Propane combustion over supported Pd catalysts

We prepared Pd catalysts supported on various metal oxides, viz. γ-Al₂O₃, α-Al₂O₃, SiO₂–Al₂O₃, SiO₂, CeO₂ and TiO₂ by an incipient wetness method and applied them to propane combustion. Several techniques: N₂ physisorption, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), CO chemisorption, temperature-programmed reduction (TPR) and temperature-programmed oxidation (TPO) were employed to characterize the catalysts. Pd/SiO₂–Al₂O₃ showed the least catalytic activity at high temperatures among Pd catalysts supported on irreducible metal oxides, viz. SiO₂, Al₂O₃ and SiO₂–Al₂O₃. Pd/γ-Al₂O₃ was much superior for this reaction to Pd/α-Al₂O₃. The Pd catalyst supported on reducible metal oxides (CeO₂ and TiO₂) with a less specific surface area showed the higher catalytic activity compared with that supported on reducible metal oxides with a higher specific surface area, even though the former had a less Pd dispersion than the latter. In the case of Pd/SiO₂–Al₂O₃, the initially reduced Pd catalyst was superior to the fully oxidized one. The oxidation of metallic Pd occurred in the presence of O₂ with increasing reaction temperature, which resulted in the change in the catalytic activity.     

Methodical aspects in the surface analysis of supported molybdena catalysts

Supported molybdena catalysts, with TiO₂, CeO₂ and Al₂O₃ supports, were studied by XPS and ISS. It was found that reliable results are obtained only when samples are calcined and transferred into the ultrahigh vacuum system without further contact with the ambient atmosphere (‘in situ calcination’). This applies also to catalysts that were previously calcined but had been stored in the ambient atmosphere. Supported Mo oxide becomes reduced under x‐ray irradiation during extended XPS data acquisition. A slight decrease of the Mo/support cation intensity ratio as a consequence of this reduction was detected by ISS in MoO₃/TiO₂ and MoO₃/CeO₂, therefore ISS analysis should be performed on freshly calcined samples without prior extended exposure to x‐rays. Because ISS spectra change rapidly due to sputtering, a correct analysis of the surface properties of the supported Mo catalyst requires extrapolation of the trend to the start of the experiment. It was established by this methodology that the surface of a 7% MoO₃/TiO₂ catalyst (5.3 Mo nm^?2) is completely covered by a monolayer of Mo oxide species, and no Ti cation is exposed. In a submonolayer MoO₃/CeO₂ catalyst the exposed support could be detected, as expected, whereas in an MoO₃/Al₂O₃ catalyst with an Mo oxide loading equal to the monolayer coverage a slight exposure of the Al support cation also was noted probably because of the high curvature of the smaller Al₂O₃ particles. Copyright © 2004 John Wiley & Sons, Ltd.     

负载型钌催化剂催化山梨醇氢解制乙二醇(英)

Supported Ru catalysts were prepared by wet impregnation to evaluate the role of different oxide supports（Al₂O₃,SiO₂,TiO₂,ZrO₂） in sorbitol hydrogenolysis to glycols.X-ray diffraction,transmission electron microscopy,hydrogen chemisorption,X-ray photoelectron spectroscopy,and NH3temperature-programmed desorption were used to characterize the catalysts,which were active in the hydrogenolysis of sorbitol.The support affected both the physicochemical properties and catalytic behavior of the supported Ru particles.The characterization results revealed that the Ru/Al₂O₃catalyst has a high surface acidity,partially oxidized Ru species on the surface,and a higher surface Ru/Al atomic ratio,which gave it the highest selectivity and yield to glycols.     

