Facet engineering is a new method of materials design with considerable potential for many technological applications. The present work uses DFT calculations to understand how this strategy can be used to accelerate the silanization of tetraethyl orthosilicate (TEOS) on the surface of ceria (CeO₂), which is a key technology in biomedical and other fields. Cubic CeO₂ nanoparticles with exposed {100} facets are shown to represent the most favorable morphology for silanization owing to (1) the facilitated adsorption of TEOS on these facets compared to the {110} and {111} facets and (2) spontaneous breakage of the Si–O bonds of TEOS, which is found to be the rate-determining step for silanization of CeO₂. The favorable adsorption on the {100} facets arises from its superior structural and electronic properties as well as higher reactivity, which are attributed to its more open arrangement of the surface atoms and consequently reduced steric hindrance, higher density of dangling bonds and surface active sites, and the larger difference in Mulliken charges between the surface and bulk atoms.

中文翻译：

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通过端面工程自发地破坏Si-O键来增强CeO ₂硅烷化

方面工程是一种材料设计的新方法，对于许多技术应用而言，它具有巨大的潜力。本工作使用DFT计算来了解如何使用此策略来加速二氧化铈（CeO ₂）表面原硅酸四乙酯（TEOS）的硅烷化，这是生物医学和其他领域的关键技术。由于{1}与{110}和{111}刻面相比，TEOS易于吸附在这些刻面上，以及（2）自发断裂，显示{100}刻面暴露的立方CeO ₂纳米颗粒代表了硅烷化的最有利形态。 TEOS的Si-O键的形成，这是CeO ₂硅烷化的决定速率的步骤。{100}面上的良好吸附是由于其优异的结构和电子性能以及较高的反应性，这归因于其表面原子更开放的排列并因此减少了位阻，悬挂键的密度更高和表面活性位点，以及表面原子和体原子之间的Mulliken电荷差异更大。