Modulation of Hydrophobic Interaction by Mediating Surface Nanoscale Structure and Chemistry, not Monotonically by Hydrophobicity.

The hydrophobic (HB) interaction plays a critical role in many colloidal and interfacial phenomena, biophysical and industrial processes. Surface hydrophobicity, characterized by the water contact angle, is generally considered the most dominant parameter determining the HB interaction. Herein, we quantified the HB interactions between air bubbles and a series of hydrophobic surfaces with different nanoscale structures and surface chemistry in aqueous media using a bubble probe atomic force microscopy (AFM). Surprisingly, it is discovered that surfaces of similar hydrophobicity can show different ranges of HB interactions, while surfaces of different hydrophobicity can have similar ranges of HB interaction. The increased heterogeneity of the surface nanoscale structure and chemistry can effectively decrease the decay length of HB interaction from 1.60 nm to 0.35 nm. Our work provides insights into the physical mechanism of HB interaction.