CeO2纳米粉体的一步熔融法制备及表征

采用熔盐法制备了氧化铈纳米粉体,探讨了改变铈与熔融盐之间的比例和烧结温度对粉体粒度的影响,确定了可控粉体的最佳实验条件.通过TG-DTA、XRD、TEM、BET等测试方法对其物相、颗粒度、分散性、颗粒形貌和比表面积等性能进行了表征.结果表明,烧结温度为400℃、熔融盐与铈比为3∶1时,制备出分散性好、呈良好的结晶状态的类球状纳米晶粒,比表面积为84.9 m2·g-1,平均粒径为10.7nm;随着烧结温度的升高,粉体的粒径逐渐增大,当烧结温度为600℃时,粒径为26nm.     

固相合成In2O3纳米晶及动力学的研究

以InCl3·4H2 O和NaOH为原料 ,利用固相反应合成前驱体 ,再经焙烧合成In2 O3纳米晶。用X射线衍射 (XRD)分析了不同焙烧温度对合成In2 O3晶粒尺寸的影响。研究结果表明 :按Scherrer公式估算合成In2 O3纳米晶的晶粒尺寸在 2 0～ 3 0nm ,焙烧温度越高 ,晶粒尺寸越大 ;根据前驱体不同升温速率下的差热 (DTA)曲线 ,用Kissinger和Ozawa法计算了合成In2 O3纳米晶的活化能分别为 167.0 3和 176.0 6kJ·mol- 1 ,差别不大 ;根据晶粒生长动力学理论计算In2 O3晶粒长大的活化能为 2 .82kJ·mol- 1 ,表明热处理过程In2 O3纳米晶粒的长大主要以界面扩散为主。     

盐酸体系中制备氢氧化铈的工艺研究

研究了用氯化铈溶液为原料制备氢氧化铈,考察了氯化铈溶液浓度、H_2O_2加入量、NH_3·H_2O用量及反应温度对氢氧化铈中铈氧化率的影响,确定最优工艺条件。结果表明:在氯化铈质量浓度120 g/L、H_2O_2用量为CeO_2质量的0. 7倍、NH_3·H_2O用量为理论量130%、反应温度50℃条件下,得到铈氧化率大于97%,w(Cl-)0. 15%的氢氧化铈,且在常温下能溶于HNO_3溶液。     

Co含量与烧结温度对纳米晶WC-Co硬质合金结构与性能的影响

WC晶粒并合生长与WC原料特性以及合金中的Co含量密切相关。以比表面平均径为70 nm的WC粉末为原料,采用VC+Cr3C2作为晶粒生长抑制剂,探讨Co含量与烧结温度对WC-Co合金结构与性能的影响。结果表明,Co含量增加能降低纳米晶WC晶粒的邻接度,进而有效抑制烧结过程中WC晶粒的并合长大。在1 330℃下加压(0.9 MPa)烧结制备WC-15Co-0.7Cr3C2-0.6VC合金,WC平均晶粒尺寸为160 nm,合金硬度为93.6 HRA,抗弯强度为4160 MPa(C型样品),Palmqvist断裂韧性KIC为10.1 MPa m0.5。热分析结果表明,合金液相出现温度在1 322~1 345℃之间,没有出现液相温度的纳米尺寸效应。     

C_2H_2/N_2气流下nc-ZrCN/a-CN_x薄膜成分、结构和力学性能的研究

采用磁过滤阴极真空弧技术(FCVA),以金属Zr为阴极靶,通入不同流速的C_2H_2和N_2气体(两者比例保持为1∶1),在单晶Si(100)晶面上制备nc-ZrCN/a-CN_x纳米复合薄膜。采用扫描电镜(SEM)、X射线衍射(XRD)、透射电镜(TEM)、X射线电子能谱(XPS)和拉曼散射能谱(Raman)多种材料分析技术研究薄膜的成分和结构。实验结果表明:薄膜是由两种相结构组成,分别为ZrCN纳米晶相(nc-ZrCN)和非晶相(a-CN_x);结构是由平均晶粒尺寸为5~12nm的nc-ZrCN弥散于非晶相a-CN_x中。纳米晶相nc-ZrCN中键态为Zr-C和Zr-N,非晶相aCN_x中键态为C-C,C=C和C-N。利用表面形貌仪(SM)和纳米力学探针(Nanotest)测量了薄膜的内应力、硬度和约化模量等力学性能。分析发现:薄膜中sp3和sp2的含量比(sp3/sp2)越大,内应力越大,内应力最大可达11.5GPa。ZrCN纳米晶粒细化和高的sp3/sp2含量比会提高薄膜的硬度和约化模量。当气流在15~35ml·min~(-1)范围时,薄膜具有很高的硬度和约化模量。当气流为25ml·min~(-1)时,硬度可达35.1GPa,约化模量达297.2GPa。     

