CuO/Al2O3、CuO/CeO2-Al2O3和CuO/La2O3-Al2O3催化剂中CuO物种被CO氧化的比较

用浸渍法制备了CuO/Al2O3 (Cu/Al)、CuO/CeO2- Al2O3 (Cu/CeAl)和CuO/La2O3-Al2O3(Cu/LaAl)催化剂. 通过原位XRD、Raman和H2-TPR方法， 对催化剂中的CuO物种以及CuO-Al2O3的固-固相反应进行了表征. 结果表明，对于Cu/Al催化剂，CuAl2O4存在于CuO与Al2O3层之间，CuO以高分散和晶相两种相态存在于催化剂的表层；对于Cu/CeAl催化剂，除了少量高分散和晶相的CuO存在于表层外，大部分CuO迁移到了CeO2的内层，     

过渡金属氧化物催化剂上NH3 分解Claus反应机理研究

运用浸渍法制备了七种过渡金属氧化物催化剂 .对于NH3 分解反应均可获得很高的NH3 转化率 ;对于NH3 分解Claus反应则可以获得较高的SO2 转化率和单质硫选择性 .通过比较发现Co3 O4 TiO2 和Fe2 O3 TiO2 催化剂的低温活性比较高 .经过XRD表征发现 ,在NH3 分解Claus反应中 ,催化剂的活性相可能是过渡金属硫化物 .结合活性评价和XRD表征结果提出了NH3 分解Claus反应的机理 .     

碳纳米管负载Cu-Co复合氧化物的富氢气氛中CO催化消除

采用超声处理辅助浸渍法制备了多壁碳纳米管负载的Cu-Co复合氧化物催化剂. 利用XRD、TEM、H₂-TPR、XPS和Raman光谱等表征了催化剂的结构性质. 在Cu和Co氧化物以及金属氧化物与碳纳米管载体间存在强相互作用. 催化剂在富氢气氛中CO催化消除反应中,与单一Cu或Co催化剂相比,Cu-Co复合氧化物催化剂表现出独特的反应特性,特别是在较高反应温度下可同时结合CO优先氧化和CO甲烷化的反应途径来实现高效CO消除. 当Cu/Co比为1/8时活性最优,可以实现在150～250 o和高反应空速 (120 L/(h·g))富氢气氛中CO的完全消除.     

费-托合成制清洁燃料用担载纳米钴基催化剂制备中热处理对其结构和催化性能的影响

" 应用浸渍法在不同的焙烧条件(90~500 ℃)制备了一系列Al2O3担载钴基催化剂(质量含量为15%);采用XRD、XPS、程序升温还原对其进行了结构表征和分析,考察其在一氧化碳选择加氢制备清洁燃料用长链烷烃的反应中的催化性能．XPS结果表明,对于在90~200 ℃焙烧的催化剂,仍可观察到未完全分解的硝酸钴的存在;对于在200~500 ℃焙烧的几个催化剂可观察到Co3O4的物相．对于经过几种热处理制备的氧化铝担载的四个纳米钴基催化剂(200~500 ℃热处理),XRD和XPS结果表明四个样品中主要是9     

CuO/Cu2(OH)3Cl的制备及其光催化降解染料光谱性能研究

以CuCl2和NaOH为原料、微波液相加热法制得CuO/Cu2(OH)3Cl粉体作为光催化剂,XRD和FTIR进行了表征.用光度分析法测定了不同光源、溶液的酸度、催化剂的用量、光照时间等条件对染料脱色率的影响.结果表明,用太阳光作为光源照射4h,溶液的酸度为pH8,CuO/Cu3(OH)3 Cl的用量为40 mg/50 mL,氨基黑、靛蓝二磺酸钠等染料脱色率达到90%以上.加入Fe3 ,H2O2等其他物质可提高染料的脱色率.通过红外光谱和紫外光谱分析,表明染料分子在催化剂和光照条件下发生了降解.     

XPS, FTIR and TPR characterization of Ru/Al2O3 catalysts

The properties of Ru/Al₂O₃ catalysts prepared using RuCl₃ as precursor and subjected to different treatments after impregnation, were studied using different techniques: XPS, FTIR, hydrogen chemisorption and thermal programmed reduction. Differences in the Ru species (Ru⁰, ruthenium oxides and ruthenium oxychloride), metal dispersion and chlorine content in the catalysts as well as in their catalytic activity and selectivity during benzene selective hydrogenation to cyclohexene, were found according to the preparation procedure used.     

