Gordon Matthew N, Junkers Laura S, Googasian Jack S, Mathiesen Jette K, Zhan Xun, Morgan David Gene, Jensen Kirsten M Ø, Skrabalak Sara E
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
Department of Chemistry and Nanoscience Center, University of Copenhagen, 2100 Copenhagen Ø, Denmark.
Nanoscale. 2024 Aug 22;16(33):15544-15557. doi: 10.1039/d4nr01749h.
The synthesis of bismuth oxyhalides as defined nanostructures is hindered by their fast nucleation and growth in aqueous solutions. Using our recently developed single-source precursor, the formation of bismuth oxychloride in such solutions can be slowed significantly. As reported herein, this advance enables BiOCl formation to be investigated by X-ray total scattering and liquid cell transmission electron microscopy. pair distribution function analysis of X-ray total scattering data reveals the local order of atomic structures throughout the synthesis, while liquid cell transmission electron microscopy allows for tracking the growth of individual nanoparticles. Through this work, the precursor complex is shown to give rise to BiOCl upon heating in solution without the observation of structurally distinct intermediates. The emerging nanoparticles have a widened interlayer spacing, which moderately decreases as the particles grow. Mechanistic insights into the formation of bismuth oxyhalide nanoparticles, including the absence of distinct intermediates within the available time resolution, will help facilitate future design of controlled BiOX nanostructures.
作为特定纳米结构的卤氧化铋的合成，因其在水溶液中快速的成核和生长而受到阻碍。使用我们最近开发的单源前驱体，可以显著减缓此类溶液中氯氧化铋的形成。如本文所报道，这一进展使得能够通过X射线全散射和液体池透射电子显微镜对氯氧化铋的形成进行研究。对X射线全散射数据的对分布函数分析揭示了整个合成过程中原子结构的局部有序性，而液体池透射电子显微镜则能够追踪单个纳米颗粒的生长。通过这项工作，结果表明前驱体络合物在溶液中加热时会生成氯氧化铋，且未观察到结构上不同的中间体。新形成的纳米颗粒具有加宽的层间距，随着颗粒的生长，层间距会适度减小。对卤氧化铋纳米颗粒形成的机理见解，包括在可用时间分辨率内不存在明显的中间体，将有助于推动未来可控BiOX纳米结构的设计。
