铜掺杂Zr0.4Ce0.6O2复合氧化物催化剂性能的研究

研究了铜掺杂Ｚｒ０．４Ｃｅ０．６Ｏ２复合氧化物的还原性和催化性能,结果表明,铜掺杂能显著提高昨合氧化物中氧化铈的还原性,降低氧化铜的还原温度,也能提高对ＣＯ氧化的催化活性和催化 这说明在铜与锆铈复合氧化物之间存在较强的相互作用,焙地催化剂样品的性能亦有一定影响。     

铜锰复合氧化物催化剂上甲苯的催化燃烧

采用碳酸盐共沉淀法在全范围内制备了一系列具有高比表面积的铜锰互相掺杂的复合氧化物,通过调变铜锰摩尔比考察了其在甲苯催化燃烧反应中的表现。铜锰复合氧化物催化剂,尤其是掺杂低浓度铜的氧化锰,在甲苯催化燃烧中表现出了超越单组分氧化物的性能。随掺杂量的变化,反应活性呈现火山状的趋势。XRD、H₂-TPR、XPS及BET等表征结果显示氧化物粒子的结晶度及分散度、催化剂的可还原性、表面氧浓度、催化剂的比表面积等诸多因素均对催化活性产生了一定的影响,然而复合氧化物催化性能上升的根本原因在于铜物种和锰物种之间存在的较强的相互协同作用。     

铜锰复合氧化物催化剂上甲苯的催化燃烧

采用碳酸盐共沉淀法在全范围内制备了一系列具有高比表面积的铜锰互相掺杂的复合氧化物,通过调变铜锰摩尔比考察了其在甲苯催化燃烧反应中的表现。铜锰复合氧化物催化剂,尤其是掺杂低浓度铜的氧化锰,在甲苯催化燃烧中表现出了超越单组分氧化物的性能。随掺杂量的变化,反应活性呈现火山状的趋势。XRD、H2-TPR、XPS及BET等表征结果显示氧化物粒子的结晶度及分散度、催化剂的可还原性、表面氧浓度、催化剂的比表面积等诸多因素均对催化活性产生了一定的影响,然而复合氧化物催化性能上升的根本原因在于铜物种和锰物种之间存在的较强的相互协同作用。     

掺铜TiO^2光催化剂光催化氧化还原性能的研究

利用浸渍法制备了掺铜二氧化钛光催化剂，分别以乙酸降解和二氧化碳还原反应为探针，研究了催化剂的光催化氧化光催化还原性能．结果表明，铜掺杂能显著提高催化剂的光催化性能；结合光电子能谱、X光衍射分析等物理表征结果，对铜掺杂改性机制进行了讨论．     

B位掺杂对LaNi_(0.7)M_(0.3)O_3复合氧化物催化性能的影响研究

本文采用水热共沉淀法制备了B位掺杂的LaNi_(0.7)M_(0.3)O_3(M=Co、Fe~(2+)、Mn、Cu)复合氧化物,用XRD、SEM、TG、TPD、TPR等实验对钙钛矿的结构与组成,微观形貌,稳定性等进行了表征,并以乙醇水蒸气重整制氢反应为探针考察了B位掺杂元素种类对其催化性能的影响。结果表明,LaNi_(0.7)Fe_(0.3)O_3复合氧化物具有较好剂还原性和吸附性能,在乙醇水蒸气重整制氢反应中的,乙醇转化率可达到95.63%,同时具有较好的抗积碳性能。     

纳米Cu-Zn复合氧化物自组装合成及可见光催化性能

采用阴阳离子表面活性剂复合囊泡相为软模板,自组装合成了Cu-Zn复合氧化物纳米材料,分析了自组装过程。研究了铜的掺杂量对纳米材料的形貌、晶型、能级变化以及电子结构的影响,评价了不同铜掺杂量的ZnO-CuO样品光催化性能。结果表明,随着铜掺杂量的增加,样品ZnO-CuO中ZnO的X射线衍射(XRD)特征峰强度逐渐降低;形貌由多面体晶粒转向片层结构;铜的引入使ZnO的发光能级发生变化,并随着铜离子的量增加,光生载流子浓度变小。可见光催化结果显示,样品ZnO-CuO光催化性能随掺杂铜离子量的增加先增加后减弱。在金属离子Cu2+和Zn2+物质的量之比为5:95时光催化效果为最佳。     

