Nanosized Pt-Co catalysts for the preferential CO oxidation

The preferential CO oxidation in the presence of excess hydrogen was studied over Pt-Co/gamma-Al2O3. CO chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectrometer (EDX) and temperature programmed reduction (TPR) were conducted to characterize active catalysts. The catalytic activity for CO oxidation and methanation at low temperatures increased with the amounts of cobalt in Pt-Co/gamma-Al2O3. This accompanied the TPR peak shift to lower temperatures. The optimum molar ratio between Co and Pt was determined to be 10. The co-impregnated Pt-Co/gamma-Al2O3 appeared to be superior to Pt/Co/gamma-Al2O3 and Co/Pt/gamma-Al2O3. The reductive pretreatment at high temperature such as 773 K increased the CO2 selectivity over a wide reaction temperature. The bimetallic phase of Pt-Co seems to give rise to high catalytic activity in selective oxidation of CO in H2-rich stream.     

Influence of Mo or Cu doping in Fe/MgO catalyst for synthesis of single-walled carbon nanotubes by catalytic chemical vapor deposition of methane

A series of mono-, bi- or tri-metallic Fe–Mo-Cu/MgO catalysts with the same metal loading of 6 wt% were prepared by impregnation method and used as catalysts for synthesis single-walled carbon nanotubes (SWCNTs) via methane decomposition. XRD, H₂-TPR, and nitrogen physisorption techniques were used to characterize the freshly calcined catalysts, while HRTEM, Raman spectroscopy and TGA were employed to investigate the morphology and microstructure of the SWCNTs product. The obtained results indicated that the introduction of Mo or Cu in the Fe/MgO catalyst enhanced the catalytic growth activity. TEM images showed that both bundles and isolated SWCNTs were obtained over Mo containing catalysts, whereas only SWCNTs bundles were grown over the Fe-Cu/MgO catalyst. The obtained SWCNTs having a diameter of around 0.9–2.4 nm. Raman analysis illustrated that all promoted catalysts produced high quality of SWCNTs compared to the unpromoted Fe/MgO catalyst.     

Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO2 Hydrogenation

Nitrogen-doped carbon nanotubes (NCNTs) were used as a support for iron (Fe) nanoparticles applied in carbon dioxide (CO₂) hydrogenation at 633 K and 25 bar (1 bar = 10⁵ Pa). The Fe/NCNT catalyst promoted with both potassium (K) and manganese (Mn) showed high performance in CO₂ hydrogenation, reaching 34.9% conversion with a gas hourly space velocity (GHSV) of 3.1 L·(g·h)⁻¹. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promoted with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction (XRD), temperature-programmed reduction (TPR) with molecular hydrogen (H₂), and in situ X-ray absorption near-edge structure (XANES) analysis. The Mn promoter stabilized wüstite (FeO) as an intermediate and lowered the TPR onset temperature. Catalytic ammonia (NH₃) decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

La0.7K0.3Ni0.9Cu0.1O3钙钛矿的制备及催化碳烟性能的研究

采用溶胶凝胶法制备了一系列La1-xKxNi1-yMyO3(M=Cu,Co,Mn)钙钛矿复合氧化物催化剂,并利用O2-TPO测试该系列催化剂催化氧化碳烟的性能。通过XRD、H2-TPR、XPS对其进行了表征,结果表明,所制备催化剂均为六方晶系钙钛矿结构。着重考察了A位K掺杂量和B位掺杂元素及其掺杂量对催化碳烟性能的影响。结果表明:当K掺杂量x=0.3时,产生更多氧空位,增加了表面吸附氧数量,同时提高了B位Ni的价态;B位Cu掺杂量y=0.1时,表面吸附氧数量增加,Ni 3+含量增大,从而提高了催化剂的活性。La0.7K0.3Ni0.9Cu0.1O3催化剂与碳烟紧密接触下,Ti、Tm分别为268.1℃和272.8℃。     

锰基催化剂的制备及其对气相邻二氯苯的催化燃烧性能

二噁英类含氯挥发性有机物（Cl-VOC）是毒性很强的环境污染物,为了筛选用于催化燃烧Cl-VOC的高效、稳定的催化剂,采用共沉淀法制备了（Fe、Co、Cu、V）-Mn催化剂,并负载于堇青石载体上,用邻二氯苯作为模型化合物对其催化性能进行评价,结果发现Cu-Mn/堇青石催化剂对气相邻二氯苯的催化燃烧性能最好。XRD结果显示Cu-Mn/堇青石催化剂煅烧之后有新的尖晶石CuMn2O4晶相出现;SEM结果表明Cu-Mn/堇青石催化剂颗粒分散均匀;反应前后EDS对比结果表明,反应后催化剂表面残留有少量氯,但是,寿命测试表明持续反应20h,邻二氯苯的降解率能稳定在65%,说明Cu-Mn/堇青石催化剂用于催化燃烧含氯有机挥发物具有较好的应用前景。     

