Preserving Both Anion and Cation Sublattice Features during a Nanocrystal Cation-Exchange Reaction: Synthesis of Metastable Wurtzite-Type CoS and MnS,Journal of the American Chemical Society

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Preserving Both Anion and Cation Sublattice Features during a Nanocrystal Cation-Exchange Reaction: Synthesis of Metastable Wurtzite-Type CoS and MnS
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2016-01-04 , DOI: 10.1021/jacs.5b10624
Anna E. Powell ₁ , James M. Hodges ₁ , Raymond E. Schaak ₁

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The ability to selectively synthesize one particular polymorph in a solid-state system having multiple crystal structures with the same composition is important for accessing desired properties. Solution-mediated reactions, including anion and cation exchange, that chemically transform colloidal nanoparticles with pre-programmed structural features into targeted products have emerged as a powerful platform for predictably accessing metastable polymorphs. While nanocrystal ion-exchange reactions that retain anion sublattice features are well known, analogous reactions that preserve cation sublattice features are much less common, and guidelines for predictably targeting such sublattice features are not well established. Here, we report that both anion and cation sublattice features--hexagonal close-packed anions and tetrahedrally coordinated cations--can be preserved during cation exchange of roxbyite-type Cu2-xS nanocrystals to selectively produce wurtzite-type CoS and MnS. These polymorphs, which are metastable in bulk systems, form relative to other accessible structures having cubic close-packed anions and/or octahedrally coordinated cations. To facilitate these transformations, the scope of existing nanocrystal cation-exchange reactions was expanded to include 3d transition metal systems that previously have not been investigated in depth.

中文翻译：

在纳米晶体阳离子交换反应中同时保留阴离子和阳离子亚晶格特征：合成亚稳态纤锌矿型 CoS 和 MnS

在具有相同组成的多种晶体结构的固态系统中选择性合成一种特定多晶型物的能力对于获得所需的特性很重要。溶液介导的反应，包括阴离子和阳离子交换，将具有预编程结构特征的胶体纳米粒子化学转化为目标产品，已成为可预测地获得亚稳态多晶型物的强大平台。虽然保留阴离子亚晶格特征的纳米晶体离子交换反应是众所周知的，但保留阳离子亚晶格特征的类似反应却很少见，并且还没有很好地建立可预测地靶向此类亚晶格特征的指导方针。这里，我们报告说，阴离子和阳离子亚晶格特征——六方密堆积阴离子和四面体配位阳离子——可以在菱铁矿型 Cu2-xS 纳米晶体的阳离子交换过程中得到保留，以选择性地生产纤锌矿型 CoS 和 MnS。这些在本体系统中是亚稳态的多晶型物相对于具有立方密堆积阴离子和/或八面体配位阳离子的其他可接近结构形成。为了促进这些转变，现有纳米晶体阳离子交换反应的范围扩大到包括以前尚未深入研究的 3d 过渡金属系统。相对于其他具有立方密堆积阴离子和/或八面体配位阳离子的可接近结构的形式。为了促进这些转变，现有纳米晶体阳离子交换反应的范围扩大到包括以前尚未深入研究的 3d 过渡金属系统。相对于其他具有立方密堆积阴离子和/或八面体配位阳离子的可接近结构的形式。为了促进这些转变，现有纳米晶体阳离子交换反应的范围扩大到包括以前尚未深入研究的 3d 过渡金属系统。

更新日期：2016-01-04

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