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1.
采用柠檬酸络合法制备了Mn/(Mn+Ce)原子比为0.4的MnO_x-CeO_2复合氧化物,使其分别在有和无脉冲介质阻挡放电条件下,多次催化氧化碳烟.采用XRD、BET、Raman和XPS对新制备未反应过的和各次反应后的MnO_x-CeO_2进行表征.结果发现,在初次反应中,脉冲介质阻挡放电对反应具有强化作用,使MnO_x-CeO_2具备更好的活性.在放电和无放电2种条件下,催化剂第2次反应的活性均较第1次有所降低,且放电条件下降幅更大,而在第3次反应时催化剂活性在两种条件下均保持稳定状态.以上现象原因为,初次反应,两种条件下高温使MnO_x-CeO_2中Mn-Ce-O固溶体发生相分离,部分Mn析出生成了Mn_3O_4;未引入放电时催化剂表面发生不可逆还原的Mn~(4+)量更少,且拥有更多Ce~(3+)并产生了本征氧空位及更多的表面氧;放电的引入,加剧了初次反应时MnO_x-CeO_2表面Mn~(4+)向Mn~(3+)和Mn~(2+)的转化,使其具备更高的活性,但也抑制了Mn~(4+)的恢复,降低了催化剂的活性.在随后的反应中,有无放电催化剂均保持了稳定.脉冲介质阻挡放电对MnO_x-CeO_2反应的关键因素Mn~(4+)、本征氧空位和表面氧产生了重要影响,这种影响在初次反应时并不可逆,进而减弱了放电对反应的强化作用,该现象不可忽视,值得进一步研究.  相似文献   

2.
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 (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), 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 CuO catalyst showed the best performance in NOx suppression. The MnOx 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   

3.
In this paper, KMnO4 was used to pre-treat Co3Fe-layered double hydroxides (LDH) precursor to prepare MnO2 decorated Co3Fe1Ox catalyst. The toluene oxidation performance of the catalyst was investigated systematically. The optimized 0.1MnCF-LDO catalyst exhibited the best catalytic performance, and the temperatures of 50% and 90% toluene conversion (T50 and T90) were 218 and 243°C, respectively. The apparent activation energy (Ea) was 31.6 kJ/mol. The characterization results showed that the pre-redox reaction by KMnO4 could increase the specific surface area, Co3+ species amount and oxygen defect concentration of the catalyst, which are the main reason of the improved toluene catalytic activity. Besides, this method was also applied to enhance toluene oxidation of iron mesh based monolithic catalyst. The 0.1MnCF-LDO/Iron mesh (IM) catalyst showed a 90% toluene conversion at around 316°C which was much lower than that of without MnO2 addition (359°C). In addition, the water resistant of all the catalysts was studied as well, all the samples showed relatively good water resistance. The toluene conversion still remained to be over >80% even in the presence of 10 vol.% water vapor.  相似文献   

4.
催化燃烧是最有效的炭黑消除手段之一,催化剂是其中的核心,其活性的提高对催化效果优化及成本控制有重要影响.然而目前报道的大量炭黑燃烧催化剂活性测试是基于不同实验环境进行的,其结果之间缺乏比较意义.为了筛选活性优异的催化剂,并总结出催化剂活性与物理化学性质之间的关系,同时为催化过程中氧物种原位定量观测建立基础,根据易得、环...  相似文献   

5.
Energy-saving and efficient monolithic catalysts are hotspots of catalytic purification of industrial gaseous pollutants. Here, we have developed an electrothermal catalytic mode, in which the ignition temperature required for the reaction is provided by Joule heat generated when the current flows through the catalyst. In this paper, Mn/NiAl/NF, Mn/NiFe/NF and Mn/NF metal-based monolithic catalysts were prepared using nickel foam (NF) as the carrier for thermal and electrothermal catalysis of n-heptane. The results indicated that Mn-based monolithic catalysts exhibit high activity in thermal and electrothermal catalysis. Mn/NiFe/NF achieve conversion of n-heptane more than 99% in electrothermal catalysis under a direct-current (DC) power of 6 W, and energy-saving is 54% compared with thermal catalysis. In addition, the results indicated that the introduction of NiAl (or NiFe) greatly enhanced the catalytic activity of Mn/NF, which attributed to the higher specific surface area, Mn3+/Mn4+, Ni3+/Ni2+, adsorbed oxygen species (Oads)/lattice oxygen species (Olatt), redox performance of the catalyst. Electrothermal catalytic activity was significantly higher than thermal catalytic activity before complete conversion, which may be related to electronic effects. Besides, Mn/NiFe/NF has good cyclic and long-term stability in electrothermal catalysis. This paper provided a theoretical basis for applying electrothermal catalysis in the field of VOCs elimination.  相似文献   

