Interaction of Au with thin ZrO2 films: influence of ZrO2 morphology on the adsorption and thermal stability of Au nanoparticles

The model catalysts of ZrO(2)-supported Au nanoparticles have been prepared by deposition of Au atoms onto the surfaces of thin ZrO(2) films with different morphologies. The adsorption and thermal stability of Au nanoparticles on thin ZrO(2) films have been investigated using synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The thin ZrO(2) films were prepared by two different methods, giving rise to different morphologies. The first method utilized wet chemical impregnation to synthesize the thin ZrO(2) film through the procedure of first spin-coating a zirconium ethoxide (Zr(OC(2)H(5))(4)) precursor onto a SiO(2)/Si(100) substrate at room temperature followed by calcination at 773 K for 12 h. Scanning electron microscopy (SEM) investigations indicate that highly porous "sponge-like nanostructures" were obtained in this case. The second method was epitaxial growth of a ZrO(2)(111) film through vacuum evaporation of Zr metal onto Pt(111) in 1 × 10(-6) Torr of oxygen at 550 K followed by annealing at 1000 K. The structural analysis with low energy electron diffraction (LEED) of this film exhibits good long-range ordering. It has been found that Au forms smaller particles on the porous ZrO(2) film as compared to those on the ordered ZrO(2)(111) film at a given coverage. Thermal annealing experiments demonstrate that Au particles are more thermally stable on the porous ZrO(2) surface than on the ZrO(2)(111) surface, although on both surfaces, Au particles experience significant sintering at elevated temperatures. In addition, by annealing the surfaces to 1100 K, Au particles desorb completely from ZrO(2)(111) but not from porous ZrO(2). The enhanced thermal stability for Au on porous ZrO(2) can be attributed to the stronger interaction of the adsorbed Au with the defects and the hindered migration or coalescence resulting from the porous structures.     

Influence of counter-ions on the self-assembly of ZrO2 nanodisks

In three strong inorganic acidic conditions (HNO(3), HCl and H(2)SO(4)), we have prepared a series of air-water interfacial zirconium dioxide (ZrO(2)) films at normal temperature via a self-assembly technique, by using dodecylbenzenesulfonic acid (DBSA) as template and Zr(OC(4)H(9))(4) as precursor. X-ray diffraction (XRD), transmission electron microscope (TEM), UV-vis and fluorescence spectra have been used to characterize the ZrO(2) films. Results show that a number of worm-like mesoporous nanodisks and ambiguously mesoporous nanodisks are observed in the ZrO(2) films with NO(3)(-) and SO(4)(2-) counter-ions, respectively. Remarkably, a great many perfect target-like multiring nanodisks are obtained in the ZrO(2) sample with Cl(-) counter-ion. The self-assembly mechanism for ZrO(2) nanodisks has been purposely discussed. A model based on the structural changes with respect to the influence of counter-ions on the self-assembly of ZrO(2) nanodisks is therefore proposed. In addition, the structural changes for the ZrO(2) films self-assembled at a higher temperature have been discussed in combination with the influence of counter-ions.     

表面活性剂和聚乙烯吡咯烷酮在ZrO2上的吸附对其悬浮体稳定性的影响

研究了水溶液中十二烷基苯磺酸钠（ＳＤＢＳ）、溴代十四烷基吡啶（ＴＰＢ）和聚乙烯吡咯烷酮（ＰＶＰ）在ＺｒＯ２上的吸附及对ＺｒＯ２水悬浮体稳定性的影响。结果表明：ｐＨ＝２．４时ＳＤＢＳ在ＺｒＯ２上的吸附等湿线为ＬＳ型，ｐＨ＝７．０时ＴＰＢ的吸附等温线为Ｓ型，吸附等温线与ＺｒＯ２粒子ζ电势变化同线有大体一致的关系。在最大吸附量时ＺｒＯ２粒子ζ电势较大，且吸附的表面活性剂离子形成大部分亲水基朝向水相的表面     

The Crystal Structure of Mer-Trans (NH3-NH2)-Potassium Trinitroglycinatoamminecobaltate(III) Monohydrate

Some new oxozirconium(IV) complexes: ZrO(An)₂, ZrO(Gly)₂, ZrO(HSal)₂, ZrO(HPth)₂, ZrO(Pic)₂(HPic)₂, and ZrO(Quin)₂(H Quin)₂ have been isolated from the reactions of ZrO(CH₃COO)₂CH₃COOH with anthranilic acid (HAn), glycine (HGly), salicylic acid (H₂Sal), phthalic acid (H₂Pth), picolinic acid (HPic), and 8-quinolinol (HQuin) respectively. Their important infrared bands and wherever possible molar conductance and molecular weight have been reported.     

