Influence of Additives Ceria and Lanthana on Performance of Pd／Al／Monolith Honeycomb Catalysts

The effects of ceria and lanthana additives on activity and thermal stabilization of the catalysts for CO oxidation were studied. The results show that the addition of CeO2 clearly improves the catalytic activity, which may derive from the synergic effect between CeO2 and PdO. The catalysts were characterized by means of temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) measurements. The XPS results of a slight increase in metal oxidation state reflect that the charge transfers from metal to ceria and ceria is slightly reduced, which leads to a decrease of the Ce-O bond strength. Pd-Ce synergism affects the reduction behavior of the catalysts. The TPR results show that the CeO2 ad-dition lowers the reduction temperature of PdO, while palladium facilitates the reduction of the ceria. For PdO/La2O3/Al2O3/monolith honeycomb catalysts, the aging test measurements at 1050 ℃ and the XRD results show that the formation of LaAlO3 which neutralizes the surface alumina defects inhibits the sintering of alumina.     

CeO2-Co3O4 Catalysts for CO Oxidation

CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method. In combination with the characterization methods of N2 adsorption/desorption, XRD, temperature-programmed reduction （TPR）, and FT-IR, the influence of the cerium content on the catalytic performance of CeO2-Co3O4 was investigated. The results indicate that the prepared CeO2-Co3O4 catalysts exhibit a better activity than that of pure CeO2 or pure Co3O4. The catalyst with the Ce/Co atomic ratio 1 ： 16 exhibits the best activity, which converts 77% of CO at room temperature and completely oxidizes CO at 45 ℃.     

Preparation, characterization and luminescence of Sm3+ or Eu3+ doped Sr2CeO4 by a modified sol-gel method

Superfine Sr2CeO4:RE3+ (RE=Eu, Sm) phosphors were synthesized at relatively low temperature by a modified sol-gel method using nitrates as raw materials, ethylenediaminetetraacetic acid (EDTA) as complexing agent. Single phase phosphors could be obtained at calcination temperature above 800 °C and pH value higher than 6.4 of initial solution. The as-prepared powders consisted of uniform crotch-like grains. The preparation process was monitored by thermogravimetric and differential thermal analysis (TG-DTA) and Raman spectra. The obtained products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS) and photoluminescence. Photoluminescence study indicated that strong energy transfer occurred between Eu3+/Sm3+ and host. The Sr2CeO4:RE3+ emission could be tuned from blue to white and red light by varying the concentration of RE3+. The strong emission and controllable light color are suitable for applications in advanced lighting and displaying fields.     

Synthesis of mesoporous CeO2-MnOx binary oxides and their catalytic performances for CO oxidation

Mesoporous CeO2-MnOx binary oxides with different Mn/Ce molar ratios were prepared by hydrothermal synthesis and characterized by scanning electron microscopy （SEM）, N2 sorption, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and H2 temperature-programmed reduction （H2-TPR）. The characterization results indicated that the CeO2-MnOx catalysts exhibited flower-like microspheres with high specific surface areas, and partial Mn cations could be incorporated into CeO2 lattice to form solid solution. The CeO2-MnOx catalysts showed better catalytic activity for CO oxidation than that prepared by the coprecipitation method. Furthermore, the CeO2-MnOx catalyst with Mn/Ce molar ratio of 1 in the synthesis gel （Ce-Mn-1） exhibited the best catalytic activity, over which the conversion of CO could achieve 90% at 135 ℃. This was ascribed to presence of more Mn species with higher oxida- tion state on the surface and the better reducibility over the Ce-Mn-I catalyst than other CeO2-MnOx catalysts.     

Structure and Catalytic Behavior of CuO-ZrO-CeO2 Mixed Oxides

The effect of doping CuO on the structure and properties of zirconia-ceria mixed oxide was studied. The results show that addition of CuO decreases the reduction temperature of ceria, and stabilizes the cubic structure of mixed oxides, and enhances catalytic activity of CuO-ZrO-CeO2 mixed oxides for CO oxidation. Increasing ceria content in the mixed oxides can enhance the catalytic activity, but some impurities such as sulfate make catalytic activity falling. There is little effect of calcination temperature on catalytic activities, implying that these catalysts are effective with good thermal stability.     