Selective CO oxidation in hydrogen-rich gas over CuO/CeO2 catalysts

A series of CuO/CeO₂ catalysts with different Cu-Ce compositions were synthesized by co-precipitation method and characterized by X-ray diffraction, H₂-TPR, CO-TPD, SEM and X-ray photoelectron spectroscopy (XPS) techniques. The effects of Cu-Ce composition and water vapor on the catalytic properties for the selective CO oxidation in the hydrogen-rich gas were investigated. The results indicated that CuO (10%)/CeO₂ catalyst remained the maximum CO conversion and selectivity at 140 and 160 °C, while the performance of CuO/CeO₂ catalysts deteriorated with the CuO molar ratio further increased. The interfacial CuO and CeO₂ interaction and synergistic effect enhanced the redox properties of CuO/CeO₂ catalyst and the highly dispersed copper species were proposed as the active sites for the selective CO oxidation. The blockage of catalytic active sites by absorbed water and the formation of CO-H₂O surface complexes reduced the activity of CuO (10%)/CeO₂ catalyst. The decreasing of surface lattice oxygen and absorbed oxygen species and the agglomeration of copper particles were the plausible interpretations for the deactivation of CuO (10%)/CeO₂ catalyst.     

CH4、CO2、O2制合成气用Ni-Ce/Al2O3催化剂的XPS研究

用XPS表征浸渍法制备的Ni-Ce／Al2O3催化剂,并与活性评价结果相关联,研究了添加Ce对催化剂性能的影响,探讨了催化剂失活的原因。结果表明,稀土Ce在反应过程中存在着部分还原变价过程(Ce^4 e→Ce^2 ),Ce^3 能够迁移至A12O3晶格,增强载体Al2O3的抗烧结能力,提高催化剂的稳定性;Ni-Ce/Al2O3催化剂表面的Ni和Ce在反应过程中向体相迁移,以及Ni晶粒的烧结是造成催化剂活性逐步下降的主要原因。     

Synthesis of CuO/g-C3N4 Composite with High Anti-Interference Ability for Enhanced Fenton-Like Catalysis

The combination of semiconductors and transition metal compounds for Fenton-like application has been widely reported. However, there are still some problems that can be further studied such as the optimization of metal species and in-depth research of mechanism. In this paper, using melamine and copper acetate as raw materials, a kind of composite of copper oxide and graphitic carbon nitride (CuO/g-C₃N₄) is synthesized by a facile hydrothermal method. The synthetic conditions such as type of transition metal salt and ratio of raw material are further optimized. With the presence of H₂O₂, the CuO/g-C₃N₄ composite shows exceptional broad-spectrum Fenton-like catalytic performance against the organic dyes in aqueous solution within a wide pH range, and the highest degradation rate of organic dyes can reach 99% within 10 min. After eight times of recycling, the catalytic activity of the composite can still remain more than 85%. More importantly, the CuO/g-C₃N₄ composite presented excellent anti-interference ability toward heavy metal ions and complex pollutants. Finally, the enhanced Fenton-like catalytic mechanism is illustrated in detail.     

Preparation of highly dispersed CuO catalysts on oxide supports for de-NO(x) reactions

CuO based catalysts dispersed on silica-alumina supports at low (0.56 wt.%) and high (13 wt.%) Al(2)O(3) content were prepared by adsorption method with or without ultrasound treatment. The catalysts obtained were studied in their bulk (atomic absorption, X-ray diffraction, temperature programmed reduction) and surface (N(2) adsorption and X-ray photoelectron spectroscopy) properties. Significant differences between the series of catalysts prepared over the two supports in terms of size of the CuO aggregates and of their redox properties were evidenced. All the catalysts were tested in the selective catalytic reduction of NO(x) using C(2)H(4) as reducing species (HC-SCR process) in highly oxidant atmosphere. The CuO-catalysts prepared using ultrasounds were the most active. Moreover, they displayed a peculiar activity being able to activate NO both by reducing it to N(2), in larger extent, and by oxidizing it to NO(2).     

