CuO/CeO2-Al2O3催化剂中CuO高温迁移和固相反应的研究

采用原位XRD、激光Raman光谱和TPR技术研究了不同温度焙烧的CuO／CeO2-Al2O3催化剂中CuO物种的存在形式及其高温固相反应。结果表明，300℃焙烧催化剂CuO以晶相和非晶相形式存在于CeO2-Al2O3的表层。600℃焙烧催化剂，表层CuO部分迁移到CeO2内层，并与载体Al2O3反应生成CuAl2O4。800℃焙烧催化剂，除了极少景CuO以晶相和非晶相形式存在于CeO2-Al2O3的表层外，大部分CuO迁移到CeO2内层，与载体反应生成CuAl2O4的量明显增加。900℃焙烧催化剂。所有的Cu物种都以CuAl2O4形式存在。表明高温焙烧有利于CuO向CeO2内层迁移及内层CuO与载体Al2O3反应生成CuAl2O4。     

CuO/CeO_2-Al_2O_3催化剂中CuO物种的原位XRD、Raman和TPR表征

采用原位XRD、激光Raman光谱和TPR(程序升温还原)技术研究了CuO(w,%)/CeO2-Al2O3催化剂中CuO物种的存在形式及其CuO物种的迁移.低温焙烧(300℃)催化剂,CuO以高分散和晶相两种形式存在于CeO2-Al2O3载体表层.随着焙烧温度的升高,CuO开始从表层向CeO2内层迁移.处于内层的CuO部分以晶相形式存在,部分与Al2O3载体反应生成CuAl2O4.高温有利于表层CuO向CeO2内层迁移,同时促进CuAl2O4生成.结果表明结合原位XRD、激光Raman光谱和TPR技术可以有效地观察催化剂中CuO物种的存在形式和分布.     

Ce1 - x Tbx O2 - δ复合氧化物氧缺位的拉曼光谱研究

采用溶胶-凝胶法制备了Ce1-xTbxO2-δ复合氧化物,利用不同Raman激发波长(514和785 nm),结合X射线衍射(XRD)、氢气-程序升温还原(H2-TPR)和氧气-程序升温脱附(O2-TPD)表征,考察了Ce1-xTbxO2-δ复合氧化物在O2,He和H2气氛下氧缺位的原位变化情况和CeO2的F2g特征Raman峰位的偏移. 实验结果表明,随着Tb掺杂量的提高,由于晶胞收缩使得CeO2的F2g特征Raman振动峰发生蓝移. 514 nm Raman激发波长反映了催化剂的表面信息,而785 nm激发波长反映了整体信息. 正是由于表面和整体变化的不一致,造成原位Raman实验过程中氧缺位浓度变化趋势的不同. 在He和H2气氛下,由于温度升高时伴随着Ce1-xTbxO2-δ中O2气的脱出,使复合氧化物的微观结构发生改变,以致Ce0.9Tb0.1O2-δ中的氧缺位浓度(A587/A465)在785 nm激发波长下出现先升高后下降的现象.     

CuO/Al2O3催化剂高温固相反应的原位XRD和Raman研究

采用原位XRD和激光Raman光谱等技术对CuO/Al2O3系列催化剂高温下的表面组成和体相结构的变化进行研究.结果表明,随着焙烧温度升高,CuO首先与载体Al2O3发生固相反应生成CuAl2O4.CuAl2O4层能阻止外层CuO进一步向载体Al2O3扩散,从而使部分CuO稳定在CuO/Al2O3催化剂的表层.     

Ce1-xTbxO2-δ复合氧化物氧缺位的拉曼光谱研究

采用溶胶-凝胶法制备了Ce1-xTbxO2-δ复合氧化物, 利用不同Raman激发波长(514和785 nm), 结合X射线衍射(XRD)、氢气-程序升温还原(H2-TPR)和氧气-程序升温脱附(O2-TPD)表征, 考察了Ce1-xTbxO2-δ复合氧化物在O2, He和H2气氛下氧缺位的原位变化情况和CeO2的F2g特征Raman峰位的偏移. 实验结果表明, 随着Tb掺杂量的提高, 由于晶胞收缩使得CeO2的F2g特征Raman振动峰发生蓝移. 514 nm Raman激发波长反映了催化剂的表面信息, 而785 nm激发波长反映了整体信息. 正是由于表面和整体变化的不一致, 造成原位Raman实验过程中氧缺位浓度变化趋势的不同. 在He和H2气氛下, 由于温度升高时伴随着Ce1-xTbxO2-δ中O2气的脱出, 使复合氧化物的微观结构发生改变, 以致Ce0.9Tb0.1O2-δ中的氧缺位浓度(A587/A465)在785 nm激发波长下出现先升高后下降的现象.     

