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Nuclear Magnetic Resonance of Physisorbed 129Xe Used as a Probe to Investigate Porous Solids 物理吸附129Xe的核磁共振探针研究多孔固体
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1999-05-01 DOI: 10.1080/01614949909353779
J. Bonardet, J. Fraissard, A. Gédéon, M. Springuel-Huet
Abstract Xenon is an inert gas with a large electronic environment that makes it sensitive to any interaction, even physical. In the case of 129Xe isotope (spin 1/2), the resulting electronic perturbation is directly transmitted to the nucleus and, therefore, affects the nuclear magnetic resonance chemical shift. In this review, we report exhaustively up to 1996 the many applications of this technique in both fundamental and applied research in the fields of microporous and mesoporous solids.
氙是一种惰性气体,具有较大的电子环境,使其对任何相互作用,甚至物理相互作用都很敏感。在129Xe同位素(自旋1/2)的情况下,产生的电子扰动直接传递给原子核,因此影响核磁共振化学位移。本文综述了自1996年以来该技术在微孔和介孔固体领域的基础研究和应用研究中的许多应用。
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引用次数: 145
Mathematical Models of Catalytic Combustors 催化燃烧器的数学模型
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1999-05-01 DOI: 10.1080/01614949909353780
G. Groppi, E. Tronconi, P. Forzatti
Abstract The various concepts of catalytic combustion for the production of energy are presented first. Then, the different configurations of catalytic combustion systems for gas turbine applications are described. The following aspects of the mathematical modeling of the catalyst section are addressed: (1) relevant physical and chemical phenomena; (2) comparison of mathematical models; (3) estimation of interphase transfer coefficients; (4) acquisition of kinetic data; (5) continuous versus discrete multichannel models. Selected examples of application of the models are then presented. Finally, the mathematical modeling of the homogeneous section is briefly discussed.
摘要首先介绍了催化燃烧生产能源的各种概念。然后,介绍了用于燃气轮机的催化燃烧系统的不同配置。对催化剂部分的数学建模进行了以下几个方面的研究:(1)相关的物理和化学现象;(2)数学模型比较;(3)相间传递系数估算;(4)动力学数据采集;(5)连续与离散多通道模型。然后给出了模型的应用实例。最后,简要讨论了均匀截面的数学建模问题。
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引用次数: 66
2p3s3p, 2p3p3p, and 2p3s3s resonant Auger spectroscopy from NiO NiO的2p3s3p, 2p3p3p和2p3s3s共振俄歇光谱
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1999-04-15 DOI: 10.1103/PHYSREVB.59.9933
M. Finazzi, N. Brookes, F. Groot
We have investigated the behavior of the 2p3s3p, 2p3p3p, and 2p3s3s Auger lines of NiO, a model compound in the class of strongly correlated 3d systems, while varying the photon energy across the Ni L3 and L2 absorption edges. The experimental data are discussed in comparison with a theoretical model based on a charge-transfer multiplet approach. When the excitation energy is below the L3 resonance, we observe the 2p3p3p and 2p3s3p peaks at a constant binding energy. This behavior is typical of nonradiative resonant Raman scattering. If the photon energy is increased further, the 2p3p3p and 2p3s3p lines rapidly transform into constant kinetic energy features, showing a normal Auger behavior. The transition from Raman- to Auger-like behavior takes place for photon energies lower than the ones corresponding to excitations of the photoelectron into ligand-hole states. This might indicate the participation of inelastic processes in the recombination of the core hole involving energies much smaller than the NiO gap, or the possible presence of nonlocal effects. On the high photon energy side of the L3 edge, the constant kinetic energy of the 2p3p3p and 2p3s3p peaks is systematically larger than the one observed for an excitation well above the L2,3 edges. We attribute this behavior to the intervention of an intermediate state of 2p^5 3d^10 character, which has very little weight but is strongly enhanced at resonance.
