Formation of Liquid-condensed mineral phases and the mechanisms of the PILP process: potential for a new morphosynthetic route to nanocomposite materials

这个Emmy Noether项目致力于阐明聚合物诱导的液体前驱体（PILP）过程的物理化学机制，特别是液体凝聚矿物前驱体的形成。PILP工艺是一种启发生物的合成路线，允许在最温和的条件下生产中晶和纳米颗粒材料。通过PILP生成固态材料遵循所谓的非经典结晶路线，即通过液体凝聚矿物前驱相的纳米液滴吸积进行。到目前为止，这些所谓的液-液相分离（LLPS）过程的起源尚不清楚，限制了对PILP过程形态合成潜力的翻译和开发。我们现在可以证明LLPS对于一系列无机离子体系是可行的：当形成足够稳定的配位配合物/簇时，无机组分的LLPS可以发生，然后代表不同的溶质种类。这些团簇独立于溶液中的单个离子而起作用，是实际的脱混物种。有了这个基本的见解，我们现在可以提供一个基于既定理论的PILP/LLPS过程的机械框架。我们的研究结果表明，无机盐的独立脱混是很容易实现的一系列离子化合物；控制停止的spinodal脱混提供了无与伦比的访问范围的形态，从自支持纳米孔网络到纳米液滴可浇铸在基材上。在这篇文章中，我们的目标是将spinodal分解演变成一种形态合成工具，它允许定制具有可调节孔径和曲率的无机组分的双连续网络。我们将进一步研究无机离子作为添加剂对独立分解的影响；将特别关注镁，这对生物矿化过程至关重要。

This Emmy Noether project is dedicated to the elucidation of the physicochemical mechanisms of the polymer-induced liquid-precursor (PILP) process in particular and the formation of liquid-condensed mineral precursors in general. The PILP process is a bio-inspired synthesis route which allows for the production of mesocrystalline and nanogranular materials at mildest conditions. The genesis of a solid-state material via PILP follows a so-called nonclassical crystallization route which proceeds by accretion of nanodroplets of a liquid-condensed mineral precursor phase. Up to now, the origin of these alleged liquid-liquid phase separation (LLPS) processes was unclear, limiting translation and exploitation of the morphosynthesis potential of PILP processes. We can now demonstrate that LLPS is feasible for a range of inorganic ionic systems: LLPS of inorganic components can occur when sufficiently stable coordination complexes/clusters are formed which then represent a distinct solute species. These clusters act independently from single ions in solution and are the actual demixing species. With this fundamental insight, we can now provide a mechanistical framework of PILP/LLPS processes which rests on established theories. Our results demonstrate that spinodal demixing of inorganic salts is readily achievable for a range of ionic compounds; controlled arrestment of the spinodal demixing gives unparalleled access to a range of morphologies from self-supporting nanoporous networks to nanodroplets castable on substrates. In this continuation, we aim at evolving spinodal decomposition into a morphosynthetic tool which allows for tailored bicontinuous networks of inorganic components with adjustable pore size and curvature. We will further look into the impact inorganic ions have as additives in spinodal decomposition; a special regard will be laid on magnesium which is of central importance for biomineralisation processes.