Preparation and characterization of Ce1-xFexO2 complex oxides and its catalytic activity for methane selective oxidation

A series of Ce1-xFexO2 （x=0, 0.2, 0.4, 0.6, 0.8, 1） complex oxide catalysts were prepared using the coprecipitation method. The catalysts were characterized by means of XRD and H2-TPR. The reactions between methane and lattice oxygen from the complex oxides were investigated. The characteristic results revealed that the combination of Ce and Fe oxide in the catalysts could lower the temperature necessary to reduce the cerium oxide. The catalytic activity for selective CH4 oxidation was strongly influenced by dropped Fe species. Adding the appropriate amount of Fe2O3 to CeO2 could promote the action between CH4 and CeO2. Dispersed Fe2O3 first returned to the original state and would then virtually form the Fe species on the catalyst, which could be considered as the active site for selective CH4 oxidation. The appearance of carbon formation was significant and the oxidation of carbon appeared to be the rate-determining step; the amounts of surface reducible oxygen species in CeO2 were also relevant to the activity. Among all the catalysts, Ce0.6Fe0.402 exhibited the best activity, which converted 94.52% of CH4 at 900 ℃.     

Influence of Nanometric Ceria Coating on Oxidation Behavior of Chromium at 900 ℃

Isothermal and cyclic oxidation behaviors of chromium samples with and without nanometric CeO2 coating were studied at 900 ℃ in air. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution electron microscopy (HREM) were used to examine the morphology and microstructure of the oxide film. It was found that ceria coating greatly improved the oxidation resistance of Cr both in isothermal and cyclic oxidizing experiments. Acoustic emission (AE) technique was used in situ to monitor the cracking and spalling of oxide film, and AE signals were analyzed in time-domain and number-domain according to related oxide fracture model. Laser Raman spectrometer was also used to study the stress of oxide film formed on Cr with and without ceria. The improvement in oxidation resistance of chromium is believed mainly due to that ceria greatly reduced the growth speed and grain size of Cr2O3. This fine-grained Cr2O3 oxide film might have better high temperature plasticity and could relieve parts of the compressive stress by means of creeping and maintained ridge character and relatively lower level of internal stress. Meanwhile, ceria application reduced the size and number of interfacial defects, remarkably enhanced the adhesive property of Cr2O3 oxide scale formed on Cr substrate.     

碳纳米管增强Cu基和Al基复合材料界面改性

在碳纳米管(carbon nanotubes,CNTs)增强Cu基和Al基复合材料的制备中,界面改性是提高复合材料性能的重要方法。金属基体和碳纳米管间的有效界面结合直接影响了复合材料中界面的载荷传递、导电以及导热性能,从而影响复合材料性能。本文综述了近几年碳纳米管增强Cu基和Al基复合材料界面改性的工艺方法,讨论了界面改性工艺对碳纳米管增强Cu基和Al基复合材料界面结构和性能的影响。     

Effect of water vapor on the CO and CH4 catalytic oxidation over CeO2-Mox (M=Cu,Mn,Fe,Co,and Ni) mixed oxide

CeO2-MOx (M=Cu, Mn, Fe, Co, and Ni) mixed oxide catalysts were prepared by a citric acid complexation-combustion method. CeO2-MOx solid solutions could be formed with M cations doping into CeO2 lattice, while NiO and Co3O4 phases were detected on the surface of CeO2-NiO and CeO2-Co3O4 by Raman spectroscopy. The presence of M in CeO2 could obviously promote its catalytic activity for CH4 catalytic combustion and CO oxidation. Among the prepared samples, CeO2-CuO exhibited the best performance for CO oxidatio...     

La-Ce-Cu复合金属氧化物的结构表征及催化性能

本文用ＮＨ４ＮＯ３共熔法合成Ｌａ－Ｃｅ－Ｃｕ系列样品。用ＸＲＤ分析了ＣｅＯ２在铜酸镧盐中的溶解度,发现大量ＣｅＯ２存在时,Ｌａ２Ｏ３、ＣｕＯ的加入导致原晶体结构发生变形,生成少量铜酸镧盐。ＸＲＦ分析了系列样品组成均为氧缺陷型化合物。ＸＰＳ研究发现,含大量ＣｅＯ２的样品高温焙烧后在ＣｅＯ２表面生成复合金属氧化物Ｌａ２ＣｕＯ４,最表面一层为少量Ｌａ２Ｏ３,并确定了其中Ｏ的属性。利用ＴＥＭ研究了部分样品的表面结构,同时研究了其ＣＯ催化氧化活性。     

CuO／CeO2 Catalysts for Selective Oxidation of Carbon Monoxide in Excess Hydrogen

CuO/CeO2 catalysts were prepared by a coprecipitation method and tested for CO removal from reformed fuels via selective oxidation. The influence of the calcination temperature on the chemical compositions and catalytic performance of CuO/CeO2 catalysts were studied. It was found that CuO/CeO2 catalysts exhibit excellent CO oxidation activity and selectivity, and the complete removal of CO is attained when the catalysts are calcined at appropriate temperatures. XRD, TPR and XPS results indicate that CuO/CeO2 catalysts exhibit higher catalytic performance in CO selective oxidation due to the strong interaction between copper oxide and cerium dioxide, which promotes the dispersion and hydrogen reduction activity of copper.     