溶胶-凝胶法制备(Ti1-xNbx)O2氧化物的物相及厚膜氧敏响应特性

研究了不同方式形成的TiO2 施主掺杂复合氧化物的气敏特性。结果表明 :用Nb2 O5对TiO2 进行施主掺杂 ,在Nb摩尔分数较小时 ,复合氧化物中极易出现非金红石结构的物相。TiO2 金红石结构物相中施主掺杂浓度很难提高。以氢氧化铌 [Nb(OH) 5] ,钛丁醇 [Ti·(OC4 H9) 4]为先驱体 ,采用溶胶凝胶法形成的TiO2 施主掺杂复合氧化物 ,当Nb摩尔分数 <0 .5 % ,可以得到理想单一金红石结构的物相 ,明显地提高了TiO2 物相的施主浓度。在 30 0～ 60 0℃的温度范围呈现出 5 0 0～ 80ms的响应速度。所制得厚膜空 /燃比传感器最大的加热功率仅在 10W左右 ,在 40s内就可以进入工作状态     

Ce-Cu复合催化剂用于对硝基苯酚废水处理研究

通过络合法制得Ce-Cu复合催化剂,采用X射线衍射、扫描电子显微镜和程序升温还原对催化剂性能进行了研究,考察了该催化剂用于废水中对硝基苯酚去除性能。结果表明,催化剂中Cu氧化物能很好地溶入CeO2晶格形成表面具有多孔结构的Ce0.86Cu0.14O2固溶体催化剂,催化剂中Cu-O键得到一定程度的削弱,使其可还原性能得到提高而提高了催化剂中氧化物的活性。Ce0.86Cu0.14O2催化剂可将废水中对硝基苯酚的质量浓度由150 mg.L-1降到1.8 mg.L-1左右,对硝基苯酚去除率可达98.8%。     

铜钴复合氧化物催化剂溶胶——凝胶法合成及二甲苯燃烧催化性能研究

溶胶——凝胶法合成了系列铜钴复合氧化物催化剂 ,用 XRD和 TPR谱对其所制样品进行了表征 ,着重研究了铜钴原子比对样品的晶体结构还原性能以及二甲苯燃烧催化活性的影响。结果表明 ,二甲苯燃烧催化活性与样品的还原温度 ,铜钴原子比密切相关 ,当 Cu/Co=2∶ 1时 ,其样品的还原温度最低 ,二甲苯的燃烧催化活性最高     

铋基卤氧化物光催化剂的改性研究进展

结合近年来国内外研究人员的最新成果及研究进展,阐述了贵金属沉积、离子掺杂以及半导体复合等改性方法对于铋基卤氧化物的光催化性能的影响.铋基卤氧化物光催化剂具有特殊的层状结构,其含铋氧化物层与卤素层之间由于电荷分布不均所诱导产生的内建电场能促进光生电荷分离,从而提高光催化效率,因此铋基卤氧化物被认为是极具潜力的一种光催化材...     

Selective oxidation of soot over Cu doped ceria/ceria–zirconia catalysts

Copper doped ceria and ceria–zirconia mixed oxides were prepared using the citric acid sol–gel method. The temperature-programmed oxidation (TPO) results showed that the Cu modification helped to improve the activity and selectivity of ceria and ceria–zirconia for soot catalytic oxidation. The CO-TPR results showed that Cu–Ce had a better reducibility than pure ceria at low temperatures. After ageing at 800 °C for 20 h in flow air, CuO–CeO₂ showed the maximum soot oxidation rate at 378 and 519 °C under tight and loose contact conditions, respectively, achieving a nearly 100% selectivity to CO₂ production. This effect may be attributed to the existence of well dispersed copper oxide species strongly interacting with the ceria surface, which may decrease the activation energy of soot oxidation. A conceivable mechanism of this synergetic effect was proposed.     

The catalytic activity of CuO–CeO2 mixed oxides for diesel soot oxidation with a NO/O2 mixture

Copper doped ceria and ceria–zirconia mixed oxides were synthesized using the citric acid sol–gel method. The temperature-programmed oxidation (TPO) results showed that the Cu modification improved the low-temperature activity and the selectivity to CO₂ of ceria for soot oxidation in the presence of NO and excess oxygen even after ageing at 800 °C for 20 h in flow air. Meanwhile, not only the segregation of Cu and sintering of CuO, but also the separation of Ce- and Zr-rich phases worsened the activity of the Cu–Ce–Zr catalyst after the high-temperature calcination.     