Electron injection into the surface states of ZrO2 nanoparticles from photoexcited quinizarin and its derivatives: effect of surface modification

The effect of surface modification on interfacial electron transfer (IET) dynamics into the surface states of ZrO(2) nanoparticles sensitized by quinizarin (Qz) and its derivatives has been carried out using time-resolved emission spectroscopy. The surface of ZrO(2) nanoparticles has been modified by sodium dodecyl benzyl sulfonate . We have observed that Qz's can form a strong charge-transfer (CT) complex with both unmodified and surface-modified (SM) ZrO(2) nanoparticles. We have confirmed electron injection into the surface states of ZrO(2) nanoparticles from the photoexcited Qz molecule in our earlier work (J. Phys. Chem. B 2004, 108, 4775; Langmuir 2004, 20, 7342). In the present investigation, we have observed electron injection from photoexcited Qz derivatives into the surface states of both unmodified and SM ZrO(2) nanoparticles and also detected CT emission. Monitoring CT emission, we have determined back electron transfer (BET) dynamics of the dye-nanoparticle systems. We have found that the BET rate for the QZs/ZrO(2) systems decreases as the relative driving force increases following Marcus inverted region kinetic behavior for an IET process. BET dynamics was found to be faster on SM ZrO(2) nanoparticles as compared to that of the unmodified (bare) one. Our time-resolved emission data indicates that upon surface modification the majority of the deeper trap states of ZrO(2) nanoparticles can be removed with the formation of some new shallower trap states in the band gap region.     

制备方法对WO3/ZrO2结构的影响

WO3/ZrO2 catalysts prepared from Zr(OH)4 and crystallized ZrO2 have been characterized by means of XRD, LRS (qualitative and quantitative), and the specific sufrace area has been measured. The influence of the preparation method, the contents of WO3 in the samples and the calcination tempearture on the specific surface areas of the samples, the phase of support and the structural states of active component has been studied. The results show: (1) WO3 can disperse on ZrO2 as a monolayer; (2) WO3 dispersed on Zr(OH)4 as a monolayer retards the crystalline growth of the support on calcination, makes it crystallizing into a metastable tetragonal modification, and prevents the inter- crystalline sintering between the crystallites of ZrO2. These factors would result in an increase in the specific surface area of WO3／ZrO2 prepared from Zr(OH)4. As the content of WO3 in the sample comes up to its monolayer capacity, this effect is displayed most fully. A chemical reaction can occur between WO3 and Zr(OH)4 (or the tetragonal ZrO2) at a high temperature(800℃),producing some superacid sites on the surface. By these views, the main experimental facts published in the literatures can been interpreted satisfactotily.     

铜基氧化锆载体合成甲醇催化剂的结构表征

以ＸＲＤ，ＥＸＡＦＳ和ＥＳＲ等手段考察了ＣｕＯ／ＺｒＯ２催化剂及其还原态的结构，结果表明，在ＣｕＯ／ＺｒＯ２中铜以ＣｕＯ的形式存在，ＺｒＯ２载体对所负载的ＣｕＯ的结构有影响，ＣｕＯ的分散度与焙烧温度有关，在适当的温度下焙烧，负载于ＺｒＯ２上的ＣｕＯ可自发分散，在还原态试样中铜主要以有金属的形式存在，但是当试样中铜的含量小，铜的分散度高时有铜的氧化物存在，其Ｃｕ－Ｏ键距介于ＣｕＯ与ＣｕＯ２之间，Ｃｕ     

CuO/ZrO2活性组分与载体相互作用及其TPR特性

铜基氧化物催化剂具有多种催化功能，许多催化工作者对铜基催化剂的结构、组成、活性组份与载体的作用等一直进行着细致深入地研究，人们尤其重视用TPR、XRD和XPS等手段[1-3]和考察CuO的还原活化过程．ZrO2是常用的催化剂载体之一，具有良好的热稳定性．因此近年来有关以氧化锡     

