Influence of the structure of TiO<Subscript>2</Subscript>, CeO<Subscript>2</Subscript>, and CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> supports on the activity of Ru catalysts in the catalytic wet air oxidation of acetic acid

Ru catalysts, supported on TiO₂, CeO₂, and CeO₂-TiO₂, were prepared by the impregnation method. The effect of the structure of the supports on the activity of Ru catalysts was investigated in the catalytic wet air oxidation (CWAO) of acetic acid under 230°C and 5 MPa in a batch reactor. Physical properties including the surface area, crystalline phase, and surface components of the Ru catalysts were characterized by N₂ adsorption, X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The CeO₂-based Ru catalysts had good activity, and the prepared RuO₂/CeO₂ catalyst showed markedly higher activity than the RuO₂/CeO₂-TiO₂ catalyst. The surface structure, the high amount of chemisorbed oxygen on the catalyst surface, and the suitable pH_pzc value of the supports played an important role in the activity of the Ru catalysts in CWAO of acetic acid.     

Catalytic wet air oxidation of phenol over RuO2/γ-Al2O3 catalyst

A kind of CWAO catalyst, RuO2/γ-Al2O3, was prepared by dipping Al2O3 into the aqueous solution of RuCl3.3H2O. XRD, SEM and TEM were used to determine the catalytic structure. Influences of the calcination temperature,the initial pH of the feed solution and degradation temperature on the activity of the RuO2/γ-Al2O3 catalyst were investigated and the reaction mechanism was preliminarily studied. Results showed that uniform dispersion of RuO2 crystallites was observed on the surface of the catalyst. The activity of the catalyst was higher at calcination temperature of 300℃ for 3 h and the particle reunion occurred and some large RuO2 crystallites were abundant at high calcination temperature of 500℃. The activity of the catalyst was better in the acid solution than in the alkaline solution. Increasing degradation temperature and using the catalyst could shorten the induction periods so that the phenol and COD removal were increased. For RuO2/γ-Al2O3 catalyst, the phenol and COD removal were respectively 98% and 80% in a temperature of 150℃, pH of 5.6 and pressure of 3 MPa after a 2 h reaction. This indicated that Ru/γ-Al2O3 catalyst had good activity.     

CeO2改性钌系催化剂的制备及催化降解氨氮废水的研究

以RuO2和CuO为活性组分和辅助活性组分,添加CeO2作为助剂,采用硝酸盐浸渍法负载在分子筛载体上,焙烧制备Ru-Cu-Ce复合催化剂。采用比表面分析仪(BET)、X射线衍射(XRD)和透射电子显微镜(TEM)等对催化剂进行表征,用静态实验评价氧化去除氨氮的催化性能。结果表明,Cu和Ce的添加能够提高Ru催化剂的性能,Ce可以抑制Cu的溶出损失。催化剂制备的最佳焙烧条件为300℃焙烧4.5 h。对200 mL初始浓度为205.8 mg/L的模拟氨氮废水,0.25%Ru-1%Cu- 1%Ce催化剂常压氧化降解的最佳条件为:初始pH=10,温度80℃,30%双氧水添加量为处理水量的1/2000,氨氮去除率可达85.6%,催化剂重复使用7次性能无明显降低。     

概括了贵金属催化剂的种类，从制备方法、载体的选择、颗粒尺寸以及催化剂活性中心结构等几个方面分析催化反应活性的影响因素，并且介绍了各种贵金属催化剂相应的催化反应。

概括了贵金属催化剂的种类,从制备方法、载体的选择、颗粒尺寸以及催化剂活性中心结构等几个方面分析催化反应活性的影响因素,并且介绍了各种贵金属催化剂相应的催化反应。     

Influence of CeO2-coating on the high-temperature oxidation of chromium

The reactive-element effect on high-temperature oxidation of chromium metal was studied at oxygen pressures of 10⁵ Pa (1 atm) and 0.67 Pa and at temperatures of 800 and 1050°C under both isothermal and cyclic conditions. The reactive element, cerium, was applied as a cerium-oxide coating by sol-gel deposition. Growth and adherence of the chromia scale on the metallic substrate were investigated by kinetic weight-gain measurements, and the microstructure was characterized by scanning electron microscopy, transmission electron microscopy, EDX-analysis, X-ray diffraction, and Auger analysis. The study of the oxidation kinetics under isothermal conditions at 800°C clearly showed a reduction in the growth rate of the oxide film when cerium oxide was present. Improvement of the oxide-scale adhesion was also observed when ceria-coated chromium was subjected to thermal cycling. The applicability of a number of models which have been used to explain the reactive-element effect is discussed.     

