MgO纳米晶负载镍催化剂用于甲烷蒸汽重整反应(英文)

Nanocrystalline MgO with a relatively high surface area and mesoporous structure was synthesized by a surfactant assisted precipitation method for use as the support of nickel catalysts for steam reforming of methane. The samples were characterized by X‐ray diffraction, N2 adsorption, temperature‐programmed reduction, temperature‐programmed oxidation, scanning electron microscopy, and transmission electron microscopy. The catalysts showed high catalytic activity and good stability in the steam reforming of methane. Increasing the nickel loading up to 10 wt% gave increased activity. Catalysts with higher nickel loadings showed more deposited carbon after reaction. The excellent anti‐coking performance of the catalysts was attributed to the formation of a nickel‐magnesia solid solution, basicity of the support surface, and nickel‐support interaction.     

CH_4 reforming with CO_2 for syngas production over La_2O_3 promoted Ni catalysts supported on mesoporous nanostructured γ-Al_2O_3

Nanostructured γ-Al2O3 with high surface area and mesoporous structure was synthesized by sol-gel method and employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by XRD, N2adsorption-desorption,TPR, TPO, TPH, NH3-TPD and SEM techniques. The BET analysis showed a high surface area of 204 m2 g-1and a narrow pore-size distribution centered at a diameter of 5.5 nm for catalyst support. The BET results revealed that addition of lanthanum oxide to aluminum oxide decreased the specific surface area. In addition, TPR results showed that addition of lanthanum oxide increased the reducibility of nickel catalyst. The catalytic evaluation results showed an increase in methane conversion with increasing lanthanum oxide to 3 mol% and further increase in lanthanum content decreased the catalytic activity. TPO analysis revealed that the coke deposition decreased with increasing lanthanum oxide to 3 mol%. SEM and TPH analyses confirmed the formation of whisker type carbon over the spent catalysts. Addition of steam and O2 to dry reforming feed increased the methane conversion and led to carbon free operation in combined processes.     

Styrene epoxidation with hydrogen peroxide over calcium oxide catalysts prepared from various precursors

A series of CaO samples were prepared by calcination of commercially available and synthesis of calcium salt precursors such as calcium acetate,carbonate,hydroxide and oxalate etc.CaO samples were found to be effective for the epoxidation of styrene using hydrogen peroxide as an oxidant in the presence of acetonitrile.To determine the influence of the physicochemical properties and surface basicity on the catalytic activity,the prepared CaO samples were characterized using thermogravimetry(TG),X-ray diffraction(XRD),scanning electron microscopy(SEM),N2-adsorption and temperature-programmed desorption of CO2(CO2-TPD).The results indicate that the amounts of very strong basic sites and high basicity strength on CaO sample are key factors for its excellent catalytic performance.In contrast,the surface area,porosity and the surface structure of CaO sample have a relatively minor effect on the catalytic activity.CaO sample,obtained by the decomposition of Ca(OH)2,prepared by precipitating calcium nitrate with sodium hydroxide in ethylene glycol solution,exhibits the highest amount of very strong basic sites and stronger strength of basic sites,and therefore it catalyses the epoxidation of styrene with the highest rate among the tested CaO samples.Under the selected reaction conditions,the selectivity of 97.5% to styrene oxide at a conversion in excess of 99% could be obtained.     

The role of nickel oxide additive in lowering the carbon dioxide sorption temperature of CaO

A new type of calcium-based regenerable carbon dioxide(CO2) sorbent, CaO-NiO, was synthesized via the sol-gel method. The as synthesized CO2 sorbent was in the form of nanoparticles. The CO2 sorption temperature and capacity of the sorbent were examined using thermogravimetric analysis(TGA). The CaO-NiO sorbent is able to capture CO2 at a lower sorption temperature(465C) than pure calcium oxide(CaO)(600C). The role of NiO in the CaO-NiO sorbent in lowering the CO2 sorption temperature was also investigated. The sorbent was characterized by X-ray diffractometer(XRD), N2adsorption-desorption analysis, high resolution transmission electron microscopy(HRTEM) and scanning electron microscopy(SEM). CaO and NiO were found to coexist in the sorbent. Neither solid solution nor mixed metal oxide was formed. NiO did not react with CO2 in the sorption process; but it worked like a catalyst to promote the CaO carbonation reaction. It is suggested that this new CaO-NiO sorbent may have a promising application as an effective CO2 sorbent with lower energy consumption.     