V2O5-CeO2/TiO2催化剂上低温氨选择性催化还原NO的性能

考察了V2O5-CeO2/TiO2催化剂中V、Ce活性组分的担载量和焙烧温度对催化剂低温催化还原NO活性的影响及其在单独SO2、H2O和两者共存气氛下的抗毒化性能。结果表明,焙烧温度400℃下制备的5V30Ce/TiO2催化剂具有良好的低温催化还原NO活性,空速为10000h-1,165℃时NO转化率达99.2%;500℃以下低焙烧温度时,添加的Ce不与V相互作用,在催化剂表面主要以CeO2形式存在,有利于增大催化剂比表面积,增强V2O5在催化剂上的分散度,提高催化活性。而在500℃以上较高焙烧温度下,Ce与V会形成CeVO4,对活性提高不利。催化剂具有良好的低温抗水中毒性能,但受SO2毒化作用明显,其在SO2、H2O共存气氛下中毒程度较单独SO2下浅。     

CeO2-Y2O3涂层和负载型Pd催化剂催化燃烧VOCs

制备了一种粘附在堇青石蜂窝陶瓷载体上的CeO2-Y2O3(CeY)复合氧化物新涂层. 以二氧化铈和柠檬酸钇为前驱体, 制备过程中无有害物质产生, 对环境友好. CeY涂层和Pd/CeY催化剂通过SEM、EDX、XRF和Raman光谱等表征. 结果表明, 此涂层的粘结强度高, 对活性组分的吸附性能好, 适合用来负载钯催化剂. Y2O3大部分进入了峰窝陶瓷的孔道内, CeO2和Pd物种则富集在载体的表面. 以CO、甲苯和乙酸乙酯的催化燃烧来评价Pd/CeY催化剂的性能, 此催化剂具有较好的催化活性和热稳定性. 500 ℃焙烧的催化剂, CO、甲苯和乙酸乙酯的T99(转化率99%以上所需的最低反应温度) 分别为150、220和310 ℃; 1050 ℃焙烧的催化剂, 它们的T99分别为180、250 和330 ℃. 高温焙烧的催化剂, 活性物种PdO的晶粒增大, 这可能导致催化剂的活性下降.     

CuO/Ce0.5Ti0.5O2的制备与表征及其对NO+CO反应的催化活性

以Ce0.5Ti0.5O2为载体, 采用浸渍法制备了不同负载量的CuO/Ce0.5Ti0.5O2催化剂, 通过TPR、XRD和激光Raman光谱等技术对其进行了表征, 并在色谱-微反装置上考察了催化剂对NO+CO反应催化性能. 结果表明, CuO/Ce0.5Ti0.5O2催化剂对NO+CO反应的活性与CuO负载量有关; 500 ℃焙烧的催化剂, 当CuO的负载量(w)为22%时, 催化剂的活性最好; 14%CuO/Ce0.5Ti0.5O2在700 ℃焙烧具有最佳催化活性, 这可能与复合载体形成了CeTi2O6的结构有关. TPR结果表明, CuO在Ce0.5Ti0.5O2上出现了四种还原能力不同的物种, α和β峰是载体表面高度分散的CuO物种, γ峰是与Ce0.5Ti0.5O2相互作用较强的孤立CuO晶簇的还原峰, δ峰是载体表面晶相CuO的还原峰; XRD结果表明700 ℃焙烧的样品中已出现了新复合氧化物CeTi2O6的晶相峰, 随焙烧温度的升高, 此晶相峰也变得更加明显, 这说明高温焙烧有利于Ce与Ti发生固相反应而形成CeTi2O6结构; Raman结果表明, 焙烧后的Ce0.5Ti0.5O2并不是简单的TiO2和CeO2的复合, 而是形成了新的晶相结构, 这也进一步验证了CeTi2O6结构的生成.     