工艺参数对引晶法制备半固态浆料组织的影响

采用引晶法(Introducing Grain Process,简称IGP)制备半固态金属浆料,研究了工艺参数对半固态A356铝合金浆料组织的影响,讨论了球状初生α(Al)晶粒的形成机制及形貌控制.结果表明:当合金温度为630℃、制备浆料为4 kg时,如果引晶尺寸为10 mm、加入量为3.5%(质量分数)和倾倒温度为611～617℃,半固态浆料中初生α(Al)晶粒的平均直径可达40~75μm,形状因子可达0.82~0.89.如果引晶尺寸为10 mm、倾倒温度为613℃、加入量为2%~4%,初生α(Al)晶粒的平均直径可达45~82μm,形状因子可达0.78~0.88.合金温度和倾倒温度适当降低、或者引晶加入量适当提高,组织越好.当QR=QA、Rh=Rc时,只要倾倒温度适宜就可以制备优质半固态浆料.引晶熔化时产生的枝晶碎块是半固态浆料中初生α(Al)晶粒的直接来源,引晶熔化时形成的温度过冷区也为异质形核提供了有利条件.     

铌对纳米晶Nd2Fe14B合金组织结构与磁性能的影响

采用熔体快淬及晶化退火工艺制备了单相Nd2Fe14B纳米晶合金。研究了添加Nb对Nd12.3Fe81.7-xNbxB6.0(x=0.5,1.0,1.5,2.0,2.5,3.0)系列合金的微观组织、磁性能和晶化行为的影响规律。结果表明:添加Nb可提高晶化温度并稳定非晶相;在退火晶化过程中,加入Nb后形成的析出相可以抑制晶粒长大,使晶粒细化且分布均匀,进而提高了材料的综合磁性能。通过对系列合金磁性能分析可知:Nd12.3Fe81.2Nb0.5B6.0合金在600℃退火处理10min后的磁性能最佳,磁能积(BH)m=141.13kJ.m-3,矫顽力Hci=867.95kA.m-1,剩磁Jr=1.02T。     

纳米二氧化锆粉体的制备

以ZrOCl_2·8H_2O为锆源,CO(NH_2)_2为沉淀剂,去离子水为溶剂,通过水热法合成单斜晶型的纳米ZrO_2。讨论水热温度和水热时间对纳米二氧化锆晶粒尺寸的影响,并利用场发射扫描电镜(SEM)和XRD衍射仪表征手段,对产品形貌及物相进行了表征分析。实验结果表明,水热温度是影响ZrO_2粉体晶化的主要因素,在140℃水热温度下,ZrOCl_2·8H_2O和CO(NH_2)_2反应生成Zr(OH)_4胶体。随着水热温度升高到160℃,大部分的Zr(OH)_4胶体分解生成ZrO_2并结晶。当水热温度继续升高至180℃时,Zr(OH)_4全部分解生成ZrO_2。水热时间的增加并不改变ZrO_2的晶型,且对ZrO_2的晶粒尺寸影响不大,随着水热时间由3 h增加到18 h,其粒径分别为51.2、46.1、45.6nm和54.3 nm,且样品具有良好的分散性。     

熔融盐法制备ZrO_2纳米粉末的研究

采用熔盐法制备了氧化锆纳米粉末,探讨了改变锆盐与熔融盐的比例和焙烧温度对粉末晶粒尺寸的影响,确定了可控粉末的最佳试验条件.借助XRD、TEM、BET、TG等测试方法对物相、粒度、分散性和比表面积以及前驱体热分解特性进行了分析.结果表明:焙烧温度为500℃、锆盐与熔融盐的质量比为1: 3时,制备出分散性好、比表面积为100.5m2/g、平均粒径为8 nm的氧化锆粉末;随着烧结温度的升高,粉末的晶粒尺寸逐渐增大.     

