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1.
A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ (x: 0–0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu 1-x Co x O 4-δ catalysts were of oxygen vacancies whereas the Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level, the oxygen vacancy density of NdSrCu 1-x Co x O 4-δ decreased while the over-stoichiometric oxygen amount of Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO 3.702 catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr -1 , and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO 3.702 NdSrCu 0.8 Co 0.2 O 3.736 NdSrCu 0.6 Co 0.4 O 3.789 Sm 1.8 Ce 0.2 Cu 0.6 Co 0.4 O 4.187 Sm 1.8 Ce 0.2 Cu 0.8 Co 0.2 O 4.104 Sm 1.8 Ce 0.2 CuO 4.045 , in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu 3+ /Cu 2+ redox ability of NdSrCu 1-x Co x O 4-δ account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.  相似文献   

2.
Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H_2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the Ce O_2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.  相似文献   

3.
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   

4.
A 0.5 wt.% Pt/TiO2 catalyst was prepared and used for the low-temperature selective catalytic reduction(SCR) of NO with C3 H6 in the presence of excess oxygen.The effects of Pt loading and O2 concentration on Pt/TiO2 catalytic performance for low-temperature SCR were investigated.It was found that optimal Pt loading was 0.5 wt.% and excess O2 favored low-temperature SCR of NOx.The mechanism of low-temperature SCR of NO with C3 H6 was investigated with respect to the behavior of adsorbed species over Pt/TiO2 at 150°C using in situ DRIFTS.The results indicated that surface nitrosyl species(Pt δ+-NO and Ti 3+-NO) and Pt 2+-CO are main reaction intermediates during the interactions of NO,C3 H6 and O2.A simplified NO decomposition mechanism for the low-temperature SCR of NO with C3 H6 was proposed.  相似文献   

5.
Simultaneous removing SO2 and NO by a new system containing cobalt complex   总被引:3,自引:0,他引:3  
Absorption and catalytic oxidation of nitric oxide can be achieved by using cobalt(Ⅲ) ethylenediamine (Co(en)3^3+. When simultaneous absorbing SO2 and NO, the precipitation of Co2(SO3)3 will be yielded and the NO removal will be decreased. A new catalyst system using Co(en)3^3+ coupled with urea has been developed to simultaneous remove NO and SO2 in the flue gas. NO is absorbed and catalytically oxidized to nitrite and nitrate by Co(en)3^3+. The dissolved oxygen in scrubbing solution from the feed stream acts as oxidant. Urea restrains the precipitation of Co2(SO3)3 by oxidizing SO3^2-to SO4^2- as COSO4 is more soluble in water. The experimental results proved that nearly all SO3^2- can be oxidized to SO4^2- and the high NO and SO2 removal could be obtained with the new system. The NO removal is influenced by gas flow rate, the concentration of Co(en)3^3+ and urea in the absorption solution, the temperature of the scrubbing solution and the content of oxygen in the flue gas. The low gas flow rate is favorable to increase the NO removal. The experiments proved that the NO removal could be maintained at more than 95% by the system of 0.02 mol/L Co(en)3^3+ and 1% urea at 50℃ with 10% O2 in the flue gas.  相似文献   

6.
Manganese oxides supported by ZSM-5 zeolite (Mn/ZSM-5) as well as their further modified by Ce promoter were achieved by simple impregnation method for ozone catalytic decomposition. The yCe20Mn/ZSM-5–81 catalyst with 8% Ce loading showed the highest catalytic activity at relative humidity of 50% and a space velocity of 360 L/(g × hr), giving 93% conversion of 600 ppm O3 after 5 hr. Moreover, this sample still maintained highly activity and stability in humid air with 50%–70% relative humidity. Series of physicochemical characterization including X-ray diffraction, temperature-programmed technology (NH3-TPD and H2-TPR), X-ray photoelectron spectroscopy and oxygen isotopic exchange were introduced to disclose the structure-performance relationship. The results indicated that moderate Si/Al ratio (81) of zeolite support was beneficial for ozone decomposition owing to the synergies of acidity and hydrophobicity. Furthermore, compared with 20Mn/ZSM-5-81, Ce doping could enhance the amount of low valance manganese (such as Mn2+ and Mn3+). Besides, the Ce3+/Ce4+ ratio of 8Ce20Mn/ZSM-5-81 sample was higher than that of 4Ce20Mn/ZSM-5-81. Additionally, the synergy between the MnOx and CeO2 could easily transfer electron via the redox cycle, thus resulting in an increased reducibility at low temperatures and high concentration of surface oxygen. This study provides important insights to the utilization of porous zeolite with high surface area to disperse active component of manganese for ozone decomposition.  相似文献   

