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固体表面微纳米液滴中的结晶行为在工业与农业领域应用广泛，如绿色打印、农药喷洒等.这些应用涉及的固体基底通常是有机材料，极性较弱或是非极性.因此，研究非极性固体上微纳米液滴内的结晶行为对于上述应用至关重要.然而，目前关于非极性固体表面微纳米液滴内离子结晶行为及其机理的研究相对匮乏，尤其是原子尺度的机制尚不清楚.本文采用分子动力学模拟方法研究了非极性固体表面氯化钠纳米液滴内离子的结晶行为及机理.研究发现，当浓度高于3.76mol/kg时，非极性固体表面的氯化钠纳米液滴内发生结晶.结晶与固体的空间限制效应有关，而与其物理性质无明显关联.在非极性固体与溶液构成的界面处，离子与固体表面之间形成水层，离子被排斥到液滴内部，从而提高了液滴内部的局域离子浓度，促进结晶.在相同条件下，氯化钾纳米液滴内也观察到结晶现象.本文为理解非极性固体表面在固液界面中的作用、调控纳米液滴的结晶行为等提供了新的理论视角.Crystallization of ions in aqueous micro-droplet or nano-droplet on solid surfaces is ubiquitous, with applications ranging from inkjet printing to pesticide spraying. The substrates involved are typically nonpolar. Yet, the atomistic mechanism of crystallization within sessile droplets on such nonpolar substrates remains elusive. Here, we employ molecular dynamics simulations to investigate the crystallization of sodium chloride inside an aqueous nano-droplet resting on a nonpolar face-centered-cubic (111) surface. Crystallization occurs inside the droplet rather than at the liquid–gas or solid–liquid interface, when the concentration of the sodium chloride in the droplet exceeds 3.76 mol/kg. The phenomenon originates from the spatial distributions of water molecules and ions: a dense interfacial water layer forms at the solid–liquid interface, whereas ions accumulate in the droplet interior, increasing the local concentration. The ion–water hydration due to the electrostatic interaction dominates over ion–solid interaction. The spatial confinement provided by the solid, rather than the physical properties of the solid, enriches ions inside the nano-droplet and thereby triggers the crystallization. We further generalize this mechanism to the isolated aqueous sodium chloride nano-droplet, where the gas phase breaks the continuous spatial distribution of ions as that in the droplet. Analogous crystallization is observed for the sessile droplet of potassium chloride solution on nonpolar solid surfaces, indicating the generality of crystallization in nano-droplets. These findings offer atomic-scale guidance for controlling crystallization in nano-droplets relevant to microelectronics, inkjet printing and related technologies.
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Keywords:
- solid-liquid interface /
- crystallization /
- hydration /
- nano-droplet /
- molecular dynamics
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