Dependence of reactivity of propagation centers of oxide catalysts for ethylene polymerization on catalyst composition and activation conditions

The propagation rate constant K_p was used as a measure of reactivity of propagation centers in ethylene polymerization with oxide catalysts. This constant was determined by a radiotracer quenching technique for oxide catalysts of different compositions and activation conditions. For catalysts based on various transition metal oxides, an increase of K_p was observed in the series W < Mo < Cr and V < Cr. In the case of chromium oxide catalyst it was shown that K_p value does not depend on the content of the transition metal in a catalyst. A change of propagation center reactivity was found when oxides of different composition (SiO₂, Al₂O₃, ZrO₂, TiO₂) were used as supports. An increase of the vacuum activation temperature of a catalyst results in increasing K_p. Pretreatment of catalyst with different reducing agents (SO₂, CO₂, NH₃, HCN) results in the change of K_p value in comparison in comparison with the catalyst activated by the vacuum treatment only. The data obtained on the variation of the reactivity of the propagation centers permit one to draw a conclusion about the composition of surface compounds as acitve centers of the oxide polymerization catalysts.     

M/Al2O3-CeO2（M=Pt-Ru，Ru，Pt）催化剂在甲胺催化湿式氧化中的活性与选择性

采用浸渍法制备了M/Al₂O₃-CeO₂（M=Pt-Ru,Ru,Pt）催化剂,并将其用于甲胺的催化湿式氧化反应（CWAO）.结果表明,Pt-Ru/Al₂O₃-CeO₂具有最佳活性和选择性.运用程序升温还原、X射线光电子能谱、X射线衍射、透射电子显微镜、N₂吸附和CO化学吸附等技术对催化剂的物化性质进行了表征.Pt组分的引入可有效提高双金属催化剂活性组分的分散度,从而明显提高了其催化性能.升降温过程中总有机碳（TOC）转化率与N₂选择性迟滞效应表明,甲胺CWAO遵循化学吸附-脱附机理.     

Metal Oxide Catalysts for Selective Reduction of NOx by Hydrocarbons: Toward Molecular Basis for Catalyst Design

Metal oxides are stable and highly durable catalysts for the selective catalytic reduction (SCR) of NO by hydrocarbons and potential candidates for practical use. This review focuses on the development as well as the fundamental understanding of metal oxide based catalysts for selective reduction of NO by hydrocarbons. Our studies on the SCR-deNOx properties of Ga₂O₃/Al₂O₃, Cu-Al₂O₃, and Ag-Al₂O₃ catalysts are presented and it is attempted to demonstrate the advantages of this type of catalysts. On the basis of several spectroscopic characterizations, the effect of important factors, such as dispersion, coordination, and the electronic states of the metal cation, on the intrinsic catalytic activity are quite well clarified. From the in situ FTIR results, the reaction mechanism is understood in terms of formation and reaction of surface molecules. The structural and kinetic information obtained at the molecular level provides a useful strategy for designing better deNOx catalysts using metal oxides.     

Metal Oxide Catalysts for Selective Reduction of NOx by Hydrocarbons: Toward Molecular Basis for Catalyst Design

Metal oxides are stable and highly durable catalysts for the selective catalytic reduction (SCR) of NO by hydrocarbons and potential candidates for practical use. This review focuses on the development as well as the fundamental understanding of metal oxide based catalysts for selective reduction of NO by hydrocarbons. Our studies on the SCR-deNOx properties of Ga₂O₃/Al₂O₃, Cu-Al₂O₃, and Ag-Al₂O₃ catalysts are presented and it is attempted to demonstrate the advantages of this type of catalysts. On the basis of several spectroscopic characterizations, the effect of important factors, such as dispersion, coordination, and the electronic states of the metal cation, on the intrinsic catalytic activity are quite well clarified. From the in situ FTIR results, the reaction mechanism is understood in terms of formation and reaction of surface molecules. The structural and kinetic information obtained at the molecular level provides a useful strategy for designing better deNOx catalysts using metal oxides.     

