Gouveia Amanda F, Lemos Samantha C S, Leite Edson R, Longo Elson, Andrés Juan
Department of Analytical and Physical Chemistry, Jaume I University (UJI), 12071 Castelló, Spain.
Brazilian Nanotechnology National Laboratory (LNNano), CNPEM, Campinas 13083-970, SP, Brazil.
Nanomaterials (Basel). 2023 Mar 8;13(6):978. doi: 10.3390/nano13060978.
Although the physics and chemistry of materials are driven by exposed surfaces in the morphology, they are fleeting, making them inherently challenging to study experimentally. The rational design of their morphology and delivery in a synthesis process remains complex because of the numerous kinetic parameters that involve the effective shocks of atoms or clusters, which end up leading to the formation of different morphologies. Herein, we combined functional density theory calculations of the surface energies of ZnO and the Wulff construction to develop a simple computational model capable of predicting its available morphologies in an attempt to guide the search for images obtained by field-emission scanning electron microscopy (FE-SEM). The figures in this morphology map agree with the experimental FE-SEM images. The mechanism of this computational model is as follows: when the model is used, a reaction pathway is designed to find a given morphology and the ideal step height in the whole morphology map in the practical experiment. This concept article provides a practical tool to understand, at the atomic level, the routes for the morphological evolution observed in experiments as well as their correlation with changes in the properties of materials based solely on theoretical calculations. The findings presented herein not only explain the occurrence of changes during the synthesis (with targeted reaction characteristics that underpin an essential structure-function relationship) but also offer deep insights into how to enhance the efficiency of other metal-oxide-based materials via matching.
尽管材料的物理和化学性质由其形态中的暴露表面所驱动，但这些表面转瞬即逝，这使得对其进行实验研究具有内在的挑战性。由于涉及原子或团簇有效碰撞的众多动力学参数，在合成过程中对其形态和传递进行合理设计仍然很复杂，而这些参数最终会导致形成不同的形态。在此，我们结合了ZnO表面能的功能密度理论计算和伍尔夫构造，开发了一个简单的计算模型，能够预测其可能的形态，以尝试指导寻找通过场发射扫描电子显微镜（FE-SEM）获得的图像。该形态图中的图形与实验FE-SEM图像相符。这个计算模型的机制如下：使用该模型时，设计一条反应路径，以在实际实验的整个形态图中找到给定的形态和理想的台阶高度。这篇概念文章提供了一个实用工具，仅基于理论计算就能在原子层面理解实验中观察到的形态演变途径及其与材料性能变化的相关性。本文所呈现的研究结果不仅解释了合成过程中变化的发生（具有支撑基本结构-功能关系的目标反应特性），还深入洞察了如何通过匹配提高其他金属氧化物基材料的效率。