Effect of Copper Substitution and Preparation Methods on the LaMnO3 Structure and Catalysis of Methane Combustion and CO Oxidation

 LaMn1-xCuxO3刡冊 perovskite oxides (x = 0, 0.2, 0.4, 0.6, 0.8, 1) were prepared by two different methods, the Pechini and sol-gel methods. The catalysts were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray fluorescence spectroscopy, N2 adsorption, and temperature-programmed reduction. Their catalytic activity in the oxidation of methane and CO was evaluated. EDS and SEM results showed that the Pechini samples had more homogeneity and smaller particles (higher specific surface area). The catalytic activity for methane combustion was highest for x = 0.2. In CO oxidation, the oxides with x = 0.2 and x = 0.4 were the most active. The Pechini samples had higher activity and stability than the sol-gel samples.     

微波辅助溶胶-凝胶法合成MgO纳米粒子及其催化合成Hantzsch1,4-二氢吡啶性能(英文)

A microwave-assisted sol-gel method was employed for the preparetion of nano-sized MgO particles using Mg(NO 3)2·6H2O as precursor and deionized water as solvent.The sample calcined at 500℃ had a high specific surface area of 243.2m2/g and particles sizes from 9.5to10.5nm.For comparison,MgO nanoparticles were also synthesized without microwave irradiation.X-ray diffraction (XRD) characterization showed the formation of smaller particles after microwave irradiation.The structure and morphology of the MgO particles were analyzed by N2 adsorption-desorption,XRD,scanning electron microscopy,and transmission electron microscopy.Their catalytic behavior was studied with the one-pot synthesis of Hantzsch1,4-dihydropyridines from the reaction of aromatic aldehydes,ethyl acetoacetate,and ammonium acetate.The MgO nanoparticles have high catalytic activity and gave the desired products in good to high yields.The catalyst can be easily recovered by filtration and was used at least three times with only a slight reduction in its catalytic activity.     

Facile synthesis and excellent catalytic activity of gold nanoparticles on graphene oxide

For the first time,Au nanoparticles on graphene oxide（GO-AuNPs） were successfully fabricated without applying any additional reductants,just by the redox reaction between AuCl₄^-1 and GO.Their structure was characterized by transmission electron microscopy and X-ray powder diffraction.The results show that flower-like AuNPs were successfully dispersed on GO surface.Importantly,they showed a high catalytic activity for the Suzuki-Miyaura coupling reaction in an aqueous medium.     

Low Temperature Solvent Evaporation-induced Crystallization Synthesis of Nanocrystalline TiO2 Photocatalyst

A novel and efficient methodology for obtaining highly active photocatalyst of bi-phase TiO2 with small particle size and high specific surface area was developed by solvent evaporation-in-duced crystallization (SEIC) method at low temperature. The prepared TiO2 powder was characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface areas. The photocatalyfic activity was evaluated by the photocatalyflc oxidation of acetone in air. The results showed that the photocatalytic activity of the TiO2 powder preDared by this method approached that of Degnssa P25. This may be atotributed to the fact that the predated TiO2 powder had larzer specific surface areas (265 m2. g- 1 ) and smaller crystallite size (about 5 nm), but relatively low crystallinity, as compared with Degussa P25.     