铈镧碳化物水解法制备La掺杂CeO_2纳米粉及性能

采用石墨坩埚,通过25 kg真空感应炉熔炼制备铈-镧稀土碳化物,然后在室温下水解铈-镧稀土碳化物后制得比表面积为131 m~2/g的镧掺杂CeO_2纳米粉。经过不同温度热处理(600℃~1000℃)的镧掺杂CeO_2纳米粉的X射线衍射、激光拉曼光谱、透射电子显微镜及其甲烷催化燃烧反应等结果表明,镧离子替代CeO_2晶格中的部分铈离子形成铈镧固溶体,与相同工艺制备的纯CeO_2纳米粉相比,La的掺杂不仅使CeO_2纳米粉热稳定性有所提高,而且还具有良好的甲烷催化氧化性能。此方法是一种可大规模制备稀土元素掺杂于CeO_2纳米粉的有效方法。     

利用含锌粉尘和铁鳞中锌和铁制备合成Ni-Zn铁氧体

摘要：以电炉粉尘（EAFD）中提取的Zn2+、铁鳞中提取的Fe3+和六水合氯化镍(NiCl2·6H2O)为原料,采用水热法直接制备合成尖晶石型Ni ZnFe2O4。首先探讨了焙烧温度、NaOH与EAFD质量比和焙烧时间对电炉粉尘中Zn2+提取率以及HCl浓度对铁鳞中Fe3+浸出率的影响,然后分析了Ni ZnFe2O4合成条件对其磁性能的影响。结果表明,当NaOH与EAFD质量比为1∶1,焙烧温度为450℃,焙烧时间为1h时,电炉粉尘中锌的提取率为88.77%;当HCl浓度为1.75mol/L时,铁鳞中Fe3+浸出率为96.89%。当EAFD中提取的Zn2+、铁鳞中提取的Fe3+和NiCl2·6H2O的摩尔比控制为1∶20∶9时,可以成功制备尖晶石型Ni-ZnFe2O4,并且对合成的Ni ZnFe2O4进行热处理之后可以显著提高其磁性能,当热处理温度从150℃提高到450℃时,尖晶石型Ni-ZnFe2O4的饱和磁感应强度从13.35（A·m2）/kg增长到40.06（A·m2）/kg。     

Preparation of High-Surface Area Nano-CeO2 by Template-Assisted Precipitation Method

The high-surface area nano-CeO2 was prepared by Ce（NO3）3 by precipitation method, with surfactant cetyhrimethyl ammonium bromide （CTAB） as templating agent. The effects of the precipitating agents, reaction temperature, ageing time, and calcination temperature on the surface area, as well as the pore structure and the mean crystallite size of nano-CeO2 were studied. It was found that the reaction of Ce（NO3）3 with NaOH in the presence of CTAB at 90℃ for 12 h yieldsed a cerium oxide/surfaetant mixture, which after calcination at 400℃ resulted in high-surface area nano-CeO2. The mean crystallite size of CeO2 was approximately 6 nm, surface area was in excess of 200 m^2· g ^- 1, pore size was approximately 9 nm, and the pore distribution was concentrative. Moreover, the surface area can still reach 147 m^2·g^- 1 after calcination at 700 ℃, which showed the good thermal stability of the CeO2. The number of oxygen vacancies in the structure of CeO2 corresponded with the surface area of CeO2, and the high surface area was propitious to the formalion of oxygen vacancies.     