我们研究了NiO的2p3s3p、2p3p3p和2p3s3s俄歇线的行为,NiO是一种强相关三维体系中的模型化合物,同时改变了Ni L3和L2吸收边的光子能量。并将实验数据与基于电荷转移多重方法的理论模型进行了比较。当激发能低于L3共振时,我们观察到2p3p3p和2p3s3p的峰值处于恒定的结合能。这是典型的非辐射共振拉曼散射。如果光子能量进一步增大,2p3p3p和2p3s3p谱线迅速转化为恒定动能特征,呈现正常的俄歇行为。从拉曼行为到类俄歇行为的转变发生在光子能量低于对应于光电子激发到配空穴态的光子能量时。这可能表明在核心洞的重组中有非弹性过程的参与,涉及的能量远小于NiO间隙,或者可能存在非局部效应。在L3边缘的高光子能量侧,2p3p3p和2p3s3p峰的恒定动能系统地大于远高于L2,3边缘的激发所观察到的动能。我们将这种行为归因于2p^5 3d^10特征的中间态的干预,该特征的权重很小,但在共振时被强烈增强。
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引用次数: 22
Composite Zeolite-Based Catalysts and Sorbents 复合沸石基催化剂和吸附剂
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1999-02-02 DOI: 10.1081/CR-100101949
P. Smirniotis, L. Davydov, E. Ruckenstein
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引用次数: 33
CO2 Reforming of CH4 CH4的重整
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1999-02-02 DOI: 10.1081/CR-100101948
M. Bradford, M. Vannice
Although technological practice should minimize environmental impact, this is not always economically feasible. During the past decade, for example, there has been increasing global concern over th...
虽然技术实践应尽量减少对环境的影响,但这在经济上并不总是可行的。例如,在过去的十年中,全球对……的关注日益增加。
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引用次数: 1150
Kinetics and Selectivity of the Fischer–Tropsch Synthesis: A Literature Review 费托合成的动力学和选择性:文献综述
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1999-01-10 DOI: 10.1081/CR-100101170
G. V. D. Laan, A. Beenackers
A critical review of the kinetics and selectivity of the Fischer–Tropsch synthesis (FTS) is given. The focus is on reaction mechanisms and kinetics of the water–gas shift and Fischer–Tropsch (FT) reactions. New developments in the product selectivity as well as the overall kinetics are reviewed. It is concluded that the development of rate equations for the FTS should be based on realistic mechanistic schemes. Qualitatively, there is agreement that the product distribution is affected by the occurrence of secondary reactions (hydrogenation, isomerization, reinsertion, and hydrogenolysis). At high CO and H2O pressures, the most important secondary reaction is readsorption of olefins, resulting in initiation of chain growth processes. Secondary hydrogenation of α-olefins may occur and depends on the catalytic system and the process conditions. The rates of the secondary reactions increase exponentially with chain length. Much controversy exists about whether these chain-length dependencies stem from differe...
本文对费托合成(FTS)的动力学和选择性进行了综述。重点研究了水气转换反应和费托反应的反应机理和动力学。综述了在产物选择性和整体动力学方面的新进展。最后得出结论:速率方程的建立应以实际的机制方案为基础。定性上,一致认为产物分布受二次反应(加氢、异构化、再插入和氢解)的发生的影响。在高CO和高H2O压力下,最重要的二次反应是烯烃的再吸附,从而引发链生长过程。α-烯烃可能发生二次加氢反应,这取决于催化体系和工艺条件。二级反应速率随链长呈指数增长。关于这些链长依赖性是否源于不同的…
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引用次数: 1000
Silica-Based Ziegler–Natta Catalysts: A Patent Review 硅基Ziegler-Natta催化剂:专利回顾
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1999-01-10 DOI: 10.1081/CR-100101172
T. J. Pullukat, R. Hoff
Silica-based Ziegler–Natta catalysts are important industrially in the manufacture of polyethylene and polypropylene. They are scientifically very interesting because of the complex effects of porous silica on catalyst performance. This patent review explains how silica–based Ziegler–Natta catalysts are related to Phillips chromium–silica catalysts and explores their value for the gas phase and slurry processes for the manufacture of polyolefins. The subcategories dealt with are the following: magnesium–titanium–silica catalysts, which are valuable for high-density polyethylene, for the ethylene copolymers called linear low-density polyethylene;and ethylene–propylene rubber, and for isotactic polypropylene; vanadium–silica catalysts, which are useful in the polymerization and copolymerization of ethylene; and vanadium plus titanium–silica catalysts which often exhibit reactivity synergism. Dual-site and multisite catalysts are also reviewed.
