A new approach of CeO_2 and La_2O_3 effects on the three-way catalysts containing low precious metals

A series of three-way catalysts (TWCs),containing a small amount of precious metals (PMs,including Pt,Pd and Rh) and a large amount of promoters CeO2 and La2O3,were prepared with different precursor compounds and various doped manners.Crystal phases,dispersion of cerium and lanthanum,textural structure and thermal stability of the catalysts were investigated by XRD,XPS and pore parameters determination.The catalytic performance was studied by the measurements of CO,C3H6 and NO conversions on dependence of temperature at stoichimetric number point (S=1.00),and from S=0.75 to 1.30 at 280℃ or 340℃ for fresh or aged samples,respectively.The correlation between the catalytic performance and the characteristics of fresh and aged samples were discussed.The results show that the sample,in which CeO2 and La2O3 are doped with mixed oxide powders,possesses poor dispersion and less thermal stability,and the conversions of NO and C3H6 are apparently lower than those of the samples aged at 850℃ The main reason is     

STUDIES OF MULTICOMPONENT COMPLEX OXIDE CATALYSTS FOR THE OXIDATIVE COUPLING OF METHANE Ⅳ CATALYSTS LiLa_(1-x)Mn_xO(2-λ)(X=0-1)

A series of catalysts LiLa_(1-x)Mn_xO_(2-λ)(x=0—1)were examined for the oxidative couplingof methane.A high C_2 yield of 22％ was obtained.The structures and physico-chemical properties ofsamples have been studied by means of XRD,IR,XPS and SEM.It was found that some complex ox-ides could be formed as X value changed,among them the K_2NiF_4-type oxide La_2Mn_(1-y)Li_yO_(4-λ)was theactive phase for methane coupling,while the Li_2MnO_3 and LiMn_2O_4 were the active phases for completeoxidation of re.ethane.The increase of catalytic activity for methane coupling was attributed to theincrease of the amount of active site,namely,oxygen vacancy in oxide La_2Mn_(1-y)Li_yO_(4-λ)     

Effects of Citric Acid Concentration and Activation Temperature on the Synthesis of Carbon Nanotubes

A series of Ni-La-Mg catalyst samples were prepared by citric acid complex method, and carbonnanotubes were synthesized by catalytic decomposition of CH4 on these catalysts. The effects of the citricacid concentration and the activation temperature on catalytic activity were investigated by CO adsorption,TEM and XRD techniques. The experimental results showed that the particle size of the catalysts preparedthrough gel auto-combustion varied with the concentration of citric acid. Therefore carbon nanotubes with different diameters were obtained correspondingly. The effect of activation temperature on the activity of catalyst was negligible from 500 to 700℃, but it became pronounced at lower or higher temperatures.     

Catalysis of the rare earth containing mixed oxides Ln_2CuO_4 in phenol hydroxylation

Mixed oxides Ln2CuO4±λ(Ln=La,Pr,Nd,Sm,Gd) with K2NiF4 structure were prepared Their crystal structures were studied with XRD and IR spectra.Meanwhile,the average valence of Cu ions and non stoichiometric oxygen (λ) were determined through chemical analyses.Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated.Results show that the catalysis of these mixed oxides has close relation with their structures and composition.Substitution of A site atom in Ln2CuO4λ has a great influence on then eatalysis in the phenol hydroxylation.     

CeO_2修饰介孔TiO_2和ZrO_2负载金催化剂催化废气中CO和挥发性有机化合物降解(英文)

Mesoporous oxides TiO2 and ZrO2, synthesized by surfactant templating via a neutral C13(EO)6–Zr(OC3H7)4 assembly pathway, and ceria-modified TiO2 and ZrO2, prepared by a deposi-tion–precipitation(DP) method, featuring high surface areas and uniform pore size distributions were used as supports for gold catalysts. The supported gold catalysts were assessed for the cata-lytic abatement of air pollutants, i.e., CO, CH3OH, and(CH3)2O. The gold was supported on the mes-oporous oxides by a DP method. The supports and catalysts were characterized by powder X-ray diffraction, high-resolution transmission electron microscopy, N2 adsorption–desorption analysis, and temperature-programmed reduction technique. A high degree of synergistic interaction be-tween ceria and mesoporous ZrO2 and TiO2 as well as a positive modification of the structural and catalytic properties by ceria was observed. The ceria additive interacts with the mesoporous oxides and induces a strong effect on the reducibility of the supports. The catalytic behavior of the catalysts was discussed to determine the role of the ceria modifying additive and possible interaction be-tween the gold nanoparticles and ceria-mesoporous oxide supports. The gold catalysts supported on ceria-modified mesoporous ZrO2 displayed superior catalytic activity(~100% conversion of CO at 10 ℃ and CH3OH at 60 ℃). The high catalytic activity can be attributed to the ability of the sup-port to assist oxygen vacancies formation. The studies indicate that the ceria-modified mesoporous oxide supports have potential as supports for gold-based catalysts.     

