催化CO氧化的铜系催化剂的研究进展

综述了近年来铜催化剂体系催化CO氧化反应的研究进展。阐述了催化剂的制备方法、制备条件及载体种类等对催化剂催化活性及稳定性的影响。通过加入添加剂、合适的制备方法和处理条件等手段是提高催化剂活性和选择性有效的途径。     

Oxidation of carbon monoxide on poly-oriented and single-crystalline platinum electrodes over a wide range of pH

The oxidative stripping of pre-adsorbed carbon monoxide has been studied on poly-oriented platinum, and on Pt(1 1 1), Pt(1 0 0) and Pt(1 1 0) single-crystal electrodes in phosphate buffer solutions as a function of pH, both stripping voltammetry and chronoamperometry. It was found that the stripping peak potential has a tendency to decrease as a function of pH until a pH of ca. 10–11, which is ascribed to a weaker adsorption of phosphate on platinum with increasing pH. Above a pH of ca. 11, the stripping peak appears to stay constant or increase, depending on the surface structure. We hypothesize that this may be due to the fact that above a pH of ca. 10–11, the main product of carbon monoxide oxidation is carbonate, which may be block active sites on the surface. By comparison with the stripping on the single-crystalline Pt, the stripping voltammetry on the poly-oriented Pt electrode appears as a convolution of the oxidation on the different facets. A similar conclusion is drawn for the chronoamperometry experiments, and it is suggested that this may be the main reason for the asymmetrical transients observed on the poly-oriented Pt electrodes, as well as on other strongly heterogeneous Pt electrodes that have been studied in the literature.     

Preferential oxidation of carbon monoxide in hydrogen-rich gas over platinum-cobalt-alumina aerogel catalysts

The performance of the platinum-cobalt catalysts in a carbon monoxide preferential oxidation (PROX) reactor was investigated for polymer electrolyte fuel cell systems. First, the PROX reaction was analyzed based on two major reactions involved in it, i.e., oxidation of carbon monoxide and the H₂-O₂ reaction. Both reactions were affected by the other reaction depending on the reaction temperature regions, but the extent of the influence is not so large. The platinum-cobalt catalysts were found to exhibit high performance in PROX of carbon monoxide in rich hydrogen as a result of catalytic synergy effect between platinum and cobalt. In order to improve such synergy effect, the catalysts were prepared by sol-gel method and subsequent supercritical drying. The platinum-cobalt catalysts prepared by the single step sol-gel procedure exhibited higher activity for PROX than the catalysts prepared by the conventional impregnation. Supercritical drying preserved the active species of platinum-cobalt phase, therefore, the platinum-cobalt composite aerogel catalyst exhibited excellent ability for the carbon monoxide removal.     

Decomposition of nitric oxide and its reduction by CO over superconducting and related cuprate catalysts

Catalytic activities of five non-conducting and three superconducting cuprates were measured for the decomposition of NO and the reduction of NO by CO. The concentration of the reactants and the space velocities approximate the conditions of automotive catalysts. In contrast to earlier results, obtained at 20 to 30 times higher partial pressures of NO and 20 to 100 times lower space velocities, none of the catalysts, including five perovskite-like cuprates, showed significant activity for the decomposition of NO at reaction temperatures up to 700 °C. All catalysts were fairly active for the reduction of NO. At temperatures above about 400 °C on the perovskite-like cuprates YBa₂Cu₃O_7-x and Ba₂CuO_3.5-x , the rates for NO reduction were higher than on CuO. All catalysts lost activity for NO reduction in the presence of oxygen (oxidizing conditions).     

A kinetic and DRIFTS study of low-temperature carbon monoxide oxidation over Au-TiO2 catalysts

