从密度功能理论与高能X射线散射和EXAFS光谱学结合的高活性分子和水氧化催化剂的溶液结构
Ke R Yang1, Adam J Matula1, Gihan Kwon2
1Yale Energy Sciences Institute and Department of Chemistry, Yale University , New Haven, Connecticut 06520-8107, United States.
Journal of the American Chemical Society
|April 19, 2016
概括
具有高活性的 (Ir) 水氧化催化剂是具有特定核心和连接体的 Ir 模体. 这项研究引入了一种新的现场方法来描述催化系统中的活性物种.
科学领域:
- 无机化学
- 催化剂
- 光谱学
背景情况:
- 水的氧化是可再生能源技术的关键过程.
- 了解活性催化剂的结构对于提高效率至关重要.
- 催化剂的活性很高,但它们的现场结构仍然难以确定.
研究的目的:
- 阐明高活性水氧化催化剂的溶液结构.
- 开发和验证一种新的现场表征方法.
主要方法:
- 将密度功能理论 (DFT) 与高能X射线散射 (HEXS) 和扩展X射线吸收细结构 (EXAFS) 光谱学相结合.
- 使用各种光谱技术,包括NMR,EPR,共振拉曼和UV-vis.
- 使用电泳作为结构支.
主要成果:
- 活性催化剂被确定为具有单μO核心的二聚物.
- 通过前体的部分氧化在现场形成的终端离子联体.
- 拟议的结构得到了一系列光谱和分析数据的支持.
结论:
- 这项研究成功地确定了高活性的IR水氧化催化剂的现场结构.
- 这些发现为催化水的氧化机制提供了宝贵的见解.
- 开发的DFT-EXAFS-HEXS方法为现场催化系统的表征提供了一个强大的新工具.
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