Effect of the oxidation state of manganese in the manganese oxides used in the synthesis of Mn-substituted cordierite on the properties of the product

Catalysts based on Mn-substituted cordierite 2MnO · 2Al₂O₃ · 5SiO₂ have been synthesized using different manganese oxides (MnO, Mn₂O₃, and MnO₂) at a calcination temperature of 1100°C. The catalysts differ in their physicochemical properties, namely, phase composition (cordierite content and crystallinity), manganese oxide distribution and dispersion, texture, and activity in high-temperature ammonia oxidation. The synthesis involving MnO yields Mn-substituted cordierite with a defective structure, because greater part of the manganese cations is not incorporated in this structure and is encapsulated and the surface contains a small amount of manganese oxides. This catalyst shows the lowest ammonia oxidation activity. The catalysts prepared using Mn₂O₃ or MnO₂ are well-crystallized Mn-substituted cordierite whose surface contains different amounts of manganese oxides differing in their particle size. They ensure a high nitrogen oxides yield in a wide temperature range. The product yield increases with an increasing surface concentration of Mn³⁺ cations. The highest NO_x yield (about 76% at 800–850°C) is observed for the MnO₂-based catalyst, whose surface contains the largest amount of manganese oxides.     

Role of ZnNb2O6 in ZnO-promoted amorphous-Nb2O5 supported Ru catalyst for the partial hydrogenation of benzene

Ruthenium catalysts supported on zinc-promoted amorphous-niobium mixed oxides were prepared, characterized, and studied in the additive-free partial hydrogenation of benzene reaction. The amorphous matrix of Nb₂O₅ was responsible for a highly active Ru/Nb₂O₅ catalyst, although less selective than those containing zinc. The ZnO-containing supports were prepared by wet impregnation technique, followed by incipient wetness of ruthenium chloride salt. The catalysts were characterized by textural analysis, X-ray fluorescence, X-ray diffraction, H₂ chemisorption, temperature-programmed reduction (TPR), Scanning electron microscopy, H₂ temperature-programmed desorption, and X-ray photoelectron spectroscopy (XPS) of the calcined-reduced samples. Chlorine retention was observed on zinc-containing samples. An unexpected ZnNb₂O₆ oxide phase, ascribed to a selectivity increase with less activity loss, was obtained for the supports at lower temperatures than those related on the literature. A very complex electronic environment of Ru- and Zn-containing species interactions was observed by TPR. The presence of surface-reduced (Ru⁰) and partially reduced (Ru^δ+) Ru species observed by XPS justified well, respectively, the activity and selectivity achieved with every catalyst. The addition of water as a solvent resulted in very constant yield to cyclohexene, as expected, despite activity diminution due to low solubility of the reactants.     

Classification of Simple Oxides: A Polarizability Approach

A simple oxide classification has been proposed on the basis of correlation between electronic polarizabilities of the ions and their binding energies determined by XPS. Three groups of oxides have been considered taking into account the values obtained on refractive-index- or energy-gap-based oxide ion polarizability, cation polarizability, optical basicity, O 1s binding energy, metal (or nonmetal) binding energy, and Yamashita-Kurosawa's interaction parameter of the oxides. The group of semicovalent predominantly acidic oxides includes BeO, B₂O₃, P₂O₅, SiO₂, Al₂O₃, GeO₂, and Ga₂O₃ with low oxide ion polarizability, high O 1s binding energy, low cation polarizability, high metal (or nonmetal) outermost binding energy, comparatively low optical basicity, and strong interionic interaction, leading to the formation of strong covalent bonds. Some main group oxides so-called ionic or basic such as CaO, In₂O₃, SnO₂, and TeO₂ and most transition metal oxides show relatively high oxide ion polarizability, O 1s binding energy in a very narrow medium range, high cation polarizability, and low metal (or nonmetal) binding energy. Their optical basicity varies in a narrow range and it is close to that of CaO. The group of very ionic or very basic oxides includes CdO, SrO, and BaO as well as PbO, Sb₂O₃, and Bi₂O₃, which possess very high oxide ion polarizability, low O 1s binding energy, very high cation polarizability, and very low metal (or nonmetal) binding energy. Their optical basicity is higher than that of CaO and the interionic interaction is very weak, giving rise to the formation of very ionic chemical bonds.     