Titania-supported gold catalysts are extremely active for room temperature CO oxidation; however, deactivation is observed over long periods of time under our reaction conditions Impregnated AuTiO₂ is most active after a sequential pretreatment consisting of high temperature reduction at 773 K, calcination at 673 K and low temperature reduction at 473 K (HTR/C/LTR); the activity after either only low temperature reduction or calcination is much lower. A catalyst prepared by coprecipitation had much smaller Au particles than impregnated AuTiO₂ and was active at 273 K after either an HTR/C/LTR or a calcination pretreatment. Deposition of TiO_x overlayers onto an inactive Au powder produced high activity; this argues against an electronic effect in small Au particles as the major factor contributing to the activity of AuTiO₂ catalysts and argues for the formation of active sites at the AuTiO_x interface produced by the mobility of TiO_x species. DRIFTS (diffuse reflectance FTIR) spectra of impregnated AuTiO₂ reveal the presence of weak reversible CO adsorption on the Au surface but not on the TiO₂; however, a band for adsorbed CO is observed on the pure TiO₂. Kinetic studies with a 1.0 wt.-% impregnated AuTiO₂ sample showed a near half-order rate dependence on CO and a near zero-order rate dependence on O₂ between 273 and 313 K with an activation energy near 7 kcal/mol. A two-site model, with CO adsorbing on Au and O₂ adsorbing on TiO₂, is consistent with Langmuir-Hinselwood kinetics for noncompetitive adsorption, fits partial pressure data well and shows consistent enthalpies and entropies of adsorption. The formation of carbonate and car☐ylate species on the titania surface was detected but it appears that these are spectator species. DRIFTS experiments under reaction conditions also show the presence of weak, reversible adsorption of CO₂ (near 2340 cm⁻¹) which may be competing with CO for adsorption sites.     

Nitric oxide reduction and carbon monoxide oxidation over carbon-supported copper-chromium catalysts

Carbon supported copper-chromium catalysts are shown to be very active for both the reduction of nitric oxide with carbon monoxide and the oxidation of carbon monoxide with oxygen. Mixed copper-chromium oxide active phases have good activity in the simultaneous removal of nitric oxide and carbon monoxide from exhaust gases. The influence of several catalyst variables has been investigated. The activity per volume of catalyst increases with increasing loading, while the intrinsic activity shows a maximum around C/M=100−50. An optimum catalyst for nitric oxide reduction and carbon monoxide oxidation has a copper/chromium ratio of 2/1. The apparent activation energy for the carbon monoxide oxidation over carbon supported copper-chromium catalysts is 77 kJ/mol, suggesting that the Cu---O bond rupture is the rate-limiting process. The reduction of nitric oxide takes place at higher temperatures. Since all catalysts have a low selectivity for molecular nitrogen formation at lower temperatures, the dissociation of nitric oxide is probably rate determining, resulting in a slightly reduced catalyst system. In an excess of carbon monoxide the reaction is first-order in nitric oxide and zero-order in carbon monoxide. Moisture inhibits the reaction by reversible competitive adsorption, whereas carbon dioxide does not. Oxygen completely inhibits the reduction of nitric oxide due to the more rapid reoxidation of the catalytic sites compared to nitric oxide. Therefore, the reduction of nitric oxide takes place only when all oxygen has been converted and, hence, is shifted to higher temperatures. As a possible consequence, the production of nitrous oxide is reduced. Nitric oxide and molecular oxygen react preferentially with carbon monoxide, so, in an excess of oxidizing component, gasification of the carbon support occurs at higher temperatures after carbon monoxide has been completely consumed.     

Temporal analysis of products (TAP) study on low temperature carbon monoxide oxidation on supported Au catalysts

TAP (temporal analysis of products) technique was used to clarify the controversial mechanism for low-temperature CO oxidation on supported Au catalysts involving unidentified moisture effects on the performances. The unique TAP transient technique, along the use of a specially prepared, highly active Au/Ti(OH) ₄ ^* catalyst, provided the information and characterization of each elementary step involving weak and reversible CO adsorption, strong and molecular O₂ adsorption, and their surface reaction, which are suppressed by the coexistence of water vapor.     

The effect of steam and hydrogen in promoting the oxidation of carbon monoxide over a platinum on alumina catalyst

Steam- and hydrogen-induced effects on carbon monoxide oxidation at temperatures below 200°C were studied over an alumina-supported Pt catalyst. These studies were complemented by measurements of rate expressions and IR spectroscopy. CO oxidation activity over alumina-supported Pt, Pd and Rh catalysts was found to be strongly promoted by the presence of steam and H₂ in the feed gas. The promotion effect decreased in the order Pi>Pd> Rh. The water-gas shift reaction did not occur under these experimental conditions. The steam and H₂ enhancement effects are attributed to the weakening of self-poisoning by CO.     

Effect of the precursor and the preparation method on copper based activated carbon catalysts for methanol decomposition to hydrogen and carbon monoxide

Copper oxide supported on activated carbon catalysts, obtained by various preparation techniques, are compared in methanol decomposition to hydrogen and carbon monoxide. The favourable role of copper deposition from ammonia solution of copper carbonate is proved. The effect of the preparation conditions on the catalysts activity and stability as well as on the nature of the catalytic active complexes is studied.     