Polyaniline film formation in hexadecyl trimethyl ammonium bromide admicelles on hydrous zirconia surface

Formation of a thin polyaniline film on hydrous zirconia (ZrO2) surface was carried out using adsorbed surfactant bilayers on ZrO2 as reaction sites. Aniline was adsolubilized in hexadecyltrimethylammonium bromide (HDTAB) admicelles formed on the surface of ZrO2 by adsorption. Subsequent polymerization of the adsolubilized aniline monomer showed effective conversion of aniline to polyaniline. The formation of the polyaniline coated ZrO2 has been confirmed by UV-visible spectroscopy, FT-IR spectroscopy, and conductivity measurements. Various parameters involved during the adsorption process were studied. Selection of pH 9.0 as the pH of all experimental feed solutions was governed by the knowledge of point of zero charge (PZC) of ZrO2. Effect of aniline concentration on HDTAB adsorption was studied and it was observed that increase in aniline concentration decreased the amount of HDTAB adsorbed on ZrO2. Addition of salt (0.05 M NaCl) in the feed solution increased HDTAB adsorption and drastically reduced the effect of aniline concentration on HDTAB adsorption.     

Transport numbers from hydrogen concentration cells over different oxides under oxidising and reducing conditions

Partial hydrogen ion conductivity in acceptor doped CaTiO(3), BaCeO(3) and ZrO(2) and nominally undoped BaTiO(3) and TiO(2) has been investigated by transport number measurements using the hydrogen concentration cell/EMF method in wet atmospheres as a function of pO(2)(10(-20)-1 atm) at 800 or 1000 [degree]C. All oxides investigated, except ZrO(2), show minor proton conductivity in oxidising atmospheres. Earlier indications of apparent negative charge transport by hydrogen under reducing conditions and high temperatures in SrTiO(3) samples have been reproduced for all the investigated oxides including ZrO(2).     

Cu/ZrO2催化剂上乙醇水蒸气重整反应的研究Ⅰ催化剂性能及其制备参数的影响

研究了Cu/ZrO2催化剂在乙醇水蒸气重整反应中的催化性能。用常规沉淀法、醇凝胶法制备了ZrO2载体;用浸渍法或共沉淀法制备了Cu/ZrO2催化剂。考察了ZrO2载体的制备方法以及Cu/ZrO2的制备参数对催化剂性能的影响。采用BET、XRD、TEM及XRF等方法对催化剂的比表面积、孔容、晶相、表面形貌以及活性组分等进行了表征。同时,制备并比较了Ni/ZrO2、Cu/10MgO-90ZrO2和Cu/10CaO-90ZrO2催化剂的性能,考察了活性组分Cu、Ni的差异以及ZrO2载体的影响。在Cu/ZrO2催化剂(Cu的质量分数为8%)上,500 ℃~600 ℃乙醇转化率达到98%~100％、H2选择性为2.0~2.6（摩尔比）。 Cu/ZrO2与Ni/ZrO2机械混合有助于H2选择性的提高。在催化剂载体中添加MgO、CaO碱性物质可以使H2选择性提高1.3倍~2.0倍。浸渍法制备的Cu/ZrO2催化剂的性能优于共沉淀法。     

EPMA of interfaces applied to the solid oxide fuel cell

Chemical interactions at the phase boundaries of materials applied for the solid oxide fuel cell (SOFC) have been studied by EPMA. The chemical reactivity at the interface of La(y-x)Sr(x)MnO(3)/ZrO(2)-Y(2)O(3) is dependent on the stoichiometry (y) and the Sr content (x) of the perovskite. Typical reaction products (zirconates) and a diffusion zone in the ZrO(2)-Y(2)O(3) have been observed. The extension of cation release (Mn) is related to the increasing chemical activity of Mn oxide in the perovskite by the Sr substitution for La. The wettability of the metal/oxide interface in the anode cermet (Ni/ZrO(2)-Y(2)O(3)) has been found to be influenced by chemical reactions resulting from the applied reducing atmosphere with high carbon activity. The disintegration of ZrO(2)-Y(2)O(3) in contact with molten Ni or Ni-Ti and Ni-Cr alloys leads to the redeposition of Y(2)O(3)-enriched oxides and also to Zr-rich intermetallic compounds and eutectics.     

