在Pt上化基基的过渡状态{111})
Pingping Ye1, Andrew J Gellman
1Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
Journal of the American Chemical Society
|June 6, 2008
概括
表面上的替代效应会影响化障碍. 增加基团极化性和化度会增加化能障碍,表明有阴离子过渡状态.
科学领域:
- 表面化学 表面化学
- 催化剂是一种催化剂.
- 物理化学 物理化学
背景情况:
- 了解替代物效应对于设计催化过程至关重要.
- Pt(111) 表面是研究表面反应的模型系统.
研究的目的:
- 调查基组在Pt上的化过渡状态上的替代效应.
- 使用线性自由能量关系,将替代剂特性与化障碍相关联.
主要方法:
- 在Pt上基和基化物分离吸附{111}.
- 与一起共同吸收,然后进行热溶解.
- 用温度编程的反应光谱测量化障碍 (ΔE(H) ‡).
主要成果:
- 化障碍物随着基极化和化程度的增加而增加.
- 在替代常数和 ΔE(H) ‡ 之间建立了线性自由能量关系.
- 测定了场反应常数 (ρF) = 27 ± 4 kJ/mol和极化反应常数 (ρα) = 19 ± 3 kJ/mol.
结论:
- 在Pt(111) 上化的过渡状态表现出轻微的阴离子性质.
- 替代效应显著调节表面反应能量.
相关概念视频
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