6.
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   

7.
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, H2-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 CeO2 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   

8.
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   

9.
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 (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), 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,NOxwas suppressedwith 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 CuO catalyst showed the best performance in NOx suppression. The MnOx 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   

10.
A series of MnM/palygorskite (PG) (M = La, W, Mo, Sb, Mg) catalysts was prepared by the wetness co-impregnation method for low-temperature selective catalytic reduction (SCR) of NO with NH3. Conversion efficiency followed the order Sb > Mo > La > W > Mg. A combination of various physico-chemical techniques was used to investigate the influence of Sb-modified Mn/PG catalysts. MnSb0.156/PG catalyst showed highest NO conversion at low temperatures in the presence of SO2 which reveals that addition of Sb oxides effectively enhances the SCR activity of catalysts. A SO2 step-wise study showed that MnSb0.156/PG catalyst displays higher durable resistance to SO2 than Mn/PG catalyst, where the sulfating of active phase is greatly inhibited after Sb doping. Scanning electron microscopy and X-ray diffraction results showed that Sb loading enhances the dispersion of Mn oxides on the carrier surface. According to the results of characterization analyses, it is suggested that the main reason for the deactivation of Mn/PG is the formation of manganese sulfates which cause the permanent deactivation of Mn-based catalysts. For Sb-doped Mn/PG catalyst, SOx ad-species formed were mainly combined with SbOx rather than MnOx. This preferential interaction between SbOx and SO2 effectively shields the MnOx as active species from being sulfated by SO2 resulting in the improvement of SO2 tolerance on Sb-added catalyst. Multiple information support that, owing to the addition of Sb, original formed MnOx crystallite has been completely transformed into highly dispersed amorphous phase accounting for higher SCR activity.  相似文献   

11.
以磷酸硅铝分子筛SAPO-5、SAPO~(-1)1和SAPO-34为载体,采用乙醇分散法制备了用于低温氨选择性还原(NH_3-SCR)NO_x的分子筛负载MnO_x催化剂.活性测试结果显示,3种分子筛催化剂均展现出优良的NH_3-SCR活性,但三者在低温区间的SCR活性存在较明显差异,其SCR活性顺序如下:MnO_x/SAPO-34MnO_x/SAPO-5MnO_x/SAPO~(-1)1.借助XRD、N2吸附-脱附、XPS、H2-TPR、NH_3-TPD、NH_3FT-IR等技术对催化剂的表面活性物种及表面酸性等进行表征分析,结果表明,MnO_x主要以无定型状态分散于载体上,负载后载体的比表面积和孔体积均有所下降.XPS和H2-TPR分析证实,不同分子筛载体上MnO_x的表面浓度与氧化态明显不同.NH_3-TPD和NH_3FT-IR分析揭示了催化剂表面均存在Bronsted酸位和Lewis酸位,其中,Lewis酸性位对低温SCR反应起着关键作用.研究表明,催化剂的催化性能会因载体不同而存在差异,高Mn4+表面浓度和丰富的Lewis酸性位对催化剂在低温区间实现优良的催化活性尤为重要.  相似文献   