Magnetic and catalytic properties of Cu0.5Zn0.5Fe2O4 nanocrystallite powders

Cu0.5Zn0.5Fe2O4 nanocrystallite powders (average size 13 nm) were synthesized from Cu-Zn spent catalyst (fertilizers) industries and ferrous sulfate wastes formed during iron and steel making. Cu-Zn catalyst (22.4% Cu and 26.4% Zn) was chemically treated with sulfuric acid at temperature 80 degrees C for 1 hr for the complete dissolving of copper and zinc into sulfate solution, then the produced solution was mixed with stoichiometric ratio of ferrous sulfate and the mixture was chemically precipitated as hydroxides followed by hydrothermal processing. The parameters affecting the magnetic properties and crystallite size of the produced ferrites powder e.g., temperature, time, and pH were systemically studied. X-ray diffraction analysis was used in order to determine the average crystallite size and phase identifications of the produced powder. The magnetic properties were studied by vibrating sample magnetometry. The results showed that the average crystallite size of the powder decreased for the ferrites powder formed at 150 degrees C and then increased by increasing the temperature to 200 degrees C. Interestingly, the saturation magnetization (Bs), remanent magnetization (Br) and coercive force (Hc) were 25.03 emu/g, 0.71 emu/g, and 4.83 Oe, respectively at hydrothermal temperature 150 degrees C for 24 hr and changed to 16.38 emu/g, 0.3864 emu/g, and 5.2 Oe at 150 degrees C and 72 hr. The produced nanoferrite powders are used for studying the catalytic activity of CO conversion to CO2 at different temperatures, pH and times. The maximum conversion (82%) is obtained at temperature 150 degrees C for 24 hrs and pH 12.     

A Comparative Analysis of Catalysts for the Preparation of Germanium through Hydrogen Reduction of Germanium Tetrachloride

We have synthesized catalysts for the hydrogen reduction of germanium tetrachloride: a catalyst based on multiwalled carbon nanotubes and a hybrid catalyst based on multiwalled carbon nanotubes whose surface was decorated with copper-containing nanoparticles. The hybrid catalyst has been characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results demonstrate that it consists of multiwalled carbon nanotubes whose surface is decorated with copper nanoparticles in a cuprous oxide shell (Cu₂O/Cu/MWCNTs). The catalytic activity of the hybrid catalyst exceeds that of the as-prepared MWCNTs. The use of the Cu₂O/Cu/MWCNT hybrid catalyst as a catalyst for the hydrogen reduction of germanium tetrachloride allows the reaction temperature to be lowered and ensures 95.7% germanium tetrachloride conversion at 873 K.     

Effect of structural promoters on the catalytic performance of cobalt-based catalysts during natural gas decomposition to hydrogen and carbon nanotubes

Catalytic thermal decomposition of natural gas to CO/CO₂-free hydrogen production was studied over cobalt catalysts supported on Al₂O₃, MgO, and SiO₂. The physico-chemical properties of the fresh catalysts were investigated by X-ray diffraction (XRD), temperature-programmed reduction (TPR), and surface area. In addition, the morphological structure of as-deposited carbon over the spent catalysts was characterized by transmission electron microscope (TEM), Raman spectroscopy, thermogravimetric analysis, and XRD. The obtained results proved that the catalytic activity and longevity of the cobalt-based catalysts strongly depended on the nature of the applied support. Among the catalysts tested, the Co/Al₂O₃ catalyst exhibited the highest activity and stability due to the higher dispersion and stabilization of cobalt particles because of formation of CoAl₂O₃ spinel phase. The lower activity of Co/SiO₂ catalyst is mainly attributed to the aggregation of cobalt metal particles because of weak metal–support interaction. It was observed that both type and morphological structure of deposited carbon were strictly depended on the nature of the support. TEM images revealed that multi-walled carbon nanotubes were produced over Al₂O₃- and MgO-supported catalysts, whereas both carbon nanofibers and amorphous carbon were formed over the Co/SiO₂ catalyst.     

Mn、Fe和Cu氧化物在低温等离子体催化氧化甲苯体系中的活性比较

采用等体积浸渍法制备了MnOx/γ-Al2O3、FeOx/γ-Al2O3和CuOx/γ-Al2O3催化剂,测定了不同催化剂在低温等离子体场内分解甲苯的活性,用X射线衍射(XRD)、氢气程序升温还原(H2-TPR)技术对催化剂进行表征。结果表明催化剂分解甲苯的活性的顺序是MnOx/γ-Al2O3>FeOx/γ-Al2O3>CuOx/γ-Al2O3。催化剂分解臭氧的实验表明,不同催化活性组分对臭氧的催化分解性能顺序与对甲苯的分解性能顺序是一致的。MnOx/γ-Al2O3催化剂的Mn负载量对其催化活性有明显影响,Mn的含量为1%(质量分数)时,催化剂的活性最高,当能量密度为19J/L时,其对甲苯催化氧化的转化率接近100%。催化剂表征结果表明当Mn含量为1%(质量分数)时,氧化锰在载体γ-Al2O3上最接近单层分散量,此时活性组分与载体表面的相互结合力最强,在载体上有很好的分散性,从而表现出对甲苯分解的最好性能。     

