Reduction of NO by CO using Pd–CeTb and Pd–CeZr catalysts supported on SiO_2 and La_2O_3–Al_2O_3

The catalytic activity of Pd catalysts supported on Ce0.73Tb0.27 O x/Si O2, Ce0.6Zr0.4O x/Si O2,Ce0.73Tb0.27 O x/La2O3–Al2O3and Ce0.6Zr0.4O x/La2O3–Al2O3was studied using the reduction of NO by CO. The catalysts were characterized by X-ray fluorescence, surface area, X-ray diffraction, temperature-programmed reduction, CO chemisorption and oxygen storage capacity. Temperature-programmed reduction results indicated that Tb or Zr incorporation improves the reducibility and oxygen storage capacity. CO chemisorption data suggested the presence of large Pd O particles due to the low CO/Pd ratio. No significant differences were obtained in light off temperatures(T Light off) for all Pd catalysts and the most active was1.5%Pd/Ce0.6Zr0.4O x/Si O2.     

VxMn(4 − x)Mo3Ce3/Ti catalysts for selective catalytic reduction of NO by NH3

A series of vanadium based catalysts(VxMn(4-x)Mo3Ce3/Ti) with different vanadium(x wt.%) and manganese((4-x) wt.%) contents have been prepared by the wet impregnation method and investigated for selective catalytic reduction(SCR) of NO_x by NH_3 in the presence of 8 vol.% H_2O and 500 ppm V SO_2.The physicochemical characteristics of the catalysts were thoroughly characterized.The SCR of NO_x by NH_3(NH_3-SCR) activity, especially the low-temperature activity, significantly increased with increasing V_2O_5 content in the catalyst until the V_2O_5 content reached 1.5 wt.%, which corresponds well with the redox properties of the catalyst.All of the metal oxides were well dispersed and strongly interacted with each other on the catalyst surface.V mainly exists in the V~(5+)state in the catalysts.The strong synergistic effect between the vanadium and cerium species led to formation of more Ce~(3+)species, and that between the vanadium and manganese species contributed to formation of more manganese species with low valences.All of the catalysts exhibited strong acidity, while the redox properties determined the NH_3-SCR activity, especially the low-temperature activity.H_2O and SO_2 had severe inhibiting effects on the activity of V1.5Mn2.5Mo3Ce3/Ti.However, good H_2O and SO_2 resistance and high NO_x conversion by V1.5Mn2.5Mo3Ce3/Ti could be achieved in the presence of SO_2 and almost no decline was observed in a long-term test at 275℃ for 168 hr in the presence of SO_2 and H_2O, which can be attributed to the sulfate species formed on the catalyst surface.     

NH3-SCR denitration catalyst performance over vanadium-titanium with the addition of Ce and Sb

Selective catalytic reduction technology using NH3 as a reducing agent(NH3-SCR) is an effective control method to remove nitrogen oxides. TiO2-supported vanadium oxide catalysts with different levels of Ce and Sb modification were prepared by an impregnation method and were characterized by X-ray diffractometer(XRD), Brunauer–Emmett–Teller(BET), Transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FT-IR), UV–Vis diffuse reflectance spectroscopy(UV–Vis DRS), Raman and Hydrogen temperature-programmed reduction(H2-TPR). The catalytic activities of V5 CexS by/TiO2 catalysts for denitration were investigated in a fixed bed flow microreactor. The results showed that cerium, vanadium and antimony oxide as the active components were well dispersed on TiO2, and the catalysts exhibited a large number of d–d electronic transitions, which were helpful to strengthen SCR reactivity. The V5 CexS by/TiO2 catalysts exhibited a good low temperature NH3-SCR catalytic activity. In the temperature range of 210 to 400℃, the V5 CexS by/TiO2 catalysts gave NO conversion rates above 90%. For the best V5Ce35Sb2/TiO2 catalyst, at a reaction temperature of 210℃, the NO conversion rate had already reached 90%. The catalysts had different catalytic activity with different Ce loadings. With the increase of Ce loading, the NO conversion rate also increased.     

Effect of lanthanum loading on nanosized CeO2-ZnO solid catalysts supported on cordierite for diesel soot oxidation

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.     

Activity and hydrothermal stability of CeO2–ZrO2–WO3 for the selective catalytic reduction of NOx with NH3

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.     

