Comparison of the activity of Au/CeO2 and Au/Fe2O3 catalysts for the CO oxidation and the water-gas shift reactions

We compare the activity and relevant gold species of nanostructured gold–cerium oxide and gold–iron oxide catalysts for the CO oxidation by dioxygen and water. Well dispersed gold nanoparticles in reduced form provide the active sites for the CO oxidation reaction on both oxide supports. On the other hand, oxidized gold species, strongly bound on the support catalyze the water-gas shift reaction. Gold species weakly bound to ceria (doped with lanthana) or iron oxide can be removed by sodium cyanide at pH ≥12. Both parent and leached catalysts were investigated. The activity of the leached gold–iron oxide catalyst in CO oxidation is approximately two orders of magnitude lower than that of the parent material. However, after exposure to H₂ up to 400 °C gold diffuses out and is in reduced form on the surface, a process accompanied by a dramatic enhancement of the CO oxidation activity. Similar results were found with the gold–ceria catalysts. On the other hand, pre-reduction of the calcined leached catalyst samples did not promote their water-gas shift activity. UV–Vis, XANES and XPS were used to probe the oxidation state of the catalysts after various treatments.     

Ambient temperature CO oxidation using copper manganese oxide catalysts prepared by coprecipitation: effect of ageing on catalyst performance

Copper manganese oxides are prepared using a coprecipitation procedure and studied for the oxidation of CO at ambient temperature. In particular, the effect of the ageing tune, i.e. the time that the precipitate remains in contact with the precipitating medium, is investigated. It is shown that this parameter is of crucial importance in controlling the catalytic performance and that catalysts which are aged for 30 min or 300 min give the best performance. Preliminary characterisation using powder X-ray diffraction indicates that a combination between CuO and copper manganese oxide may be responsible for the enhanced activity observed with these samples.     

The effect of high-temperature pre-treatment and water on the low temperature CO oxidation with Au/Fe2O3 catalysts

The low temperature activity of Au/Fe₂O₃ catalysts towards CO oxidation was examined with respect to the temperature of pre-treatment and presence of water. The activity of all the prepared catalysts decreased as a result of a high temperature treatment (HTT) at 400 °C. The inclusion of water in the gas stream significantly enhanced the oxidation of CO at room temperature. When tested under water gas shift reaction (WGSR) conditions, significantly higher temperatures were required to convert CO to CO₂, thereby excluding the possibility of the WGSR during CO oxidation in the presence of H₂O at room temperature. The loss of activity for CO oxidation is attributed to the loss of hydroxyl groups and reduction of Au³⁺ to metallic gold during HTT. The observations are consistent with the model for hydroxyl promotion of the decomposition of a carbonate intermediate by transformation to less stable bicarbonate.     

Influence of modifying additives on the catalytic activity and stability of Au/Fe2O3–MO x catalysts for the WGS reaction

The activity and stability of Au/Fe₂O₃–MO_x catalysts (M = Zr, Mg, Ca, Ni, La, Cu, Zn, Al, Ba, Cr, Co, Ce, Mo, Bi, Ti, Mn) in water-gas shift reaction were investigated extensively. The WGS activity and stability of Au/Fe₂O₃ is improved significantly upon addition of ZrO₂ and to a lesser extend MgO, CaO, NiO, La₂O₃, Cr₂O₃, CuO. In contrast, Bi, Ti and Mn oxides seriously decrease the catalytic activity while additions of Zn, Al, Ba, Co, Ce and Mo oxides do not influence evidently the catalytic activity and its stability. Based on the characterization using the methods of BET-surface area and pore structure XRF, XRD, and H₂–TPR for some of as-prepared and spent samples, it could be concluded that the catalytic activity of gold catalysts supported on composite oxide of Fe₂O₃–MO_x depends not only on the dispersion of the gold particles but also on the reduction property of composite oxide supports, regardless of the fluctuation of gold loading and some change of specific surface area and pore structure due to introduction of the modifying metal oxides. The improvement of catalytic stability may be attributed to the comparative stabilization of high dispersion of gold particles and uneasily sintering of Fe₃O₄ crystallites during the catalytic operation. However, the chemical (electronic) effects exerted by the modifying addition of metal oxides on the catalytic performance of gold catalyst may not be ruled out.     