Untersuchungen an Metallkatalysatoren. XXVII. Zum Einfluß verschiedener Träger auf die Dispersität von Nickel

Investigations on Metal Catalysts. XXVII. On the Influence of Several Carriers on the Dispersion of Nickel Nickel supported catalysts (carrier: η-, ?-, α-Al₂O₃, TiO₂) were characterized by chemically determined degree of reduction, CO chemisorption, magnetic susceptibility measurements and FMR. The influence of interaction between carrier and active component in the unreduced state on the size and number of Ni crystallites is discussed.     

Dehydrogenation activities of highly dispersed transition metal oxides on NaY zeolite

Highly dispersed α-Fe_2O_3/NaY,NiO/NaY,and CuO/NaY catalyst systems were pre-pared by impregnation method.Dispersion thresholds of the transition metal oxides on NaY" zeolitewere determined by XRD phase analysis.The dispersion capacities of the transition metal oxides on NaYzeolite are much lower than that estimated on the basis of a closed packed monolayer in the micropores.The catalytic activity and selectivity of the highly dispersed oxide catalyst systems for ethylben-zene and cyclohexane dehydrogenation reactions were reported.     

Carbon Dioxide Reforming of Methane over Ni Catalysts Supported on Al2O3 Modified with La2O3, MgO, and CaO

The preparation of synthesis gas from carbon dioxide reforming of methane (CDR) has attracted increasing attention. The present review mainly focuses on CDR to produce synthesis gas over Ni/MO_x/Al₂O₃ (X = La, Mg, Ca) catalysts. From the examination of various supported nickel catalysts, the promotional effects of La₂O₃, MgO, and CaO have been found. The addition of promoters to Al₂O₃-supported nickel catalysts enhances the catalytic activity as well as stability. The catalytic performance is strongly dependent on the loading amount of promoters. For example, the highest CH₄ and CO₂ conversion were obtained when the ratios of metal M to Al were in the range of 0.04–0.06. In the case of Ni/La₂O₃/Al₂O₃ catalyst, the highest CH₄ conversion (96%) and CO₂ conversion (97%) was achieved with the catalyst (La/Al = 0.05 (atom/atom)). For Ni/CaO/Al₂O₃ catalyst, the catalyst with Ca/Al = 0.04 (atom/atom) exhibited the highest CH₄ conversion (91%) and CO₂ conversion (92%) among the catalysts with various CaO content. Also, Ni/MgO/Al₂O₃ catalyst with Mg/Al = 0.06 (atom/atom) showed the highest CH₄ conversion (89%) and CO₂ conversion (90%) among the catalysts with various Mg/Al ratios. Thus it is most likely that the optimal ratios of M to Al for the highest activities of the catalysts are related to the highly dispersed metal species. In addition, the improved catalytic performance of Al₂O₃-supported nickel catalysts promoted with metal oxides is due to the strong interaction between Ni and metal oxide, the stabilization of metal oxide on Al₂O₃ and the basic property of metal oxide to prevent carbon formation.     

Effect of rare earth oxides (CeO2, La2O3) on properties of Pd/Al2O3 catalysts for reduction of nitrogen oxides by methane

We have established that the thermal stability of supported Pd/Al₂O₃ catalysts is increased after they are modified by rare earth oxides (La₂O₃, Ce₂O₃). We have observed the effect of thermal activation of an aluminopalladium catalyst modified by lanthanum oxide. This effect is apparent in the increase of the specific catalytic activity in the reaction of high-temperature reduction of nitrogen oxides by methane after heat treatment of the catalyst at 850 °C. We have used X-ray photoelectron spectroscopy (XPS) to show that the reason for the thermal activation effect is stabilization of palladium in the Pd¹⁺ state. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 1, pp. 44–48, January–February, 2006.     