Ce1-xGdxO2-δ固溶体中缺陷物种的拉曼光谱研究

采用溶胶-凝胶法制备一系列Ce1-xGdxO2-δ固溶体。利用紫外(325 nm)和可见(514 nm)Raman光谱,X射线粉末衍射(XRD),透射电子显微镜(TEM)和紫外可见漫反射光谱(UV-Vis DRS),考察了Ce1-xGdxO2-δ固溶体的缺陷物种的分布以及Gd含量对缺陷浓度的影响。结果表明:Ce1-xGdxO2-δ固溶体中存在氧缺位(～560 cm-1)和GdO8型缺陷结构(～600 cm-1)。根据样品对Raman激发光的吸收,紫外Raman光谱反映样品的表层信息,可见Raman光谱反映样品的整体信息。Ce1-xGdxO2-δ固溶体表层氧缺位(να)和GdO8型缺陷物种的浓度(νβ)均高于固溶体体相,这归因于缺陷物种的表面富集。然而,相比于GdO8型缺陷物种,体相中氧缺位浓度增加较表层中的更显著。     

吸附相反应技术制备MnO_x/CeO_2/SiO_2催化剂及其低温选择性催化还原NO_x

采用吸附相反应技术制备得到了MnOx/CeO2/SiO2催化剂,通过X射线衍射(XRD)、透射电子显微镜(TEM)、高分辨透射电子显微镜(HRTEM)、紫外激光拉曼(Raman)等手段对催化剂进行了表征.HRTEM分析表明活性组分MnOx与CeO2都均匀分布在载体SiO2表面;XRD分析表明Mn3O4特征峰随着CeO2含量的增加逐渐减小至完全消失,CeO2的加入降低了MnOx的结晶程度,增加了MnOx的分散性;Raman光谱表明催化剂表面的Mn离子能够进入CeO2晶格,激发出空穴氧,随着CeO2负载量的增加,催化剂氧空穴浓度先升高后降低.以NH3为还原剂,考评催化剂的NOx低温选择性催化还原(SCR)性能,催化剂催化活性随CeO2负载量增加先升高后降低,与催化剂氧空穴浓度变化规律一致,说明催化剂活性受氧空穴浓度影响,氧空穴浓度升高,催化剂催化活性升高.     

立方Nd2O3上过氧物种光诱导生成的18O同位素示踪考察

采用原位显微Raman光谱和¹⁸O同位素示踪技术,以325 nm激光为激发光源,对立方Nd₂O₃上过氧物种的光诱导生成过程进行了详细表征,进一步证实过氧源于分子氧对晶格氧的氧化反应. 结果还表明,325 nm激光在室温下即可诱导过氧的生成,在实验条件下,生成的过氧物种可与Nd₂O₃的晶格氧发生快速的氧交换反应,位于Nd₂O₃体相的晶格氧也可迁移至样品表层进而参与过氧的生成. 325 nm激光照射有助于促进晶格氧的迁移以及晶格氧与分子氧之间的氧交换反应.     

吸附相反应技术制备MnOx/CeO2/SiO2催化剂及其低温选择性催化还原Nox

采用吸附相反应技术制备得到了MnO_x/CeO₂/SiO₂催化剂,通过X 射线衍射（XRD）、透射电子显微镜（TEM）、高分辨透射电子显微镜（HRTEM）、紫外激光拉曼（Raman）等手段对催化剂进行了表征. HRTEM分析表明活性组分MnO_x与CeO₂都均匀分布在载体SiO₂表面;XRD分析表明Mn₃O₄特征峰随着CeO₂含量的增加逐渐减小至完全消失,CeO₂的加入降低了MnO_x的结晶程度,增加了MnO_x的分散性;Raman光谱表明催化剂表面的Mn离子能够进入CeO₂晶格,激发出空穴氧,随着CeO₂负载量的增加,催化剂氧空穴浓度先升高后降低.以NH₃为还原剂,考评催化剂的NO_x低温选择性催化还原（SCR）性能,催化剂催化活性随CeO₂负载量增加先升高后降低,与催化剂氧空穴浓度变化规律一致,说明催化剂活性受氧空穴浓度影响,氧空穴浓度升高,催化剂催化活性升高.     

