Effect of controlling nano-sized copper by silver in copper-based catalyst on catalytic oxidation of toluene

Catalytic oxidation of VOC (toluene) over a copper based catalyst was carried out to assess its properties and performance. The Brunauer Emmett Teller (BET) method, X-ray diffraction (XRD), temperature programmed reduction (TPR), N2O pulse titration and energy dispersive spectroscopy (EDS) were used to characterize a series of 5 wt% Cu/gamma-Al2O3 catalysts modified with silver. The experimental results revealed that the addition of silver to 5 wt% Cu/gamma-Al2O3 catalyst highly enhanced its catalytic activity. With increasing addition amount of silver, the light-off curve for complete oxidation of toluene shifted to lower temperature. In addition, the increase of the addition amount of silver caused the copper particle size of 5 wt% Cu/gamma-Al2O3 catalyst to gradually increase. Subsequently, it demonstrated that the increase in the copper particle size is closely associated with the increase in catalytic activity.     

The catalytic oxidation of aromatic hydrocarbons over supported metal oxide

The catalytic activity of metals (Cu, Mn, Fe, V, Mo, Co, Ni, Zn)/gamma-Al2O3 was investigated to bring about the complete oxidation of benzene, toluene and xylene (BTX). Among them, Cu/gamma-Al2O3 was found to be the most promising catalyst based on activity. X-ray diffraction (XRD), Brunauer Emmett Teller method (BET), electron probe X-ray micro analysis (EPMA) and temperature programmed reduction (TPR) by H2 were used to characterize a series of supported copper catalysts. Increasing the calcination temperature resulted in decreasing the specific surface areas of catalysts and, subsequently, the catalytic activity. Copper loadings on gamma-Al2O3 had a great effect on catalytic activity, and 5 wt.% Cu/gamma-Al2O3 catalyst was observed to be the most active, which might be contributed to the well-dispersed copper surface phase. Using TiO2 (anatase), TiO2 (rutile), SiO2 (I) and SiO2 (II) as support instead of gamma-Al2O3, the activity sequence of 5 wt.% Cu with respect to the support was gamma-Al2O3 > TiO2 (rutile) > TiO2 (anatase)>SiO2 (I) > SiO2 (II), and this appeared to be correlated with the distribution of copper on support rather than with the specific surface area of the catalyst. The smaller particle size of copper, due to its high dispersion on support, had a positive effect on catalytic activity. The activity of 5 wt.% Cu/gamma-Al2O3 with respect to the VOC molecule was observed to follow this sequence: toluene > xylene > benzene. Increasing the reactant concentration exerted an inhibiting effect on the catalytic activity.     

The operating performance and products distribution of the catalytic oxidation of methyl-isobutyl-ketone over a Pt/gamma-Al2O3 catalyst

Catalytic oxidation is one of the cost-effective technologies to solve the troublesome volatile organic compounds. This study treated methyl-isobutyl-ketone (MIBK) by a commercial catalyst, Pt/gamma-Al(2)O(3), in a fixed-bed reactor. The effects of operating factors, such as operating temperature, MIBK concentration, space velocity, and O(2) concentration, on the performance of the catalyst were investigated. The products and reactants distributions from the oxidation of MIBK over Pt/gamma-Al(2)O(3) were observed. The results show that the products containing carbon atoms are CO, CO(2), and C(3)H(6)O. Two catalyst life-tests were also carried out to characterize the deactivation effect of MIBK. The result shows that the deactivation effect may be due to the coke on the catalyst surface at 423 K. From the statistical analysis, the operating temperature is the most effective factor on the conversion of MIBK. The catalysts were also characterized by surface area analysis and elemental analysis before and after the test. The results show that the catalytic deactivation may be due to carbon coating. At low temperature (423 K), the phenomenon of carbon coating was more obvious than that at high temperature (573 K). The product distributions from the oxidation of MIBK over Pt/gamma-Al(2)O(3) were analyzed by GC. The results indicate that the C(3)H(6)O is formed from the beginning, presenting a peak at 423 K, 6.54 ppm. The CO concentration also peaked at the same temperature, 6.84 ppm.     

