在olefin转化中的活体位点在现场生成
Kazuhiko Amakawa1, Sabine Wrabetz, Jutta Kröhnert
1Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany.
Journal of the American Chemical Society
|June 19, 2012
概括
了解异质催化剂需要识别活性位点. 这项研究揭示了氧化物催化剂在甲基转化中的多步机制,挑战了以前的模型并改进了催化剂设计.
科学领域:
- 不同质的催化剂.
- 表面化学 表面化学
- 材料科学是一种材料科学.
背景情况:
- 在异质催化剂中精确识别和量化活性位点仍然具有挑战性.
- 了解活性部位的分子结构对于促进催化作用至关重要.
- 在氧/氧2的烯转化中,只有很小的一小部分 (1.5%) 的原子形成了活性中心.
研究的目的:
- 阐明氧化物催化剂中活性位点的 in situ 形成机制,用于甲基转化.
- 为了确定在催化剂表面限制活性点度的途径.
- 为基于知识的催化剂改进提供见解.
主要方法:
- 操作的红外光谱学.
- 微热量计是指微热量计.
- 使用同位素标记的反应性研究.
- 监测催化剂的形成和表面反应.
主要成果:
- 活性Mo(VI) - - 化基因部分是通过涉及基质的多步表面反应产生的.
- 该机制包括质子化,异氧化氧化到,和氧化添加.
- 这种顺序机制与先前公认的单步模型形成鲜明对比.
- 优化热处理后的烯吸附使催化活性翻了一番.
结论:
- 这项研究揭示了MoOx/SiO2催化剂中活性位形成的新多步骤机制.
- 了解这些途径可以实现有针对性的催化剂改进,通过增强活动来证明这一点.
- 这些发现为异质催化中的结构-活性关系提供了新的视角.
相关概念视频
Olefin Metathesis Polymerization: Overview
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
Radical Chain-Growth Polymerization: Chain Branching
The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
Ziegler–Natta Chain-Growth Polymerization: Overview
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta catalyst, high molecular...
Radical Chain-Growth Polymerization: Mechanism
The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into the...