Interaction of a ceria‐based anode functional layer with a stabilized zirconia electrolyte: Considerations from a materials perspective

We report on the materials interaction of gadolinium‐doped ceria (GDC) and yttria‐stabilized zirconia (YSZ) in the context of high‐temperature sintering during manufacturing of anode supported solid oxide fuel cells (AS–SOFC). While ceria‐based anodes are expected to show superior electrochemical performance and enhanced sulfur and coking tolerance in comparison to zirconia‐based anodes, we demonstrate that the incorporation of a Ni–GDC anode into an ASC with YSZ electrolyte decreases the performance of the ASC by approximately 50% compared to the standard Ni–YSZ cell. The performance loss is attributed to interdiffusion of ceria and zirconia during cell fabrication, which is investigated using powder mixtures and demonstrated to be more severe in the presence of NiO. We examine the physical properties of a GDC–YSZ mixed phase under reducing conditions in detail regarding ionic and electronic conductivity as well as reducibility, and discuss the expected impact of cation intermixing between anode and electrolyte.     

Catalytic combustion of diesel soot particles on copper catalysts supported on TiO2. Effect of potassium promoter on the activity

We have prepared a TiO₂ supported copper catalyst and studied the effect of potassium on its activity in the oxidation of soot particles. The catalysts, with a K/Cu atomic ratio varying between 0 and 2, were calcined at 1073 K. They were characterized by BET surface area measurements, X-ray diffraction and temperature-programmed reduction under hydrogen. The catalytic activity was measured in a microbalance by means of temperature-programmed oxidation in air or argon. The catalytic activity of copper was enhanced by the presence of potassium. This effect was attributed to the formation of mixed K---Ti oxides which inhibit the sintering of the TiO₂ support and thus increases the surface area of the catalyst. Although a redox mechanism can explain the catalytic combustion, no correlation could be established between the reducibility of the different solids and their activity in soot combustion.     

Gold catalysts supported on ceria-modified mesoporous zirconia for low-temperature water–gas shift reaction

New gold catalytic system prepared on ceria-modified mesoporous zirconia used as water–gas shift (WGS) catalyst is reported. Mesoporous zirconia was synthesized using surfactant templating method through a neutral [C₁₃(EO)₆-Zr(OC₃H₇)₄] assembly pathway. Ceria modifying additive was deposited on mesoporous zirconia by deposition–precipitation method. Gold-based catalysts with different gold content (1–3 wt. %) were synthesized by deposition–precipitation of gold hydroxide on mixed metal oxide support. The supports and the catalysts were characterized by powder X-ray diffraction, high-resolution transmission electron microscopy, N₂ adsorption analysis and temperature programmed reduction. The catalytic behavior of the gold-based catalysts was evaluated in WGS reaction in a wide temperature range (140–300 °C) and at different space velocities and H₂O/CO ratios. The influence of gold content and particle size on the catalytic performance was investigated. The WGS activity of the new Au/ceria-modified mesoporous zirconia catalysts was compared with that of gold catalysts supported on simple oxides CeO₂ and mesoporous ZrO₂, revealing significantly higher catalytic activity of Au/ceria-modified mesoporous zirconia. A high degree of synergistic interaction between ceria and mesoporous zirconia and a positive modification of structural and catalytic properties by ceria have been achieved. It is clearly revealed that the ceria-modified mesoporous zirconia is of much interest as potential support for gold-based catalyst. The Au/ceria-modified mesoporous zirconia catalytic system is found to be effective catalyst for WGS reaction.     

Catalytic performance of Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite oxides for methane combustion: Influence of catalyst pretreatment temperature and oxygen concentration in the reaction mixture

The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration (λ = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ containing 30 wt.% of Co₃O₄. The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples).

Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g⁻¹ h⁻¹). The catalytic performance of Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ were compared with those of two pure Co₃O₄ oxides, a sample obtained by the precipitation method and a commercial reference. Characterization studies by X-ray diffraction (XRD), BET and temperature-programmed reduction (TPR) show that the catalytic activity is related to the dispersion of crystalline phases, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ as well as to their reducibility. Particular attention was paid to the thermal stability of the Co₃O₄ phase in the temperature range of 750–800 °C, in both static (in a furnace) and dynamic conditions (continuous flow). The results indicate that the thermal stability of the phase Co₃O₄ heated up to 800 °C depends on the size of the cobalt oxide crystallites (fresh or aged samples) and on the oxygen content (excess λ = 8, stoichiometric λ = 1) in the reaction mixture. A stabilizing effect due to the presence of ceria or ceria–zirconia against Co₃O₄ decomposition into CoO was observed.

Moreover, the role of ceria and ceria–zirconia is to maintain a good combustion activity of the cobalt composite oxides by dispersing the active phase Co₃O₄ and by promoting the reduction at low temperature.     

