of X-ray diffraction patterns(XRD), Scanning electron microscopy(SEM), Transmission electron microscopy(TEM), N_2 sorption-desorption, nuclear magnetic resonance(NMR), Inductively Coupled Plasma-Atomic Emission spectrometer(ICP-AES), X-ray absorption spectroscopy(XPS),Temperature-programmed desorption of ammonia(NH_3-TPD), Ultraviolet visible diffuse reflectance spectroscopy(UV-Vis DRS) and Temperature programmed reduction(TPR).The analysis results indicate that the high activities of Cu-SAPO-34 catalysts could be attributed to the enhancement of redox property, the formation of mesopores and the more acid sites. Furthermore, the kinetic results verify that the formation of mesopores remarkably reduces diffusion resistance and then improves the accessibility of reactants to catalytically active sites. The 1.0-Cu-SAPO-34 catalyst exhibited the high NO conversion( 90%) among the wide activity temperature window in the range of 150–425℃.  相似文献   

10.
Highly active mesoporous TiO_2 of about 6 nm crystal size and 280.7 m~2/g specific surface areas has been successfully synthesized via controlled hydrolysis of titanium butoxide at acidic medium. It was characterized by means of XRD(X-ray diffraction), SEM(scanning electron microscopy), TEM(transmission electron microscopy), FT-IR(Fourier transform infrared spectroscopy), TGA(thermogravimetric analysis), DSC(differential scanning calorimetry) and BET(Brunauer–Emmett–Teller) surface area. The degradation of dichlorophenol-indophenol(DCPIP) under ultraviolet(UV) light was studied to evaluate the photocatalytic activity of samples. The effects of different parameters and kinetics were investigated. Accordingly, a complete degradation of DCPIP dye was achieved by applying the optimal operational conditions of 1 g/L of catalyst, 10 mg/L of DCPIP, pH of 3 and the temperature at 25 ± 3°C after 3 min under UV irradiation. Meanwhile, the Langmuir–Hinshelwood kinetic model described the variations in pure photocatalytic branch in consistent with a first order power law model.The results proved that the prepared TiO_2 nanoparticle has a photocatalytic activity significantly better than Degussa P-25.  相似文献   

11.
A catalyst composed of manganese oxides supported on titania(MnO_x/TiO_2) synthesized by a sol–gel method was selected to remove nitric oxide and mercury jointly at a relatively low temperature in simulated flue gas from coal-fired power plants. The physico-chemical characteristics of catalysts were investigated by X-ray fluorescence(XRF), X-ray diffraction(XRD), and X-ray photoelectron spectroscopy(XPS) analyses, etc. The effects of Mn loading,reaction temperature and individual flue gas components on denitration and Hg~0 removal were examined. The results indicated that the optimal Mn/Ti molar ratio was 0.8 and the best working temperature was 240°C for NO conversion. O_2 and a proper ratio of [NH_3]/[NO]are essential for the denitration reaction. Both NO conversion and Hg~0 removal efficiency could reach more than 80% when NO and Hg~0 were removed simultaneously using Mn0.8 Tiat 240°C.Hg~0 removal efficiency slightly declined as the Mn content increased in the catalysts. The reaction temperature had no significant effect on Hg~0 removal efficiency. O_2 and HCl had a promotional effect on Hg~0 removal. SO2 and NH_3were observed to weaken Hg~0 removal because of competitive adsorption. NO first facilitated Hg~0 removal and then had an inhibiting effect as NO concentration increased without O_2, and it exhibited weak inhibition of Hg~0 removal efficiency in the presence of O_2. The oxidation of Hg~0 on Mn O x/TiO_2 follows the Mars–Maessen and Langmuir–Hinshelwood mechanisms.  相似文献   