Preparation of birnessite-supported Pt nanoparticles and their application in catalytic oxidation of formaldehyde

Flaky and nanospherical birnessite and birnessite-supported Pt catalysts were successfully prepared and characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and N₂ adsorption-desorption. Effects of the birnessite morphology and Pt reduction method on the catalytic activity for the complete oxidation of formaldehyde (HCHO) were investigated. It was found that flaky birnessite exhibited higher catalytic activity than nanospherical birnessite. The promoting effect of Pt on the birnessite catalyst indicated that the reduction method of the Pt precursor greatly influenced the catalytic performance. Flaky birnessite-supported Pt nanoparticles reduced by KBH₄ showed the highest catalytic activity and could completely oxidize HCHO into CO₂ and H₂O at 50℃, whereas the sample reduced using H₂-plasma showed lower activity for HCHO oxidation. The differences in catalytic activity of these materials were jointly attributed to the effects of pore structure, surface active sites exposed to HCHO and the dispersion of Pt nanoparticles.     

Enhanced catalytic complete oxidation of 1,2-dichloroethane over mesoporous transition metal-doped γ-Al_2O_3

High-surface-area mesoprous powders of γ-Al2O3 doped with Cu2+, Cr3+, and V3+ions were prepared via a modified sol–gel method and were investigated as catalysts for the oxidation of chlorinated organic compounds. The composites retained high surface areas and pore volumes comparable with those of undoped γ-Al2O3 and the presence of the transition metal ions enhanced their surface acidic properties. The catalytic activity of the prepared catalysts in the oxidation of 1,2-dichloroethane(DCE) was studied in the temperature range of 250–400°C. The catalytic activity and product selectivity were strongly dependent on the presence and the type of dopant ion. While Cu2+- and Cr3+-containing catalysts showed100% conversion at 300°C and 350°C, V3+-containing catalyst showed considerably lower conversion. Furthermore, while the major products of the reactions over γ-alumina were vinyl chloride(C2H3Cl) and hydrogen chloride(HCl) at all temperatures, Cu- and Cr-doped catalysts showed significantly stronger capability for deep oxidation to CO2.     

Effect of Ce doping of TiO2 support on NH3-SCR activity over V2O5-WO3/CeO2-TiO2 catalyst

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.     

Mo-modified Pd/Al2O3 catalysts for benzene catalytic combustion

Mo-modified Pd/Al2O3catalysts were prepared by an impregnation method and tested for the catalytic combustion of benzene. The catalysts were characterized by N2 isothermal adsorption, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, temperatureprogrammed desorption of NH3（NH3-TPD）, H2temperature-programmed reduction（H2-TPR）, and high-angle annular dark-field scanning transmission electron microscopy（HAADF-STEM）. The results showed that the addition of Mo effectively improved the activity and stability of the Pd/Al2O3catalyst by increasing the dispersion of Pd active components, changing the partial oxidation state of palladium and increasing the oxygen species concentration on the surface of catalyst. In the case of the Pd-Mo/Al2O3catalyst,benzene conversion of 90% was obtained at temperatures as low as 190°C, which was 45°C lower than that for similar performance with the Pd/Al2O3catalyst. Moreover, the 1.0% Pd-5% Mo/Al2O3catalyst was more active than the 2.0% Pd/Al2O3catalyst. It was concluded that Pd and Mo have a synergistic effect in benzene catalytic combustion.     

Choice of precipitant and calcination temperature of precursor for synthesis of NiCo2O4 for control of CO–CH4 emissions from CNG vehicles

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.     

Size effect of Pt nanoparticles in acid-assisted soot oxidation in the presence of NO

Pt/Al₂O₃ catalysts with mean Pt particle size ranged from 2.7 to 7.1 nm were synthesized by chemical reduction method, and the sulfated counterparts were prepared by impregnation of sulfuric acid. The turnover frequency of platinum for soot oxidation under loose contact conditions in a feed flow containing NO and O₂ are positively correlated with the size of platinum. The sulfated Pt/Al₂O₃ exhibits higher catalytic activity for soot oxidation in the presence of NO despite their reduced ability for NO₂ production. Such a contradiction is more significant for those catalysts with smaller platinum particles. Herein, the catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), transmission electron microscopy (TEM), inductive coupled plasma (ICP) emission spectrometry, CO chemisorption, thermogravimetric analysis (TGA), NH₃ temperature-programmed desorption (NH₃-TPD), NO temperature-programmed oxidation (TPO) and NO_x temperature-programmed desorption (TPD). Possible effect of Pt particle size for the catalytic oxidation of soot in the presence of NO was presented based primarily on the promoted NO₂ transfer efficiency onto the soot pushed by the acidic catalysts.     

Cu-K型低温碳烟氧化催化剂的合成及表征

柴油机排放中碳烟的低温氧化是近年来研究的热点.通过原位合成法制备Cu2K/Al2O3和CuK／Al2O3两种碳烟氧化催化剂,并采用低温氮吸附/脱附实验、X射线衍射、X射线光电子能谱、程序升温氧化对其结构进行系统表征,并用U碳模拟柴油机碳烟,研究其催化活性,评测其对柴油机排气中碳烟颗粒的净化效果.研究表明,Cu2K/Al...     