Catalytic oxidation of formaldehyde over CeO_2-Co_3O_4 catalysts

A series of CeO_2-Co_3O_4 mixed oxide catalysts with different Co/(Co+Ce) atomic ratios were synthesized by citric acid sol-gel method and used for catalytic oxidation of formaldehyde(HCHO). Many techniques such as Brumauer-Emmett-Teller(BET), X-ray diffraction(XRD), scanning electron microscopy(FE-SEM), temperature programmed reduction(H_2-TPR), temperature-programmed desorption(O_2-TPD) and X-ray photoelectron spectroscopy(XPS) were used to characterize catalysts. The results of catalytic performance tests showed that the catalyst CeO_2-Co_3O_4 with Co/(Co+Ce) ratio of 0.95 exhibited the best performance, and the temperature of complete oxidation of HCHO was 80 oC. The analytical results indicated that the addition of CeO_2 enhanced the specific surface area of Co_3O_4 and the fine dispersion of both of them. Moreover, the strong interaction between CeO_2 and Co_3O_4 resulted in the unique redox properties, which enhanced the available surface active oxygen and led to high valence state of cobalt oxide species. All those effects played crucial roles in the excellent performance of CeO_2-Co_3O_4 for the HCHO oxidation.     

Preparation of Well Dispersed and Ultra-Fine Ce （Zr）O2 Mixed Oxide by Mechanochemical Processing

Ultra-fine CeO2-ZrO2 mixed oxide was successfully synthesized by wet-solid phase mechanochemical processing, Ce2(CO3)3·8H2O, ZrOCl2·xH2O and ammonia were used as reactants. It is found that the crystalline Ce2(CO3)3·8H2O and ZrOCl2·xH2O are changed to amorphous cerium and zirconium hydroxide precursor after milling with ammonia, and Ce0.15Zr0.85O2 mixed oxide with pure tetragonal phase structure and medium particle size(D50)less than 1μm is formed by calcining precursor over 673 K. The XRD patterns indicate that the crystal unite size increases with rising calcining temperature due to crystal growth. However, the particle size and BET surface area of the Ce(Zr)O2 mixed oxide decreases with rising calcining temperature, which may be attributed to the contract of particles and the vanish of holes inside grains.     

Influence of cobalt on performance of Cu-CeO_2 catalysts for preferential oxidation of CO

Copper and cobalt oxides supported on CeO_2 were investigated for preferential oxidation of carbon monoxide(CO-PROX) in the presence of excess hydrogen and CO_2.(Cuo)_(1-x)(Co_3 O_4)_(x/3)-(CeO_2)_(2.5)(x=0,0.25,0.50,0.75,0.85 and 1) catalysts were prepared by coprecipitation method.These mixed oxide catalysts were characterized by several physicochemical techniques,such as BET surface area(S_(BET)),X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM),temperature programmed reduction(TPR) and X-ray photoelectron spectroscopy(XPS).XRD studies show the peaks related to CuO and Co_3 O_4 phases in copper and cobalt containing CeO_2 catalysts.The average particle size of the CeO_2 crystallites is in the range of 8-10 nm as evaluated from HRTEM studies.XPS studies demonstrate that Cu,Co and Ce in(cuO)_(1-x)(Co_3O_4)_(x/3)-(CeO_2)_(2.5) catalysts are presented in+2 and +1,+3 and +2 and +4 and +3 oxidation states,respectively.The catalyst with x=0.75 shows better activity and selectivity towards CO-PROX.Though the catalyst with only copper(CuO-CeO_2,x=0) shows good activity but reverse water gas shift(RWGS) reaction is noticed at high temperature.On the other hand,RWGS reaction is suppressed on the cobalt containing CuO-ceO_2 catalyst.Cobalt on CeO_2 with x=1 shows hardly any activity for PRoX reaction at low temperatures.No methanation activity is observed on CuO-CeO_2 or Co_3O_4-CeO_2 catalysts.In contrast,combination of copper and cobalt on CeO_2 shows methanation of CO where enhanced activity is observed with increasing in cobalt content.     

