γ-Fe2O3抗As2O3中毒能力的分子模拟

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摘要采用密度泛函理论研究了γ-Fe₂O₃表面As₂O₃的吸附以及掺杂改性提高抗As₂O₃中毒性能的作用机理.计算了As₂O₃在完整以及O缺陷γ-Fe₂O₃（001）表面的吸附性能，包括吸附位点、吸附结构、吸附能、PDOS等.同时建立了Mo、Ti、Mg掺杂的γ-Fe₂O₃模型，探讨了助剂掺杂对抗砷中毒能力的作用机制，并考虑了掺杂量的影响.结果表明：As₂O₃倾向于以O端化学吸附在γ-Fe₂O₃（001）表面Fe_oct位，吸附过程发生强烈的相互作用和电荷转移.当表面存在O缺陷时，As₂O₃的吸附能得到提高.Mo、Ti、Mg倾向于掺杂在Fe_oct位，增强了对As₂O₃的吸附能力，并且增大Mo的掺杂量可以强化As₂O₃的吸附.As₂O₃倾向于与活性较强的Mo、Ti、Mg发生反应，从而保护活性Fe位不受砷中毒，Ti和Mg的掺杂还抑制了相邻Fe位对As₂O₃的吸附.Mo、Ti、Mg的掺杂还促进了催化剂表面对NH₃的吸附，增强了表面酸性强度，有利于SCR反应.Mo、Ti、Mg原子的掺杂有利于提高γ-Fe₂O₃催化剂的抗砷中毒性能.

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关键词 ： As₂O₃, 吸附, γ-Fe₂O₃, O缺陷, Mo、Ti、Mg掺杂, 密度泛函理论

Abstract：The γ-Fe₂O₃ catalyst, due to its advantages in low cost and high catalytic performance, is thought to be a promising medium-low temperature SCR catalyst, but the As₂O₃ in the flue gas likely becomes seriously deactivated. In this study, the density functional theory was used to characterize the adsorption of As₂O₃ on the γ-Fe₂O₃ surface as well as the mechanism of doping modification to improve the anti-As₂O₃ poisoning performance. The adsorption properties of As₂O₃ on the intact and O-deficient γ-Fe₂O₃(001) surfaces were examined, including adsorption site, adsorption structure, adsorption energy, PDOS, etc. At the same time, the catalyst model of γ-Fe₂O₃ doped with Mo, Ti, and Mg was established to understand the mechanism of doping additives on improving the resistance to arsenic poisoning. The results show that the As₂O₃ tends to be chemically adsorbed on Fe_oct sites on the γ-Fe₂O₃(001) surface with the O-terminus, and strong interaction and electron transfer occur during the adsorption process. When there are O defects on the surface, the adsorption energy of As₂O₃ molecules increases. Mo, Ti, and Mg tend to be doped in Fe_oct sites, which thus enhances the adsorption capacity of As₂O₃. Increasing the doping amount of Mo can promote the adsorption of As₂O₃. As₂O₃ tends to react with the more active Mo, Ti, and Mg, thereby protecting the active Fe sites from arsenic poisoning. The doping of Ti and Mg also inhibits the adsorption of As₂O₃ on adjacent Fe sites. The doping of Mo, Ti, and Mg also promotes the adsorption of NH₃ on the catalyst surface and elevates the acidity of the surface, which is beneficial to the SCR reaction and to improving the anti-arsenic poisoning performance of the γ-Fe₂O₃ catalyst.

Key words： As₂O₃ adsorption γ-Fe₂O₃ O defect Mo, Ti, and Mg doping density functional theory (DFT)

收稿日期: 2022-01-19

PACS:

X511

基金资助:山东省重大科技创新工程项目（2019JZZY020305）

通讯作者: 牛胜利,教授,nsl@sdu.edu.cn E-mail: nsl@sdu.edu.cn

作者简介: 周文波(1997-),男,山东青岛人,山东大学硕士研究生,主要从事燃烧与污染物控制等领域研究.发表论文2篇.

引用本文:

周文波, 牛胜利, 刘思彤, 王栋, 韩奎华, 王永征. γ-Fe₂O₃抗As₂O₃中毒能力的分子模拟[J]. 中国环境科学, 2022, 42(8): 3600-3609. ZHOU Wen-bo, NIU Sheng-li, LIU Si-tong, WANG Dong, HAN Kui-hua, WANG Yong-zheng. Molecular simulation study on the anti-As₂O₃ poisoning ability of γ-Fe₂O₃. CHINA ENVIRONMENTAL SCIENCECE, 2022, 42(8): 3600-3609.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2022/V42/I8/3600

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