7.
The deposition of NH4HSO4 and the poisoning effect of SO2 on SCR catalyst are the main obstacles that restrict the industrial application of CeO2-doped SCR catalysts. In this work, deposited NH4HSO4 decomposition behavior and SO2 poisoning over V2O5–MoO3/TiO2 catalysts modified with CeO2 and SiO2 were investigated. By the means of characterization analysis, it was found that the addition of SiO2 into VMo/Ti–Ce had an impact on the interaction existed between catalyst surface atoms and NH4HSO4. Temperature-programmed methods and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments indicated that the doping of SiO2 promoted the decomposition of deposited NH4HSO4 on VMo/Ti–Ce catalyst surface by reducing the thermal stability of NH4HSO4 and enhancing the NH4HSO4 reactivity with NO in low temperature. And this improvement may be the reason for the better catalytic activity than VMo/Ti–Ce in the case of NH4HSO4 deposition. Accompanied with cerium sulfate species generated over catalyst surface, the conversion of SO2 to SO3 was inhibited in SiCe mixed catalyst. The addition of SiO2 could promote the decomposition of cerium sulfate, which may be a potential strategy to enhance the resistance of SO2 poisoning over CeO2-modifed catalysts.  相似文献   

8.
Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst,V_2O_5–WO_3/TiO_2,to investigate mercury oxidation in the presence of NO and O_2.Mercury oxidation was improved by NO,and the efficiency was increased by simultaneously adding NO and O_2.With NO and O_2 pretreatment at 350°C,the catalyst exhibited higher catalytic activity for Hg~0 oxidation,whereas NO pretreatment did not exert a noticeable effect.Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O_2.Although NO promoted Hg~0 oxidation at the very beginning,excessive NO counteracted this effect.The results show that NO plays different roles in Hg~0oxidation; NO in the gaseous phase may directly react with the adsorbed Hg~0,but excessive NO hinders Hg~0 adsorption.The adsorbed NO was converted into active nitrogen species(e.g.,NO_2) with oxygen,which facilitated the adsorption and oxidation of Hg~0.Hg~0 was oxidized by NO mainly by the Eley–Rideal mechanism.The Hg~0 temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O_2.  相似文献   

9.
MnxCe1- xO2(x: 0.3–0.9) prepared by Pechini method was used as a catalyst for the thermal catalytic oxidation of formaldehyde(HCHO). At x = 0.3 and 0.5, most of the manganese was incorporated in the fluorite structure of Ce O2 to form a solid solution. The catalytic activity was best at x = 0.5, at which the temperature of 100% removal rate is the lowest(270°C). The temperature for 100% removal of HCHO oxidation is reduced by approximately 40°C by loading 5 wt.% Cu Oxinto Mn0.5Ce0.5O2. With ozone catalytic oxidation, HCHO(61 ppm) in gas stream was completely oxidized by adding 506 ppm O3 over Mn0.5Ce0.5O2 catalyst with a GHSV(gas hourly space velocity) of 10,000 hr-1at 25°C. The effect of the molar ratio of O3 to HCHO was also investigated. As O3/HCHO ratio was increased from 3 to 8, the removal efficiency of HCHO was increased from 83.3% to 100%. With O3/HCHO ratio of 8, the mineralization efficiency of HCHO to CO2 was 86.1%. At 25°C, the p-type oxide semiconductor(Mn0.5Ce0.5O2) exhibited an excellent ozone decomposition efficiency of 99.2%,which significantly exceeded that of n-type oxide semiconductors such as Ti O2, which had a low ozone decomposition efficiency(9.81%). At a GHSV of 10,000 hr-1, [O3]/[HCHO] = 3 and temperature of 25°C, a high HCHO removal efficiency(≥ 81.2%) was maintained throughout the durability test of 80 hr, indicating the long-term stability of the catalyst for HCHO removal.  相似文献   