Preparation and characterization of nanosized gold catalysts supported on Co3O4 and their activities for CO oxidation

Gold catalysts supported on Co3O4 were prepared by co-precipitation (CP), deposition-precipitation (DP), and impregnation (IMP) methods. The Au/Co3O4 catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and temperature programmed reduction (TPR) to understand the different activities for CO oxidation with different preparation methods. Gold particles below 5 nm supported on Co3O4 by DP method were found to be more exposed to the surface than those by CP and IMP methods, and this catalyst was highly active and stable in CO oxidation. Finally, catalytic activity of Au/Co3O4 catalyst for CO oxidation was strongly dependent on the gold particle size.     

Preparation of platinum nanoparticle and its catalytic activity for toluene oxidation

Colloidal Pt nanoparticles are prepared using H2PtCl6 as a precursor, polyvinylpyrrolidone (PVP: molecular weight = 10,000 and 40,000) and hydrogen as a stabilizing agent and a reducing agent, respectively. The amounts of the precursor and the stabilizing agent and the molecular weight of PVP have an effect on the formation of Pt nanoparticles. Supported Pt catalyst (CSPt) is prepared from colloidal Pt nanoparticles and y-Al2O3. Another supported Pt catalyst (ISPt) is prepared by using the conventional incipient wetness impregnation method with an aqueous H2PtCl6 solution and gamma-Al2O3. The catalytic activities of CSPt and ISPt catalysts are compared for VOC (toluene) oxidation. Transmission Electron Microscopy (TEM), UV-vis, X-ray diffraction (XRD) and temperature programmed reduction (TPR) are used to characterize CSPt and ISPt catalysts. The experimental results reveal that the catalytic activity of CSPt is superior to that of ISPT.     

石墨烯负载Pt-Co纳米粒子及其在氧化还原反应中的应用

采用微波-乙二醇方法还原氧化石墨烯和Pt(v)、Co(Ⅱ)粒子混合物,再经300℃H2还原,制备了石墨烯负载Pt-Co合金催化剂(Pt-Co/G).利用透射电镜、X-射线能谱、X-射线衍射和光电子能谱对所制催化剂进行表征.Pt-Co合金的粒径为3nm～8 nm,均匀地分散在石墨烯片上.与单金属的Pt/G和商品化的Pt/C催化剂相比,所制合金化的Pt-Co/G催化剂对氧还原反应展现出高的催化活性和可比拟的稳定性,显示了其在燃料电池中的应用潜力.     

Effect of water addition on catalytic activity of nanosized gold catalysts for CO oxidation

The effect of water in the reactant gas on the catalytic activity for CO oxidation over Au/Co3O4 catalysts has been investigated. Water in the reactant gas had a negative effect on the catalytic activity for CO oxidation in Au/Co3O4 catalyst. Furthermore, it was observed that the average particle size of gold on Au/Co3O4 catalysts increased after stability testing both in dry and wet conditions.     

Influence of physicochemical treatments on iron-based spent catalyst for catalytic oxidation of toluene

The catalytic oxidation of toluene was studied over an iron-based spent and regenerated catalysts. Air, hydrogen, or four different acid solutions (oxalic acid (C2H2O4), citric acid (C6H8O7), acetic acid (CH3COOH), and nitric acid (HNO3)) were employed to regenerate the spent catalyst. The properties of pretreated spent catalyst were characterized by the Brunauer Emmett Teller (BET), inductively coupled plasma (ICP), temperature programmed reduction (TPR), and X-ray diffraction (XRD) analyses. The air pretreatment significantly enhanced the catalytic activity of the spent catalyst in the pretreatment temperature range of 200-400 degrees C, but its catalytic activity diminished at the pretreatment temperature of 600 degrees C. The catalytic activity sequence with respect to the air pretreatment temperatures was 400 degrees C>200 degrees C>parent>600 degrees C. The TPR results indicated that the catalytic activity was correlated with both the oxygen mobility and the amount of available oxygen on the catalyst. In contrast, the hydrogen pretreatment had a negative effect on the catalytic activity, and toluene conversion decreased with increasing pretreatment temperatures (200-600 degrees C). The XRD and TPR results confirmed the formation of metallic iron which had a negative effect on the catalytic activity with increasing pretreatment temperature. The acid pretreatment improved the catalytic activity of the spent catalyst. The catalytic activity sequence with respect to different acids pretreatment was found to be oxalic acid>citric acid>acetic acid>or=nitric acid>parent. The TPR results of acid pretreated samples showed an increased amount of available oxygen which gave a positive effect on the catalytic activity. Accordingly, air or acid pretreatments were more promising methods of regenerating the iron-based spent catalyst. In particular, the oxalic acid pretreatment was found to be most effective in the formation of FeC2O4 species which contributed highly to the catalytic combustion of toluene.     