氧化锆担载镍甲烷干重整催化剂的载体形貌效应

煤层气是储量十分丰富的煤炭伴生资源,也是煤炭开采中最大的安全隐患之一,同时还是重要的温室气体.研究煤层气的高效、清洁资源化利用具有资源和环境双重意义.因此,世界主要产煤国均十分重视煤层气的开发和利用.煤层气的主要成分是甲烷,目前主要通过两种方式实现其资源化利用:(1)直接转化,主要通过氧化偶联、催化氧化官能团化或脱氢芳构化等途径将其转化为高碳烃、含氧化合物及芳烃等;(2)间接转化,甲烷首先经催化重整反应制取合成气,而后再经Fischer-Tropsch合成、甲醇化和氢甲酰化等过程来合成饱和烃、烯烃、甲醇及其他含氧化物.对于前者,由于热力学限制,反应收率很低,应用前景较差,而经由合成气这一平台产物的间接转化路线被认为是一条甲烷资源化利用颇具工业前景的转化路线.因此,甲烷催化重整制合成气备受关注.研究表明,贵金属具有较好的甲烷重整催化性能,但其储量有限、价格昂贵的内在缺陷不利于甲烷大规模转化和资源化利用.Ni基催化剂具有与贵金属可比的催化活性和选择性,且其储量丰富,价格低廉,因此在甲烷重整反应中备受青睐.但是,相对于贵金属,Ni基催化剂易于积碳和烧结失活,这已成为制约其大规模工业化应用的瓶颈.迄今,大量文献报道关注如何提高Ni基催化剂的催化稳定性.而载体形貌调控是调节负载型催化剂的有效途径.本文开展了用作载Ni催化剂的氧化锆载体的形貌调控研究,以期可以有效调节载Ni催化剂的物化性质,进而调控载Ni催化剂的甲烷重整催化性能.采用水热法成功制备了松球状和鹅卵石状的单斜相氧化锆载体,进一步负载镍,制备了载镍催化剂,用于甲烷重整制合成气反应.具有分级结构的松球状氧化锆载Ni催化剂(Ni/ZrO2-ipch)展示出比鹅卵石状氧化锆和常规氧化锆纳米粒子载Ni催化剂显著好的催化活性和稳定性.采用XRD、N2吸附、TEM、H2-TPR、CO化学吸附、CO2-TPD、XPS和TGA等手段研究了松球状氧化锆载Ni催化剂高催化活性和稳定性的原因和机制.发现,其较高的催化活性主要归因于高的Ni分散度、改善的可还原性、促进的氧流动性以及较多的碱性位和较强的碱性,这些物化性质依赖于氧化锆载体的独特形貌.分级结构的松球状氧化锆载Ni催化剂高的甲烷重整催化稳定性主要源于催化剂的高抗烧结、抗积碳性能.加强的金属载体效应和介孔限域效应可以阻止金属Ni的高温烧结,而优良的抗积碳稳定性主要源于催化剂良好的氧流动性、较多的碱性位、较强的碱性以及小的Ni粒子尺寸.鉴于分级结构松球状氧化锆载Ni催化剂高的催化活性和优良的抗积碳、抗烧结稳定性,该催化剂用于甲烷重整制合成气具有广阔前景.而所制备的分级结构松球状氧化锆由于具有独特的结构和优良的热稳定性,可以作为性能优良的载体用于其他反应,尤其对于高温转化过程可望表现出明显优势.     

Low temperature preparation of crystalline ZrO2 coatings for improved elevated-temperature performances of Li-ion battery cathodes

Ultrathin crystalline ZrO(2) nanofilms have been facilely deposited on LiMn(2)O(4) particles at 120 °C using atomic layer deposition. The ZrO(2) coating shows high crystallinity, conformality and homogeneity, which contribute to considerably improved electrochemical performance of LiMn(2)O(4) at elevated temperature in lithium-ion batteries.     

