辉钼矿(001)和(100)表面结构与水分子吸附的密度泛函理论研究

陆益新, 李泽宇, 陈石佥顺, 罗芳莹, 赵晓川, 李玉琼. 辉钼矿(001)和(100)表面结构与水分子吸附的密度泛函理论研究[J]. 矿产保护与利用, 2025, 45(3): 68-75. doi: 10.13779/j.cnki.issn1001-0076.2025.03.007
引用本文: 陆益新, 李泽宇, 陈石佥顺, 罗芳莹, 赵晓川, 李玉琼. 辉钼矿(001)和(100)表面结构与水分子吸附的密度泛函理论研究[J]. 矿产保护与利用, 2025, 45(3): 68-75. doi: 10.13779/j.cnki.issn1001-0076.2025.03.007
LU Yixin, LI Zeyu, CHEN SHI qianshun, LUO Fangying, ZHAO Xiaochuan, LI Yuqiong. DFT−D Study on Surface Structure and Water Adsorption of Molybdenite (001) and (100)[J]. Conservation and Utilization of Mineral Resources, 2025, 45(3): 68-75. doi: 10.13779/j.cnki.issn1001-0076.2025.03.007
Citation: LU Yixin, LI Zeyu, CHEN SHI qianshun, LUO Fangying, ZHAO Xiaochuan, LI Yuqiong. DFT−D Study on Surface Structure and Water Adsorption of Molybdenite (001) and (100)[J]. Conservation and Utilization of Mineral Resources, 2025, 45(3): 68-75. doi: 10.13779/j.cnki.issn1001-0076.2025.03.007

辉钼矿(001)和(100)表面结构与水分子吸附的密度泛函理论研究

  • 基金项目: 国家自然科学基金项目(52364023);广西壮族自治区大学生创新训练计划自治区级基金项目(S202310593267)
详细信息
    作者简介: 陆益新(2002—),男(壮族),广西百色人,学士,主要从事矿物浮选研究工作,E-mail:2323361062@qq.com
    通讯作者: 李玉琼(1982—),女,广西桂林人,博士,教授,博士生导师,主要从事矿物浮选研究工作,E-mail:yql@gxu.edu.cn
  • 中图分类号: TD954;TD91

DFT−D Study on Surface Structure and Water Adsorption of Molybdenite (001) and (100)

More Information
  • 浮选法通过添加药剂改变矿物表面的亲疏水性来实现不同矿物间的分离,同时在浮选体系中水分子也会吸附在矿物表面上,从而对表面亲疏性产生影响。因此,研究辉钼矿表面的性质以及辉钼矿表面与水分子的相互作用对于揭示辉钼矿微观浮选机理和选择合适的浮选药剂有指导性意义。通过基于色散力校正的密度泛函理论(DFT−D)平面波赝势方法研究了辉钼矿(001)面和(100)面的结构和性质,对比了辉钼矿不同表面的表面能、表面弛豫以及态密度计算结果,并考察了不同表面的水分子吸附结构,计算了水分子在不同表面不同吸附位点的吸附能。结果表明,(001)面的表面能极低,约为0.012 J/m2,而(100)面的表面能是(001)面的10倍左右,说明(100)面具有更大的活性;也说明辉钼矿(001)面比(100)面更加稳定,辉钼矿会更倾向于平行(001)面解离。(100)面上的Mo和S原子在费米能级处具有较高的电子态密度,表面原子活性强于(001)面;(100)面第一层的Mo和第二层的S发生了一定程度的弛豫,而辉钼矿(001)面没有发生表面弛豫。水分子在(001)面上的吸附非常弱,主要由水分子中的H与矿物表面S发生弱作用,而在(100)面上的Mo位吸附能达到−94.16 kJ/mol。这说明(001)面疏水性非常好,而(100)面具有一定的亲水性,也说明非极性捕收剂更易作用于辉钼矿(001)面,而极性捕收剂更易作用于(100)面。

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  • 图 1  辉钼矿单胞模型

    Figure 1. 

    图 2  截断能与晶胞体系能量的关系

    Figure 2. 

    图 3  辉钼矿(001)面(a)和(100)面(b)模型

    Figure 3. 

    图 4  辉钼矿体相和表面的分态密度(费米能级设置在能量0点处)

    Figure 4. 

    图 5  水分子在(001)表面的吸附构型(两个位置或化学键之间的距离单位为Å)

    Figure 5. 

    图 6  水分子在(100)表面上的吸附构型(两个位置或化学键之间的距离单位为Å)

    Figure 6. 

    表 1  不同交换关联泛函测试结果

    Table 1.  Test results of different exchange correlation functionals

    交换关联泛函晶格常数/Å禁带宽度
    /eV
    相对实验值误差/%
    abcabc禁带宽度
    GGA−PW913.1853.18515.2971.460.380.3820.7619.86
    GGA−PW91−OBS3.172 1721723.17212.6691.030.030.030.0111.97
    GGA−PBE−Grimme3.1853.18512.4270.990.380.383.3115.38
    GGA−PBESOL3.1413.14112.6501.011.001.000.1313.68
    GGA−PBE−TS3.1543.15412.0490.770.600.604.8234.19
    实验值3.1733.17312.6671.170000
    下载: 导出CSV

    表 2  辉钼矿(100)和(001)面的表面能

    Table 2.  Energy of molybdenite(100) and (001) surfaces /(J·m−2)

    原子层数 (100)面 (001)面
    4 0.1179 0.0112
    6 0.1186 0.0122
    8 0.1200 0.0124
    10 0.1212 0.0125
    下载: 导出CSV

    表 3  辉钼矿(001)表面原子的位移

    Table 3.  Displacement of atoms on the surface of molybdenite( 001 )

    原子层 原子类型 原子位移/Å
    Δx Δy Δz
    1 Mo1 0 0 −0.114
    1 S1 0 0.032 0.025
    1 S2 0 −0.028 0.025
    2 Mo2 0 0 0.024
    2 S3 0 −0.040 0.172
    2 S4 0 0.039 0.172
    3 Mo3 0 0 0.053
    3 S5 0 −0.024 0.005
    3 S6 0 −0.024 0.005
    4 Mo4 0 0 −0.050
    4 S7 0 −0.025 0.008
    4 S8 0 −0.026 0.008
    下载: 导出CSV
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收稿日期:  2025-02-06
刊出日期:  2025-06-15

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