Su Lin-Lin, Li Rong-Jian, Huang Na, Zhu Ting-Ting, Deng Shi-Huai, Wang Xian-Xiang, Yang Gang, Zhang Yan-Zong, Long Lu-Lu
Institute of Ecological and Environmental Sciences, Sichuan Agricultural University, Sichuan 611130, China.
CAS Key Laboratory of Urban Pollutant Conversion, Department of Applied Chemistry, University of Science and Technology of China, Hefei 230026, China.
J Colloid Interface Sci. 2022 Dec 15;628(Pt A):955-965. doi: 10.1016/j.jcis.2022.08.022. Epub 2022 Aug 8.
Most metal sites and some non-metallic sites such as carbon and nitrogen are usually considered to be traditional active sites during peroxymonosulfate (PMS) activation. However, as an important non-metallic element, the actual role of silicon (Si) in PMS activation still remains unclear. In this work, taking iron silicate (FeSi) as an example, the role of the Si region in PMS activation was clearly revealed. The experiments and density functional theory (DFT) calculation results showed that besides the traditional Fe sites, the Si also played a non-negligible role during PMS activation. In FeSi containing oxygen vacancies (Ovac), Fe-Si was the active site instead of Fe-Fe. The Bard charge results implied that the presence of Ovac tuned the electronic properties of FeSi, making the Si participate in PMS activation. This work deepened understanding of the role of Si in silicates for PMS activation and provided a theoretical basis for the development of excellent Si-based catalysts.
在过一硫酸盐（PMS）活化过程中，大多数金属位点以及一些非金属位点（如碳和氮）通常被认为是传统的活性位点。然而，作为一种重要的非金属元素，硅（Si）在PMS活化中的实际作用仍不清楚。在这项工作中，以硅酸铁（FeSi）为例，明确揭示了Si区域在PMS活化中的作用。实验和密度泛函理论（DFT）计算结果表明，除了传统的Fe位点外，Si在PMS活化过程中也发挥了不可忽视的作用。在含有氧空位（Ovac）的FeSi中，Fe-Si是活性位点而非Fe-Fe。Bard电荷结果表明，Ovac的存在调节了FeSi的电子性质，使得Si参与PMS活化。这项工作加深了对Si在用于PMS活化的硅酸盐中作用的理解，并为开发优异的硅基催化剂提供了理论依据。
