溶胶-凝胶法制备稀土CeO2掺杂纳米钨粉的研究

以偏钨酸铵(AMT)、柠檬酸和硝酸铈为原料,用溶胶-凝胶法(sol-gel)制备稀土CeO2掺杂纳米钨粉。通过热重-差热(TG-DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)、比表面积法(BET)等测试手段对复合粉体的合成工艺、物相、颗粒形貌和粒径进行了分析。结果表明:当pH值为1时,还原后的粉体颗粒呈准球形,无团聚,稀土元素以CeO2形式存在且均匀地分布在钨粉中,平均颗粒粒径为80nm左右,满足制备高性能掺杂稀土氧化物亚微米结构浸渍阴极的要求。     

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.     

Synthesis and Characterization of Mesoporous Titanium Dioxide Spheres

Mesoporous titanium dioxide spheres were synthesized by a convenient solvothermal method at room temperature with tetraethyl titanate as a procursor. Investigation by means of X-ray diffraction(XRD), transmission electron microscopy(TEM), scanning electron microscopy(SEM), and N<,2> adsorption-desorption isotherms confirms that the sample has a mesostructure with a higher specific surface area and shows that the mesoporous TiO<,2> spheres have a diameter of 2 μm, the average pore size is about 5.9 nm, and the BET surface area and specific pore volume are about 236 m<'2>/g and 2.116 cm<'3>/g, respectively. The anatase and rutile mesoporous TiO<,2> spheres calcined at 700 ℃ show much better photocatalytic activity than the samples calcined at other temperatures and is comparable to an uncaicined sample in the photodegradation of Methyl Blue(MB) under the UV irradiation.     

钇掺杂对Ce0.33Zr0.67O2储氧性能的影响

采用柠檬酸溶胶凝胶法制备了一系列钇掺杂的富锆铈锆复合氧化物Ce0.33YxZr0.67-xO2,并通过XRD,BET,OSC,XPS,in-situ CO-FTIR等测试,系统研究了钇掺杂后铈锆复合氧化物储放氧性能的变化规律及其影响因素。结果表明,钇离子能够进入铈锆晶格形成固溶体,并提高铈锆体系的结构热稳定性。对于新鲜样,钇掺杂可大幅提升Ce0.33Zr0.67O2材料的比表面积,提高单位质量铈锆材料的储氧能力;但老化后,钇掺杂样品的储氧性能随着掺杂量的增加而减小。通过XPS及原位红外吸附性能测试证实,钇在Ce0.33Zr0.67O2材料表面主要取代锆离子,其掺杂会降低样品的表面吸附能力,抑制铈的氧化还原反应,从而导致该体系储氧性能的下降。     

Impedance Characteristics of MgO-ZrO2 Ceramics Doped with CeO2

The ultrafine CexMg0.06Zr1-xO1.94 （ x = 0 16% ） powders were synthesized by a chemical co-precipitated method. The pressed compacts were sintered in air at 1300, 1400, 1500, 1600℃ for 3 h, respectively. The phase of the ceramics was characterized by the X-ray diffraction （XRD） method. The conductivity of the ceramics was measured by the AC complex impedance technique at 700- 1200 ℃. The ratio of the cubic phase in the ceramics improves with increasing CeO2 content, leading to a enlargement of the oxygen ionic migration channel. The contact resistance between conductive phase particles decreases with increasing CeO2 content, leading to a lower migration hindrance of the oxygen ionic. Consequently, the ionic conductivity of the ceramics improves with increas- ing CeO2 content. Additionally, an analysis for this phenomenon was also presented.     

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。     

Study of cerium-promoted rhodium alumina catalyst as a steam reforming catalyst for treatment of spent solvents

This study attempted to develop an appropriate catalyst used for the steam reforming of gasified spent solvents. Rh2O3/ CeOE-Al2O3 catalysts with various CeO2 loadings were prepared and heated at different temperatures of 500 and 800 ℃, and their surface properties were studied using X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, transmission electron microscopy （TEM）, temperature programmed reduction （TPR） and Bmmauer-Emmett-Teller （BET） analyses. Rhodium existed in the form of Rh2O3, regardless of the sample composition as well as the heating temperature. In the tested range of cerium addition （up to 12 times the rhodium mass）, no significant changes in BET surface areas and binding energy corresponding to Rh 3d5/2 were observed. Instead, the addition of cerium led to a greatly enhanced dispersion of rhodium nanoparticles, and no agglomeration of rhodium was observed for samples heated even at 800 ℃. Honeycomb monolith rhodium catalysts promoted with cerium were fabricated and tested for the steam reforming of a gasified spent solvent, mainly consisting of butylene （C4H8）. The test results suggested that a cerium-promoted rhodium catalyst could be used as an appropriate reforming catalyst for treating low-quality non-methane hydrocarbons without the formation of coke at high temperatures of up to 900 ℃.     

