高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

氢氟酸体系锰杂质络合机制：基于DFT的配位结构与反应路径解析

田阳1,郭其景1,杨华春2,刘海霞2,薛峰峰2,易浩1,宋少先1   

  1. 1. 武汉理工大学资源与环境工程学院 2. 多氟多新材料股份有限公司
  • 收稿日期:2025-07-07 修回日期:2025-10-17 网络首发:2025-10-20 发布日期:2025-10-20
  • 通讯作者: 易浩 E-mail:yihao287@whut.edu.cn
  • 基金资助:
    国家重点研发计划项目（批准号：2022YFC2904805）资助

Complexation mechanism of manganese impurities in hydrofluoric acid system: DFT-based ligand structure and reaction pathway analysis

TIAN Yang1, GUO Qijing1, YANG Huachun2, LIU Haixia2, XUE Fengfeng2, YI Hao1, SONG Shaoxian   

  1. 1. School of Resource and Environmental Engineering, Wuhan university of technology 2. Do-Fluoride New Materials Limited Company
  • Received:2025-07-07 Revised:2025-10-17 Online First:2025-10-20 Published:2025-10-20
  • Contact: YI Hao E-mail:yihao287@whut.edu.cn
  • Supported by:
    Supported by the National Key Research and Development Program of China(No. 2022YFC2904805)

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摘要： 针对电子级氢氟酸中痕量杂质反应机理不明晰的问题，本研究以氟锰酸盐类金属络合物为研究对象，通过密度泛函理论（DFT）计算，系统研究了氢氟酸体系中痕量杂质Mn与其他金属杂质离子（以Na+、Ca2+、Al3+为典型的一、二、三价杂质离子）的反应路径，结合静电荷分布、差分电荷密度及结合能计算等手段，揭示了反应产物（AlMnF8、CaMnF6、NaMnF6）的稳定性及其与氢氟酸（HF）分离潜力。研究结果表明：Al3+与Mn反应生成的AlMnF8具有最低的体系总能量（-1.135Ha），结构最稳定；结合能分析进一步证实，AlMnF8与HF的结合能绝对值（0.018 Ha）低于NaMnF6（0.028 Ha）和CaMnF6（0.029 Ha），表明其在HF溶液中更易通过物理分离方式脱除。本研究为电子级氢氟酸中痕量锰络合物的高效去除提供了理论依据。

关键词: 电子级氢氟酸, 密度泛函理论计算, 氟锰酸盐, 痕量杂质去除

Abstract: Aiming to address the unclear reaction mechanisms of trace impurities in electron-grade hydrofluoric acid, this study focuses on fluoromanganate-like metal complexes. It systematically investigates the reaction pathways of trace impurity manganese (Mn) and other metal impurity ions (sodium [Na+], calcium [Ca2+], and aluminum [Al3+], representing typical mono-, di-, and tri-valent impurity ions) within the hydrofluoric acid system. This is achieved through density functional theory (DFT) calculations, combined with analyses of electrostatic charge distributions, differential charge density, and binding energy calculations to reveal the stability of the reaction products (AlMnF8, CaMnF6, NaMnF6) and their potential for separation from hydrofluoric acid (HF). The results show that AlMnF8, generated by the reaction of Al3+ with Mn, has the lowest total system energy (-1.135 Ha) and the most stable structure; the binding energy analysis further confirms that the absolute value of the binding energy of AlMnF8 with HF (0.018 Ha) is lower than that of NaMnF6 (0.028 Ha) and CaMnF6 (0.029 Ha), which suggests that it can be more easily detached from HF solution by physical separation. indicating that it is easier to be removed by physical separation in HF solution. This study provides a theoretical basis for the efficient removal of trace manganese complexes in electronic grade HF.

Key words: Electronic grade hydrofluoric acid, Density functional theory calculations, Fluoromanganate, Trace impurity removal

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