Mazur Ursula, Hipps K W
Chemistry Department and Materials Science and Engineering Program, Washington State University, Pullman, WA 99164-4630, USA.
Chem Commun (Camb). 2015 Mar 21;51(23):4737-49. doi: 10.1039/c4cc09840d.
A focused review is presented on the evolution of our understanding of the kinetic and thermodynamic factors that play a critical role in the formation of well ordered organic adlayers at the solution-solid interface. While the current state of knowledge is in the very early stages, it is now clear that assumptions of kinetic or thermodynamic control are dangerous and require careful confirmation. Equilibrium processes at the solution-solid interface are being described by evolving thermodynamic models that utilize concepts from the thermodynamics of micelles. A surface adsorption version of the Born-Haber cycle is helping to extract the thermodynamic functions of state associated with equilibrium structures, but only a very few systems have been so analyzed. The kinetics of surface phase transformation, especially for polymorphic phases is in an early qualitative stage. Adsorption and desorption kinetics are just starting to be measured. The study of kinetics and thermodynamics for organic self-assembly at the solution-solid interface is experiencing very exciting and rapid growth.
本文重点综述了我们对动力学和热力学因素认识的演变，这些因素在溶液 - 固体界面形成有序有机吸附层的过程中起着关键作用。尽管目前的知识状态尚处于非常早期的阶段，但现在很清楚的是，动力学或热力学控制的假设是危险的，需要仔细确认。溶液 - 固体界面的平衡过程正通过不断发展的热力学模型来描述，这些模型利用了来自胶束热力学的概念。玻恩 - 哈伯循环的表面吸附版本有助于提取与平衡结构相关的热力学状态函数，但目前仅有极少数系统经过了这样的分析。表面相变动力学，特别是多晶型相的动力学，仍处于早期定性阶段。吸附和解吸动力学刚刚开始被测量。溶液 - 固体界面有机自组装的动力学和热力学研究正经历着非常令人兴奋且迅速的发展。