Effect of cerium oxide prepared under different hydrothermal time on electrocatalytic performance of Pt-based anode catalysts

In this paper,CeO_2 with a pore size of 2-4 nm was synthesized by hydrothermal method.The CeO_2 modified graphene-supported Pt catalyst was prepared by the microwave-assisted ethylene glycol reduction chloroplatinic acid method,and the effect of the addition of CeO_2 prepared by different hydrothermal reaction time on the catalytic performance of Pt-based catalysts was investigated.The microstructures of CeO_2 and catalysts were characterized by X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),specific surface area and pore size analyzer(BET),scanning electron microscopy(SEM) and electron spectroscopy(EDAX),transmission electron microscopy(TEM),and the catalysts electrochemical performance was tested by electrochemical workstation.The results show that the catalytic performance of the four catalysts with CeO_2 is better than that of the catalyst without CeO_2.Adding CeO_2 with a specific surface area of 120.15 m~2/g prepared by hydrothermal reaction time of 39 h to Pt/C synthesis catalyst,its electrocatalytic performance,stability and resistance to poisoning are the best.The electrochemical active surface area is 102.83 m~2/g,the peak current density of ethanol oxidation is 757.17 A/g and steady-state current density of 1100 s is 108.17 A/g which shows the lowest activation energy for ethanol oxidation reaction.When the cyclic voltammogram is scanned for 500 cycles,the oxidation peak current density retention rate is 87.74%.     

Effect of Ce doping into V_2O_5-WO_3/TiO_2 catalysts on the selective catalytic reduction of NO_x by NH_3

In this work, the effectiveness of V_2O_5-WO_3/TiO_2 catalysts modified with different CeO_2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V_2O_5-WO_3/CeO_2-TiO_2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%(All Ce contents are in mass fractions), but the NO conversion of V_2O_5-WO_3/CeO_2/TiO_2 catalysts modified by impregnation methods was lower than V_2O_5-WO_3/CeO_2-TiO_2 catalysts especially beyond 2.5% Ce doping contents. The V_2O_5-WO_3/CeO_2-TiO_2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce~(3+)species and more Br?nsted acid sites than that by impregnation. The vacancies caused by more Ce~(3+)species were favorable for more NO oxidation to NO_2, and the interaction between Ce species and WOxspecies generated more Br?nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V_2O_5-WO_3/CeO_2-TiO_2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V_2O_5-WO_3/TiO_2 catalysts.     

电炉粉尘预处理对其合成Ni-Zn铁氧体性能的影响

摘要：尖晶石型铁氧体MFe2O4（M=Ni、Zn、Mn和Mg等）由于其良好的稳定性和优越的磁电性能,在磁电领域受到广泛应用。以电炉粉尘为原料,先利用NaOH溶液对电炉粉尘进行预处理,然后加入不同含量的NiCl2·6H2O,通过水热方法直接合成具有尖晶石结构的Ni-Zn铁氧体（(Ni,Zn)Fe2O4）,最后详细探讨了不同浓度的NaOH预处理除硅和配入不同量NiCl2·6H2O对合成(Ni,Zn)Fe2O4磁性能的变化规律。结果表明,当NaOH浓度从0增加到10mol/L时,预处理后电炉粉尘中SiO2质量分数从6.85%降低到1.49%,合成的Ni-Zn铁氧体的饱和磁感应强度从19.5A·m2/kg升高到32.3A·m2/kg;而预处理后电炉粉尘与NiCl2·6H2O的质量比从1∶0.7降低到1∶0.9时,所得样品的饱和磁感应强度从28.4A·m2/kg增长到32.3A·m2/kg。该工艺不仅简化了电炉粉尘的处理工艺流程,而且实现了其高附加值利用。     

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.     

CeO_2/CuO catalysts using different template agent for preferential CO oxidation in H_2-rich stream

The CeO_2/CuO catalysts using different template agent(F68 L64, F127 and P123) were synthesized by the simple template and impregnation method. They were characterized by FESEM, XRD, N2 physisorption and H2-TPR techniques. It is found that the CeO_2/CuO catalysts are double pore distribution, and CeO_2 can enter into the gap of CuO supports and form the contact interface of copper and cerium. Among the asprepared catalysts, the CeO_2/CuO-F127 catalyst displays better activity at lower temperature and the CeO_2/CuO-P123 catalyst presents higher activity at higher temperature. The CeO_2/CuO-P123 catalyst has the smallest crystallite sizes of CuO and CeO_2 as well as the largest size of cubes, which may improve the interaction of copper and cerium and enhance the performance of CO oxidation.