硅基齐格勒-纳塔催化剂在聚乙烯和聚丙烯的生产中具有重要的工业意义。由于多孔二氧化硅对催化剂性能的复杂影响,它们在科学上非常有趣。本专利综述解释了硅基Ziegler-Natta催化剂与菲利普斯铬-二氧化硅催化剂的关系,并探讨了它们在聚烯烃气相和浆料工艺中的价值。所涉及的子类别如下:镁-钛-硅催化剂,用于高密度聚乙烯,用于称为线性低密度聚乙烯的乙烯共聚物,以及乙烯-丙烯橡胶和等规聚丙烯;钒-硅催化剂,用于乙烯的聚合和共聚;钒+钛-二氧化硅催化剂通常表现出反应性协同作用。对双点和多点催化剂也进行了综述。
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引用次数: 74
Raman Spectroscopy of Monolayer-Type Catalysts: Supported Molybdenum Oxides 负载型氧化钼单层催化剂的拉曼光谱研究
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1998-11-01 DOI: 10.1080/01614949808007114
G. Mestl, T. K. Srinivasan
Abstract Oxides of the group VIb metals (Cr, Mo, W) and oxides of vanadium, rhenium, and niobium supported on a second high-surface-area metal oxide such as Al2O3, TiO2, Si02, ZrO2, and so forth are recognized as industrially important catalysts or catalyst precursors for various reactions [1–11], These materials frequently have been described as so-called monolayer catalysts based on a structural model which assumed spreading of the active oxide over the support surface. These catalysts have been investigated by a variety of techniques, conventional bulk sampling techniques as well as by surface-sensitive electron and ion spectroscopies, in an attempt to elucidate the nature of the catalyst surface species, and to study the coordination environment of the active metal center(s). Electronic spectroscopy gives rise to broad bands and the spectra are less informative than vibrational spectra. In addition, although techniques such as Auger electron spectroscopy (AES) and x-ray photoelectron spectroscopy (XPS...
VIb族金属的氧化物(Cr、Mo、W)和钒、铼、铌的氧化物(如Al2O3、TiO2、sio2、ZrO2等)被认为是工业上重要的催化剂或各种反应的催化剂前驱体[1-11],这些材料经常被描述为所谓的单层催化剂,其结构模型假设活性氧化物在支撑表面上扩散。为了阐明催化剂表面物质的性质,并研究活性金属中心的配位环境,研究人员采用了多种技术,包括传统的批量取样技术以及表面敏感电子和离子光谱技术对催化剂进行了研究。电子光谱产生宽频带,光谱比振动光谱信息量少。此外,虽然俄歇电子能谱(AES)和x射线光电子能谱(XPS)等技术…
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引用次数: 319
Claus catalysis and H2S selective oxidation 克劳斯催化和H2S选择性氧化
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1998-11-01 DOI: 10.1080/01614949808007113
A. Pieplu, Odette Saur, J. Lavalley, O. Legendre, C. Nedez
Abstract This review article deals with the development of sulfur recovery from the Claus process to H2S selective oxidation. Governments are constantly tightening regulations to limit the emission of sulfur compounds into the air. This makes it necessary to constantly enhance the level of sulfur recovery from natural, refinery, or coal gasification geses, and many improvements in the Claus process have been introduced to this end. In this review, emphasis has been put on the mechanism of reactions occurring in most of the sulfur recovery units, reactions between H2S and SO2 or O2 and side reactions such as hydrolysis of COS and CS2 or sulfation of the catalyst.
摘要本文综述了克劳斯法硫回收到H2S选择性氧化的研究进展。各国政府不断收紧法规,限制向空气中排放含硫化合物。这使得有必要不断提高从天然,炼油厂或煤气化geses中回收硫的水平,并且为此目的引入了克劳斯过程的许多改进。本文重点介绍了大多数硫回收装置中发生的反应机理、H2S与SO2或O2之间的反应以及COS和CS2水解或催化剂磺化等副反应。
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引用次数: 214
Synthesis and Characterization of Mesostructured Materials 介观结构材料的合成与表征
IF 10.9 2区 化学 Q1 Chemistry Pub Date : 1998-08-01 DOI: 10.1080/01614949808007111
S. Biz, M. Occelli
Abstract Catalysis and heterogeneous catalysts are essential to our present technology for the production and consumption of fuels, the manufacture and processing of chemical feedstocks and plastics [1,2]. It had been estimated that the introduction of this technology has permitted savings of more than 400 million barrels of oil each year [l]. Today, worldwide catalysts sales exceed $5.9 billion per year, and it has been estimated that catalysts generate fuels and chemicals worth $2.4 trillion annually, equivalent to half the U.S. Gross National Product [1,2].
催化和多相催化剂对于我们目前的燃料生产和消费、化学原料和塑料的制造和加工技术至关重要[1,2]。据估计,这项技术的引入每年可节省4亿多桶石油[1]。如今,全球催化剂的年销售额超过59亿美元,据估计,催化剂每年产生的燃料和化学品价值达2.4万亿美元,相当于美国国民生产总值的一半[1,2]。
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引用次数: 301
期刊
Catalysis Reviews-Science and Engineering
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