Ru/Mn-Ce/TiO2及Ru/TiO2催化剂对丁二酸的催化湿式氧化研究

采用浸渍法制备了2个系列的Ru／Mn-Ce/TiO2及Ru/TiO2催化剂,并用XRD、TEM、BET等方法对催化剂进行表征。在T=270℃和Po2=1．5MPa条件下,在间歇式反应釜中对丁二酸进行降解实验。结果表明60min内丁二酸降解的总有机碳(TOC)去除率为80％～99．8％;在钌含量相同的情况下,Ru／Mn-Ce／TiO2催化剂的催化活性高于Ru/TiO2催化剂;Ru含量较低的情况下,Mn、Ce对提高催化活性有很大作用,但Ru含量增加时Mn、Ce的作用减弱;氢还原的温度对Ru/TiO2系列催化剂的催化氧化活性有明显影响,500℃还原钌所得催化剂对丁二酸的催化氧化活性优于350℃。     

Influence of superficial coating of CeO2 on the oxidation behavior of AISI 304 stainless steel

The effect of a superficially-applied, cerium-oxide coating on the non-isothermal oxidation behavior of AISI 304 stainless steel in dry air has been investigated. The heating rate employed was 3 K/min up to a final temperature of 1423 K. The reactive oxide coating not only reduced the reaction rate but also facilitated scale adhesion to the alloy substrate. Post-oxidation analyses of the alloy/scale combination using optical microscopy, SEM, EDAX, and XRD provide evidence for a changeover in the mechanism of oxide growth from the scale/gas interface to the alloy/scale interface for the coated steel.     

片状与粉末触媒对石墨转化成金刚石的催化效率研究

为了研究片状与粉末的镍基或铁基触媒对石墨转化为金刚石的催化性能的影响,采用金刚石成核和生长动力学方法分别计算了片状与粉末触媒参与下金刚石生长的活化能与比表面能。结果表明,无沦是片状还是粉末触媒,这两种触媒对金刚石生长活化能与比表面能的影响差异很小,比表面能与金刚石的结晶形态有关,决定于合成的温度压力条件。然而,粉末触媒的催化效率比片状触媒高得多,更有利于石墨转化为金刚石。     

Influence of fluorine on the structure and photocatalytic activity of TiO2 film prepared in tungstate-electrolyte via micro-arc oxidation

TiO₂ films were prepared on pure titanium substrate via micro-arc oxidation (MAO) technique in tungstate-electrolyte. The influence of fluorine ion concentration in electrolyte on the microstructure and photocatalytic activity of TiO₂ films was investigated. The results showed that the porosity, element content and phase composition of TiO₂ films were affected by fluorine ion concentration in electrolyte. The number of pores, the content of tungsten and the content of anatase phase all increased when appropriate fluorine ion was added into the electrolyte. Thus, the photocatalytic activity of TiO₂ films could be promoted by adding appropriate fluorine ion into the electrolyte. The addition of fluorine ion did not alter the iso-electric points of TiO₂ films. It was confirmed by UV–Vis spectrophotometer that the photocatalytic activity of the film prepared in electrolyte containing 2 g/L NaF was higher than that of the films prepared in other electrolytes during the degradation of methyl orange.     

