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

这项艾美奖诺伊特项目致力于阐明聚合物诱导的液体前体(PILP)过程的物理化学机制，以及一般液体凝聚矿物前体的形成。PILP工艺是一种受生物启发的合成路线，允许在最温和的条件下生产介晶和纳米颗粒材料。通过PILP的固态材料的形成遵循所谓的非经典结晶路线，该路线是通过液体凝聚矿物前驱物相的纳米液滴的积累进行的。到目前为止，这些所谓的液-液相分离(LLP)过程的起源尚不清楚，限制了PILP过程的形态合成潜力的翻译和开发。我们现在可以证明，LLP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络合物/簇合物时，可以发生无机组分的LLP，然后形成代表不同溶质物种的LLP。这些团簇独立于溶液中的单个离子发挥作用，是实际的分离物种。有了这个基本的见解，我们现在可以提供一个建立在既定理论基础上的PILP/LLP过程的机制框架。我们的结果表明，对于一系列离子化合物来说，无机盐的旋节分离是很容易实现的；旋节分离的受控阻止使我们能够获得从自支撑的纳米孔道网络到可在衬底上浇铸的纳米液滴等一系列形貌。在本文中，我们的目标是将旋节分解演变为一种形态合成工具，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在调幅分解中的影响；特别关注对生物矿化过程至关重要的镁。

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.