Al2O3为载体的催化剂净化贫燃汽车尾气研究

在富氧条件下,考察了C₃H₆和C₂H₅OH在Ag/Al₂O₃、In/Al₂O₃、Sn/Al₂O₃、Co/Al₂O₃、Pt/Al₂O₃和Ag/Al₂O₃+Pt/Al₂O₃组合催化剂上选择性还原NO的性能.结果表明,Ag/Al₂O₃具有最高的NO还原活性.在负载型过渡金属氧化物催化剂上,会生成显著量的CO,其HC和CO氧化转化温度也远远高于Pt/Al₂O₃催化剂.串联组合Ag/Al₂O₃+Pt/Al₂O₃催化剂可显著拓宽活性温度范围,促进HC和CO氧化,降低N₂O和CH₃CHO生成量.     

A novel four-way combining catalysts for simultaneous removal of exhaust pollutants from diesel engine

A novel four-way combining catalysts containing double layers was applied to simultaneously remove four kinds of exhaust pollutants(NOx,CO,HC and PM) emitted from diesel engine.The four-way catalysts were characterized using scanning electron microscope(SEM) and Ultraviolet visible diffuse reflectance spectroscopy(UV-Vis DRS).Their catalytic performances were evaluated by temperature-programmed reaction technology.The double layer catalysts could effectively remove the four main pollutants.The highest catalytic activity was given by the two-layered catalysts of La0.6K0.4CoO3/Al2O3 and W/HZSM-5.Under the simulated exhaust gases conditions,the peak temperature of the soot combustion was 421°C,the maximal conversion of NO to N2 was 74%,the temperature of the HC total conversion was 357°C,and the maximum conversion ratio of CO was 99%.     

纳米CeO2催化氧化甲苯的形貌效应研究

采用水热法合成CeO2纳米棒、纳米颗粒和纳米立方体,利用XRD、BET-N2、TEM/HRTEM、Raman、O2-TPD和H2-TPR等表征手段进行表征,并利用连续流固定床反应法研究各催化剂对甲苯的催化氧化性能.结果表明,CeO2纳米棒因具有高比表面积和细颗粒尺寸,且表面主要暴露高活性的{100}/{110}晶面,拥有更多的氧空位和高活性氧物种,因此,催化活性最高,CeO2纳米颗粒次之,立方体最低.原位红外甲苯催化氧化机理分析进一步表明,CeO2纳米颗粒和纳米立方体上生成的羧酸盐物质难以进一步深度氧化,而纳米棒能在贫氧和低温条件下诱导甲苯的完全氧化和产物脱附,使甲苯得以快速降解.     

Low-temperature VOCs oxidation performance of Pt/zeolites catalysts with hierarchical pore structure

Different zeolites supported Pt catalysts with micro-mesoporous structure were prepared by organic base tetrapropylammonium hydroxide (TPAOH) treatment and their catalytic oxidation activity for various volatile organic compounds (VOCs) were evaluated. The results reveal that the synergistic effect between Pt nanoparticles and surface acid sites plays an important role in VOCs low-temperature removal. The small size and high dispersion of Pt nanoparticles on the surface of the zeolites would promote the catalytic oxidation of aromatics and alkanes over the Pt/zeolite catalysts, while strong acidity and abundant acid sites of catalysts are in favour of the oxidation of the VOCs containing N and O heteroatoms. In addition, it was found that Pt/ZSM-5 catalyst exhibits the highest oxidation activity for various VOCs low-temperature removal amongst all the catalysts due to the balance of both Pt dispersion and abundant acid sites in the catalyst. This comprehensive consideration should be very helpful when designing and preparing novel catalysts for the low-temperature removal of VOCs.     

OMS-2负载Pt催化剂的制备及其催化氧化性能研究

采用前掺杂法、沉积-沉淀法和浸渍法制备了氧化锰八面体分子筛(OMS-2)负载Pt催化剂(Pt/OMS-2),对所制催化剂进行了结构和织构表征。并研究了不同制备方法和沉积-沉淀法中不同制备(Pt负载量和溶液的pH值)对Pt/OMS-2催化氧化CO性能的影响。结果表明,沉积-沉淀法制备的Pt/OMS-2-DP催化剂活性最好(T100=100℃)。这与Pt/OMS-2-DP催化剂中Pt颗粒大小及OMS-2载体与Pt之间存在强相互作用有关。Pt负载量明显影响Pt/OMS-2-DP催化剂的催化活性,3Pt/OMS-2-DP催化剂(Pt=3.0 wt%)催化活性最高,这是由于适当Pt负载量,Pt颗粒较小,并与载体OMS-2的相互作用较强,能较好地活化OMS-2晶格氧。pH值对Pt/OMS-2-DP催化剂催化性能影响较大,这与OMS-2的等电点和Pt在不同溶液中存在不同Pt配位体形式有关。