Bairan Espano Jeremy R, Macdonald Janet E
Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, United States.
Vanderbilt Institute of Nanoscale Science and Engineering, Vanderbilt University, Nashville, Tennessee 37235, United States.
J Am Chem Soc. 2023 Aug 30;145(34):18948-18955. doi: 10.1021/jacs.3c05653. Epub 2023 Aug 18.
The identity and repeating arrangement of atoms determine the properties of all solids. Even combinations of two atoms can have multiple crystal structures of varying stoichiometries and symmetries with vastly different electronic and chemical behaviors. The conditions of existing bottom-up routes for achieving one phase over another are serendipitous, and the links among precursor reactivity, decomposition mechanism, temperature, and time are elusive. Our studies take a systematic approach to understanding the role that the precursor kinetic decomposition has in the synthesis of iron sulfides, isolating it from other mechanistic factors. The data suggest that phase determination in binary solids can be logically predicted through the consideration of the anion stacking and thermodynamic relationships between phases. Mapping these relationships allows for the rational synthetic targeting of metastable crystalline phases.
原子的特性及重复排列决定了所有固体的性质。即使是两种原子的组合也能具有多种不同化学计量比和对称性的晶体结构，其电子和化学行为差异极大。现有自下而上制备一种相而非另一种相的方法的条件是偶然的，前驱体反应性、分解机制、温度和时间之间的联系难以捉摸。我们的研究采用系统方法来理解前驱体动力学分解在硫化铁合成中的作用，将其与其他机理因素区分开来。数据表明，通过考虑阴离子堆积以及各相之间的热力学关系，可以合理预测二元固体中的相。绘制这些关系图有助于对亚稳晶相进行合理的合成靶向。