Catalytic combustion of ethyl acetate over CeMnO_x and CeMnZrO_x compounds synthesized by coprecipitation method

Ce0.6Mn0.4O2 catalysts with different sources of manganese and Ce0.6-xZrxMn0.4O2 mixed oxide catalysts were prepared by coprecipitation method and were characterized by N2 adsorption-desorption,TPR,XRD,and XPS techniques.The activities of the prepared catalysts for ethyl acetate combustion,and the effects of calcination temperature and space velocity on catalytic activity were investigated.The results showed that partial replacement of Mn(NO3)2 with KMnO4 as sources of manganese could improve activities of catalysts.Ce0.45Zr0.15Mn0.4O2 catalyst exhibited the best catalytic activity and high thermal stability,e.g.,T90 could be still below 210℃ even if space velocity was up to 20000h-1.     

用于NO和C_(10)H_(22)氧化及C_(10)H_(22)选择性还原NO的(La_(0.8)A_(0.2))MnO_3(A=Sr,K)钙钛矿催化剂(英文)

In this work, we studied the catalytic activity of LaMnO3 and(La0.8A0.2)MnO3(A = Sr, K) perovskite catalysts for oxidation of NO and C10H22 and selective reduction of NO by C10H22. The catalytic per‐formances of these perovskites were compared with that of a 2 wt% Pt/SiO2 catalyst. The La site substitution increased the catalytic properties for NO or C10H22 oxidation compared with the non‐substituted LaMnO3 sample. For the most efficient perovskite catalyst,(La0.8Sr0.2)MnO3, the results showed the presence of two temperature domains for NO adsorption:(1) a domain corre‐sponding to weakly adsorbed NO, desorbing at temperatures lower than 270 °C and(2) a second domain corresponding to NO adsorbed on the surface as nitrate species, desorbing at temperatures higher than 330 °C. For the Sr‐substituted perovskite, the maximum NO2 yield of 80% was observed in the intermediate temperature domain (around 285 °C). In the reactant mixture of NO/C10H22/O2/H2O/He,(La0.8Sr0.2)MnO3 perovskite showed better performance than the 2 wt% Pt/SiO2 catalyst: NO2 yields reaching 50% and 36% at 290 and 370 °C, respectively. This activity improvement was found to be because of atomic scale interactions between the A and B active sites, Sr2+ cation and Mn4+/Mn3+ redox couple. Thus,(La0.8Sr0.2)MnO3 perovskite could be an alternative free noble metal catalyst for exhaust gas after treatment.     

Effects of the partial replacement of La by M(M=Ce,Ca and Sr) in La_(2-x)M_xCuO_4 perovskites on catalysis of the water-gas shift reaction

The performance of La2-x M x CuO4 perovskites (where M=Ce,Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290℃ and 360℃.The catalysts were characterized by EDS,XRD,N2 adsorption-desorption,XPS and XANES.The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure),suggesting the incorporation of metals in the perovskite structure.The XPS and XANES results showed the presence of Cu2+ on the surface.The perovskites that exhibited the best catalytic performance were La 2 x Ce x CuO 4 perovskites,with CO conversions of 85% 90%.Moreover,these perovskites have higher surface areas and larger amounts of Cu on the surface.And Ce has a higher filled energy level than the other metals,increasing the energy of the valence band of Ce and providing more electrons for the reaction.Besides,the La1.80Ca0.20CuO4 perovskite showed a good catalytic performance.     

Effects of the partial replacement of La by M (M=Ce, Ca and Sr) in La2-xMxCuO4 perovskites on catalysis of the water-gas shift reaction

The performance of La2-xMxCuO4 perovskites (where M = Ce, Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290 ℃ and 360 ℃. The catalysts were characterized by EDS, XRD, N2 adsorption-desorption, XPS and XANES. The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure), suggesting the incorporation of metals in the perovskite structure. The XPS and XANES results showed the presence of Cu²⁺ on the surface. The perovskites that exhibited the best catalytic performance were La2-xCexCuO4 perovskites, with CO conversions of 85%-90%. Moreover, these perovskites have higher surface areas and larger amounts of Cu on the surface. And Ce has a higher filled energy level than the other metals, increasing the energy of the valence band of Ce and providing more electrons for the reaction. Besides, the La1.80Ca0.20CuO4 perovskite showed a good catalytic performance.     