Catalytic reduction of nitrous oxide with carbon monoxide over calcined Co–Mn–Al hydrotalcite

The N₂O catalytic reduction by carbon monoxide over Co–Mn–Al calcined hydrotalcite was studied. The effect of oxygen and that of CO/N₂O molar ratio on the rate of N₂O decomposition was examined. CO strongly enhanced N₂O conversion when O₂ was absent in the feed gas. In the presence of oxygen, carbon monoxide acts as a non-selective reductant thereby inhibiting N₂O destruction. Continuing excess of CO over N₂O without presence of O₂ led to a very slow reduction of the catalyst, which caused noticeable N₂O conversion decrease with progressing catalyst reduction. The simultaneous reduction of N₂O by CO and direct N₂O decomposition took place when CO was limiting reactant (CO/N₂O < 1) but only at temperatures, at which the direct decomposition is possible without presence of reductant. Simple reduction was observed when reactants ratio was CO/N₂O ≥ 1.     

Catalytic synthesis of methanethiol from hydrogen sulfide and carbon monoxide over vanadium-based catalysts

The direct synthesis of methanethiol, CH₃SH, from CO and H₂S was investigated using sulfided vanadium catalysts based on TiO₂ and Al₂O₃. These catalysts yield high activity and selectivity to methanethiol at an optimized temperature of 615 K. Carbonyl sulfide and hydrogen are predominant products below 615 K, whereas above this temperature methane becomes the preferred product. Methanethiol is formed by hydrogenation of COS, via surface thioformic acid and methylthiolate intermediates. Water produced in this reaction step is rapidly converted into CO₂ and H₂S by COS hydrolysis.

Titania was found to be a good catalyst for methanethiol formation. The effect of vanadium addition was to increase CO and H₂S conversion at the expense of methanethiol selectivity. High activities and selectivities to methanethiol were obtained using a sulfided vanadium catalyst supported on Al₂O₃. The TiO₂, V₂O₅/TiO₂ and V₂O₅/Al₂O₃ catalysts have been characterized by temperature programmed sulfidation (TPS). TPS profiles suggest a role of V₂O₅ in the sulfur exchange reactions taking place in the reaction network of H₂S and CO.     

Oxidation with air of cyclohexanone to carboxylic diacids on carbon catalysts

Carbons derived from phenolic resins were used as catalysts for the aqueous phase oxidation of cyclohexanone at 140°C under air pressure. The reaction yielded mainly adipic, glutaric and succinic acids. The samples were modified by heat treatments in CO₂, air or N₂ at different temperatures and characterized to determine their surface area and porosity and to evaluate the functional groups on the surface. Treatments under CO₂ or air increased the oxidation activity. The selectivity to adipic acid was maximum (33%) after activation in air which greatly increased the surface concentration of oxygen-containing functional groups. However, it was not possible to attribute the selectivity to specific acidic, neutral or basic groups present at the surface of carbons. This revised version was published online in June 2006 with corrections to the Cover Date.     

The electro-oxidation of carbon monoxide, hydrogen/carbon monoxide and methanol in acid medium on Pt-Sn catalysts for low-temperature fuel cells: A comparative review of the effect of Pt-Sn structural characteristics

The electrocatalytic activity for CO, H₂/CO and CH₃OH oxidation of Pt-Sn catalysts has been extensively investigated for a possible use as anode materials for low-temperature fuel cells. This paper presents an overview of the relationship between the structural characteristics of the catalysts (catalyst composition, degree of alloying, presence of oxides) and their electrocatalytic activity for the oxidation of the different fuels.     

The influence of surface structure on the catalytic activity of alumina supported copper oxide catalysts. Oxidation of carbon monoxide and methane

X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and electron spin resonance (ESR) have been used to characterize a series of Cu/Al₂O₃ catalysts. The information obtained from surface and bulk characterization has been correlated with CO and CH₄ oxidation activity of the catalysts. For catalysts with Cu/Al atomic ratios 0.051, XPS data indicated that most of the Cu was present as a dispersed surface phase. ESR results showed that the ratio of isolated/interacting copper surface phase decreased with increasing Cu content. For catalysts with Cu/Al atomic ratio 0.077, large CuO crystallites were detected by XRD. XPS results indicated that Cu dispersion decreased with increasing Cu content. The turn over frequency (TOF) for CO oxidation increased with increasing Cu content. This has been attributed to an increase in the amount of crystalline CuO present in the catalysts. The TOF for CH₄ oxidation decreased with increasing Cu content up to Cu/Al = 0.051. This was paralleled by a significant decrease in the relative Cu ESR signal measured for the catalysts. We propose that the isolated Cu surface phase is more active for CH₄ oxidation than the interacting copper surface phase or crystalline CuO. CH₄ oxidation activities were similar for the catalysts with Cu/Al atomic ratio 0.077.     