12.
TiO_2 nanotube(Ti NT) electrodes anodized in fluorinated organic solutions were successfully prepared on Ti sheets. Field-emission scanning electron microscopy(FE-SEM) and X-ray diffraction(XRD) were performed to characterize the TiNT electrodes. The linear voltammetry results under irradiation showed that the TiNT electrode annealed at 450°C presented the highest photoelectrochemical activity. By combining photocatalytic with electrochemical process, a significantly synergetic effect on ammonia degradation was observed with Na_2SO_4 as supporting electrolyte at pH 10.7. Furthermore, the photoelectrocatalytic efficiency on the ammonia degradation was greatly enhanced in presence of chloride ions without the limitation of pH. The degradation rate was improved by 14.8 times reaching 4.98 × 10~(-2) min~(-1) at pH 10.7 and a faster degradation rate of 6.34 × 10~(-2) min~(-1)was obtained at pH 3.01. The in situ photoelectrocatalytic generated active chlorine was proposed to be responsible for the improved efficiency. On the other hand, an enhanced degradation of ammonia using TiNT electrode fabricated in fluorinated organic solution was also confirmed compared to TiNT electrode anodized in fluorinated water solution and TiO_2 film electrode fabricated by sol–gel method. Finally, the effect of chloride concentration was also discussed.  相似文献   

13.
采用超声辅助浸渍法成功合成了高铁含量的Fe MOR-5%-UL催化剂,并且测试其催化还原NO性能.研究发现在超声辅助条件下浸渍制得的催化剂可以引入更高比例的离子交换位上的孤立的Fe~(3+),这些铁离子具有更强的NO还原活性,因此超声辅助浸渍法制备的催化剂催化性能显著高于传统的离子交换法和浸渍法.其中活性最高的FeMOR-5%-UL催化剂在添加SO_2等多种气氛时,催化活性下降不显著.并且在持续100 h的汽车尾气条件下进行的稳定性实验中,FeMOR-5%-UL的催化活性没有明显下降.FeMOR-5%-UL的优异的催化活性和稳定性非常具有应用前景和研究价值.  相似文献   

14.
The influence of the various preparation methods of Cu-SAPO-34 nanocatalysts on the selective catalytic reduction of NO with NH3 under excess oxygen was studied. Cu-SAPO-34 nanocatalysts were prepared by using four techniques: conventional impregnation (IM), ultrasound-enhanced impregnation (UIM), conventional deposition precipitation (DP) using NaOH and homogeneous deposition precipitation (HDP) using urea. These catalysts were characterized in detail by various techniques such as N2-sorption, XRD, TEM, H2-TPR, NH3-TPD and XPS to understand the catalyst structure, the nature and the dispersed state of the copper species, and the acid sites for NH3 adsorption. All of the nanocatalysts showed high activities for NO removal. However, the activities were different and followed the sequence of Cu-SAPO-34 (UIM) > Cu-SAPO-34 (HDP) > Cu-SAPO-34 (IM) > Cu-SAPO-34 (DP). Based on the obtained results, it was concluded that the NO conversion on Cu-SAPO-34 nanocatalysts was mainly related to the high reducibility of the isolated Cu2 + ions and CuO species, the number of the acid sites and the dispersion of CuO species on SAPO-34.  相似文献   

15.
CeO2–TiO2composite supports with different Ce/Ti molar ratios were prepared by a homogeneous precipitation method, and V2O5–WO3/CeO2–TiO2catalysts for the selective catalytic reduction(SCR) of NOx with NH3 were prepared by an incipient-wetness impregnation method. These catalysts were characterized by means of BET, XRD, UV–Vis,Raman and XPS techniques. The results showed that the catalytic activity of V2O5–WO3/TiO2 was greatly enhanced by Ce doping(molar ratio of Ce/Ti = 1/10) in the TiO2 support.The catalysts that were predominantly anatase TiO2 showed better catalytic performance than the catalysts that were predominantly fluorite CeO2. The Ce additive could enhance the surface adsorbed oxygen and accelerate the SCR reaction. The effects of O2 concentration, ratio of NH3/NO, space velocity and SO2 on the catalytic activity were also investigated. The presence of oxygen played an important role in NO reduction. The optimal ratio of NH3/NO was 1/1 and the catalyst had good resistance to SO2 poisoning.  相似文献   