CO2 reforming of methane over nickel catalysts supported on nanocrystalline MgAl2O4 with high surface area

In this paper dry reforming of methane (DRM) was carried out over nanocrystalline MgAl2O4-supported Ni catalysts with various Ni loadings. Nanocrystalline MgAl2O4 spinel with high specific surface area was synthesized by a co-precipitation method with the addition of pluronic P123 triblock copolymer as surfactant, and employed as catalyst support. The prepared samples were characterized by X-ray diffraction (XRD), N2 adsorption, H2 chemisorption, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), temperature- programmed desorption (TPD) and transmission and scanning electron microscopies (TEM, SEM) techniques. The obtained results showed that the catalyst support has a nanocrystalline structure (crystal size: about 5 nm) with a high specific surface area (175 m2 g-1) and a mesoporous structure. Increasing in nickel content decreased the specific surface area and nickel dispersion. The prepared catalysts showed high catalytic activity and stability during the reaction. SEM analysis revealed that whisker type carbon deposited over the spent catalysts and increasing in nickel loading increased the amount of deposited carbon. The nickel catalyst with 7 wt% of nickel showed the highest catalytic activity.     

Effect of Addition of Base on Ceria and Reactivity of CuO/CeO2 Catalysts for Low-Temperature CO Oxidation

In this work, we have reported the influence of the addition of base (KOH) on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Furthermore, the prepared CeO2 was used as the support to prepare CuO/CeO2 catalysts via the wet impregnation method. The samples were characterized by N2 adsorption-desorption, X-ray powder diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and temperature-programmed reduction by H2 (H2-TPR). The catalytic properties of the CuO/CeO2 catalysts for low-temperature CO oxidation were studied using a microreactor-GC system. The crystal size of CeO2-A was much smaller than that of CeO2-B, and the corresponding copper oxide catalysts exhibited higher catalytic activity than that of the CeO2-B-supported catalysts under the same reaction conditions. The alcohothermal mechanism indicated that KOH plays a key role in determining the physicochemical and catalytic properties of ceria-based materials.     

陈化体系组成对Ce0.65Zr0.35O2储氧材料性能的影响

采用共沉淀法制备了Ce_0.65Zr_0.35O₂(CZ)储氧材料, 在传统的水陈化体系中引入了乙醇, 研究了乙醇的加入对CZ储氧材料性能的影响. 对所制备样品进行了傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)、粉末X射线衍射(XRD)、扫描电镜(SEM)、N₂吸附-脱附、储氧量(OSC)和H₂程序升温还原(H₂-TPR)的表征, 并考察了以CZ储氧材料为载体制备的单钯催化剂的三效性能. 结果表明, 乙醇引入陈化体系对样品的结构和性能有显著影响. 以醇水共存体系陈化制备的CZ储氧材料颗粒小、堆积松散、孔径分布宽、孔容大, 具有优异的储氧性能和热稳定性, 经1000 °C焙烧后, 比表面积为29.3 m²·g^-1, 储氧量仍高达520 μmol·g^-1. 以此为载体制备的单钯催化剂, 空燃比操作窗口宽, 对C₃H₈、CO、NO的转化明显优于水陈化体系制备的储氧材料所制备的催化剂.     

固相浸渍法制备NiO/CeO2催化剂及其在CO氧化反应中的应用

采用固相浸渍法制备了一系列NiO/CeO2催化剂,并通过与常规湿浸渍法比较,考察了制备方法对催化剂和CO氧化反应性能的影响.同时结合X射线衍射(XRD),N2吸附-脱附(BET),透射电镜(TEM),氢气-程序升温还原(H2-TPR),拉曼(Raman)光谱,X射线光电子能谱(XPS)等手段对催化剂的结构和表面物种分散状态进行了表征.CO氧化活性测试结果表明,当镍负载量相同时,固相浸渍法制备的催化剂相比于湿浸渍法表现出更好的催化性能.TEM、XPS、H2-TPR结果表明,固相浸渍法更有利于加强镍铈间的相互作用和得到高分散的镍物种,从而促进镍物种的还原.Raman结果表明固相浸渍法相比于湿浸渍法能产生更多氧空位,这有利于氧气在催化剂表面的活化,使得CO氧化反应更容易进行.     