FT-IR study of Au/Fe2O3 catalysts for CO oxidation at low temperature

Coprecipitated Au/Fe₂O₃ catalysts used for low-temperature catalytic oxidation of carbon monoxide have been studied by FT-IR spectroscopy of adsorbed CO. The FT-IR results have shown that after preparation and exposure to a CO/O₂ mixture gold is present on the surface mainly as Au¹⁺ and Au⁰ species. It has been found that in the CO oxidation Au¹⁺ is more active and less stable than Au⁰. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of preparation variables on the activity of Ni-W/Al2O3 hydrotreating catalysts

Studies have been carried out on the influence of preparation parameters on the activity of nickel-tungsten (Ni-W) catalysts, used to promote the hydrotreatment of model compounds representative of nitrogen, sulphur, oxygen and aromatic containing compounds which typically occur in coal derived liquids. The preparation variables considered for optimisation were the pH of the impregnating solution, the impregnation order, the starting Ni salts, the Ni/Ni + W ratio, the drying conditions and the calcination temperature. It was found that changes in pH, within the range where binding of the starting ions to alumina takes place, is not a significant variable influencing the activity. The use of nickel nitrate as a precursor yields better catalysts. If W is impregnated first it is redistributed during subsequent nickel impregnation, and better catalysts are obtained when Ni is impregnated first. The optimum Ni/Ni + W ratio is between 0.3 and 0.4, based on the total active metals present on the catalyst. The hydrodesulphurisation hydrodeoxygenation and hydrogenation activities decrease with increase in the drying temperature; the reverse is true for hydrodenitrogenation. An optimum activity is obtained when drying at 100°C in a closed oven. The optimum calcination temperature was found to be 500°C.     

The effects of sulfation on the activity of Fe2O3 catalysts for methane oxidation

The effects of sulfation on iron oxides prepared from goethite and ferrihydrite for methane oxidation have been investigated. Reaction performance has been shown to be influenced by the iron oxide precursor. Sulfation produces a number of general effects, in addition to enhancing catalyst surface area, it suppresses the oxidation activity of Fe₂O₃ observed at 400°C and below, whilst enhancing that at higher temperatures. Selective partial oxidation products – CH₃OH and C₂H₆ – are also observed in some instances with sulfated systems. This revised version was published online in August 2006 with corrections to the Cover Date.     

改进的二步共沉淀法制备Cu/ZnO/Al2O3甲醇合成催化剂

采用改进的二步共沉淀法制备了Cu/ZnO/Al₂O₃甲醇合成催化剂。用XRD、SEM和BET等手段对催化剂结构和形貌进行了表征。采用流动固定床微型反应器在5.0 MPa和空速5 000 h^-1条件下,考察了其催化合成气合成甲醇的活性,并在同一条件下用一种工业催化剂做对比测试。结果表明,改进的二步法制备的甲醇合成催化剂结晶度较低,基本以无定形状态的固溶体形式存在,铜锌之间的协同作用大,催化剂粒度较小,尺寸分布较均匀,比表面积较大,催化剂单位面积活性达98.54 mg·m^-2。     

焙烧温度对Au/Fe2O3-ZrO2水煤气变换催化剂的影响

采用共沉淀法制得Au/Fe₂O₃-ZrO₂水煤气变换催化剂。研究了焙烧温度对催化剂的水煤气变换反应性能的影响。并对样品进行了BET、XRD和TPR表征。结果表明，焙烧条件对催化剂的结构和催化活性均有显著影响，焙烧温度越高，催化剂载体结晶度越大，被还原的难度越大，催化剂对低温水煤气变换反应的催化活性越低。Au/α-Fe₂O₃-ZrO₂催化剂的最佳焙烧温度为300 ℃。在此温度下焙烧的催化剂，其载体主相为无定形态，催化活性较好。     

负载型Pt-Fe/Al2O3催化剂用于室温催化氧化甲醛

采用胶体沉积法制备不同载体（Ni₂O₃、Co₃O₄、TiO₂、Al₂O₃）的Pt-Fe/MeO_x催化剂用于甲醛室温催化氧化。活性测试表明,以γ-Al₂O₃为载体的Pt-Fe/Al₂O₃催化剂具有较高的催化活性,在25℃时甲醛的转化率可达到100%,而且Pt-Fe/ Al₂O₃催化剂还表现出良好的稳定性。采用各种表征技术对Pt-Fe/Al₂O₃的形貌、价态及氧化还原性等物理化学性质进行了研究,结果表明：Pt-Fe/Al₂O₃催化剂中Pt物种和Fe物种在Al₂O₃载体的表面上均匀分散;二者之间存在着较强的相互作用,在Al₂O₃载体的表面上形成一些类似Pt-O-Fe活性物种,有效促进了Pt-Fe/Al₂O₃催化性能,从而显示出较高的氧化活性。     

CO removal from reformed fuel over Cu/ZnO/Al2O3 catalysts prepared by impregnation and coprecipitation methods