臭氧在SnO2表面吸附的红外光谱研究

以SnO2催化臭氧化降解高浓度糖蜜酒精废水为探针反应,研究SnO2催化臭氧化降解糖蜜酒精废水的活性,并采用红外光谱研究臭氧在SnO2及金属氧化物改性的SnO2催化剂表面的吸附行为。结果表明:由纯氧源制得的O3在SnO2表面吸附的红外光谱上的1 027和1 055 cm-1及2 099和2 122 cm-1处存在两处明显的吸收双峰,而空气制备的O3在SnO2表面与CO及CO2等存在竞争吸附,使得O3的吸附减少,催化臭氧化降解糖蜜废水的降解率下降。催化剂助剂对SnO2催化臭氧化降解糖蜜酒精废水有较大的影响。采用Fe2O3,NiO,CuO,ZnO,MgO,SrO及BaO等金属氧化物为助剂改性的SnO2在2 236和2 213 cm-1,1628和1 599 cm-1出现强度相似的吸收峰,但是几种催化剂对CO2和CO的吸附差别较大,过渡金属改性的SnO2在1 580~1 070 cm-1处出现较宽的吸收峰,碱土金属氧化物改性的SnO2催化剂在1 580~1 070 cm-1之间,出现了1 298和1 274 cm-1两个新的峰,从而引起了不同助剂催化臭氧化的活性差别,碱土金属改性的SnO2对糖蜜酒精废水的催化臭氧化脱色效果明显优于过渡金属改性的SnO2,其中BaO改性的SnO2催化剂的活性最好。     

Mechanistic study of the CO oxidation reaction on the CuO (111) surface during chemical looping combustion

Cu-based oxides oxygen carriers and catalysts are found to exhibit attractive activity for CO oxidation, but the dispute with respect to the reaction mechanism of CO and O₂ on the CuO surface still remains. This work reports the kinetic study of CO oxidation on the CuO (111) surface by considering the adsorption, reaction and desorption processes based on density functional theory calculations with dispersion correction (DFT-D). The Eley–Rideal (ER) CO oxidation mechanism was found to be more feasible than the Mars-van-Krevelen (MvK) and Langmuir–Hinshelwood (LH) mechanisms, which is quite different from previous knowledge. The energy barrier of ER, LH, and MvK mechanisms are 0.557, 0.965, and 0.999 eV respectively at 0 K. The energy barrier of CO reaction with the adsorbed O species on the surface is as low as 0.106 eV, which is much more active in reacting with CO molecules than the lattice O of CuO (111) surface (0.999 eV). A comparison with the catalytic activity of the perfect Cu₂O (111) surface shows that the ER mechanism dictates both the perfect Cu₂O (111) and the CuO (111) surface activity for CO oxidation. The activity of the perfect Cu₂O (111) surface is higher than that of the perfect CuO (111) surface at elevated temperatures. A micro-kinetic model of CO oxidation on the perfect CuO (111) surface is established by providing the rate constants of elementary reaction steps in the Arrhenius form, which could be helpful for the modeling work of CO catalytic oxidation.     

New advanced in situ carbon monoxide sensor for the process application

Mixed potential solid electrolyte CO sensors with sensing electrodes based on composite with various semiconducting oxides were extensively studied in the temperature range 500–650 °C for sensitivity, stability and cross-sensitivity besides CO to other combustion components like CO₂, H₂O, O₂, and SO₂. The highest CO sensitivity was found for the CO sensor with composite electrode based on Au/Ga₂O₃ showing also good reproducibility and stability in hazardous combustion environment. CO sensor response behavior in non equilibrated oxygen containing gas mixtures is mainly determined by the catalytic activity of the measuring electrode and depends strongly on preparation and measuring conditions. Mixed oxides based on doped chromites show only a little sensitivity to CO. CO sensor based on Au/Ga₂O₃ composite electrodes was showing good CO selectivity in the presence of other combustion gas species and finally was tested in combustion environment at power plant. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

甲烷部分氧化制合成气Pt/Al_2O_3催化剂的表征及其反应性能评价

采用浸渍法制备了3种不同负载量的Pt/Al2O3催化剂,考察了催化剂的甲烷选择氧化性能,并用程序升温还原技术,程序升温脱附技术以及微型脉冲催化色谱技术对催化剂进行表征。结果表明,随着Pt的负载量升高,甲烷催化氧化的性能也越好,对CO与H2的选择性也越高。其中,在750℃原料气组成CH4/O2为2∶1,4%Pt负载量的催化剂,甲烷转化率达到98%以上。     

CuO based catalysts on modified acidic silica supports tested in the de-NOx reduction

A series of dispersed CuO catalysts supported on modified silica supports with Al2O3 (SA), TiO2 (ST), and ZrO2 (SZ) were prepared optimising the adsorption method of copper deposition assisted by ultrasound treatment, already reported in a previous paper (S. Bennici, A. Gervasini, V. Ragaini, Ultrason. Sonochem. 10 (2003) 61). The obtained catalysts were characterized in their bulk (atomic absorption, X-ray diffraction, temperature programmed reduction) and surface (N2 adsorption, X-ray photoelectron spectroscopy, scanning electron microscopy) properties. The morphology of the finished materials was not deeply modified compared with that of the relevant supports. The employed complemented techniques evidenced a well dispersed CuO phase with a copper-support interaction on the most acidic supports (SA and SZ). The catalyst performances were studied in the reaction of selective catalytic reduction of NOx with ethene in oxidizing atmosphere in a flow apparatus under variable times (0.360-0.072 s) and temperatures (200-450 degrees C). The catalysts prepared on the most acidic supports (SA and SZ) were the most active and selective towards N2 formation. They showed a particular interesting activity in the reaction of NO2 reduction besides that of NO reduction.     