Mixed activation and mixed inhibition of the oxidoreductase activity of Rhus vernicifera laccase by different Pd~(2 ) ion concentration

Kinetic experiments were performed to study the effects of Pd2 ion on the oxidation of 5,6-dibro-mo-2,3-dicyanohydroquinone catalyzed by Rhus vernicifera laccase under condition of pH 4.5 and 30 × 0. 1℃ . The results showed that the mixed activation could be observed when Pd2 ion was at low concentrations. The competitive and non-competitive activation constants were 9 × 10 and 2 × 10-6 mol/L, respectively. With the increase of Pd2 ion concentration, the activation was gradually converted into mixed inhibition, and the competitive and non-competitive inhibition constants were 6 × 10-6 and 32 × 10-6 mol/L, respectively.     

Realization approach of Pd-only three-way catalysts with high catalytic performance and thermal stability

Pd-only three-way catalyst(TWC),Pd supported on washcoating(the mixture of alumina and Ce-Zr solid solution)/cordierite,was prepared and its catalytic performance and the operation window(λ-value)at 450°C were evaluated with the simulated automotive exhaust feed gas.Surfactants such as Tween-80 and Span-20 were added in the process of preparing the catalyst in order to improve the thermal stability and catalytic performance of Pd-only TWC.The fresh and aged catalysts at 1000°C for4 h were characterized by low-temperature N2 adsorption,XRD,XPS,and H2-TPR techniques.The results show that the presence of surfactants in the synthesis slurry could influence the physicochemical properties of the final Pd-only TWC.The FTS catalyst prepared with the mixed surfactant of Tween-80 and Span-20 exhibited excellent three-way catalytic performance.After being aged at 1000°C for 4 h,the catalytic performances of Pd-only TWCs slightly decreased,but the FTS catalyst still demonstrated higher catalytic performance and better thermal stability compared with the Pd-only catalysts prepared with single surfactant or without any surfactant.And the FTS catalyst has a widerλvalue(operation window)than other catalysts,even after being aged at 1000°C.     

Insights into support effects on Ce-Zr-O mixed oxide-supported gold catalysts in CO oxidation

Au/Ce1xZrxO2 catalysts (x=0-0.8) were prepared by a deposition-precipitation method using Ce1xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning transmission electron microscopy and X-ray photoelectron spectroscopy (XPS). These Au catalysts possessed similar sizes and crystalline phases of Ce1xZrxO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au 0 especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303 333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Ce1xZrxO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Ce1xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.     

Catalytic properties of Cu/Co/Zn/Zr oxides prepared by various methods

The new Cu-Co based （Cu/Co/Zn/Zr） catalysts for higher-alcohol synthesis were prepared using coprecipitation method, plasma enhanced method and reverse coprecipitation method under ultrasound irradiation. The catalysts were investigated by the means of BET, SEM, XRD, H2-TPR and XPS. Catalytic properties of the catalysts prepared by various methods were examined using CO hydrogenation reaction. It was found that plasma enhanced method and reverse coprecipitation method under ultrasound irradiation were both effective in enhancing the catalytic properties of Cu/Co/Zn/Zr mixed oxides. The small particle size, high dispersion of active components, the improvement of specific surface area and surface contents of active phases could account for the excellent performance of the experimental Cu/Co/Zn/Zr catalysts.     

LaZnxFe1-xO3 钙钛矿型纳米催化剂的制备、表征及其甲苯燃烧性能

 Nanostructured LaFeO3 and substituted LaZnxFe1-xO3 (x = 0.01, 0.05, 0.1, 0.2, and 0.3) perovskites were synthesized by the sol-gel auto-combustion method and used in the catalytic combustion of toluene. Their structures and surface properties were investigated by X-ray diffraction, Fourier transmission infrared spectroscopy, BET surface area, and scanning electron microscopy. Characterization data revealed that the total insertion of zinc into LaFeO3 takes place when x ≤ 0.1. However, ZnO segregation occurs to some extent, especially at x > 0.1. The performance of these perovskites was evaluated by toluene combustion. The catalytic activity of the catalysts increased substantially with an increase in zinc substitution. These results can be attributed to the cooperative effect between LaZnxFe1-xO3 and the zinc oxide phases. The relative concentration of these phases determines their oxygen activation ability and reactivity.     

纯相和镍取代的Co_3O_4尖晶石催化剂用于N_2O直接分解(英文)

A series of NixCo1-xCo2O4(0 ≤ x ≤ 1) spinel catalysts were prepared by the co-precipitation method and used for direct N2O decomposition. The decomposition pathway of the parent precipitates was characterized by thermal analysis. The catalysts were calcined at 500 °C for 3 h and characterized by powder X-ray diffraction, Fourier transform infrared, and N2 adsorption-desorption. Nickel cobaltite spinel was formed in the solid state reaction between NiO and Co3O4. The N2O decomposition measurement revealed significant increase in the activity of Co3O4 spinel oxide catalyst with the partial replacement of Co2+ by Ni2+. The activity of this series of catalysts was controlled by the degree of Co2+ substitution by Ni2+, spinel crystallite size, catalyst surface area, presence of residual K+, and calcination temperature.     

