Department of Chemistry, Zhejiang University, Hangzhou, China.
Department of Physics, Research Institute for Biomimetics and Soft Matter, Jiujiang Research Institute, Xiamen University, Xiamen, China.
Nature. 2019 Oct;574(7778):394-398. doi: 10.1038/s41586-019-1645-x. Epub 2019 Oct 16.
Inorganic materials have essential roles in society, including in building construction, optical devices, mechanical engineering and as biomaterials. However, the manufacture of inorganic materials is limited by classical crystallization, which often produces powders rather than monoliths with continuous structures. Several precursors that enable non-classical crystallization-such as pre-nucleation clusters, dense liquid droplets, polymer-induced liquid precursor phases and nanoparticles-have been proposed to improve the construction of inorganic materials, but the large-scale application of these precursors in monolith preparations is limited by availability and by practical considerations. Inspired by the processability of polymeric materials that can be manufactured by crosslinking monomers or oligomers, here we demonstrate the construction of continuously structured inorganic materials by crosslinking ionic oligomers. Using calcium carbonate as a model, we obtain a large quantity of its oligomers (CaCO) with controllable molecular weights, in which triethylamine acts as a capping agent to stabilize the oligomers. The removal of triethylamine initiates crosslinking of the (CaCO) oligomers, and thus the rapid construction of pure monolithic calcium carbonate and even single crystals with a continuous internal structure. The fluid-like behaviour of the oligomer precursor enables it to be readily processed or moulded into shapes, even for materials with structural complexity and variable morphologies. The material construction strategy that we introduce here arises from a fusion of classic inorganic and polymer chemistry, and uses the same cross-linking process for the manufacture the materials.
无机材料在社会中具有重要作用，包括在建筑结构、光学器件、机械工程和生物材料中的应用。然而，无机材料的制造受到经典结晶的限制，通常只能得到粉末，而不是具有连续结构的整体材料。已经提出了几种能够实现非经典结晶的前体物质，如预成核簇、密集液滴、聚合物诱导的液相前体相和纳米颗粒，以改善无机材料的构建，但这些前体物质在整体材料制备中的大规模应用受到可用性和实际考虑的限制。受可通过交联单体或低聚物制造的聚合物材料的可加工性的启发，我们在此展示了通过交联离子低聚物来构建具有连续结构的无机材料的方法。以碳酸钙为例，我们获得了大量具有可控分子量的碳酸钙低聚物，其中三乙胺作为封端剂来稳定低聚物。三乙胺的去除引发了（CaCO）低聚物的交联，从而快速构建了纯整体碳酸钙，甚至是具有连续内部结构的单晶。低聚物前体的类流体行为使其能够很容易地进行加工或成型，即使是对于具有复杂结构和可变形态的材料也是如此。我们在这里介绍的材料构建策略源于经典无机化学和聚合物化学的融合，并使用相同的交联过程来制造材料。