不同助剂对合成甲醇工业催化剂二氧化碳加氢性能的影响

采用浸渍法制备了以工业铜基催化剂C301为基体,含CeO2、ZrO2、La2O3、MnO2、Pr2O3、SrO、V2O5助剂的一系列催化剂,在微型固定床反应器上考察了其对CO2加氢合成甲醇的催化性能及影响,并采用XRD、BET、H2-TPR和CO2-TPD等手段进行了表征。研究结果表明,除助剂Pr2O3外,CeO2、ZrO2、La2O3、MnO2、SrO、V2O5助剂的加入均促进了C301催化剂的CO2加氢合成甲醇活性,其中ZrO2的加入使CO2转化率提高了近5%,甲醇收率提高了近8%。     

Inorganic nanofibers with tailored placement of nanocatalysts for hydrogen production via alkaline hydrolysis of glucose

Monoaxial silica nanofibers containing iron species as well as coaxial nanofibers with a pure silica core and a silica shell containing high concentrations of iron nanocrystals were fabricated via electrospinning precursor solutions, followed by thermal treatment. Tetraethyl-orthosilicate (TEOS) and iron nitrate (Fe(NO(3))(3)) were used as the precursors for the silica and iron phases, respectively. Thermal treatments of as-spun precursor fibers were applied to generate nanocrystals of iron with various oxidation states (pure iron and hematite). Scanning electron microscopy (SEM), x-ray diffraction (XRD), and transmission electron microscopy (TEM) were used to probe the fiber morphology and crystal structures. The results indicated that the size, phase, and placement of iron nanocrystals can be tuned by varying the precursor concentration, thermal treatment conditions, and processing scheme. The resulting nanofiber/metal systems obtained via both monoaxial and coaxial electrospinning were applied as catalysts to the alkaline hydrolysis of glucose for the production of fuel gas. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and bulk weight change in a furnace with residual gas analysis (RGA) were used to evaluate the performance of the catalysts for various ratios of both Fe to Si, and catalyst to glucose, and the oxidation state of the iron nanocrystals. The product gas is composed of mostly H(2) (>96 mol%) and CH(4) with very low concentrations of CO(2) and CO. Due to the clear separation of reaction temperature for H(2) and CH(4) production, pure hydrogen can be obtained at low reaction temperatures. Our coaxial approach demonstrates that placing the iron species selectively near the fiber surface can lead to two to three fold reduction in catalytic consumption compared to the monoaxial fibers with uniform distribution of catalysts.     

Fe-PPy-TsOH/C用作质子交换膜燃料电池氧电极催化剂的研究

氧电极催化剂是制约质子交换膜燃料电池(PEMFCs)发展和应用的一个重要因素, 开发低价高效的非贵金属催化剂对PEMFCs来说已成为当务之急。本研究选择氮掺杂的碳载过渡金属(M-N/C)类催化剂为研究对象, 以铁盐作为金属前驱体, BP2000为碳源, 聚吡咯(PPy)为氮源, 对甲基苯磺酸(TsOH)为掺杂剂, 合成了非贵金属催化剂Fe-PPy-TsOH/C, 探究了不同的热处理温度及钴原子的掺杂对其氧还原催化性能的影响。研究结果表明: 800℃制备的Fe-PPy-TsOH/C催化剂因结晶度高、颗粒大小适中且分布均匀而具有最佳的氧还原催化性能; 一定量的钴原子取代可以改善Fe-PPy-TsOH/C的氧还原催化性能, 当钴的掺杂量为33.33%时(铁钴原子比为2︰1), 催化剂的性能达到最优。     

Autothermal reforming of propane on Ni-supported perovskite, hydrotalcite, and metal oxide catalysts

This study evaluated the autotherrmal reforming of propane over Ni-supported perovskite (LaAlO3), hydrotalcite as a layered structure (MgAl), and metal oxide (alpha-Al2O3, ZrO2) catalysts. The catalysts were also characterized via physicochemical property analysis, XRD, SEM, TEM, and TPR. The order of catalytic activity was ZrO2 > or = LaAlO3 > Al2O3 > MgAl, and coincided with the reducibility of these catalysts to reduce the Ni2+ metallic ion of the NiO, as measured via TPR. Finally the reducility of Ni in the form of NiO was important to the reaction in the ATR process. The diffraction peak of Ni was observed after a 600 degrees C reduction in ZrO2, LaAlO3, and alpha-Al2O3.