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摘要:
辉钼矿的晶面各向异性导致其"表面"和"棱面"具有截然不同的性质，进而影响到辉钼矿的浮选效果。通过密度泛函理论，从原子级别直观地阐释了辉钼矿"表面"和"棱面"性质差异的原因，并分别讨论了水、煤油和黄药在辉钼矿表面的作用。结果表明辉钼矿的"表面"为强疏水面，"棱面"为强亲水面。此外，煤油主要是通过静电作用吸附在辉钼矿的含S原子面，而黄药则是通过其C-S单键中S原子与辉钼矿"棱面"Mo原子的成键作用吸附于辉钼矿的"棱面"。
Abstract:The crystal anisotropy of molybdenite makes its "surface" and "edge" have very different properties, which further affects the flotation behavior of molybdenite. Through density functional theory, the reasons for the differences in the properties of molybdenite "surface" and "edge" are demonstrated from the atomic level, and the effects of water, kerosene, and xanthate on the surface of molybdenite are discussed. The results show that the "surface" of the molybdenite is strongly hydrophobic and the "edge" is strongly hydrophilic. In addition, kerosene is mainly adsorbed on the S-containing atomic face of molybdenite by electrostatic interactions, whereas xanthate is adsorbed on molybdenum "edge" by the bonding interaction of the S atom in its C-S single bond with Mo atom at the molybdenite "edge".
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Key words:
- molybdenite /
- density functional theory /
- surfaces properties /
- adsorption
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图 4 (a) 直链烷烃和(b)直链芳香烃吸附在辉钼矿(0001)面的电荷密度图；(c)直链烷烃和(d)直链芳香烃吸附在辉钼矿(1010)面的电荷密度图
Figure 4.
图 5 (a) 甲基黄原酸钠和(b)丁基黄原酸钠吸附在辉钼矿(0001)面的电荷密度图；(c)甲基黄原酸钠和(d)丁基黄原酸钠吸附在辉钼矿(1010)面的电荷密度图
Figure 5.
表 2 辉钼矿(0001)面和(1010)面弛豫前后的参数 /Å
Table 2. Parameters of molybdenite (0001) and (1010) surfaces before and after relaxation
参数 0001 (1010) 弛豫前 弛豫后 弛豫前 弛豫后S面 弛豫后Mo面 Mo-S 2.411 2.411 2.411 2.370 2.548 2.291 S-S(1010) 3.119 3.119 3.119 1.975 - S-S((0110)) 3.185 3.185 3.185 3.184 - Mo-Mo(表面) 3.185 3.185 3.185 - 2.264 Mo-Mo(层间) 3.185 3.185 3.185 - 3.068 表面能/(J·m-2) - 0.004 - 3.577 3.577 
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表 3 体相与弛豫后辉钼矿(0001)面和(1010)面的Mulliken电荷布居值
Table 3. Mulliken charge populations of molybdenite bulk and relaxed molybdenite (0001) and (1010) surfaces
表面 原子 电荷布居/e 电荷/e s p d 体相 S 1.86 4.16 0.00 -0.02 Mo 2.48 6.45 5.03 0.04 (0001)面 S 1.86 4.16 0.00 -0.02 Mo 2.48 6.45 5.03 0.04 (1010)面 S1 1.91 4.20 0.00 -0.11 S2 1.90 4.10 0.00 0.00 Mo4 2.44 6.32 5.08 0.16 Mo1/2 2.59 6.16 5.16 0.09 Mo3 2.46 6.42 5.01 0.11 S3/4/5/6 1.86 4.20 0.00 -0.06
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表 4 水和浮选药剂在辉钼矿(0001)面和(1010)面的吸附能 /(kcal·mol-1)
Table 4. Adsorption energies of water and flotation reagents on molybdenite (0001) and (1010)
种类 (0001)面 (1010)面 水 106.96 -165.58 直链烷烃(C12H26) -24.05 -44.06 直链芳香烃(C12H18) -76.51 -104.80 甲基黄原酸钠 87.62 -227.02 丁基黄原酸钠 49.42 -299.69
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