V2O5-TiO2复合半导体光催化材料结构及光响应性能研究

采用溶胶凝胶法制备了V₂O₅-TiO₂复合半导体材料，通过Raman、XRD及UV-Vis DRS等实验方法研究了V₂O₅与TiO₂复合对材料表面组成、晶体结构以及光响应性能的影响。结果表明：钒加入后优先与TiO₂作用形成较为稳定的金红石型TiVO₄晶相，其中V⁴⁺是促进TiO₂发生相变的关键；随着钒加入量的增加，V₂O₅由表面高分散状态逐渐聚集形成晶相，并释放部分Ti⁴⁺使之形成锐钛矿型TiO₂晶相，使得体相中金红石型TiO₂的含量有所下降；复合后形成的TiVO₄晶相显著提高了材料对可见光的吸收率，并使其吸光域红移至460 nm左右。     

Nanosized CeO2–SiO2, CeO2–TiO2, and CeO2–ZrO2 Mixed Oxides: Influence of Supporting Oxide on Thermal Stability and Oxygen Storage Properties of Ceria

The influence of SiO₂, TiO₂, and ZrO₂ on the structural and redox properties of CeO₂ were systematically investigated by various techniques namely, X-ray diffraction (XRD), Raman spectroscopy (RS), UV–Vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HREM), BET surface area, and thermogravimetry methods. The effect of supporting oxides on the crystal modification of ceria was also mainly focused. The investigated oxides were obtained by soft chemical routes with ultrahigh dilute solutions and were subjected to thermal treatments from 773 to 1073 K. The XRD results suggest that the CeO₂–SiO₂ sample primarily consists of nanocrystalline CeO₂ on the amorphous SiO₂ surface. Both crystalline CeO₂ and TiO₂-anatase phases were noted in the case of CeO₂–TiO₂ sample. Formation of cubic Ce_0.75Zr_0.25O₂ and Ce_0.6Zr_0.4O₂ (at 1073 K) were observed in the case of CeO₂–ZrO₂ sample. The cell ‘a’ parameter estimations revealed an expansion of the ceria lattice in the case of CeO₂–TiO₂, while a contraction is noted in the case of CeO₂–ZrO₂. The DRS studies suggest that the supporting oxides significantly influence the band gap energy of CeO₂. Raman measurements disclose the presence of oxygen vacancies, lattice defects, and displacement of oxide ions from their normal lattice positions in the case of CeO₂–TiO₂ and CeO₂–ZrO₂ samples. The XPS studies revealed the presence of silica, titania, and zirconia in their highest oxidation states, Si(IV), Ti(IV), and Zr(IV) at the surface of the materials. Cerium is present in both Ce⁴⁺ and Ce³⁺ oxidation states. The HREM results reveal well-dispersed CeO₂ nanocrystals over the amorphous SiO₂ matrix in the case of CeO₂–SiO₂, isolated CeO₂ and TiO₂ (A) nanocrystals and some overlapping regions in the case of CeO₂–TiO₂, and nanosized CeO₂ and Ce–Zr oxides in the case of CeO₂–ZrO₂ sample. The exact structural features of these crystals as determined by digital diffraction analysis of HREM experimental images reveal that the CeO₂ is mainly in cubic fluorite geometry. The oxygen storage capacity (OSC) as determined by thermogravimetry reveals that the OSC of mixed oxides is more than that of pure CeO₂ and the CeO₂–ZrO₂ exhibits highest OSC.     

UV and visible Raman studies of oxygen vacancies in rare-earth-doped ceria

Surface properties of rare-earth (RE) doped ceria (RE = Sm, Gd, Pr, and Tb) were investigated by UV (325 nm) and visible (514, 633, and 785 nm) Raman spectroscopy, combined with UV-vis diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectra techniques. It was found that the optical absorption property of samples, the wavelength of detecting laser line, and the inhomogeneous distribution of the dopants significantly affected the obtained surface information, namely, the peak intensity and shape at ca. 460 and 570 cm(-1), as well as the observed oxygen vacancy concentration (A(570)/A(460)). The UV laser line detected the surface information of RE-doped ceria and disclosed the presence of many oxygen vacancies in the samples. The visible laser lines penetrated into the inner layer of the Sm- or Gd-doped CeO(2) and reflected the whole information of samples because of their weak absorptions of the visible laser. However, the Pr- or Tb-doped CeO(2) absorbed visible light strongly; thus, the laser can only determine the outer surface information of the sample.     