Enhanced catalytic performance for direct synthesis of dimethyl ether from syngas over a La2O3 modified Cu-ZrO2/γ-Al2O3 hybrid catalyst

A series of hybrid catalysts were made by physically mixing Cu-ZrO 2 and γ-Al 2 O 3,for former it was modified with different loadings of La 2 O 3 prepared by co-precipitation method.The catalysts were characterized by BET,XRD,N 2 O-adsorption,EXAFS,H 2-TPR,NH 3-TPD techniques and evaluated in the synthesis of dimethyl ether from syngas.The results show that La 2 O 3 promoted catalysts displayed a significantly better catalytic performance compared with Cu-ZrO 2 /γ-Al 2 O 3 catalyst in CO conversion and DME selectivity,and the optimum catalytic activity was obtained when the content of La 2 O 3 was 12 wt%.The characterizations reveal that high copper dispersion,facile reducibility of copper particles and appropriate amount of acidic sites are responsible for the superior catalytic performance.     

Synthesis of Ni／Mg／Al Layered Double Hydroxides and Their Use as Catalyst Precursors in the Preparation of Carbon Nanotubes

Ni/Mg/Al layered double hydroxides(LDHs) with different n(Ni) : n(Mg) : n(Al) ratio values were prepared via a coprecipitation reaction. Then Ni/Mg/Al mixed oxides were obtained by calcination of these LDHs precursors. Carbon nanotubes were produced in the catalytic decomposition of propane over the Ni/Mg/Al mixed oxide catalysts. The quality of as-made nanotubes was investigated by SEM and TEM. The nanotubes were multiwall with a high length-diameter ratio and appeared to be flexible. The catalytic activities of these mixed oxides increased with increasing the Ni content. The Ni/Mg/Al mixed oxide with the highest Ni content [ n( Ni)/n( Mg)/n(Al) = 1/1/1 ] showed the highest activity and the carbon nanotubes grown on its surface had the best quality.     

Effects of Carrier on CuO／TiO2 and CuO／Ti0.5Zr0.5O2 Catalysts in the NO＋CO Reaction

Using TiO2 and Ti0.5Zr0.5O2 as carriers, the CuO/TiO2 and CuO/Ti0.5Zr0.5O2 catalysts were prepared by the impregnation method with Cu(NO3)2 as active component. The catalytic activities in NO CO reaction were investigated using a microreactor-GC system, and structure and reducibility of catalysts were characterized by means of physical adsorption, TPR, XRD, NO-TPD technologies. It was found that the activity of CuO/Ti0.5Zr0.5O2 catalyst was higher than that of CuO/TiO2, probably due to the large specific surface area of Ti0.5Zr0.5O2 that played an important role in NO CO reaction.     

Double perovskite oxides Sr_2Mg_(1-x)Fe_xMoO(6-δ) for catalytic oxidation of methane

The double perovskite oxides Sr2Mg1-xF exMoO6-δ were investigated as catalysts for the methane oxidation.The structural properties of catalysts were characterized in detail by X-ray diffraction,X-ray photoelectron spectroscopy and X-ray absorption spectroscopy.The catalytic property was strongly influenced by the Fe substitution.The relation between catalytic performance and the degree of Fe substitution was examined with regard to the structure and surface characteristics of the mixed oxides.The Fe-containing catalysts exhibited higher activity attributable to the possible(Fe2+,Mo6+) and (Fe3+,Mo5+)valency pairs,and the highest activity was observed for Sr2Mg0.2Fe0.8MoO6-δ.The enhancement of the catalytic activity may be correlated with the Fe-relating surface lattice oxygen species and was discussed in view of the presence of oxygen vacancies.     

纳米Co3O4的制备、 表征及CO低温催化氧化

Various nanometer Co₃O₄ samples were prepared and the catalytic performance of CO oxidation were examined. It was found that the activities of the catalysts were greatly changed with variation of the preparation methods and pretreatment conditions. Among the samples tested, Co₃O₄ prepared by using dodecylbenzene sulfonic acid sodium salt(DBS) as the surfactant, calcined at 300 ℃ showed the highest activity and it was able to oxidize completely CO even at -78 ℃. Characterization of these samples by XRD and BET means showed that the catalytic acitivity increased with the decrease of the average particle size, suggests that the average particle size of nanometer Co₃O₄ samples is the main controlling factor of the catalytic activity.