Multinuclear NMR Spectroscopy of Inorganic Materials

虽然固体状态通常是由长程顺序定义的，但通常是偏离这种周期性提供了材料的有趣的物理和化学性质。在这些情况下，了解材料在不同长度尺度和不同时间尺度上的结构至关重要。核磁共振波谱为了解局部结构环境提供了理想的探针，并且是基于衍射的方法的补充。此外，平均结构和局部结构之间的联系可以通过第一性原理计算和核磁共振参数的计算来辅助。这对无机材料特别有用，因为文献中存在的数据少得多，无法帮助谱分配和解释，而感兴趣的原子核更多。在这里，我们将探索结合使用先进的核磁共振方法学和最先进的周期计算，以了解局部结构，无序和化学反应性在一系列无机材料，包括微孔固体和陶瓷。特别令人感兴趣的是17O核磁共振波谱的使用，其中O的这种唯一的核磁共振活性同位素（0.037%）的自然丰度很低，需要昂贵的同位素富集。因此，这项工作的总体目标包括：陶瓷和微孔固体中17O富集的成本效益和原子效率方法的开发与应用。优化最先进的核磁共振方法，旨在提高灵敏度和分辨率。3. 使用第一性原理DFT计算和生成结构模型的新方法。将这些方法应用于氧化陶瓷、沸石和金属有机框架，以了解局部结构、无序性和化学反应性。

Although the solid state is usually defined by long-range order, it is often the deviation from this periodicity that provides the interesting physical and chemical properties of materials. In these cases, understanding the structure of a material on different lengthscales and over different timescales is vital. NMR spectroscopy offers an ideal probe for understanding the local structural environment, and is complementary to diffraction-based approaches. Furthermore, the link between average structure and local structure can be aided by first-principles calculations and the prediction of NMR parameters using computation. This is particularly useful for inorganic materials, where much less data exists in the literature to aid spectral assignment and interpretation, and many more nuclei are of interest. Here, we will explore the combined use of advanced NMR methodology and state-of-the-art periodic calculations to understand local structure, disorder and chemical reactivity in a range of inorganic materials, including microporous solids and ceramics. Of particular interest is the use of 17O NMR spectroscopy, where the low natural abundance of this only NMR-active isotope of O (0.037%) requires expensive isotopic enrichment. General goals of the work therefore include1. The development and application of cost-effective and atom-efficient methods for 17O enrichment of ceramics and microporous solids.2. Optimisation of state-of-the-art NMR methodology aimed at improving sensitivity and resolution. 3. Use of first-principles DFT calculations and new methods for generating structural models.4. Application of these methods to oxide ceramics, zeolites and metal-organic frameworks to understand local structure, disorder and chemical reactivity.