以碱土金属为助剂的CuO/CeO_2水煤气变换催化剂的催化性能

采用共沉淀法制备了系列CuO/CeO_2-MO(M=Mg、Ca、Sr和Ba)催化剂,通过X射线粉末衍射、M_2物理吸附、N_2O选择性化学吸附、H_2程序升温还原和循环伏安法等手段对催化剂的物化性能进行表征,考察了富氢条件下水煤气变换反应中碱土金属氧化物作为助剂对CuO/CeO_2催化剂性能的影响。结果表明,BaO作为助剂可降低载体CeO_2和CuO的晶粒度,有效增大催化剂的比表面积,提高铜组分的表面分散度,并有利于更多与载体表面氧空位有强相互作用的CuO物种的形成,从而获得较高的催化活性。MgO、CaO和SrO的添加对催化剂活性影响较小。关联活性数据和结构表征结果,推断CuO/CeO_2催化剂在水煤气变换反应中的有效活性位是与载体CeO_2表面氧空位强相互作用的单质Cu。     

Ceria–zirconia mixed oxides: Synthetic methods and applications

The primary objective of this review was to illustrate the significance of ceria–zirconia (CZ) mixed oxides as catalysts and catalyst supports as employed for a wide variety of catalytic applications both in the liquid and gaseous phases. In particular, we were interested in bringing together the recent literature pertaining to these mixed oxides with catalysis perspective. The most prominent application of CZ mixed oxides is in three-way catalysis (TWC) as oxygen storage and release material for several years by replacing cerium dioxide as it shows better efficiency and a high thermal stability. Doping with zirconium oxide, as it is alone a non-reducible oxide, makes the CZ mixed oxide a highly reactive, thermally stable, and more reducible with elevated oxygen storage capacity (OSC) that are important for TWC applications. Apart from the TWC use, the CZ mixed oxides have a huge number of applications, as a direct component or a support, ranging from water–gas shift reaction, reforming of hydrocarbons, dehydration of alcohols, CO₂ utilization, catalytic combustion of pollutants, fine chemicals production, photocatalysis, and so on. All these applications are mainly dependent on three parameters of the mixed oxides, namely, OSC or redox nature, acid–base properties, and crystalline phases. Besides, most of the applications are influenced by the physical properties such as specific surface area, pore volume, pore diameter, crystallite size, and so on. In this review, many details pertaining to the synthesis of these mixed oxides by various conventional and non-conventional methods, their characterization by several techniques, and their application for various reactions of energy and environmental significance, as reported in the literature, are assessed.     

EPR study on oxygen handling properties of ceria, zirconia and Zr–Ce (1 : 1) mixed oxide samples

The characteristics of ceria, zirconia and Zr–Ce (1 : 1 molar ratio) samples prepared by using inverse microemulsions have been studied to obtain information on the modifications produced in the oxygen handling properties of the single oxides by the formation of the mixed oxide. The structural characteristics of the samples are compared on the basis of XRD and Raman spectroscopy data, which show that the Zr–Ce sample forms a homogeneous mixed oxide structure corresponding to the (pseudocubic) tetragonal phase t″ while CeO₂ presents, as expected, a cubic fluorite structure and ZrO₂ is formed mainly by a tetragonal phase with only traces of the thermodynamically most stable monoclinic phase. Evaluation by EPR of the type and intensity of superoxide radicals generated upon oxygen adsorption on the outgassed samples reveals a higher surface reducibility in the mixed oxide sample, associated vacancies defects being generated on it in higher amounts and at lower temperatures than on pure ceria. It is also shown that both Ce and Zr ions participate in the oxygen chemisorption process on the mixed oxide sample, actually giving rise to much larger amounts of O₂ ^-–Zr⁴⁺ species than the pure ZrO₂ sample; the latter species show a higher thermal stability than O₂ ^-–Ce⁴⁺ species. This revised version was published online in July 2006 with corrections to the Cover Date.     

ACr_2O_4尖晶石氧化物(A=Co,Zn,Mn,Cu)上二氯甲烷的催化燃烧:A位阳离子的影响

采用溶胶-凝胶法制备4种不同ACr_2O_4尖晶石氧化物(A=Co,Zn,Mn,Cu),考察A位阳离子对ACr_2O_4尖晶石氧化物的性质以及对二氯甲烷催化燃烧性能的影响,并对催化剂进行SEM、HRTEM、H_2-TPR、NH_3-TPD以及XPS等表征。结果表明,A位离子显著影响催化剂的可还原性和表面酸性,催化剂催化活性顺序为CoCr_2O_4Zn Cr_2O_4Mn Cr_2O_4CuCr_2O_4。结合表征结果,认为催化剂活性与其可还原性能和表面酸性存在密切关系。CoCr_2O_4由于具有最佳的可还原性和较高的表面酸性,具有最高的催化活性;而CuCr_2O_4由于具有最低的表面酸性导致其催化活性最低。