12.
陈长伟  于艳科  陈进生  何炽 《环境科学》2013,34(12):4724-4733
采用共沉淀法和等体积浸渍法制备了CuCeO x复合催化剂,对材料的物化性质进行了XRD、低温N2吸脱附、H2-TPR和O2-TPD表征.以石化行业典型VOCs(苯、甲苯和正己烷)为探针污染物,研究了污染物组成与浓度、反应空速、O2浓度、H2O浓度和催化剂种类对其氧化行为的影响,并对反应动力学参数进行了模型拟合.共沉淀得到的催化剂具有均匀的活性相、好的低温可还原性能和较多的活性表面氧物种.甲苯氧化率随着污染物浓度升高而降低,高转化率下苯浓度与其氧化率无相关性,正己烷的氧化率与入口浓度呈正比.苯能够显著抑制甲苯的氧化,而甲苯加入有利于苯的氧化.正己烷对苯氧化的影响较小,但能够促进甲苯的转化,苯系物对正己烷氧化有明显的抑制作用.低空速和高氧浓度都有利于污染物的氧化,氧浓度的变化对正己烷和苯的氧化影响较小.水汽对甲苯的氧化有明显的抑制作用,而对苯和正己烷氧化有明显的促进作用.共沉淀催化剂具有更好的甲苯和苯氧化性能,而无水条件下浸渍催化剂具有更好的正己烷氧化性能.拟一级动力学模型能够很好地模拟不同条件下污染物的氧化行为.  相似文献   

13.
采用浸渍法制备了Pt/CeO_2和Pt/Al2O_3催化剂,并通过XRD、BET、ICP-OES、H2-TPR、XPS等手段表征其物理化学性质.结果发现,Pt/CeO_2和Pt/Al2O_3催化剂上Pt负载量约为0.6%,Al2O_3载体上Pt颗粒尺寸更小,Pt/CeO_2的可还原性更强.甲苯催化氧化活性评价结果表明,Pt/CeO_2催化剂表现出更好的催化活性,T50=170℃,T90=190℃.通过UV-Raman、甲苯TPD、GC/MS、In-situ FTIR等手段进一步研究发现,Pt/CeO_2活化甲苯及反应供氧的机制与Pt/Al2O_3存在区别,其活性更好是因为:(1)负载在CeO_2表面存在高电子密度的Pt原子,具有更强的活化甲苯能力,可以直接使苯基和甲基间的C—C链发生断裂;(2)Pt的负载促进了CeO_2氧空位形成,进一步提高了CeO_2的储氧性能,加速氧循环.除了Pt解离气相氧之外,CeO_2还可以提供活性氧物种参与催化氧化甲苯的反应,进一步提高甲苯催化氧化效率.  相似文献   

14.
Three perovskite-type catalysts prepared by citric acid method are applied to remove phenol from gas streams with the total flow rate of 300 mL/min, corresponding to a GHSV of10,000/hr. LaMnO_3 catalyst is first prepared and further partially substituted with Sr and Cu to prepare La_(0.8)Sr_(0.2)MnO_3 and La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3, and catalytic activities and fundamental characteristics of these three catalysts are compared. The results show that phenol removal efficiency achieved with La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3 reaches 100% with the operating temperature of 200°C and the rate of mineralization at 300°C is up to 100%, while the phenol removal efficiencies achieved with La_(0.8)Sr_(0.2)MnO_3 and LaMnO_3 are up to 100% with the operating temperature of 300°C and 400°C, respectively. X-ray photoelectron spectroscopy(XPS) analysis shows that the addition of Sr and Cu increases the lattice oxygen of La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3, and further increases mobility or availability of lattice oxygen. The results indicate that La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3 has the best activity for phenol removal among three catalysts prepared and the catalytic activity of phenol oxidation is enhanced by the introduction of Sr and Cu into LaMnO_3. Apparent activation energy of 48 k J/mol is calculated by Mars–Van Krevelen Model for phenol oxidation with La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3 as catalyst.  相似文献   

15.
O3 decomposition catalysts with excellent performance still need to be developed. In this study, Ag-modified manganese oxides (AgMnOx) were synthesized by a simple co-precipitation method. The effect of calcination temperature on the activity of MnOx and AgMnOx catalysts was investigated. The effect of the amount of Ag addition on the activity and structure of the catalysts was further studied by activity testing and characterization by a variety of techniques. The activity of 8%AgMnOx for ozone decomposition was significantly enhanced due to the formation of the Ag1.8Mn8O16 structure, indicating that this phase has excellent performance for ozone decomposition. The weight content of Ag1.8Mn8O16 in the 8%AgMnOx catalyst was only about 33.76%, which further indicates the excellent performance of the Ag1.8Mn8O16 phase for ozone decomposition. The H2 temperature programmed reduction (H2-TPR) results indicated that the reducibility of the catalysts increased due to the formation of the Ag1.8Mn8O16 structure. This study provides guidance for a follow-up study on Ag-modified manganese oxide catalysts for ozone decomposition.  相似文献   