Characteristic of macroporous CeO2-ZrO2 oxygen carrier for chemical-looping steam methane reforming

Chemical-looping steam methane reforming （CL-SMR） is a novel process towards the production of pure hydrogen and syngas, consisting ofa syngas production reaction and a hydrogen production reaction. Macroporous CeQ-ZrO2 oxygen carders with different pore sizes prepared by colloidal crystal templating method and characterized by techniques of scalming electron microscopy （SEM）, transmission electron microscopy （TEM）, Brunauer-Emmett-Teller （BET）, X-ray diffraction （XRD） and temperature pro- grammed reduction （H2-TPR） were tested in CL-SMR process. For comparison, nonporous CeO2-ZrO2 oxygen carrier prepared by precipitation method was also investigated. It was found that macroporous CeO2-ZrO2 oxygen carriers owned higher reducibility and reactivity in CL-SMR process than nonporous samples. For the macroporous CeO2-ZrO2 sample, the decline of pore size could im- prove the reducibility and reactivity. The macroporous sample with a pore size of 100 nm （labeled as Ce-Zr-100） showed the highest performance for the co-production of syngas and hydrogen during the successive CL-SMR redox cycles. After 10 redox cycles, it still retained good porous structure and reducibility. It was found that the porous structure could accelerate the oxygen release from bulk to surface, leading to a good mobility of oxygen and higher reducibility. In addition, it was also favorable for diffusion and penetration of methane and water steam into the sample particles to accelerate the reaction rate.     

Surface and Texture Properties of Tb-Doped Ceria-Zirconia Solid Solution Prepared by Sol-Gel Method

The three-way catalysts （TWCs） promoters Ce0.6Zr0.4- x TbxO2-y were prepared by sol-gel method. BET surface areas analysis indicated that an increase of the dopant Tb content from x = 0.05 to x = 0.15 favors an increase of surface area from 66.8 to 80.4 m^2· g^-1 compared with the undoped sample Ce0 .6oZr0.40O2 65.1 m^2·g^- 1 after calcination at 650℃. Transmission electron microscopy （TEM） observation indicated that the doped samples have a higher thermal stability. The XRD and Raman spectra confirmed that the Ce0.6Zr0.4-xTbxO2-y cubic solid solution is formed. XPS analysis revealed that Ce and Tb mainly existed in the form of Ce^4＋ and Tb^3 ＋ , and Zr existed in the form of Zr^4＋ on the surface of the samples. The doped samples were homogenous in composition ; the introduction of Tb into the CeO2-ZrO2 promoters resuited in the formation of a solid solution, and the concentration of surface lattice oxygen was increased.     

Catalytic oxidation of CO on mesoporous codoped ceria catalysts:Insights into correlation of physicochemical property and catalytic activity

Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts. In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe_(1-x-y)O_2,Cu_xCe_(1-x)O_2,Mn_xCe_(1-x)O_2 and pure CeO_2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD, SEM, EDS, BET, Raman, H2-TPR, XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity. The doped samples maintain the cubic fluorite structure of CeO_2 with high crystallinity and small crystallite size, forming Ce-based solid solutions. The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm. The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids. The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies, pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst, thereby enhancing the catalytic activity for CO oxidation. Besides, the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.     