以表面活性剂为模板ZrO2薄膜在空气-水界面的自组装研究

采用三种阴离子表面活性剂: 十二烷基磺酸钠(SDS), 十二烷基苯磺酸钠(DBS-Na), 十二烷基苯磺酸(DBS-H)作模板, 在空气-水界面上组装ZrO₂薄膜. 结果表明, 采用SDS组装的薄膜具有良好的机械强度. 经X射线能量扫描谱原位检测以及X射线衍射(XRD)谱检测证实, 所获薄膜为层状结构, 其层间距在2.70～3.54 nm之间. 利用所建立的层状结构模型解释了各种阴离子表面活性剂组装ZrO₂薄膜并控制层间距变化的机理.     

Flexible transparent conducting single-wall carbon nanotube film with network bridging method

Hollow ZrO(2) microspheres with mesoporous shells have been synthesized by a novel hydrothermal reaction of zirconium oxychloride in the presence of urea, hydrochloric acid, and ethanol. The morphology and shell thickness of the hollow microspheres can be controlled by varying synthesis conditions. After calcination at high temperature, the morphologies of the hollow microspheres are essentially preserved. Pt catalyst supported on the hollow calcined ZrO(2) microspheres exhibits more excellent catalytic performance in CO oxidation than those on ZrO(2) powders derived from conventional precipitation methods.     

Remarkable nanosize effect of zirconia in Au/ZrO2 catalyst for CO oxidation

Nanosize effect of ZrO2 in Au/ZrO2 catalyst was studied by deposition-precipitation of Au nanoparticles in similar sizes (4-5 nm) on ZrO2 nanoparticles of varying sizes. The catalysts were characterized with XRD, TEM, XPS, and nitrogen adsorption to understand the effect of ZrO2 particle size on the catalytic nanostructures. Nanocomposite Au/ZrO2 catalysts consisting of comparably sized Au-metal (4-5 nm) and ZrO2 (5-15 nm) nanoparticles are found advantageous over those containing similarly sized Au-metal but larger ZrO2 (40-200 nm) particles for CO oxidation. This finding may have important implications on the designed preparation of advanced nanostructured catalysts and other chemical materials.     

The synthesis of Lewis acid ZrO2 nanoparticles and their applications in phospholipid adsorption from Jatropha oil used for biofuel

ZrO(2) nanoparticles were successfully fabricated via a facile hydrothermal process. The diameter and surface area of the as-prepared ZrO(2) nanoparticles were approximately 5-10 nm and 102 m(2)/g, respectively. For the first time, Zr atoms with partial positive charges in a Lewis acid ZrO(2) nanoparticle adsorbent were used for the adsorption of negatively charged phospholipids from Jatropha oil. The capacity for phospholipid adsorption using the ZrO(2) nanoparticles was better than that of commercial ZrO(2) powder due to the larger surface area of the ZrO(2) nanoparticles. Phospholipid removal makes Jatropha oil a potential oil for biofuel applications.     

Ag/ZrO2 and Ag/Fe–ZrO2 catalysts for the low temperature total oxidation of toluene in the presence of water vapor

Transition Metal Chemistry - New mesoporous and well-structured Ag-based catalysts (xAg/ZrO2 and xAg/Fe–ZrO2 with x = 2 wt%) have been investigated in the total...     

空心球形In2O3/ZrO2-TiO2纳米复合材料多模式光催化

本文以聚苯乙烯(PS)胶球为模板,通过一步水浴法结合煅烧后处理制备了不同比例的In_2O_3/ZrO_2-TiO_2空心球状复合材料(简写为In_2O_3/ZrO_2-TiO_2-H)。通过X-射线衍射、扫描电镜、X-射线光电子能谱、紫外-可见漫反射吸收光谱和氮气吸附-脱附等测试手段对该系列复合材料的结构、组成和形貌进行了表征。结果表明,In_2O_3/ZrO_2-TiO_2复合材料经PS模板处理后呈现空心球状结构,球壁由纳米粒子堆积而成。将In_2O_3与ZrO_2-TiO_2复合后其光吸收性能呈现了一定的红移现象,且In_2O_3/ZrO_2-TiO_2-H(1∶4)的比表面积较大(66.92m~2·g~(-1))。同时,为了考察该复合材料的光催化性能,在多模式光催化条件下对甲基橙的降解情况进行了研究。结果表明,In_2O_3/ZrO_2-TiO_2-H(1∶4)表现出较好的光催化性能,其光催化活性高于P25、ZrO_2、In_2O_3/ZrO_2-TiO_2及其他体积比的In_2O_3/ZrO_2-TiO_2-H。