Hong Junsung, Heo Su Jeong, Singh Prabhakar
Department of Materials Science and Engineering, University of Connecticut, Storrs, CT, 06269, USA.
Department of Materials Science and Engineering, Northwestern University, Evanston, IL, 60208, USA.
Sci Rep. 2021 Feb 9;11(1):3368. doi: 10.1038/s41598-021-82651-0.
Morphology-controlled strontianite nanostructures have attracted interest in various fields, such as electrocatalyst and photocatalysts. Basic additives in aqueous strontium solutions is commonly used in controlling strontianite nanostructures. Here, we show that trace water also serves an important role in forming and structuring vertically oriented strontianite nanorod arrays on strontium compounds. Using in situ Raman spectroscopy, we monitored the structural evolution from hydrated strontium to strontianite nanorods, demonstrating the epitaxial growth by vapor-liquid-solid mechanism. Water molecules cause not only the exsolution of Sr liquid droplets on the surface but also the uptake of airborne CO followed by its ionization to CO. The existence of intermediate SrHO-OCO phase indicates the interaction of CO with SrOH in Sr(OH)(HO) cluster to orient strontianite crystals. X-ray diffraction simulation and transmission electron microscopy identify the preferred-orientation plane of the 1D nanostructures as the (002) plane, i.e., the growth along the c-axis. The anisotropic growth habit is found to be affected by the kinetics of carbonation. This study paves the way for designing and developing 1D architecture of alkaline earth metal carbonates by a simple method without external additives at room temperature.
形貌可控的菱锶矿纳米结构在电催化剂和光催化剂等多个领域引起了人们的兴趣。锶水溶液中的碱性添加剂常用于控制菱锶矿纳米结构。在此,我们表明痕量水在锶化合物上形成垂直取向的菱锶矿纳米棒阵列及其结构形成过程中也起着重要作用。通过原位拉曼光谱,我们监测了从水合锶到菱锶矿纳米棒的结构演变,证明了气-液-固机制的外延生长。水分子不仅导致表面上Sr液滴的析出,还导致空气中CO的吸收,随后其离子化为CO。中间SrHO-OCO相的存在表明CO与Sr(OH)(HO)簇中的SrOH相互作用以使菱锶矿晶体取向。X射线衍射模拟和透射电子显微镜确定一维纳米结构的择优取向平面为(002)平面,即沿c轴生长。发现各向异性生长习性受碳酸化动力学的影响。本研究为在室温下通过无外部添加剂的简单方法设计和开发碱土金属碳酸盐的一维结构铺平了道路。