10.
We report the application of a solid lanthanum–ceria–zinc catalyst in the catalytic regeneration of diesel particulate filters(DPF) in diesel engines.We synthesized a CeO_2–ZnO–La_2O_3(Ce–Zn–La) mixed oxide by a lactic acid-mediated sol–gel method,which efficiently coated cordierite substrates for soot capture and combustion.We studied the effects of La loading on the physicochemical and catalytic properties of Ce–Zn mixed oxide during lowtemperature soot combustion processes.We characterized the synthesized catalysts by X-ray diffraction(XRD),Fourier-transform infrared spectroscopy(FTIR),N2 adsorption,Raman spectroscopy,oxygen storage capacity(OSC),and scanning and transmission electron microscopy(SEM and TEM).Thermogravimetric and differential thermal analysis(TGA/DTA)confirmed that the catalysts effectively reduced the soot oxidation temperature.The ternary Ce–Zn–La mixed oxide catalyst with Ce/Zn/La atomic ratio of 2:1:0.5 had the highest catalytic activity and promoted soot oxidation at temperatures below 390°C.This indicated that the large number of oxygen vacancies in the catalyst structure generated oxygen species at low temperatures.Raman spectroscopy measurements revealed the presence of oxygen vacancies and lattice defects in Ce–Zn–La samples,which were key parameters concerning the stability and redox properties of the prepared catalysts.  相似文献   

11.
Three groups of cobalt mixed oxide catalysts(Mg/Zn-Co, Mg/Zn-Ce-C, K/Na-Mg/Zn-Ce-Co)were prepared by sol-gel or impregnation methods. The synergistic effects of transition metal, rare earth metal and alkali metal on cobalt mixed catalysts for nitrous oxide(N2O)decomposing to N2 and O2were investigated. The experimental results revealed that the catalytic activity for N2 O decomposition was promoted as Co2+was replaced partially by Zn2+/Mg2+, moreover, the characterization analysis by XRD and XPS showed that Zn2+/Mg2+replaced Co2+successfully into the spinel structure of Co3O4 and promoted significantly the catalytic activity. Especially, the addition of CeO2 and K2O/Na2O decreased the binding energy and resulted in an increase in the density of the electron cloud around Co and an improvement of the catalytic activity. Of the investigated cobalt mixed catalysts, the best catalytic activity was shown by 2% K-Zn0.5-Ce0.05-Co catalyst.  相似文献   

12.
In the study,the catalyst precursors of Ce-modified γ-MnO_2 were washed with deionized water until the pH value of the supernatant was 1,2,4 and 7,and the obtained catalysts were named accordingly.Under space velocity of 300,000 hr~(-1),the ozone conversion over the pH=7 catalyst under dry conditions and relative humidity of 65% over a period of 6 hr was 100% and 96%,respectively.However,the ozone decomposition activity of the pH=2 and 4 catalysts distinctly decreased under relative humidity of 65% compared to that under dry conditions.Detailed physical and chemical characterization demonstrated that the residual sulfate ions on the pH=2 and 4 catalysts decreased their hydrophobicity and then restrained humid ozone decomposition activity.The pH=2 and 4 catalysts had inferior resistance to high space velocity under dry conditions,because the residual sulfate ion on their surface reduced their adsorption capacity for ozone molecules and increased their apparent activation energies,which was proved by temperature programmed desorption of O_2 and kinetic experiments.Long-term activity testing,X-ray photoelectron spectroscopy and density functional theory calculations revealed that there were two kinds of oxygen vacancies on the manganese dioxide catalysts,one of which more easily adsorbed oxygen species and then became deactivated.This study revealed the detrimental effect of surface acid ions on the activity of catalysts under humid and dry atmospheres,and provided guidance for the development of highly efficient catalysts for ozone decomposition.  相似文献   