一氧化碳吸附干燥器的技术改进

针对原吸附干燥器存在内部盘管焊接接头容易泄漏、设备使用寿命短、材质浪费较大等问题,对其进行了改进。将其中的气体分布改为筛孔板结构,在盘管和总管之间增加异径接头,在夹套与内筒之间增加加强圈,改进后的吸附干燥器结构合理,投资省,效率高,运行平稳。     

Gold and iron supported on Y-type zeolite for carbon monoxide oxidation

Gold and iron supported on Y-type zeolite for carbon monoxide oxidation have been studied. They were prepared by ion exchange of gold(III) compounds with Y-type zeolite, iron-impregnated Y-type zeolite, or iron-exchanged Y-type zeolite in a chloroauric acid solution. The as-prepared gold/Y sample possessed high activity for carbon monoxide oxidation, but it gradually and irreversibly deactivated during the reaction. The deactivation was attributed to the transformation of some gold ions to gold metal. The activities of as-prepared gold/iron/Y samples were poor when compared with that of gold/Y, but their activities were markedly promoted by a high-temperature reduction treatment at 570°C. This is ascribed to the fact that the reduced gold/iron/Y catalyst could catch and release oxygen at low temperature.     

一氧化碳干燥技术及应用

本文阐述了光气生产中一氧化碳冷冻脱水-分子筛吸附的干燥技术,使得干燥后一氧化碳水份含量≤100ppm,提高了光气及光气化产品的质量和设备使用寿命,保证了光气安全生产。     

Hydrogenation of carbon monoxide under mechanical activation conditions

The work focuses on the hydrogenation of carbon monoxide over solid catalysts undergoing mechanical activation by ball milling. The rate of carbon monoxide conversion at individual ball impacts was estimated by measuring the impact frequency, the mass of powders involved in individual impacts and their duration. The rate of the mechanochemical hydrogenation process was compared with the one of the corresponding thermal process. An enhancement of the catalyst activity under mechanical activation conditions is observed.     

Investigation of CO oxidation and NO reduction on three-way monolith catalysts with transient response techniques

The kinetics of CO oxidation and NO reduction reactions over alumina and alumina-ceria supported Pt, Rh and bimetallic Pt/Rh catalysts coated on metallic monoliths were investigated using the step response technique at atmospheric pressure and at temperatures 30–350°C. The feed step change experiments from an inert flow to a flow of a reagent (O₂, CO, NO and H₂) showed that the ceria promoted catalysts had higher adsorption capacities, higher reaction rates and promoting effects by preventing the inhibitory effects of reactants, than the alumina supported noble metal catalysts. The effect of ceria was explained with adsorbate spillover from the noble metal sites to ceria. The step change experiments CO/O₂ and O₂/CO also revealed the enhancing effect of ceria. The step change experiments NO/H₂ and H₂/NO gave nitrogen as a main reduction product and N₂O as a by-product. Preadsorption of NO on the catalyst surface decreased the catalyst activity in the reduction of NO with H₂. The CO oxidation transients were modeled with a mechanism which consistent of CO and O₂ adsorption and a surface reaction step. The NO reduction experiments with H₂ revealed the role of N₂O as a surface intermediate in the formation of N₂. The formation of NN bonding was assumed to take place prior to, partly prior to or totally following to the NO bond breakage. High NO coverage favors N₂O formation. Pt was shown to be more efficient than Rh for NO reduction by H₂.     

Preparation and characteristics of pretreated Pt/alumina catalysts for the preferential oxidation of carbon monoxide

The polymer electrolyte membrane fuel cell (PEMFC) needs purified hydrogen fuel from hydrocarbon reforming and water-gas shift (WGS) reaction. Concentration of CO should be 10 ppm level to avoid poisoning of the platinum anode electrode. For this, preferential oxidation of carbon monoxide (PROX) reaction is essential. In this study, a novel pretreatment technique was applied to a conventional Pt/γ-Al₂O₃ catalyst. Oxygen-treated, water-treated, and conventional Pt/γ-Al₂O₃ catalyst were prepared and their performances in the PROX reaction were investigated in a simulated hydrogen-rich reaction conditions. Our results showed that catalytic activity of the oxygen-treated 5% Pt/γ-Al₂O₃ catalyst for the CO conversion increased dramatically especially at the low temperature below 100 °C. The enhancement is attributed to the formation of well-dispersed small Pt particles.