固态 47/49 Ti NMR 光谱中的Ti 位点的NMR 签名和电子结构
Lukas Lätsch1, Christoph J Kaul1, Alexander V Yakimov1
1ETH Zurich, Department of Chemistry and Applied Biosciences, Vladimir-Prelog Weg 2, CH-8093 Zurich, Switzerland.
Journal of the American Chemical Society
|July 7, 2023
概括
泰坦酸-1 (TS-1) 氧化催化剂的活性位点已经得到讨论. 新的47/49Ti核磁共振和计算研究揭示了Ti环境,有助于区分TS-1结构中的Ti位置.
科学领域:
- 材料科学
- 催化剂
- 固态核磁共振光谱
背景情况:
- 泰坦酸-1 (TS-1) 是一种高效的工业氧化催化剂.
- 在TS-1中活性 (Ti) 位点的精确结构仍然是正在进行的研究和辩论的主题.
- 之前的研究集中在缺陷部位和外框架Ti物种上.
研究的目的:
- 使用先进的固态NMR技术,阐明TS-1中 (Ti) 的局部结构环境.
- 将NMR特征与特定的Ti位点位置和局部结构特征相关联.
- 调查 47/49Ti NMR 对 TS-1 微妙结构变化的敏感性.
主要方法:
- 使用高灵敏度的47/49Ti固态核磁共振 (使用CryoProbe的魔法角旋转).
- 合成和特征化了分子类型的[Ti(OTBOS) 4和[Ti(OTBOS) 3 (OPr) ].
- 在集群模型上进行密度功能理论 (DFT) 计算以解释NMR数据.
主要成果:
- 脱水的TS-1呈现出与四面体Ti相一致的47/49Ti NMR化学转移,类似于分子类型.
- 在TS-1中较大的四极合常数分布表明与分子模型相比,Ti环境更不对称.
- 核磁共振信号对局部结构变化具有高度敏感性,有助于区分Ti的位置.
结论:
- 这项研究证实了TS-1中Ti的四面体协调,与X射线吸收光谱的发现一致.
- 在Ti环境中观察到的不对称性表明TS-1内部具有特定的结构特征.
- 47/49Ti NMR光谱是一种强大的工具,用于探测TS-1中的Ti分化和位置,从而能够区分各种T位点位置.
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