Preparation of SO2-4/TiO2-WO3 solid superacid and its catalytic activity in acetalation and ketalation

SO2-4/TiO2-WO3 was prepared and its catalytic activity under different synthetic conditions was discussed with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. The optimum conditions are found that the mass fraction of H2WO4 used in the compound is 12.5%, the calcination temperature is 580℃, the calcination time is 3 h, and the soaked consistency of H2SO4 is 1.0 mol.L-1. Then SO2-4 /TiO2-WO3 was applied as the catalyst in the catalytic synthesis of eight similar important ketals and acetals under the optimum conditions and revealed high catalytic activity. On condition that the molar ratio of aldehyde/ketone to glycol is 1:1.5, the mass fraction of the catalyst used in the reactants is 0.5%, and the reaction time is 1.0 h, the yields of ketals and acetals can reach 64.2%-95.1%. Moreover, it can be easily recovered and reused.     

硫掺杂对纳米TiO2的结构相变及可见光催化活性的影响

采用酸催化溶胶凝胶法合成硫掺杂纳米TiO2光催化剂。可见光光催化降解亚甲基蓝实验结果表明:当硫脲与钛酸丁酯摩尔比为3.50时,催化剂经500℃热处理后表现出最佳的可见光光催化降解效果。TEM、XRD和Raman光谱等表征结果表明:硫掺杂大大提高了纳米TiO2晶粒的分散程度,有利于制备均一分散的纳米晶粒;另外,硫掺杂有效地抑制了纳米TiO2在热处理过程中由锐钛矿向金红石的转变,一部分硫进入TiO2的晶格取代部分Ti4 而导致一定程度畸变,产生氧缺位,从而大大提高催化剂的可见光催化活性。     

炭载铂族金属催化剂中铂、钯、铑、钌的化学分析进展

介绍了国内炭载催化剂中铂、钯、铑、钌化学分析技术的进展,对该类催化剂的制备过程及化学分析特点、试样的前处理、铂族金属含量的测定方法进行了评述,并对未来试样的前处理和提高电感耦合等离子体原子发射光谱法(ICP-AES)测定高量铂族金属的准确度、精密度技术进行了展望。     

Influence of Ru additions on the corrosion behaviour of WC-Co cemented carbide alloys in sulphuric acid

The aim of the study is to investigate the influence of ruthenium (Ru) additions on the corrosion behaviour of WC-Co cemented carbides when exposed in a reducing acid medium. The study involved the characterization of the microstructures, morphologies and phases present by using the optical microscopy, SEM, XRD and Raman spectroscopy before and after corrosion. The corrosion behaviour was investigated using the electrochemical polarization tests and chronoamperometry. Ruthenium affects the cathodic Tafel constant (β_c) in 1 M H₂SO₄, which indicates that it influences the cathodic part of the corrosion reaction. It also appears that Ru is more effective in improving corrosion resistance than a small vanadium carbide addition. Therefore, ruthenium additions of up to 3 wt.% Ru increased the corrosion resistance of the WC-Co alloys.     

The effect of water content on the electropolishing behavior of Inconel 718 alloy in perchloric–acetic acid mixtures

The electropolishing behavior of Inconel 718 alloy was studied in perchloric–acetic acid mixtures using a rotating disc electrode. The electropolishing behavior of an Inconel 718 weld, which was prepared with electron beam welding, was also investigated. A leveled but not brightened surface can be achieved when Inconel 718 alloy is potentiostatically polished in the acid mixture with 20 vol.% perchloric acid. Interestingly, a brightening effect could be obtained in this acid mixture by adding 10–50 ml l⁻¹ water or by being at rest at room temperature for several days. When electropolishing in acid mixture with 40 vol.% perchloric acid, leveling and brightening of the Inconel 718 surface can be detected. When electropolished in this acid mixture, the fusion zone of the Inconel 718 weld cannot be leveled together with its nearby base metal. Nevertheless, a good polished surface of the Inconel 718 weld can be achieved with the acid mixture with 20 vol.% perchloric acid by adding 40 ml l⁻¹ of water. Electropolishing was performed in the limiting diffusion current region where the transport of water to the anode seemed to be the rate-determining process.     