13.
Characteristics of toluene decomposition and formation of nitrogen oxide(NOx) by-products were investigated in a dielectric barrier discharge(DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide(Mn Ox), iron oxide(Fe Ox), cobalt oxide(Co Ox) and copper oxide(Cu O), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density(SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the Cu O catalyst showed the best performance in NOx suppression. The Mn Ox catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.  相似文献   

14.
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   

15.
LnMnO3+σ (Ln = La, Pr, Nd, Sm, Eu, Gd or Dy) perovskites synthesized by sol-gel method were employed for gaseous elemental mercury (Hg0) removal from coal-fired flue gas. Characterization results revealed the structure of the perovskites presented a phase transition process from rhombohedral system to O- and O'-orthorhombic structure with the change of A-site rare earth elements. The perovskites showed satisfactory Hg0 removal capacity in a narrow temperature range of 100–150°C. NdMnO3+σ with an O-O’ orthorhombic structure presented the best Hg0 removal performance, which markedly depends on four factors: crystal structure, oxygen vacancy density, Mn4+/Mn3+ ratio and surface element segregation. The Hg0 removal mechanism was illustrated based on the mercury temperature programmed desorption experiment and X-ray photoelectron spectroscopy characterization. Both chemisorption and catalytic oxidation played a role in the Hg0 removal process. Chemisorption dominated the Hg0 removal, due to the slow catalytic oxidation rate at low temperature. This work preliminarily established the relation between the structure of rare earth manganese perovskite and Hg0 removal performance.  相似文献   

16.
Binary oxide systems(Cu Cr2O4, Cu Co2O4), deposited onto cordierite monoliths of honeycomb structure with a second support(finely dispersed Al2O3), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine’s gas exhausts(O2, NOx, H2 O, CO2) and O3 as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO2. Oxidants used can be arranged with reference to decreasing their activity in a following series: O3 NO2> H2 O > NO > O2> CO2. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O3 occurs intensively(in the presence of copper chromite based catalyst) even at closing to ambient temperatures.Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.  相似文献   

17.
Pt supported on mesoporous silica SBA-15 was investigated as a catalyst for low temperature selective catalytic reduction(SCR) of NO by C 3 H 6 in the presence of excess oxygen.The prepared catalysts were characterized by means of XRD,BET surface area,TEM,NO-TPD,NO/C 3 H 6-TPO,NH 3-TPD,XPS and 27 Al MAS NMR.The effects of Pt loading amount,O 2 /C 3 H 6 concentration,and incorporation of Al into SBA-15 have been studied.It was found that the removal efficiency increased significantly after Pt loading,but an optimal loading amount was observed.In particular,under an atmosphere of 150 ppm NO,150 ppm C 3 H 6,and 18 vol.% O 2,0.5% Pt/SBA-15 showed remarkably high catalytic performance giving 80.1% NOx reduction and 87.04% C 3 H 6 conversion simultaneously at 140°C.The enhanced SCR activity of Pt/SBA-15 is associated with its outstanding oxidation activities of NO to NO 2 and C 3 H 6 to CO 2 in low temperature range.The research results also suggested that higher concentration of O 2 and higher concentration of C 3 H 6 favored NO removal.The incorporation of Al into SBA-15 improved catalytic performance,which could be ascribed to the enhancement of catalyst surface acidity caused by tetrahedrally coordinated AlO 4.Moreover,the catalysts could be easily reused and possessed good stability.  相似文献   