A composition of Cu/ZnO/Al₂O₃ catalysts prepared by the impregnation method was optimized for water gas shift reaction (WGSR) coupled with CO oxidation in the reformed gas. The optimum composition of the impregnated catalyst for high WGSR activity was 5 wt.% Cu/5 wt.% ZnO/Al₂O₃. The optimum loading amounts of Cu and ZnO in the impregnated catalyst were smaller than those in the coprecipitated catalyst. Its catalytic activity above 200 °C was comparable to that of the conventional coprecipitated Cu/ZnO/Al₂O₃ catalyst. However, the activity of the impregnated Cu/ZnO/Al₂O₃ catalysts was significantly lowered at 150 °C, whereas no deactivation was observed for the coprecipitated catalyst at the same temperature. It was found that deactivation occurred over impregnated catalysts with H₂O and/or O₂ in the reaction gas; it prevented CO adsorption on the surface.     

Effect of method of preparation on activity of Pd/Al2O3 monolith catalysts

Pd/Al₂O₃ monolithic catalyst of different washcoat thicknesses were prepared by two methods and tested for the activity of hydrogenation of α‐methyl styrene. These catalysts were prepared by two methods; either the palladium was impregnated on γ‐alumina and this Pd/Al₂O₃ powder was used to prepare the slurry for washcoating (Cat 1) or γ‐alumina washcoating was followed by impregnation of palladium (Cat 2). The effect of slurry concentration, pH of the slurry, and addition of binders on the catalyst properties was investigated. The monolithic catalysts were characterised by determination of metal dispersion, surface area, scanning electron microscopy, and weight loss of washcoat during ultrasonication. Well‐adhered washcoats were obtained with slurry prepared using milled γ‐alumina, whereas the adhesion of the washcoat prepared using Pd/Al₂O₃ powders was very poor. Addition of binders significantly improved the adhesion of the washcoats prepared from Pd/Al₂O₃. Metal dispersion for Cat 2 decreased with washcoat loading but did not change with loading for Cat 1. The activity tests were conducted at different washcoat loadings and the productivity of the monolithic catalyst prepared in both methods has been compared.     

The oxidation and scrambling of CO with oxygen at room temperature on Au/ZnO

An FTIR and quadrupole mass study of CO adsorption and oxidation with¹⁶O₂ and¹⁸O₂ on Au/ZnO catalysts is presented. The experimental results indicate that: (i) CO is activated by gold in two molecular forms, a linear carbonyl species bonded at terrace Au sites and a carbonyl species bonded to Au peripheral sites; (ii) a band related to CO adsorbed on Au oxidized sites and a scrambling reaction between CO and¹⁸O₂ indicate that oxygen is also activated on gold sites. The oxygen adsorbed on gold is probably strongly basic, as is the oxygen adsorbed on silver and on copper, and it can easily oxidize CO to CO₂.     

Catalytic oxidation of CO by O2 over nanosized CuO–ZnO system prepared under various conditions

A series of copper and zinc mixed oxides composed of equimolar ratio and treated with 0.05 Al₂O₃/mol catalyst has been prepared by coprecipitation method using their nitrates in presence of 1 M NaOH solution. The precipitation was carried out at a pH 9.5 and 50°C. The results revealed that the bulk of various solids consisted of CuO and ZnO having ratios varying between 0.84 and 0.98. On the other hand, the values of surface concentrations of copper and zinc were bigger than those present in the bulk. The values of surface Cu/Zn ratio varied between 1.04 and 1.46 depending on the mode of preparation and calcination conditions. The mixed solids existed as nanocrystalline CuO and ZnO phases. The surface characteristics are strongly dependent on mode of coprecipitation and calcination temperature. The computed S_BET values varied between 146 and 23 m²/g depending on mode of coprecipitation and calcination temperature. The increase of calcination temperature of different adsorbents within 300–400°C led to a significant progressive decrease in the BET‐surface area with subsequent increase in the values of mean pore radius. All adsorbents are mesoporous solids. All prepared solids showed a good catalytic activity in CO oxidation by O₂, which proceeds via first order kinetics in all cases. The activation energy of the catalysed reaction was determined for various solids and the computed values were very small indicating the big catalytic activity of the investigated solids.     