16.
考察了在常温常压条件下,等离子体分别协同SiO2、Al2O3、NiO/Al2O3降解甲苯的性能,并从材料的介电常数、对甲苯的吸附性及臭氧分解能力等角度分析了不同活性表现的原因,同时,采用原位红外技术研究了甲苯降解过程中催化剂表面吸附物种的变化.结果表明,当甲苯浓度为100 ppm,气体流量为100 mL·min-1时,一定范围内,甲苯降解率随着能量密度、介电常数、吸附性及臭氧分解能力的提高而提高.甲苯在催化剂表面的吸附对其降解途径有十分重要的影响:在放电区域中加入SiO2,甲苯仍然在气相中完成降解;而存在Al2O3 及NiO/Al2O3时,甲苯氧化成苯甲酸的过程主要发生在催化剂表面,是甲苯催化降解的关键步骤,苯甲酸在活性位点的积累将降低催化剂的反应活性.  相似文献   

17.
Me/SAPO-34 (Me = Mn, Ni, Co) series of catalysts were prepared by a wetness impregnation method and investigated for the selective catalytic reduction of nitrogen oxides with ammonia (NH3-SCR). Among them, Mn/SAPO-34 catalyst was found as the most promising candidate based on its superior low-temperature activity. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy images (TEM), nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and desorption (TPR and TPD), and diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) of NH3/NOx adsorption. Mn/SAPO-34 is obviously different from Ni/SAPO-34 and Co/SAPO-34 in the active species state and distribution. Surface MnOx species which play an essential role in NO oxidation and NO2 adsorption, act as better active sites than nickel and cobalt mostly in the form of the aluminates and silicates.  相似文献   

18.
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   

19.
利用水热法制备了3种不同形貌(纳米棒、纳米颗粒、纳米立方体)的CeO_2催化剂,并通过比表面积测试(BET)、扫描电子显微镜(SEM)、拉曼光谱分析(Raman)、O_2程序升温脱附(O_2-TPD)手段表征其物理化学性质,结果发现,CeO_2纳米棒的表面氧空位和氧物种最多.等离子体与催化协同降解甲醇性能评价实验结果显示,CeO_2纳米棒展现出最好的催化性能.进一步设计实验(甲醇-TPD、不同气氛常温催化、催化剂内后置比较、O_3催化氧化)推测在等离子体场内CeO_2表面活性氧物种来源及其作用.结果表明:①在等离子体场内参与CeO_2表面催化反应的活性氧物种有两个来源,一是催化剂本身存在的表面氧物种,二是等离子体区域产生的短寿命物种及长寿命物种(主要是O_3),其中,O_3分解产生的活性氧物种是提高催化性能的主要因素.②不同形貌CeO_2由于表面氧空位含量不同,导致O_3在催化剂上分解产生的活性氧物种的量不同,最终影响等离子体催化性能.  相似文献   

20.
为了有效去除高含盐废水中的有机染料污染物,利用有序介孔硅材料作为模板剂,通过硬模板法制备了新型锰系氧化物(MnOx)介孔材料作为类Fenton催化剂.催化剂的结构表征结果表明,模板剂在锰前驱物溶液中浸渍和后续煅烧成型过程决定了氧化锰介孔材料的结构.浸渍-煅烧成型重复次数越多,MnOx介孔材料中孔道结构的有序度和氧化锰的结晶度越好.浸渍-煅烧成型次数过少,MnOx介孔材料中孔道呈现无序状态,比表面积较大但氧化锰结晶度不足;次数过多则形成更为致密的小孔径的孔道结构,从而使MnOx介孔材料的比表面积减小.由于对罗丹明B(RhB)良好的选择性吸附能力和较多的Mn3+/Mn4+对,具有有序规则孔道的氧化锰介孔材料具有优异的类Fenton催化活性,对高含盐废水中RhB的5 h降解去除率最高可达90%左右.  相似文献   

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