Effect of CeO2 doping on catalytic activity of Fe2O3/gamma-Al2O(3) catalyst for catalytic wet peroxide oxidation of azo dyes

In order to find a catalyst with high activity and stability for catalytic wet peroxide oxidation (CWPO) process under normal condition, with Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) catalysts prepared by impregnation method, the effect of CeO(2) doping on the structure and catalytic activity of Fe(2)O(3)/gamma-Al(2)O(3) for catalytic wet peroxide oxidation of azo dyes at 25 degrees C and atmospheric pressure is evaluated using BET, SEM, XRF, XRD, XPS and chemical analysis techniques, and test results show that, better dispersion and smaller size of Fe(2)O(3) crystal can be achieved by adding CeO(2), and the content of chemisorbed oxygen can also be increased on the surface of catalyst. CWPO experimental results indicate that azo dyes in simulated wastewater can be efficiently mineralized and the catalytic activity of Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) can be increased by about 10% compared with that of Fe(2)O(3)/gamma-Al(2)O(3) because of the promotion of the structural and redox properties of the ferric oxide by ceria doped. Leaching tests indicate that Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) are stable with a negligible amount of irons found in the aqueous solution after reaction for 2h. It can therefore be concluded from results and discussion that in comparison with Fe(2)O(3)/gamma-Al(2)O(3), Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) is a suitable catalyst, which can effectively degrade contaminants at normal temperature and atmospheric pressure.     

Transmitted-light microscopy - a new method for surface structure analysis of cleanable non-woven dust filter media

A series of CeO(2)-ZrO(2) mixed oxides were prepared using coprecipitation method and characterized by BET, oxygen storage capacity (OSC), X-ray diffraction (XRD) and H(2)-temperature-programmed reduction (H(2)-TPR). The catalytic activities toward toluene combustion were investigated in a micro-reactor. The results demonstrate that the catalytic activity of Pt/gamma-Al(2)O(3)/Ce(0.50)Zr(0.50)O(2) monolithic catalyst can be greatly improved by doping metal into Ce(0.50)Zr(0.50)O(2). When doping Y and Mn into Ce(0.50)Zr(0.50)O(2) simultaneously, the catalyst Pt/gamma-Al(2)O(3)/Ce(0.40)Zr(0.40)Y(0.10)Mn(0.10)O(X) shows the highest activity. The T(10) (the temperature of 10% toluene conversion) and the complete conversion temperature (the temperature of 90% toluene conversion) of toluene are 443 and 489K, respectively. Gas hourly space velocity (GHSV) results show that the prepared catalyst can be applied in a wide range of GHSV (from 12,000 to 20,000h(-1)). The catalyst prepared shows great potential for practical application.     

Catalytic activity of CuOn-La2O3/gamma-Al2O3 for microwave assisted ClO2 catalytic oxidation of phenol wastewater

In order to develop a catalyst with high activity and stability for microwave assisted ClO2 catalytic oxidation, we prepared CuOn-La2O3/gamma-Al2O3 by impregnation-deposition method, and determined its properties using BET, XRF, XPS and chemical analysis techniques. The test results show that, better thermal ability of gamma-Al2O3 and high loading of Cu in the catalyst can be achieved by adding La2O3. The microwave assisted ClO2 catalytic oxidation process with CuOn-La2O3/gamma-Al2O3 used as catalyst was also investigated, and the results show that the catalyst has an excellent catalytic activity in treating synthetic wastewater containing 100 mg/L phenol, and 91.66% of phenol and 50.35% of total organic carbon (TOC) can be removed under the optimum process conditions. Compared with no catalyst process, CuOn-La2O3/gamma-Al2O3 can effectively degrade contaminants in short reaction time and with low oxidant dosage, extensive pH range. The comparison of phenol removal efficiency in the different process indicates that microwave irradiation and catalyst work together to oxidize phenol effectively. It can therefore be concluded from results and discussion that CuOn-La2O3/gamma-Al2O3 is a suitable catalyst in microwave assisted ClO2 catalytic oxidation process.     

Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production

Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production was carried out at 225 degrees C, 23 bar and LHSV = 4 h(-1). The Ni-based catalyst was prepared by an incipient wetness impregnation method. The catalysts before and after the reaction were characterized by N2 physisorption, CO chemisorption, XRD, TPR, SEM and TEM techniques. It was found that Ni(20 wt%)-Co(3 wt%)/gamma-Al2O3 catalyst showed higher glycerol conversion and hydrogen selectivity than Ni(20 wt%)/gamma-Al2O3 catalyst. There are no major changes in Ni particles after the reaction over Ni-Co/gamma-Al2O3 catalyst. The results suggest that the Ni-Co/gamma-Al2O3 catalyst can be applied to the hydrogen production system using APR of glycerol.     

Pt/C催化剂制备及CO催化氧化性能研究

采用大气压介质阻挡放电辅助氢气热还原方法和氢气热还原方法制备Pt/C催化剂,考察了制备方法及Pt负载量对Pt/C催化性能的影响。采用X-射线衍射(XRD)、循环伏安法、CO催化氧化反应研究Pt/C催化剂的晶相结构、电催化性能和CO催化氧化活性。结果表明:大气压介质阻挡放电辅助氢气热还原所制备的样品具有更高的电化学活性和CO催化氧化活性。当Pt负载量在2%到10%之间变化时,Pt/C-PC催化活性随负载量增加而增加。XRD测试结果显示当Pt负载量为2%,5%和10%时,Pt粒径分别为:10.6 nm,9.1 nm和6.4 nm,说明采用等离子体辅助氢气热还原方法制备的Pt/C-PC催化剂,Pt负载量越大,Pt粒径越小,CO催化氧化活性更高。     

Mesoporous Co3O4 for low temperature CO oxidation: effect of calcination temperatures on their catalytic performance

Mesoporous Co3O4 particles are prepared by using mesoporous silica KIT-6 (with double gyroid Ia-3d symmetry) as a hard-template and Co(No3)2 x 6H2O as an inorganic precursor. In the former section, we investigate the effect of the calcination temperatures at which the Co salts are converted into Co3O4 inside the mesopores on the textural parameters of the products. The results of N2 adsorption-desorption analysis indicates that the calcination temperatures do not obviously affect the textural parameters such as the surface areas and pore volumes. However, when the calcination temperature reaches 800 degrees C, the mesostructural ordering is dramatically decreased, resulting in the reduction of the surface areas and pore volumes. After 800 degrees C calcination, the formation of large Co3O4 grains is partially confirmed on the particle surface by SEM observation. The grain size is much larger than the mesopore size of the original KIT-6, meaning the crystal growth is continuously occurred by breaking the rigid silica frameworks. In the latter section, we discuss the effect of the calcination temperatures and textural parameters on the catalytic activity for CO oxidation by both steady state and kinetic measurements. All mesoporous Co3O4 particles show a high catalytic activity, for example, -72 degrees C for sample calcined at 450 degrees C. Only 10 degrees C difference in T50 (the temperature of 50% conversion of CO) is found between the samples with the highest and lowest catalytic activity. The values of activation energy (Ea) and pre-exponential factor (A) per unit area are almost the same between two samples calcined at 450 degrees C and 800 degrees C. It is demonstrated that calcination process can not alter the essential catalytic property of mesoporous Co3O4 particles.     

Complete oxidation of formaldehyde at ambient temperature over supported Pt/Fe2O3 catalysts prepared by colloid-deposition method

The catalytic properties of iron oxide supported platinum catalysts (Pt/Fe(2)O(3)), prepared by a colloid deposition route, were investigated for the complete oxidation of formaldehyde. It is found that all the Pt/Fe(2)O(3) catalysts calcined at different temperatures (200-500°C) were active for the oxidation of formaldehyde. Among them, the catalysts calcined at lower temperatures (i.e., 200 and 300°C) exhibited relatively high catalytic activity and stability, which could completely oxidize HCHO even at room temperature. Based on a variety of physical-chemical characterization results, it is proposed that the presence of suitable interaction between Pt particles and iron oxide supports, which is mainly in the form of Pt-O-Fe bonds, should play a positive role in determining the catalytic activity and stability of the supported Pt/Fe(2)O(3) catalysts.     

Aqueous phase reforming of glycerol over the Pd loaded Ni/Al2O3 catalysts

Bifunctional catalysts containing (0.5-1.5 wt%) palladium and 15 wt% of Nickel supported on gamma-Al2O3 were prepared via an impregnation technique and catalysts were characterzed by XRD BET surface area and SEM, respectively. The aqueous phase reforming of glycerol (APR) was conducted over alumina-supported catalysts at different reaction conditions for catalytic activity. Finally, we concluded that the 1.0 wt% Pd 15 wt% Ni/gamma-Al2O3 catalyst evidences higher conversion, hydrogen selectivity, lower alkane selectivity and CO production. This indicate that Pd loaded Ni/gamma-Al2O3 could be a potential catalyst for the APR of glycerol.     

