The sulfur fixation mechanisms of COS and SO2 on perfect and defect surfaces of CaO (001) investigated by DFT combined with XPS

IF 6.3 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science Pub Date : 2025-01-15 DOI:10.1016/j.apsusc.2025.162427

Yong Li, Huiqing Guo, An Yan, Tong Shi, Yanqiu Lei, Fenrong Liu

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Abstract

In this study, Erdos (ED) coal with high inorganic sulfur content was selected to investigate the sulfur fixation mechanisms of COS and SO₂ on CaO (001) perfect and defective surfaces by Density functional theory (DFT) combined with X-ray photoelectron spectroscopy (XPS). Pyrolysis and gas chromatography (Py-GC) was used to analyze the release behaviors of COS and SO₂ during coal pyrolysis. XPS proves that CaS and CaSO₄ peaks significantly increase after the co-pyrolysis of ED coal and CaO. The electronic structure analysis reveals that the O vacancy belongs to a strong electron-donator, indicating O vacancy would facilitate the stable adsorption of COS and SO₂ on this surface. The most possible sulfur fixation Path of COS would occur on the O vacancy surface accompanied by the formation of CaS and CO. However, SO₂ would be more inclined to be fixed in the form of sulfates similar to calcium sulfate on perfect and defective surfaces. These DFT calculation results are consistent with the experimental results. Thus, this study could provide theoretical support for the sulfur fixation mechanisms on the different surfaces of CaO (001) and for the improvement of the CaO sulfur-fixing agents.

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用DFT结合XPS研究了COS和SO2在CaO（001）完美表面和缺陷表面的固硫机理

采用密度泛函理论（DFT）结合x射线光电子能谱（XPS）技术，研究了COS和SO2在CaO（001）完美和缺陷表面的固硫机理。采用热解气相色谱法（Py-GC）分析了煤热解过程中COS和SO2的释放行为。XPS证明，ED煤与CaO共热解后，CaS和CaSO4峰明显增加。电子结构分析表明，O空位属于强电子给体，表明O空位有利于COS和SO2在该表面的稳定吸附。COS最可能的固硫路径发生在O空位表面，并伴有CaS和CO的形成，而SO2更倾向于以类似硫酸钙的硫酸盐形式固定在完美和缺陷表面。计算结果与实验结果吻合较好。因此，本研究可为CaO（001）在不同表面的固硫机理及CaO固硫剂的改进提供理论支持。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Applied Surface Science 工程技术-材料科学：膜

CiteScore

12.50

自引率

7.50%

发文量

3393

审稿时长

67 days

期刊介绍： Applied Surface Science covers topics contributing to a better understanding of surfaces, interfaces, nanostructures and their applications. The journal is concerned with scientific research on the atomic and molecular level of material properties determined with specific surface analytical techniques and/or computational methods, as well as the processing of such structures.