18.
Mn-Ni oxides with different compositions were prepared using standard co-precipitation(CP) and urea hydrolysis-precipitation(UH) methods and optimized for the selective catalytic reduction of nitrogen oxides(NO_x) by NH_3 at low temperature.Mn((2))Ni_((1))O_x-CP and Mn_((2))Ni_((1))O_x-UH(with Mn:Ni molar ratio of 2:1) catalysts showed almost identical selective catalytic reduction(SCR) catalytic activity,with about 96% NO_x conversion at 750 C and-99%in the temperature range from 100 to 250℃.X-ray diffraction(XRD) results showed that Mn_((2))Ni_((1))O_x-CP and Mn_((2))Ni_((1))O_x-UH catalysts crystallized in the form of Mn_2NiO_4 and MnO_2-Mn_2NiO_4 spinel,respectively.The latter gave relatively good selectivity to N_2,which might be due to the presence of the MnO_2 phase and high metal-O binding energy,resulting in low dehydrogenation ability.According to the results of various characterization methods,it was found that a high density of surface chemisorbed oxygen species and efficient electron transfer between Mn and Ni in the crystal structure of Mn_2NiO_4 spinel played important roles in the high-efficiency SCR activity of these catalysts.Mn_((2))Ni_((1))O_x catalysts presented good resistance to H_2O or/and SO_2 with stable activity,which benefited from the Mn_2NiO_4 spinel structure and Eley-Rideal mechanism,with only slight effects from SO_2.  相似文献   

19.
As one of the most important water pollutants, ammonia nitrogen emissions have increased year by year, which has attracted people's attention. Catalytic ozonation technology, which involves production of ·OH radical with strong oxidation ability, is widely used in the treatment of organic-containing wastewater. In this work, MgO-Co_3O_4 composite metal oxide catalysts prepared with different fabrication conditions have been systematically evaluated and compared in the catalytic ozonation of ammonia(50 mg/L) in water. In terms of high catalytic activity in ammonia decomposition and high selectivity for gaseous nitrogen, the catalyst with MgO-Co_3O_4 molar ratio 8:2, calcined at 500°C for 3 hr, was the best one among the catalysts we tested, with an ammonia nitrogen removal rate of 85.2% and gaseous nitrogen selectivity of44.8%. In addition, the reaction mechanism of ozonation oxidative decomposition of ammonia nitrogen in water with the metal oxide catalysts was discussed. Moreover, the effect of coexisting anions on the degradation of ammonia was studied, finding that SO_2-4 and HCO-3 could inhibit the catalytic activity while CO_2-3 and Br-could promote it. The presence of coexisting cations had very little effect on the catalytic ozonation of ammonia nitrogen. After five successive reuses, the catalyst remained stable in the catalytic ozonation of ammonia.  相似文献   

20.
Fe203 particle catalysts were experimentally studied in the low temperature selective catalytic reduction (SCR) of NO with NH3. The effects of reaction temperature, oxygen concentration, [NH3]/[NO] molar ratio and residence time on SCR activity were studied. It was found that Fe203 catalysts had high activity for the SCR of NO with NH3 in a broad temperature range of 150-270℃, and more than 95% NO conversion was obtained at 180℃ when the molar ratio [NH3]/[NO] = 1, the residence time was 0.48 seconds and 02 volume fraction was 3%. In addition, the effect of SO2 on SCR catalytic activity was also investigated at the temperature of 180℃. The results showed that deactivation of the Fe2O3 particles occurred due to the presence of SO2 and the NO conversion decreased from 99.2% to 58% in 240 min, since SO2 gradually decreased the catalytic activity of the catalysts. In addition, X-ray diffraction, Thermogravimetric analysis and Fourier transform infrared spectroscopy were used to characterize the fresh and deactivated Fe2O3 catalysts. The results showed that the deactivation caused by SO2 was due to the formation of metal sulfates and ammonium sulfates on the catalyst surface during the de-NO reaction, which could cause pore plugging and result in suppression of the catalytic activity.  相似文献   

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