Wang Mengying, Cui Zixiang, Xue Yongqiang
Department of Chemistry, Taiyuan University of Technology, Taiyuan 030024, China.
Langmuir. 2021 Dec 14;37(49):14463-14471. doi: 10.1021/acs.langmuir.1c02431. Epub 2021 Dec 4.
The unique physical and chemical properties and performances of nanomaterials are closely related to the interfacial tension. However, there is no method to accurately measure the interfacial tension of nanomaterials. In addition, the effect of particle size on the interfacial tension of nanoparticles is unclear, and there exist conflicting conclusions about the value and sign of Tolman length. In this paper, a novel method of determining the interfacial tension (solid-liquid and solid-gas interfaces), temperature coefficient of interfacial tension, and Tolman lengths of nanomaterials by adsorption thermodynamics and kinetics was presented. The interfacial tension and its temperature coefficient of the solid-liquid interface of nano cadmium sulfide before adsorption were obtained, and further, the Tolman length was also obtained. The experimental results show that the particle size of nanoparticles has significant effects on the interfacial tension and its temperature coefficient. When the radius is larger than 10 nm, the interfacial tension and its temperature coefficient are almost constant with the decrease of the radius. When the radius is less than 10 nm, the interfacial tension decreases sharply and the temperature coefficient increases sharply with the decrease of the radius, and the temperature coefficient of the interfacial tension is negative. The Tolman length of the solid-liquid interface of nanoparticles is proved to be positive, and the particle size also has a significant effect on the Tolman length. The Tolman length decreases with the decrease of particle size. However, the effects of particle size on the Tolman length become significant only when the particle radius approach or reach the order of magnitudes of molecular (or atomic) radius. The effects of particle size on interfacial tension and Tolman length of nano cadmium sulfide obtained in this paper can provide significant references for the research and applications of interface thermodynamics of other nanomaterials.
纳米材料独特的物理化学性质和性能与界面张力密切相关。然而,目前尚无准确测量纳米材料界面张力的方法。此外,粒径对纳米颗粒界面张力的影响尚不清楚,关于托尔曼长度的值和符号存在相互矛盾的结论。本文提出了一种通过吸附热力学和动力学测定纳米材料界面张力(固 - 液和固 - 气界面)、界面张力温度系数以及托尔曼长度的新方法。得到了吸附前硫化镉纳米颗粒固 - 液界面的界面张力及其温度系数,进而还得到了托尔曼长度。实验结果表明,纳米颗粒的粒径对界面张力及其温度系数有显著影响。当半径大于10 nm时,界面张力及其温度系数随半径减小几乎保持恒定。当半径小于10 nm时,界面张力随半径减小急剧下降,温度系数急剧增大,且界面张力温度系数为负。证明了纳米颗粒固 - 液界面的托尔曼长度为正,粒径对托尔曼长度也有显著影响。托尔曼长度随粒径减小而减小。然而,只有当颗粒半径接近或达到分子(或原子)半径量级时,粒径对托尔曼长度的影响才变得显著。本文得到的粒径对硫化镉纳米颗粒界面张力和托尔曼长度的影响可为其他纳米材料界面热力学的研究和应用提供重要参考。