焙烧温度对共沉淀法合成Ni/Al_2O_3甲烷化催化剂性能的影响

采用并流共沉淀法制备Ni负载质量分数为15%的Ni/Al2O3催化剂,用于CO加氢甲烷化反应。结合紫外可见光漫反射、氢气程序升温还原、N2物理吸附-脱附和X射线粉末衍射等技术,考察焙烧温度对催化剂结构、活性与稳定性的影响。结果表明,低温[(350-500)℃]焙烧的样品中活性组分Ni主要以孤立的Ni O物种和高分散的无定形Ni O物种存在,相应的还原态样品中Ni粒子尺寸较小,是其新鲜态样品低温活性较高的主要原因。800℃焙烧的样品中活性组分Ni主要以高分散的无定形Ni O物种和Ni Al2O4尖晶石微晶形式存在于催化剂表面,活性组分Ni与载体Al2O3间的作用力较强,稳定性较高,且经过800℃水热老化处理10 h后仍具有较大的比表面积(125 m2·g-1),是其具有较佳低温活性同时突显良好水热稳定性的主要原因。     

Influence of the calcination temperature on the Au/FeOx/Al2O3 catalyst

The effect of calcination temperature on the electronic structure of gold catalyst was investigated in this paper. CO oxidation was employed as a test reaction to correlate the phase changes to the catalytic activity. The TPR, XPS and XRD characterization showed that the highly active Au/FeO_x/Al₂O₃ catalyst contained both gold atoms and ions. The catalytic performance of gold catalyst may depend on the Au⁰/Au³⁺ ratio. The best activity in the present work was obtained when the Au⁰/Au³⁺ ratio was about 0.89. Copyright © 2006 Society of Chemical Industry     

制备方法对V_2O_5-WO_3/TiO_2选择性催化还原催化剂性能的影响

采用共沉淀法、溶胶-凝胶法和浸渍法制备了V2O5质量分数4%和WO3质量分数6%的V2O5-WO3/TiO2选择性催化还原催化剂,对比了3种方法制备的催化剂选择性催化还原NO性能。采用X射线衍射、热重、N2吸附-脱附和程序升温还原等对制备的V2O5-WO3/Ti O2催化剂的结构和性质进行表征,结果表明,共沉淀法制备的V2O5-WO3/TiO2催化剂具有更好的选择性催化还原NO活性和更大的比表面积,影响共沉淀法选择性催化还原NO活性的主要因素是催化剂的热稳定性、表面羟基数量、比表面积、粒径分布以及V、W与Ti之间的内在作用。     

ZnO对CuO-ZnO/Al2O3催化剂催化甘油氢解性能的影响

以氧化铝为载体,采用浸渍法制备了负载型CuO-ZnO/Al2O3催化剂,通过XRD、XPS、TPR手段表征催化剂上CuO和ZnO的分布和化学形态。结果表明,CuO-ZnO/Al2O3催化剂催化甘油氢解反应中,CuO是活性组分,ZnO的引入可以降低CuO与载体氧化铝的相互作用强度,有利于CuO的还原,提高催化剂甘油氢解活性;催化剂表面呈缺电子状态的Cu物种是甘油氢解的活性中心。当活性组分CuO质量分数为12%,n(Cu)∶n(Zn)=1∶1.5时,CuO-ZnO/Al2O3催化剂催化甘油氢解活性最高,甘油转化率可达97.82%,对1,2-丙二醇选择性达94%。     

Improved Performance of Au/Fe2O3 Catalysts Promoted with ZrO2 and Nb2O5 in the WGS Reaction under Hydrogen-rich Conditions

Effect of addition of the ZrO₂ and Nb₂O₅ promoters on the activity and stability of the Au/Fe₂O₃ catalysts in the WGS reaction under hydrogen-rich conditions was studied. Results showed that this new catalyst possesses enhanced activity and stability under conditions common in fuel processors. Its CO conversion almost reached the maximum value 99% at 200 °C and maintained better stability compared with unmodified samples within 50 h on-stream. Detailed characterization including BET, XRD, HRTEM, XPS, XRF and H₂-TPR revealed that ZrO₂ and Nb₂O₅ acted as structural promoters and a strong interaction between ZrO₂ and Nb₂O₅ existed. The enrichment of Zr and Nb on the surface kept the gold and magnetite particles apart delaying sintering. More active gold sites, larger surface area and smaller magnetite particles were the main reasons for the enhanced performance.     

Characterization and catalytic activity of unpromoted and alkali (earth)-promoted Au/Al2O3 catalysts for low-temperature CO oxidation

Various unpromoted and alkali (earth) promoted gold catalysts were characterized by means of XRD, HRTEM, DR/UV–Vis and TPR. Based on the results we conclude that metallic Au is the active species in CO oxidation and that the reduction of Au³⁺ to Au⁰ proceeds below 200 °C. Pretreatment at mild temperatures, viz. 200 °C, results in the highest catalytic performance of Au/Al₂O₃ in low-temperature CO oxidation. Alkali (earth) metal oxide additives are most probably structural promoters. The best promoting effect is found for BaO.