Hydroflux Syntheses — Reactions in Ultrabasic Media at Moderate Temperatures

Hydroflux 合成 â 中等温度下超碱性介质中的反应

• 批准号: 438795198
• 负责人: Professor Dr. Michael Ruck
• 金额: --
• 依托单位: Professur für Anorganische Chemie II
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/438795198?language=en
• 关键词: Hydroflux; Syntheses; Reactions; Ultrabasic; Media; Hydroflux; Syntheses; Reactions; Ultrabasic; Media

Hydroflux synthesis, using very highly concentrated alkaline solutions, is a promising new time-, energy-, and atom-efficient synthesis approach, especially but not exclusively for oxides and hydroxides. The conditions differ from those in hydrothermal reactions as well as those in alkaline salt melts. Previous work has shown that the range of main-group and transition elements that can be reacted, as well as of the oxidation states that can be addressed, is much wider than initially expected. We will explore the potential of hydroflux synthesis and gain further knowledge about the crucial reaction parameters and the ongoing chemical processes. Key chemical, structural, and physical properties of the obtained solid products shall be determined. We will specifically follow two directions. First, the low activity of water in the hydroflux provides options for a virtually anhydrous acid-base chemistry at moderate temperature. Common mineral acids and their anhydrides will be reacted with the aim of crystallizing metal salts of complex anions with various degree of protonation and condensation. There is a high probability that the compounds formed are new, will have non-centrosymmetric structures and exhibit non-linear optical properties. Second, the redox chemistry under hydroflux conditions will be investigated. The tabulated electrochemical standard potentials no longer apply, particularly in systems that depend on pH. Together with the hygroscopic properties of hydroflux, this makes soluble oxometalates in intermediate oxidation states unexpectedly strong reducing agents whose potential will be explored. On the other hand, there is a lively redox chemistry between oxide, peroxide, superoxide and molecular oxygen depending on the pH and the alkali metal cation of the flux. By using solid oxygen sources or hydrogen peroxide solutions, the oxidation potential can be increased in a controlled manner, which will be studied in detail and exploited to stabilize high oxidation states of transition metals.

使用非常浓缩的碱性溶液，HydroFlux合成是一种有希望的新的时间，能量和原子效率合成方法，尤其是但不仅用于氧化物和氢氧化物。与水热反应以及碱性盐融化的条件不同。先前的工作表明，可以反应的主组和过渡元素以及可以解决的氧化状态的范围比最初预期的要宽得多。我们将探讨氢氟胰合成的潜力，并获得有关关键反应参数和正在进行的化学过程的进一步知识。应确定所获得的固体产物的关键化学，结构和物理性质。我们将特别遵循两个方向。首先，水力流中水的低活性为中等温度下的几乎无水酸基化学反应提供了选择。常见的矿物质及其酸酐将以各种质子化和凝结度的复杂阴离子的金属盐结晶的目的反应。形成的化合物是新的，将具有非中心对称结构并具有非线性光学特性。其次，将研究在氢氟化条件下的氧化还原化学。列表的电化学标准电位不再适用，尤其是在依赖pH的系统中。与HydroFlux的湿气特性一起，这使得中间氧化状态中的可溶性氧气含量出乎意料地探索了潜力的强大还原剂。另一方面，根据通量的pH和碱金属阳离子，氧化物，过氧化物，超氧化物和分子氧之间存在活泼的氧化还原化学。通过使用固体氧源或过氧化氢溶液，可以以受控的方式增加氧化电位，并将详细研究并利用以稳定过渡金属的高氧化状态。