Fe/Al-PILC催化C_3H_6选择性还原NO的实验研究

采用浸渍法制备了负载于铝柱撑黏土的铁基催化剂(Fe/Al-PILC),在固定床反应器上测试其催化C3H6选择性还原NO的性能。通过N2吸附-脱附、X射线衍射(XRD)、H2的程序升温还原(H2-TPR)、紫外可见光谱(Uv-vis)、吡啶吸附红外光谱(Py-FTIR)等手段对催化剂的物理化学性质进行表征。结果表明,9Fe/Al-PILC在400-550℃能够还原98%以上的NO,而且SO2和水蒸气对其催化性能的影响很小。XRD、N2吸附-脱附表征结果表明,Fe/Al-PILC催化剂中铁氧化物高度分散在载体表面,催化剂有较大的比表面积和孔容。H2-TPR结果表明,催化剂的活性主要由Fe_2O_3物相的还原性能决定。Uv-vis结果表明,催化剂的活性与铁氧低聚物种FexOy呈正相关性。Py-FTIR结果表明,催化剂表面同时存在Lewis酸和Brnsted酸,L酸性位是NO和C3H6反应的主要催化活性中心。     

Oxidative dehydrogenation of ethylbenzene over γ-Al2O3 supported ceria-lanthanum oxide catalysts: Influence of Ce/La composition

A series of CeO₂/γ-Al₂O₃ (CA) catalysts with CeO₂ loading of 5, 10, 15 and 20 wt% were prepared by a facile incipient wetness impregnation technique. Another series of La³⁺ doped catalysts (LCA) were prepared, wherein, 1, 3 and 5 wt% of La₂O₃ was doped in 15 wt%CeO₂/γ-Al₂O₃, which were designated as 1LCA, 3LCA and 5LCA catalysts. Both CA and LCA catalysts were characterized by thermogravimetric analysis (TGA), BET surface area, X-ray diffraction (XRD), Infrared (FT-IR) spectroscopy, UV–vis diffuse reflectance spectra (UV–vis DRS), transmission electron microscopy (TEM), temperature programmed desorption of NH₃ (TPD of NH₃) temperature programmed reduction (TPR), CO₂ pulse chemisorption and O₂ pulse chemisorption techniques. All CA and LCA catalysts were evaluated for ethylbenzene (EB) oxidative dehydrogenation to styrene (ST) in vapor phase under atmospheric pressure with CO₂ as an oxidant. Albeit CA and LCA catalysts are active, 15CA and 3LCA catalysts are found to be the best catalysts of the respective series. Apart from compatible acid-base and redox characteristics, sufficient amount of solid solution clusters (Ce_xLa_1-xO_2-δ) are responsible for superior activity of 3LCA catalyst.     

介孔氧化铝负载Ni-Co氧化物催化剂上丙烷氧化脱氢制丙烯

以非离子型三嵌段共聚物作为模板剂, 异丙醇铝为氧化铝的前驱物, 采用一锅法合成了一系列介孔氧化铝负载镍氧化物、钴氧化物以及镍-钴双金属氧化物催化剂, 并以介孔氧化铝为载体, 采用浸渍法制备了负载Ni-Co 氧化物催化剂. 采用N₂吸附-脱附、高分辨透射电镜(HRTEM)、X射线粉末衍射(XRD)、H₂程序升温还原(H₂-TPR)以及激光拉曼光谱(LRS)等技术对催化剂的结构与性质进行表征, 并考察了催化剂的丙烷氧化脱氢反应性能. 结果表明: 一锅法制备的各催化剂均有大的比表面积和规整的孔道结构, 且负载的金属氧化物高度分散; 而浸渍法制备的催化剂, 其载体的介孔结构被破坏并有Co₃O₄晶相生成. 在考察的催化剂中, 一锅法合成的介孔氧化铝负载Ni-Co 氧化物催化剂表现出最佳的丙烷氧化脱氢性能. 在450 °C、C₃H₈:O₂:N₂的摩尔比为1:1:4和空速(GHSV)为10000 mL·g^-1·h^-1条件下, 该催化剂上丙烯产率为10.3%, 远高于浸渍法制备的催化剂上所获得的丙烯产率(2.4%). 关联催化剂表征和反应结果, 讨论了催化剂结构与性能之间的关系.     

