为探索水合阳离子对煤泥矿物颗粒表面水化的微观影响机理，以煤泥中主要矿物高岭石和石英为研究对象，依据煤泥水溶液环境构建了[Na(H₂O)₅]⁺及[Ca(H₂O)₈]²⁺两种煤泥水中常见的水合阳离子构型，并采用密度泛函理论对这2种水合阳离子在高岭石(001)面、($ 00overline 1 $)面和α−石英(001)面的单一吸附及与水分子间的竞争吸附进行了模拟计算。模拟结果表明，单一水合阳离子在3种表面的吸附能均比水分子的吸附能低出50%以上，其在矿物表面的吸附稳定性顺序为：α−石英(001)面 > 高岭石(001)面 > 高岭石($ 00overline 1 $)面；在竞争吸附作用下，竞争稳定构型的吸附能比单一水合阳离子在高岭石、石英表面上的吸附能低出34%～57%，其中2种吸附条件下[Ca(H₂O)₈]²⁺构型均比[Na(H₂O)₅]⁺构型更稳定。水合阳离子在3种表面上单一吸附时，与表面形成强氢键作用，比水分子与高岭石、石英表面间的氢键作用更强，2种水合阳离子在矿物表面的氢键强弱顺序均为：高岭石(001)面 > α−石英(001)面 > 高岭石($ 00overline 1 $)面；在竞争吸附作用下，[Na(H₂O)₅]⁺与矿物表面间的氢键作用增强，[Ca(H₂O)₈]²⁺与矿物表面间的氢键作用减小；由于氢键作用不能完全对应吸附能的变化，经分析可知，吸附构型中存在静电作用，水合阳离子单一吸附构型中的静电作用比水分子吸附时更强，而在竞争吸附作用下，水合阳离子与矿物表面间静电作用增强，同时[Ca(H₂O)₈]²⁺比[Na(H₂O)₅]⁺与对应矿物表面间的静电作用更强。由于水合阳离子在高岭石、石英表面的强吸附作用，导致煤泥颗粒脱水更加困难，同时可能增加颗粒间的水化斥力，从而导致颗粒在煤泥水中分散更稳定。

To elucidate the microscopic mechanisms underlying the impact of hydrated cations on the surface hydration of slime mineral particles (specifically, kaolinite and quartz, the primary minerals in slime), this study focused on constructing two common hydrated cations in slime water: [Na(H₂O)₅]⁺ and [Ca(H₂O)₈]²⁺. Using density functional theory, the adsorption of these two hydrated cations on the surfaces of kaolinite (001), ($ 00overline 1 $) and α-quartz (001), as well as their competitive adsorption with water molecules were simulated. The simulation results revealed that the adsorption energy of hydrated cations on all three surfaces was over 50% lower than that of water molecules. The adsorption stability on mineral surfaces was as follows: α-quartz (001) surface > kaolinite (001) surface > kaolinite ($ 00overline 1 $) surface. The adsorption energy of the competitively stable configuration was 34%–57% lower than that of a single hydrated cation on kaolinite and quartz. Additionally, the [Ca(H₂O)₈]²⁺ configuration exhibited a greater stability than the [Na(H₂O)₅]⁺ configuration under both adsorption conditions. When the hydrated cations adsorbed onto three surfaces, strong hydrogen bonds formed with surface, surpassing the strength of hydrogen bonds between water molecules and kaolinite/quartz surfaces. The hierarchy of hydrogen bonds between two hydrated cations on mineral surfaces was as follows: kaolinite (001) surface > α-quartz (001) surface > kaolinite ($ 00overline 1 $) surface. Under a competitive adsorption, the hydrogen bond between [Na(H₂O)₅]⁺ and mineral surface strengthened, while the bond between [Ca(H₂O)₈]²⁺ and mineral surface weakened. Although hydrogen bonding did not entirely correlate with changes in adsorption energy, electrostatic interactions in the adsorption configuration were identified. The electrostatic interaction in the single adsorption configuration of hydrated cations proved stronger than that in water molecular adsorption. Under a competitive adsorption, the electrostatic interactions between hydrated cations and mineral surfaces intensified, with [Ca(H₂O)₈]²⁺ demonstrating stronger interaction than [Na(H₂O)₅]⁺. Given the robust adsorption of hydrated cations on the surfaces of kaolinite and quartz, the dehydration of slime particles becomes more challenging. This could increase hydration repulsion between particles, resulting in a more stable dispersion of particles in slime water.