A novel nonenzymatic hydrogen peroxide sensor based on MnO2/graphene oxide nanocomposite

A new electrocatalyst, MnO₂/graphene oxide hybrid nanostructure was successfully synthesized for the nonenzymatic detection of H₂O₂. The morphological characterization was examined by scanning electron microscopy and transmission electron microscopy. The MnO₂/graphene oxide based electrodes showed high electrochemical activity for the detection of H₂O₂ in alkaline medium. The nonenzymatic biosensors displayed good performance along with low working potential, high sensitivity, low detection limit, and long-term stability, which could be attributed to the high surface area of graphene oxide providing for the deposition of MnO₂ nanoparticles. These results demonstrate that this new nanocomposite with the high surface area and electrocatalytic activity offers great promise for new class of nanostructured electrode for nonenzymatic biosensor and energy conversion applications.     

介孔Fe-Cu复合金属氧化物纳米粉催化剂催化低温CO氧化

以环氧丙烷为凝胶剂,采用简便低廉的无表面活性剂的溶胶-凝胶法制备了一系列不同Cu/Fe摩尔比的高比表面积介孔Fe-Cu复合氧化物纳米粉末。运用微反应器-色谱体系考察了它们在低温CO氧化反应中的催化性能。采用X射线衍射、N2吸附-脱附、热重-差热分析、程序升温还原、傅里叶变换红外光谱和透射电镜对所制样品进行了表征。结果表明,这些介孔Fe-Cu复合氧化物催化剂具有纳米晶结构、窄的孔径分布和高的比表面积,在低温CO氧化反应中表现出高的活性和稳定性。 CuO的添加影响了Fe2O3的结构和催化性能。当CuO含量为15 mol%时,催化剂具有最高的比表面积和催化活性,在低温CO氧化反应中表现出较高的催化稳定性。     

Effect of La2O3 on Catalytic Performance of Au/TiO2 for CO Oxidation

Pure TiO₂ and La-doped TiO₂ were prepared by the sol-gel method. Au was supported on TiO₂ by the deposition-precipitation (DP) method, and its catalytic activity for CO oxidation was tested. The results showed that doping La in Au/TiO₂ could improve its catalytic activity obviously for CO oxidation. The analyses of X-ray diffraction (XRD), temperature-programmed desorption (TPD), and Brunauer-Emmett-Teller (BET) surface area further showed that the presence of La in TiO₂ not only increased its surface area and restrained the growth of TiO₂ crystallites, but could also enhance the microstrain of TiO₂. In terms of O₂-TPD, a new adsorbed species O⁻ appeared on the surface of La-doped TiO₂. The results of in-situ Fourier transform-infrared (FT-IR) spectroscopy illustrated that the high activity of Au/La₂O₃-TiO₂ was attributed to the presence of La promoting the reactivity of CO adsorbed on the Au site and the formation of the second active site on the surface of TiO₂     

Monolith Manganese-Based Catalyst Supported on ZrO2-TiO2 for NH3-SCR Reaction at Low Temperature

Monolith catalysts were prepared using TiO₂ and ZrO₂-TiO₂ as supports with MnO₂ as active component and Fe₂O₃ as promoter. The catalytic activities at low temperature and stability at high temperature for selective catalytic reduction of NO_x with NH₃ (NH₃-SCR) in the presence of excessive O₂ were studied after the catalysts calcined at different temperatures. The catalysts were characterized by X-ray diffraction (XRD), specific surface area measurements (BET), oxygen storage capacity (OSC), and temperature programmed reduction (H₂-TPR). The results indicated that the catalyst supported on ZrO₂-TiO₂ had excellent stability at high temperature, and possessed high specific surface area and oxygen storage capacity, and had strong redox property. The results of the catalytic activities indicated that the monolith manganese-based catalyst using ZrO₂-TiO₂ as support had evidently improved the activity of NH₃-SCR reduction reaction at low temperature, and it showed great potential for practical application.     

