Thermally Driven Transformation of Water Clustering Structures at Self-Assembled Monolayers

Water clustering structures are considered to play key roles in various temperature-dependent life activities. However, our fundamental understanding of the temperature-dependent water structures remains murky because of the limits of the real-time and real-condition monitoring techniques at the molecular level. We propose an in situ ATR-IR approach combining Gaussian fitting to qualitatively and quantitatively explore the temperature-dependent structural stability and transformation of the three water components, multimer water (MW), intermediate water (IW), and network water (NW), on interfaces with different wettabilities. Our results show that the transformation between NW and IW/MW will occur with a change in temperature. This conversion process shows reversibility on hydrophilic Au NPs film/ZnSe, while it is irreversible on a hydrophobic mercaptohexane self-assembled monolayer due to the irreversibility of the monolayer structure and the hydrophobic confinement effect. The established approach enables us to explore the change in the water properties at any interfaces upon external stimuli.