V2O5/TiO2 Catalytic Xerogels Raman and EPR Studies

Raman spectroscopy and Electron Paramagnetic Resonance (EPR) studies were performed on a series of V₂O₅/TiO₂ catalysts prepared by a modified sol-gel method in order to identify the vanadium species. Two species of surface vanadium were identified by Raman measurements, monomeric vanadyls and polymeric vanadates. Monomeric vanadyls are characterized by a narrow Raman band at 1030 cm^–1 and polymeric vanadates by two broad bands in the region from 900 to 960 cm^–1 and 770 to 850 cm^–1. The Raman spectra do not exhibit characteristic peaks of crystalline V₂O₅. These results are in agreement with those of X-ray Diffractometry (XRD) and Fourier Transform Infrared (FT-IR) previously reported (C.B. Rodella et al., J. Sol-Gel Sci. Techn., submitted). At least three families of V⁴⁺ ions were identified by EPR investigations. The analysis of the EPR spectra suggests that isolated V⁴⁺ ions are located in sites with octahedral symmetry substituting for Ti⁴⁺ ions in the rutile structure. Magnetically interacting V⁴⁺ ions are also present as pairs or clusters giving rise to a broad and structureless EPR line. At higher concentration of V₂O₅, a partial oxidation of V⁴⁺ to V⁵⁺ is apparent from the EPR results.     

Effect of capping and particle size on Raman laser-induced degradation of γ-Fe2O3 nanoparticles

Diol capped γ-Fe₂O₃ nanoparticles are prepared from ferric nitrate by refluxing in 1,4-butanediol (9.5 nm) and 1,5-pentanediol (15 nm) and uncapped particles are prepared by refluxing in 1,2-propanediol followed by sintering the alkoxide formed. X-ray diffraction (XRD) shows that all the samples have the spinel phase. Raman spectroscopy shows that the samples prepared in 1,4-butanediol and 1,5-pentanediol and 1,2-propanediol (sintered at 573 and 673 K) are γ-Fe₂O₃ and the 773 K-sintered sample is Fe₃O₄. Raman laser studies carried out at various laser powers show that all the samples undergo laser-induced degradation to α-Fe₂O₃ at higher laser power. The capped samples are however, found more stable to degradation than the uncapped samples. The stability of γ-Fe₂O₃ sample with large particle size (15.4 nm) is more than the sample with small particle size (10.2 nm). Fe₃O₄ having a particle size of 48 nm is however less stable than the smaller γ-Fe₂O₃ nanoparticles.     

Dispersion state and catalytic properties of vanadia species on the surface of V<Subscript>2</Subscript>O<Subscript>5</Subscript>/TiO<Subscript>2</Subscript> catalysts

The dispersion state and catalytic properties of anatase-supported vanadia species are studied by means of X-ray diffraction (XRD), laser Raman spectroscopy (LRS), H₂ temperature-programmed reduction (TPR) and the selective oxidation of o-xylene to phthalic anhydride. The almost identical values of the experimental dispersion capacity of V₂O₅ on anatase and the surface vacant sites available on the preferentially exposed (001) plane of anatase suggest that the highly dispersed vanadium cations are bonded to the vacant sites on the surface of anatase as derived by the incorporation model. When the loading amount of V₂O₅ is far below its dispersion capacity, the dispersed vanadia species might mainly consist of isolated VO_x species bridging to the surface through V-O-Ti bonds. With the increase of V₂O₅ loading the isolated vanadia species interact with their nearest neighbors (either isolated or polymerized vanadia) through bridging V-O-V at the expenses of V-O-Ti bonds, resulting in the increase of the ratio of polymerized to isolated vanadia species and the decrease of the reactivity of the associated surface oxygen anions and, consequently, although the activity increases with loading to reach a maximum value, the turn over number (TON) of the V₂O₅/TiO₂ catalyst decreases linearly. When the loading amount of V₂O₅ is higher than its dispersion capacity, the turn over number decreases more rapidly with the increase of V₂O₅ loading due to the formation of V₂O₅ crystallites in which the oxygen anions associated with V-O-V bonds are less reactive and only partially exposed on the surface.     

Characterization of thin metastable vanadium oxide films by Raman spectroscopy

Thin films are potentiodynamically generated on vanadium in Ba²⁺/acetate electrolyte systems at high voltages. The influence of the anodic potential up to 400 V on the composition and structure of the about 500 nm thin anodic conversion films are investigated. Raman spectroscopy indicates that different film types depend on the electrochemical process parameters. The relationship between the Raman laser excitation power and the amorphous or microcrystalline film structure is also discussed. Beside metastable disordered structures the films contain crystalline phases of V₂O₅, V₄O₉ and barium vanadate, respectively.