The nature of transition-metal-oxide surfaces

The surfaces of the 3d-transition-metal oxides form a rich and important system in which to study the effects of atomic geometry, ligand coordination and d-orbital population on surface electronic structure and chemisorption. This article considers the properties of those surfaces in terms of the types of surface structures that can exist, including steps and point defects, and their relation to the experimental data that is available for well characterized, single-crystal surfaces. The electronic structure of nearly perfect surfaces is very similar to that of the bulk for many of the oxides that have been studied; atoms at step sites also appear to have properties similar to those of atoms on terraces. Point defects are often associated with surfaces 0 vacancies and attendant transfer of electrons to adjacent metal cations. Those cations are poorly screened from each other, and the excess charge is presumably shared between two or more cations having reduced ligand coordination. Point defects are generally more active for chemisorption than are perfect surfaces, however for Ti₂O₃ and V₂O₃, whose cations have 3d¹ and 3d² electronic configurations respectively, the cleaved (047) surface is more active than are surfaces having a high density of defects. The chemisorption behavior of both nearly perfect and defect surfaces of 3d-transition-metal oxides varies widely from one material to another, and it is suggestive to correlate this with cation d-orbital population. However, too few oxides have yet been studied to draw any firm conclusions. Additional theoretical work on perfect surfaces, defects and chemisorption is also necessary in order to gain a more complete understanding of transition-metal-oxide surfaces.     

Pt/TiO2催化剂上CO氧化反应动力学研究

利用沉积沉淀法制备了Pt/TiO₂催化剂, 将其在不同温度下焙烧, 以得到不同颗粒尺寸的Pt. 并将这些样品用于CO催化氧化反应以及反应动力学研究. 结果表明: 焙烧温度对催化剂有明显影响, Pt 颗粒尺寸随着焙烧温度的升高而增加; 与此同时, CO催化活性随焙烧温度的升高呈先增加后降低的趋势, 其中, 400℃焙烧的样品表现出最高的催化活性. 反应动力学结果表明, 催化剂上CO氧化反应表观速率方程为r=5.4×10^-7p_CO^0.17p_O2^0.36,说明在该催化剂上CO氧化遵循Langmuir-Hinshelwood机理. 同时, 对催化剂进行了CO化学吸附红外光谱和O₂化学吸附表征. 结果表明, 随着焙烧温度的升高, 催化剂上CO和O₂吸附量均呈现先升高后降低的趋势, 这与反应结果和反应动力学方程一致, 说明反应受到催化剂表面上CO和O₂吸附浓度的影响. 而在400℃焙烧的催化剂上, CO和O₂吸附量均最高, 因此其反应活性也最好. 这可能是焙烧过程影响了Pt 和TiO₂之间的相互作用引起的.     

硬模板法制备铈基复合氧化物及其对甲苯燃烧的催化性能

采用硬模板法制得CeM-HT(M=Cu、Mn、Fe和Co)复合氧化物催化剂,借助XRD、BET、O₂-TPD和H₂-TPR研究了催化剂的物理化学性质,通过甲苯催化燃烧探针反应评价了催化剂的催化性能。结果表明,CuO、MnO_x、FeO_x和Co₃O₄能溶入CeO₂晶格形成Ce-O-Cu、Ce-O-Mn、Ce-O-Fe和Ce-O-Co固溶体,Cu和Mn离子的溶入导致CeO₂晶格发生了较大程度的晶格畸变,Fe和Co离子对CeO₂晶格的影响较小,且在CeCo-HT氧化物催化剂中还存在微量晶相Co₃O₄。所制得的CeM-HT氧化物催化剂表现出了优越的甲苯催化燃烧性能,在反应温度为300、270、260和230 ℃时,CeFe-HT、CeCo-HT、CeMn-HT和CeCu-HT氧化物催化剂上甲苯的催化燃烧转化率分别达93.7%、95.0%、96.5%和95.0%以上。Ce基复合氧化物催化剂的甲苯催化燃烧活性顺序与其氧脱附性能、储氧性能和可还原性能具有正相关性,遵从顺序为CeCu-HT > CeMn-HT > CeCo-HT > CeFe-HT。