Effect of yttrium addition on water-gas shift reaction over CuO/CeO2 catalysts

This paper presented a study on the role of yttrium addition to CuO/CeO2 catalyst for water-gas shift reaction. A single-step co-precipitation method was used for preparation of a series of yttrium doped CuO/CeO2 catalysts with yttrium content in the range of 0-5wt.%. Properties of the obtained samples were characterized and analyzed by X-ray diffraction (XRD), Raman spectroscopy, H2-TPR, cyclic voltammetry (CV) and the BET method. The results revealed that catalytic activity was increased with the yttrium content at first, but then decreased with the further increase of yttrium content. Herein, CuO/CeO2 catalyst doped with 2wt.% of yttrium showed the highest catalytic activity (CO conversion reaches 93.4% at 250℃) and thermal stability for WGS reaction. The catalytic activity was correlated with the surface area, the area of peak y of H2-TPR profile (I.e., the reduction of surface copper oxide (crystalline forms) interacted with surface oxygen vacancies on ceria), and the area of peak C2 and A1 (Cu0→Cu2+ in cyclic voltammetry process), respectively. Besides, Raman spectra provided evidences for a synergistic Cu-Ovacancy interaction, and it was indicated that doping yttrium may facilitate the formation of oxygen vacancies on ceria.     

ACF/CNT复合材料的制备及其对Cr(Ⅵ)的吸附性能

以硝酸镍为催化剂前驱体,C2H2为碳源,H2为还原气,N2为载气,采用化学气相沉积法(CVD)在活性炭纤维(ACFs)毡体的纤维表面催化生长碳纳米管(CNTs),制备ACF/CNT复合材料。经测定,所制复合材料比表面积可达62.56 m2/g;扫描电镜分析表明,CNTs在ACFs表面分布均匀而致密,经过表面修饰可以作为1种良好的吸附材料。选择低浓度的六价铬(Cr(Ⅵ))溶液进行吸附研究,考察振荡时间、溶液pH值以及溶液的初始浓度等因素对吸附行为的影响。实验结果表明,初始Cr(Ⅵ)浓度为1 mg/L,在25℃时,随着振荡时间的增长溶液中Cr(Ⅵ)的脱除率逐渐增加,在150 min时达到最大值49.48%。溶液中Cr(Ⅵ)的脱除率随着pH的减小而增大,当pH值为2.0时脱除率达91.50%,对Cr(Ⅵ)的吸附量随着溶液初始浓度的增加而增大,但是当初始浓度到达5.0 mg/L时,脱除效率到达最大值后开始降低。并对ACF/CNT复合材料的吸附机制进行了探讨。     

Role of Surface Adsorption in Fast Oxygen Storage/Release of CeO2 -ZrO2 Mixed Oxides

Four kinds of CeO2-ZrO2 mixed oxides, i.e., a physical mixture of ceria and zirconia （CZP）, zirconia-coated ceria （ZCC）, ceria-coated zirconia （CCZ） and a chemical mixture of celia and zirconia （CZC）, were prepared. The oxygen storage capacity （OSC） measurements at 500℃ were performed under transient and stationary reaction conditions. All the curves of CO2 evolution during CO-O2 cycles presented a bimodal shape. The fast peak was primarily the result of the reaction of CO with the oxygen from the oxides, which was mainly determined by the nature of the material The sec- ond peak was mostly related to the CO2 adsorption behavior and was highly influenced by the surface area and the number of surface active sites. As a result, OSC activity of the samples followed in the order of CZC 〉 CCZ 〉 ZCC=CZP.     