Catalytic decomposition of 1,2-dichlorobenzene using Pt-loaded nanoporous zeolite MFI catalyst

Nanoporous zeolite MFI was prepared by using HClO4 as a promoter. A significant proportion of the synthesized zeolite MFI nanoparticles exhibited nanoporous characteristics. Although the synthesis of the zeolite MFI was completed within 6 h, the crystallinity of all the zeolite MFI was shown to be high. The synthesis time of approximately 6 h used in this study was much shorter than the conventional hydrothermal method. The feasibility of the new nanoporous zeolite MFI towards the gas phase catalytic oxidation of a model for dioxin, 1,2-dichlorobenzene, was tested by comparing the catalytic activity of Pt/nanoporous zeolite MFI with that of a Pt/gamma-Al2O3 catalyst. The catalytic activity of the Pt/nanoporous zeolite MFI was higher than that of the Pt/gamma-Al2O3 catalyst. The internal surface area and acidity appears to be a major factor for the decomposition of 1,2-dichlorobenzene.     

Effect of pretreatment conditions on particle size of bimetallic pt-au catalysts supported on ZnO/Al2O3 and its activity for toluene oxidation

Bimetallic Pt-Au catalysts supported on ZnO/Al2O3 were prepared by incipient wetness impregnation (IW-IMP) method with different pretreatment conditions such as flow velocity, calcination temperature, and heating rate under H2 during the calcination procedure, and characterized by X-ray diffraction (XRD), CO chemisorption, and scanning transmission electron microscopy (STEM) equipped energy dispersive spectroscopy (EDS). Furthermore, catalytic activity for complete oxidation of toluene was measured using a flow reactor under atmospheric pressure. Finally, relationship between the particle sizes with pretreatment conditions and catalytic activity for toluene on the bimetallic Pt-Au catalysts was discussed. In these results, nanosized bimetallic Pt-Au particles on ZnO/Al2O3 could be prepared by IW-IMP method. Relationship between the Pt and Au particle size and activity for toluene oxidation was clearly observed.     

Steam reforming of glycerol into hydrogen over nano-size Ni-based hydrotalcite-like catalysts

Steam reforming (SR) of glycerol for the production of hydrogen was investigated over the nano-sized Ni-based catalysts. The Ni-based catalysts were prepared by solid phase crystallization and impregnation methods, and characterized by N2 physisorption, CO chemisorption, XRD, SEM, and TEM techniques. The Ni/gamma-Al2O3 catalyst showed higher conversion and H2 selectivity. However, it was slowly deactivated due to the carbon formation on the surface of catalyst and the sintering. It was found that the Ni based hydrotalcite-like catalyst (spc-Ni/MgAl) showed higher catalytic activity to prevent carbon formation than Ni/gamma-Al2O3 catalyst in the SR of glycerol.     

Catalytic activity of active carbons impregnated before activation of pinewood sawdust and nutshells to be used on the control of atmospheric emissions

This work analyses the catalytic activity of metal oxides impregnated on activated carbons to be used for the complete oxidation of benzene present in atmospheric emissions. When the impregnation step is performed before CO2 activation, the knowledge about catalytic activity is as yet quite scarce, being the main objective of the study here reported. Pinewood sawdust and nutshells were recycled to produce the activated carbons. Non-expensive metal oxides (CoO, Co3O4 and CrO3) were impregnated. When the impregnation was performed before CO2 activation instead of after activation, at 523 K the kinetic constants were 3.6-4.3 times higher for sawdust carbons, and 2.1-2.7 times higher for nutshell carbons, due to a better metal oxide dispersion on higher mesopore areas and on wider micropores. With Co3O4 as catalyst, a benzene conversion of 90% was reached at a lower temperature than with CrO3 (472 and 558 K, respectively). The carbons impregnated before CO2 activation allowed very good conversions at temperatures that guarantee carbon stability (lower than 575 K). The results obtained led to the conclusion that activated carbon is a suitable support for metal oxide catalyst aiming the complete oxidation of benzene, mainly if an adequately porous texture is induced, proceeding to the impregnation before CO2 activation.