制备方法对CuO/CeO_2-ZrO_2催化CO低温氧化活性的影响

采用微波加热分解法(一步法)和微波加热处理共沉淀+浸渍法(两步法)制备了CuO/CeO2-ZrO2催化剂,并对其进行了X射线衍射、低温氮气吸附/脱附和程序升温还原等表征,采用色谱流动法考察了催化剂的催化CO低温氧化性能.结果表明,一步法比两步法更有利于使催化剂表面CuO高度分散,CuO与CeO2-ZrO2间的相互作用更强,CuO更容易被还原,从而具有更高的催化CO氧化活性.与CeO2-ZrO2有相互作用的高分散和小颗粒CuO有利于催化剂活性的提高,与CeO2-ZrO2无相互作用的大颗粒CuO对催化剂的活性有抑制作用.     

CuO/Ti0.5Zr0.5O2催化剂对NO+CO反应的催化作用

环境治理是当今社会面临的一大主要问题。目前,城市空气污染日趋严重,特别是工厂和汽车排放的大量未燃烧的烃类、CO、NOx是主要的空气污染物。其中,氮氧化物(NOx)排放状况尤其严重,它的排放会给环境和人们生活带来严重危害,因此,如何有效地消除NOx已成为目前环境保护中一个非常     

铜物种对Cu/Fe2O3水煤气变换反应催化剂性能的影响

采用共沉淀法制备了系列铜负载量不同的Cu/Fe₂O₃水煤气变换(WGS)催化剂,并考察了铜负载量对催化剂结构和水煤气变换反应性能的影响. 结果表明,Cu/Fe₂O₃催化剂呈现出良好的水煤气反应性能,当CuO质量分数为20%时,催化剂的WGS性能最优,250 ℃时CO转化率高达97.2%,同时热稳定性也最好. 运用X射线粉末衍射(XRD)、N₂物理吸脱附和H₂程序升温还原(H₂-TPR)等手段对Cu/Fe₂O₃催化剂的物相、织构特征及还原性能进行了表征,结果表明,CuFe₂O₄物种的存在极大地改善了催化剂的还原性能和WGS反应活性. 这是由于CuFe₂O₄特殊的尖晶石结构有利于Cu微晶的稳定;同时,CuFe₂O₄在低温下即被还原为单质铜,有利于促进催化剂体系中电子的转移. 此外,通过(NH₄)₂CO₃溶液处理,研究了独立相CuO对Cu/Fe₂O₃催化剂WGS反应性能的影响,结果发现,独立相CuO的存在,有利于H原子在各组分传递,从而促进催化剂的CuFe₂O₄的还原,改善Cu/Fe₂O₃催化剂的WGS反应性能.     

焙烧与预处理条件对 Co3O4 催化氧化 CO 性能的影响

采用沉淀法制备了 Co₃O₄, 考察了焙烧和预处理条件对其结构、低温催化氧化 CO 性能的影响. 热重分析表明, 未经焙烧的样品以 Co(OH)₂CO₃ 的形式存在, 150~400 ^oC 空气气氛中焙烧后, 样品以立方相 Co₃O₄ 的形式存在. N2 吸附-脱附法、X 射线衍射、透射电镜及活性测试结果表明, 以纳米颗粒物存在的 Co₃O₄ 的比表面积、颗粒尺寸、催化氧化 CO 活性与焙烧温度密切相关. 正电子湮没寿命谱、O₂-程序升温脱附与定温条件下 CO 氧化测试结果表明, 合适温度 (150~250 ^oC) 下 N₂ 预处理有利于 Co₃O₄ 表面氧空穴团的形成, 它在吸附活化分子氧以及 CO 催化氧化反应中起到关键作用. 同时讨论了预处理作用下Co₃O₄表面氧空穴的再构机制.