镀钨碳纳米管增强镁基复合材料的摩擦磨损性能研究

以羰基钨为前驱体, 采用金属有机化学气相沉积在碳纳米管表面镀覆了金属钨, 利用磁力搅拌混粉和放电等离子体烧结制备了镀钨碳纳米管增强镁基复合材料((W-CNTs) /Mg), 研究了W-CNTs质量分数对复合材料摩擦磨损性能的影响。结果表明: W-CNTs的加入可对镁基体起到降低摩擦系数、减少磨损量的作用; 当W-CNTs质量分数为0.75%时, 复合材料的摩擦系数和磨损量均最小, 分别较纯镁降低了43.7%和71.4%;增加或降低复合材料中的W-CNTs质量分数, 材料的摩擦系数、磨损量均将增大。(W-CNTs) /Mg复合材料的摩擦磨损性能高于CNTs/Mg复合材料。     

Effect of Manganese Doping on Oxygen Storage Capacity of Ceria-Zirconia Mixed Oxides

CeO2-ZrO2-MnOx mixed oxide series were prepared by sol-gel method. CO pulse and CO-O2 cycle measurements were carried out to examine the oxygen storage complete capacity （OSCC） and dynamic oxygen storage capacity （OSC） of the samples. The doping method brought about strong interactions between manganese oxide and ceria, both in the bulk and on the surface. Only a small part of Mn cations are incorporated into the ceria lattice to form solid solutions and the remaining are left on the surface as finely dispersed Mn3O4. The OSC behaviors of the materials are influenced by the doping amount of Mn and the solubility of Mn in the CeO2 lattice. The OSC is more easily affected by available contents of oxygen storage components when the measurement frequency is low. Comparatively, the concentration of lattice defects, which affects the mobility of bulk oxygen, is the determining factor under high frequency.     

Structures and oxygen storage capacities of CeO2-ZrO2-Al2O3 ternary oxides prepared by a green route： supercritical anti-solvent precipitation

CeO2-ZrO2-Al2O3 ternary oxides were successfully prepared by a green route of supercritical anti-solvent precipitation with supercritical CO2 as anti-solvent and methanol as solvent.The structures and oxygen storage capacities of these ternary oxides were characterized by XRD,Raman spectra and oxygen storage capacity measurements.It was found that Al 3+ and Zr 4+ inserted into CeO2 lattice,forming CeO2-ZrO2-Al2O3 solid solution.The concentration of aluminium isopropoxide in the solution affected the concentration of oxygen vacancy and the distortion of oxygen sublattice which were responsible for the oxygen storage capacity.The rapidest oxygen uptake/release rate and maximum total oxygen storage capacity(122.0 mmolO2/molCeO2)were obtained with the aluminium isopropoxide concentration at 0.2 wt.% in the solution.     

镀钨碳纳米管增强铜基复合材料的制备及性能

采用羰基热分解法对多壁碳纳米管表面进行镀钨处理,并以镀钨碳纳米管和电解铜粉为原料,进行机械球磨混粉和放电等离子体烧结,制备了镀钨碳纳米管/铜基复合材料.采用场发射扫描电镜观察了粉体和复合材料的组织形貌,并对复合材料物相进行了X射线衍射分析.探讨了镀钨碳纳米管含量和放电等离子体烧结温度对复合材料致密度、抗拉强度、延伸率和电导率的影响.结果表明,镀钨碳纳米管质量分数为1%和烧结温度为850℃时,复合材料的致密度、抗拉强度和电导率最高.与烧结纯铜相比,复合材料的抗拉强度提高了103.6%,电导率仅降低15.9%.      

TiO2纳米管的制备及其光催化降解甲基橙的研究

以TiO2和NaOH为原料,采用水热法制备了TiO2纳米管（titania nanotube,简称TNT）,通过X射线衍射（XRD）、扫描电子显微镜（SEM）对TiO2纳米管的结构与形貌进行了研究,以甲基橙（Methyl Orange）为反应物,考察了TiO2纳米管光催化降解甲基橙的效果。研究结果表明：400℃焙烧时,TiO2纳米管主晶相为钛酸,500℃焙烧时,其组成为锐钛矿相;制备的TiO2纳米管可以有效的降解甲基橙,且在光催化降解中起主要作用的是锐钛矿相。     

Valence State of Active Copper in CuOx/CeO2 Catalysts for CO Oxidation

CuOx/CeO2 catalysts were prepared by adsorption-impregnation method, CO conversion was tested over the catalysts pretreated under different conditions for preferential CO oxidation in H2, and the catalysts were characterized with X-ray photoelectron spectroscopy and temperature programmed reduction. Experimental results show that there are two kinds of copper, which are Cu^＋ and Cu^2＋ in calcined CuOx/CeO2, Among them, the Cu^＋ is the key active component for CO oxidation. The main reason is as follows： CO is activated by copper for CO oxidation over CuOx/CeO2, while CO can not be activated by Cu^2＋. Only when Cu^2＋ is reduced to Cu ^＋ or Cu^0, the copper may be active for CO oxidation, moreover, the experimental results show that the reduction of Cu^2＋ does not lead to an increase of catalytic activity. So the active species is Cu^＋ in CuOx/CeO2 catalysts.