Rare earth application for heat-resisting alloys

High-temperature oxidation resistance of Al2O3-and Cr2O3-forming heat-resisting alloys with rare earths(yttrium-implanted FeCrAl,-added FeCrAl,-added FeCrAlPt alloys,Y2O3-or CeO2-coated NiCrSi,yttrium-or lutetium-added NiCr and NiCrSi) was studied in oxygen at high temperatures,by mass gain measurements,mass change measurements,amount of spalled oxide,observation of surface appearance,X-ray diffraction(XRD),scanning electron microscopy(SEM),electron probe X-ray microanalysis(EPMA) and transmission electron microscopy(TEM).After oxidation at 1573 K for 18 ks in oxygen,oxide scale on FeCrAl alloy spalled from the entire surface,however,yttrium-implanted FeCrAl alloys showed good oxide adherence.After oxidation at 1473 K for 18 ks in oxygen,mass gain of FeCrAlY alloys decreased with increasing yttrium of up to 0.1 wt.% follwed by an increase with the yttrium content,and the mass gain of FeCrAl0.005Pt0.05Y alloy with appropriate additions of platinum and yttrium was lower than that of FeCrAl0.1Y alloy.Yttrium-added FeCrAl alloys showed good oxide adherence.TEM analysis revealed that the alumina/alloy interface of FeCrAl0.005Pt0.05Y alloy showed good coherency.The scale surface of FeCrAl alloy was rough,however,those of FeCrAlY and FeCrAlPtY alloys were smooth.Cyclic oxidation of NiCrSi,Y2O3-or CeO2-coated NiCrSi alloys was studied up to 10 cycles(1 cycle:300 s) at 1523 K in oxygen.Mass change of NiCrSi alloy increased up to 3 cycles and then decreased up to 10 cycles because of oxide spallation during cooling.On the other hand,mass change of Y2O3-or CeO2-coated NiCrSi alloy increased up to 10 cycles,and these alloys showed good oxide adherence.Granular Cr2O3 particles on Y2O3-coated NiCrSi alloy were in size smaller than these on CeO2-coated NiCrSi alloy.This result suggested that oxidation rate of Y2O3-coated NiCrSi alloy was lower than that of CeO2-coated NiCrSi alloy.After oxidation at 1473 and 1573 K for 18 ks in oxygen,mass gain of yttrium-or lutetium-added NiCr and NiCrSi alloys decreased.Oxide scales on NiCrS     

Effects of ZrO2 Content on Structure and Performance of Cu/CeO2-ZrO2 Catalysts for Water-Gas Shift Reaction

Water-gas shift(WGS)is a critical step in fuelprocessors for preli minary COclean-up and additionalhydrogen generation prior to the CO clean-up stage,which opened up new potential applications for WGScatalysts.Recently several formulations of noble-met-al…     

无机盐模板剂法合成介孔CeO_2

以自制碳酸镁为模板,通过高速搅拌,加入硝酸铈溶液,以及以氨水为沉淀剂,获得介孔CeO_2前驱体,再通过低温焙烧后用弱酸去除模板剂碳酸镁,即得到介孔CeO_2.并采用XRD,BET,HRTEM,FT-IR等手段对其进行了表征.结果表明,利用无机盐碳酸镁为模板剂合成的介孔CeO_2,比表面为129m~2/g,平均孔径为5nm.     

Oxygen Storage Capacity of Pt-, Pd-, Rh/CeO2-Based Oxide Catalyst

CZO （CeO2-ZrO2） and CZYO （CeO2-ZrO2-Y2O3） series of mixed oxides were prepared by coprecipitaion, and a part of these oxides were loaded with precious metals （PM）. XRD, BET, and oxygen storage capacity （OSC） investigations were performed on samples aged at 750, 900, and 1050 ℃. It was observed that BET surface area and OSC showed a marked decrease in CeO2 aged at high temperature, and the erystallite size showed an obvious increase. The CZO samples consist of cubic- and tetragonal crvstal phases, and their crystallite size increase rapidly when aged at high temperature. The CZYO samples consist of single crystal phase when the content of Y exceeds 0.15 mol, and their erystallite size increases slowly during high-temperature aging. It is concluded that additive Y can stabilize the performance of CZYO oxides. In the aged CZO and CZYO mixed-oxide systems, addition of a small amount of precious metals （Pt, Pd, Rh） increased the rate of reduction and led to an obvious improvement in OSC. OSC of CZO and CZYO with precious metals are related to their composition and the type of precious metal.     

