Solid-state transformations for clean and energy-efficient synthesis

提出的研究开发了高效的固体化学合成方法，作为传统溶剂基方法的潜在替代品。感兴趣的反应性是基于最近发现的，但尚未完全理解的催化效应，这种催化效应允许惰性无机材料（例如金属氧化物或硫化物）转化为有价值的产品，包括金属药物和多孔金属有机框架（mof），其速率与传统溶液合成的速率相当或更高。拟议的方法将是低能耗和无溶剂的，有可能大大降低实验室和工业研究的能源、溶剂和材料成本。我们将解释和开发新的“加速老化”反应，使用催化盐添加剂，在有机或水蒸气的帮助下，使用很少的能量输入和无溶剂将惰性前体完全转化为产品。这些易于扩展的反应是针对低能源和无溶剂矿物制造，金属提取或核废料隔离的潜在应用。我们将建立一个合理的理解最近发现的催化机械合成，提供有价值的产品在温和的条件下，使用的能量和溶剂比传统的溶剂热方法少得多。该研究计划将基于筛选实验的系统设计，探索“加速老化”和机械化学反应的范围和机制。反应筛选将与各种尖端的衍射、光谱学、显微镜和热分析技术相结合，用于产品表征、逐步反应监测和实时观察反应。除了使新型高效的固态反应模式合理化之外，机械化学筛选还将用于在没有溶液干扰的情况下如何控制mof的拓扑结构、孔隙度和水分敏感性的首次系统研究。本研究和培训计划将发展机械化学条件下的可逆共价合成，用于非对称分子的高效合成和多孔共价框架的室温合成。

The proposed research develops highly efficient methods of chemical synthesis in the solid state as potential alternatives to conventional solvent-based procedures. The reactivity of interest is based on recently discovered and not yet fully understood catalytic effects that allow the transformations of inert inorganic materials (e.g. metal oxides or sulfides) into valuable products, including metallodrugs and porous metal-organic frameworks (MOFs), at rates comparable to or higher than those in conventional solution synthesis. Proposed methodologies will be low-energy and solvent-free, with potential to greatly reduce energy, solvent and materials costs of laboratory and industrial research. We will explain and develop novel "accelerated aging" reactions that use catalytic salt additives, aided by organic or water vapors, to fully convert inert precursors into products using little energy input and no solvent. These readily scalable reactions are targeted for potential applications in low-energy and solvent-free mineral manufacturing, metal extraction or nuclear waste sequestration. We will establish a rational understanding of recently discovered catalytic mechanosynthesis which provides valuable products under mild conditions and using significantly less energy and solvent than traditional solvothermal methods. The research program will be based on a systematic design of screening experiments which explore the scope and mechanisms of "accelerated aging" and mechanochemical reactions. Reaction screening will be coupled to a variety of cutting-edge diffraction, spectroscopy, microscopy and thermal analysis techniques for product characterization, stepwise reaction monitoring and real-time observation of reactions. In addition to rationalizing new and efficient modes of solid-state reactivity, mechanochemical screening will be used for the first systematic study of how topology, porosity and moisture sensitivity of MOFs are controlled in the absence of solution interferences. This research and training program will develop reversible covalent synthesis under mechanochemical conditions for the efficient synthesis of non-symmetrical molecules and room-temperature synthesis of porous covalent frameworks.