The preparation and properties of highly conductive nonstoichiometric oxide catalysts

Inter-oxide compounds of rare earth and transition metal oxides can be made highly nonstoichiometric by the partial substitution of divalent ions, such as strontium, for the rare earth element. These compounds become highly conductive when suitably treated in oxygen at high temperatures, and have been found to function as efficient oxidation catalysts at low temperatures between 100–300°C. The thermodynamics, transport properties and catalytic behavior for CO and CH₄ oxidation of some systems having the perovskite or the K₂NiF₄ structure are discussed, e.g. La_1−xSr_xMO_3−δ(M=Cr,Mn,Fe,Co,Y) and La_2−xSr_xCuO_4−δ. The catalytic behavior is similar for the Cr,Mn,Fe and Co perovskites, but the solid electrolyte La_0.8Sr_0.2YO_2.9 has no effect in CO oxidation but the greatest activity for CH₄ oxidation.     

热氧化铜箔中的起皱和CuO纳米线的生长机

在500 oC大气条件下热氧化0.5 mm厚的铜箔0.5～10 h有起皱现象,且皱的大小随氧化时间的增加而增大,在皱的侧面和顶部均有生长CuO纳米线,皱侧面生长纳米线的长度比皱顶部的纳米线的长,密度也高;CuO纳米线的生长方向垂直于纳米线的生长表面. 通过计算波动阶段中皱内部的局部电场,发现皱的侧面和顶部的电场强度的数值相差很小,表明在CuO纳米线生长过程中驱动铜离子扩散的主要驱动力不是局部的电场力而是内应力.     

不同制备工艺钒系SCR催化剂理化及催化性能研究

本文研究了制备工艺对 TiO2-WO3-V2O5- 载体型催化剂理化特性及其在 NH3-SCR 反应中催化性能的影响.通过 XRD、TG/DTA 等分析方法考察了煅烧温度等对催化剂中各组分晶体结构的影响,确定了制备负载型催化剂的最佳煅烧温度为 500℃.不同制备工艺催化剂理化性能的对比表明,多步浸渍法不仅提高了锐钛矿型 TiO2 向金红石型 TiO2 的转变温度,而且使更多的钒氧化物处于较低的价态,有利于提高还原反应的催化性能;催化活性评价试验也表明使用多步浸渍法制备的 SCR 催化剂具有较高的催化活性和更宽的高活性反应温度窗口.最后考察了反应空速对多步浸渍法所制备催化剂 NOx 转化效率的影响,结果表明:随空速的增加,NOx 转化效率逐渐降低.     

Characterization and catalytic performance of pure and Li2O-doped CuO/CeO2 catalysts

Pure and Li₂O-doped CuO/CeO₂ catalysts calcined at 500 °C were prepared by impregnation method. The catalysts are characterized by DTA, TG-DTG, XRD, IR, TEM, nitrogen adsorption at −196 °C and the catalytic decomposition of hydrogen peroxide at 30 °C.The effects of molar ratio, heat treatment time and the doping on the structural, surface and catalytic properties of nanocrystalline Cu/Ce-mixed oxides system have been studied. It was found that the catalytic activity of ceria-supported copper oxide catalysts increased by increasing both the heat treatment time and dopant content. However, the pure Cu/Ce-mixed oxide solids containing 10 wt.% CuO exhibited the best performance. The characterization results indicated that the higher surface area, the formation of solid solution between copper and cerium oxides, and the high dispersion of copper species on the ceria were responsible for the high catalytic activity of the CuO/CeO₂ catalysts.     

In2O3/CuO纳米异质结的制备和光催化性质研究

通过溶胶-凝胶结合静电纺丝过程制备了In₂O₃/CuO纳米异质结。XRD和Raman光谱的研究表明,随着前驱物中Cu/In比例的增加,CuO相的含量逐渐增加。吸收光谱研究表明,随着CuO含量的增加,复合纳米结构的可见光吸收明显增强。光催化实验研究结果表明,In₂O₃/CuO纳米异质结具有比单一相的In₂O₃和CuO更强的光催化性能,其主要来源于异质结所导致的增强的光生电子和空穴的分离效率。