集群化学:依赖大小的反应性,由反向溢出作用引起
Martin A Röttgen1, Stephane Abbet, Ken Judai
1Lehrstuhl für Physikalische Chemie I, Technische Universität München, Lichtenbergstrasse 4, 85748 Garching, Germany.
Journal of the American Chemical Society
|July 10, 2007
概括
(Pd) 集群上的CO氧化率取决于CO分子的输送. 反向溢出影响影响较小的Pd(8) 集群不同于较大的Pd(30) 集群,影响反应概率.
科学领域:
- 不同质的催化剂.
- 表面科学是一门科学.
- 纳米材料是一种纳米材料.
背景情况:
- 了解支持金属集群上的CO氧化对于催化是至关重要的.
- 碳化合物扩散 (反向溢出) 对反应速率的作用尚未完全理解.
- 金属集群的大小依赖的催化活性是研究的一个关键领域.
研究的目的:
- 为了研究大小选择的 (Pd) 集群上的CO氧化率.
- 为了确定反向溢出对不同PD集群大小的催化活性的影响.
- 为了区分直接流量供应的CO与扩散的反应概率.
主要方法:
- 脉冲分子束实验被用来研究CO氧化.
- 在MgO薄膜上支持的大小选择的Pd集群 (Pd(8) 和Pd(30)) 被使用.
- 集群覆盖范围因集群大小而异,以改变CO流量比率.
- 采集区模型被用来模拟二氧化碳流向集群.
主要成果:
- 对于Pd(8) 和Pd(30) 集群,CO氧化率因集群覆盖率而异.
- 对于小的Pd(8) 集群,反应概率是独立于CO供应方法 (直接或扩散).
- 对于较大的Pd(30) 集群,通过反向溢出供应的CO,与直接流相比,反应概率降低.
结论:
- 反向溢出显著影响受支持的Pd集群上的CO氧化率.
- 反向溢出对反应概率的影响取决于集群大小.
- 催化剂设计应考虑二氧化碳扩散对反应动力学的影响,以获得最佳性能.
相关概念视频
Chain Reactions
Chain reactions involve highly reactive transient species, such as atoms or free radicals, as intermediates. These intermediates facilitate rapid reactions over an extended period. The process includes a series of steps: a reactive intermediate is consumed, reactants are converted to products, and the intermediate is regenerated. This cycle enables continuous repetition, amplifying the production of products with a small amount of intermediate. Chain reactions often utilize free radicals as...
Radical Reactivity: Overview
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired molecule. These three...
Radical Reactivity: Concentration Effects
In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
Radical Reactivity: Intramolecular vs Intermolecular
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak carbon–halogen...
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
Chemical Reactions
A balanced chemical equation provides the information of chemical formulas of the reactants and products involved in the chemical change. A reaction’s stoichiometry helps predict how much of the reactant is needed to produce the desired amount of product, or in some cases, how much product will be formed from a specific amount of the reactant.
The relative amounts of reactants and products represented in a balanced chemical equation are often referred to as stoichiometric amounts. However, in...
The relative amounts of reactants and products represented in a balanced chemical equation are often referred to as stoichiometric amounts. However, in...


![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)