约束弧等离子体制备铝纳米粉体的研究

利用自行研制的约束弧等离子体制备金属纳米粉试验装置,成功制备了平均粒度为44nm的铝纳米粉体。利用X射线衍射(XRD)、BET吸附法、透射电子显微镜(TEM)和相应选区电子衍射(SAED)等测试手段对所制备样品的晶体结构、形貌、粒度及其分布、比表面积进行性能表征。试验结果表明:约束弧等离子体法制备的铝纳米粉晶体结构为fcc结构的晶态,与体材料相比晶格常数发生膨胀。比表面积为41m2.g-1,粒径范围分布在20~70nm之间,平均粒径为44nm,粒度均匀,分散性好,呈规则球形链状分布。     

Photocatalytic activity of Eu3＋-doped ZnO nanorods synthesized via microwave assisted technique

The doped ZnO nanorods as a photocatalyst with different Eu contents were prepared by microwave assisted method and they were characterized by means of X-ray diffraction(XRD),energy-dispersive X-ray spectroscopy(EDS),UV-Vis spectroscopy,surface area Brunauer-Emmett-Teller(BET),X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The average crystallite size and band gap energy of Eu-doped ZnO were varied with the Eu content.The XRD pattern of Eu-doped ZnO indicated hexagonal crystal structure with an average crystallite size of 25 nm.The presence of europium with trivalent state and its doping successfully into the crystal lattice of ZnO matrix were confirmed by XPS technique.The photocatalytic activity of Eu-doped ZnO nanorods was evaluated for methyl orange degradation.The photocatalytic experiments showed ～91% degradation of methyl orange over 0.2 mol.% Eu doped ZnO sample within 3 h under UV light(365 nm).     

不同沉淀剂制备氧化铈抛光粉

氧化铈(CeO₂)抛光粉在光学玻璃、手机盖板、集成电路等领域内有着广泛的应用。合成高端CeO₂抛光粉主要采用液相沉淀得到前驱体,再经过煅烧转型制得CeO₂。前驱体是决定CeO₂抛光粉性质和性能的关键因素之一。通过模拟工业上常用的制备方法,以氯化铈(CeCl₃)为铈源,使用碳酸钠(Na₂CO₃)、碳酸铵[(NH₄)₂CO₃]、碳酸氢铵(NH₄HCO₃)、二水合草酸(H₂C2O₄·2H₂O)和氢氧化钠(NaOH)为沉淀剂,合成了一系列CeO₂抛光粉的前驱体。利用X-射线衍射仪(XRD)、扫描电子显微镜(SEM)、激光粒度仪等手段表征了前驱体的晶相、形貌、粒度等性质,并研究了前驱体煅烧转型后的CeO₂性质及其对K9光学玻璃的...     

碳酸氢铵沉淀法制备氧化铈抛光粉

利用碳酸氢铵做沉淀剂制备氧化铈抛光粉,通过L16(44)正交试验,研究了温度、硝酸铈浓度、滴加速度和搅拌速度对氧化铈粒度和比表面积的影响。得到的最佳粒度制备工艺条件为:温度60℃、硝酸铈浓度50g/L、搅拌速率500r/min、滴加速度50mL/min。并对最佳制备工艺条件下制取的抛光粉进行粒度、形貌和抛蚀量进行研究。     

Modified-EISA synthesis of mesoporous high surface area CeO_2 and catalytic property for CO oxidation

Mesoporous CeO2 particles with high surface area were synthesized using a modified evaporation-induced self assembly(EISA) method which combined citric acid as complexing agent.As-prepared powder and further thermal treatment samples were characterized by X-ray diffraction(XRD),transmission electron microscopy(TEM),selected area electron diffraction(SAED),Fourier transform infrared spectrometer(FTIR),thermogravimetry and differential thermal analysis(TG-DTA),Brunauer-Emmett-Teller(BET) and Barrett-Joyner-Ha...     

Preparation and Characterization of Porous Yttrium Oxide Powders with High Specific Surface Area

Y2O3isoftenusedinthemanufactureofphos phorsandceramics[1～3].However,itisalsousedas selectivecatalysts[1,4,5],suchasforthedehydrationof2alkanols,thedimerizationofmethane,1butene isomerization,hydrogenationof1,3butadieneandac etonealdoladdition,andsupport[6,7]formetalsthat catalyzetheformationofmethanolfromCO2andH2.It iswidelyacceptedthatthecatalysispropertiesofox idesdependstronglyontheirphysicalcharacteristics,especiallyontheirspecificsurfaceareaandporous structure.Agreatdealofattentionhasb…