16.
采用共沉淀法合成了TiO_2及TiO_2-Fe_2O_3载体,并对硫酸氢铵与上述载体之间的相互作用及硫酸氢铵的具体分解行为进行了研究.结果表明,催化剂载体表面含硫官能团主要以双齿硫酸盐的形式存在,含氮官能团以铵根离子的形式存在.当硫酸氢铵沉积于催化剂载体表面时,由于硫酸根离子具有较强的电负性,Ti原子及Fe原子处于电子缺失状态.对于TiO_2载体,硫酸根离子主要与Ti原子相连;而对于TiO_2-Fe_2O_3载体,Ti原子及Fe原子均为硫酸根离子主要的附着位点.采用热分析方法及原位红外对硫酸氢铵在TiO_2及TiO_2-Fe_2O_3载体表面的分解行为进行了研究,发现铁氧化物的添加显著促进了硫酸氢铵在低温区间内的分解行为;与铵根离子相比,硫酸根离子具有更高的热稳定性.催化剂稳定性测试结果表明,铁氧化物的添加显著提高了低温抗硫抗水性能,为实现低温SCR技术的工业应用提供了理论基础.  相似文献   

17.
Carbon-modified titanium dioxide(TiO2) was prepared by a sol-gel method using tetrabutyl titanate as precursor, with calcination at various temperatures, and tested for the photocatalytic oxidation(PCO) of gaseous NH3 under visible and UV light. The test results showed that no samples had visible light activity, while the TiO2 calcined at 400℃ had the best UV light activity among the series of catalysts, and was even much better than the commercial catalyst P25. The catalysts were then characterized by X-ray diffractometry, Brunauer-Emmett-Teller adsorption analysis, Raman spectroscopy, thermogravimetry/differential scanning calorimetry coupled with mass spectrometry, ultraviolet-visible diffuse reflectance spectra, photoluminescence spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy. It was shown that the carbon species residuals on the catalyst surfaces induced the visible light adsorption of the samples calcined in the low temperature range( 300℃). However, the surface acid sites played a determining role in the PCO of NH3 under visible and UV light over the series of catalysts. Although the samples calcined at low temperatures had very high SSA, good crystallinity, strong visible light absorption and also low PL emission intensity, they showed very low PCO activity due to their very low number of acid sites for NH3 adsorption and activation. The TiO2 sample calcined at 400℃ contained the highest number of acid sites among the series of catalysts, therefore showing the highest performance for the PCO of NH3 under UV light.  相似文献   

18.
V2O5/TiO2催化剂中毒机理的试验研究   总被引:1,自引:0,他引:1  
选择性催化还原(SCR)催化剂是SCR烟气脱硝技术的核心,是整个SCR系统脱硝效率和经济性的决定因素.本文工作的主要研究思路是以钒钛SCR催化剂为研究对象,研究了H2O和SO2,以及相同含量下K、Na、Ca、Pb的氧化物对钒钛催化剂NO转化率的影响.H2O的存在会抑制V2O5/TiO2催化剂脱硝活性,而SO2在一定程度上促进(V2O5/TiO2)催化剂的SCR脱硝反应,提高NO转化率;碱金属K对钒钛催化剂的钝化作用都是最强,K2O和Na2O的掺入会抑制钒钛催化剂上V2O5的还原能力,而CaO和PbO的掺入对钒钛催化剂上V2O5的还原能力影响较小.  相似文献   

19.
A novel visible light-active photocatalyst formulation(NdT/OP) was obtained by supporting N-doped TiO_2(NdT) particles on up-conversion luminescent organic phosphors(OP). The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon(TOC) of aqueous solution,and CO and CO_2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO_2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity(58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT). We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as "photoactive support",able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.  相似文献   

20.
We describe here a one-step method for the synthesis of Au/TiO2 nanosphere materials, which were formed by layered deposition of multiple anatase TiO2 nanosheets. The Au nanoparticles were stabilized by structural defects in each TiO2 nanosheet, including crystal steps and edges, thereby fixing the Au–TiO2 perimeter interface. Reactant transfer occurred along the gaps between these TiO2 nanosheet layers and in contact with catalytically active sites at the Au–TiO2 interface. The doped Au induced the formation of oxygen vacancies in the Au–TiO2 interface. Such vacancies are essential for generating active oxygen species (*O) on the TiO2 surface and Ti3 + ions in bulk TiO2. These ions can then form Ti3 +–O–Ti4 + species, which are known to enhance the catalytic activity of formaldehyde (HCHO) oxidation. These studies on structural and oxygen vacancy defects in Au/TiO2 samples provide a theoretical foundation for the catalytic mechanism of HCHO oxidation on oxide-supported Au materials.  相似文献   

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