新型Nd掺杂PbO2阳极性能及对AOII的电催化氧化研究

采用电沉积法制备了稀土金属Nd改性PbO2电极（Nd-PbO2）,并通过扫描电镜（SEM）、X射线衍射（XRD）、X射线光电子能谱（XPS）、荧光光谱（FP）、线性极化扫描（LSV）、强化寿命测试（ALT）、循环伏安扫描（CV）等方法表征了其表面结构和电化学性能,探讨了对酸性橙II（AOII）的电催化氧化性能。SEM、XRD、XPS测试结果表明,Nd以Nd3 形式掺杂进入电极镀层,同时对表面形貌、元素组成均有不同程度的改变,但不改变镀层表面的β-PbO2晶型;电化学性能测试表明,Nd掺杂可有效提高电极的析氧电位和稳定性;CV测试及AOII降解实验结果表明,Nd-PbO2电极对AOII还表现出直接氧化作用,电催化氧化AOII能力更强;FP分析表明,Nd-PbO2具有较强的催生羟基自由基能力,可增强电极降解有机物的催化活性。     

溶液钙浓度和水热合成条件对微弧氧化TiO2／羟基磷灰石复合膜层形貌和组成的影响

钛在含钙磷的溶液中微弧氧化，表面形成含有钙磷元素的，均匀多孔的氧化膜层，水热合成后转化为含羟基磷灰石晶体的复合氧化膜。研究表明：钙离子浓度未使膜层的形貌和相组成发生明显变化；仅在较低的浓度下增加溶液Ca^2 的浓度，膜层中Ca，P元素的相对含量和Ca／P比都会增加；在不同的水热温度和溶液钙浓度下，得到的羟基磷灰石具有不同的晶体形貌，相对含量和Ca／P比；缩短恒温时间可以使HA晶粒细化。这为优化生物医用钛表面TiO2／羟基磷灰石复合膜层的成分和形貌提供了依据。     

Effect of thermal oxidation on the corrosion resistance of Ti6Al4V alloy in hydrochloric and nitric acid medium

The characteristics of Ti6Al4V alloy subjected to thermal oxidation in air atmosphere at 650 °C for 48 h and its corrosion behavior in 0.1 and 4 M HCl and HNO₃ medium are addressed. When compared to the naturally formed oxide layer (～4–6 nm), a relatively thicker oxide scale (～7 µm) is formed throughout the surface of Ti6Al4V alloy after thermal oxidation. XRD pattern disclose the formation of the rutile and oxygen‐diffused titanium as the predominant phases. A significant improvement in the hardness (from 324 ± 8 to 985 ± 40 HV_0.25) is observed due to the formation of hard oxide layer on the surface followed by the presence of an oxygen diffusion zone beneath it. Electrochemical studies reveal that the thermally oxidized Ti6Al4V alloy offers a better corrosion resistance than its untreated counterpart in both HCl and HNO₃ medium. The uniform surface coverage, compactness and thickness of the oxide layer provide an effective barrier towards corrosion of the Ti6Al4V alloy. The study concludes that thermal oxidation is an effective approach to engineer the surface of Ti6Al4V alloy to increase its corrosion resistance in HCl and HNO₃ medium.     

Composition and structure of coatings on Ti-6Al-4V alloy by micro-plasma oxidation in NaAlO2 solution

Compound ceramic coatings on Ti-6Al-4V alloy were prepared for different time by pulsed bi-polar micro-plasma oxidation (MPO) in NaAlO2 solution. The phase composition was studied by XRD. And the electrochemical impedance spectra (EIS) of the coatings were measured to study the structure of the coatings, combined with the surface morphology. Using the proper EIS interpreting software, the "equivalent circuit" of the coatings was established, and meanwhile fitting values of equivalent element were obtained. The results show that the coating is composed of Al2 TiO5, α-Al2O3 and rutile TiO2, of which Al2 TiO5 is the main crystalline. Increasing the MPO time, the contents of Al2TiO5, rutile TiO2 and α-Al2O3 in the surface of the coating increase. And the EIS analysis and the surface morphology of the coatings illustrates the double-layer structure of the coatings, and the outer layer is loosen and the inner layer is compact. With the increase of the oxidizing time, the surface coarse degree of the coatings and the porosity of the outer layer of the coating are increased while the compactness of the inner layer of the coating is improved.