Chemical modulation of solid–liquid interfacial films: New insights intoformation, stability, and performance

The solid–liquid interface plays a crucial role in determining the physicochemical
behavior of both natural and engineered systems, influencing processes such as
lubrication, corrosion resistance, catalysis, energy storage, and biomedical
interactions. Interfacial films are formed through complex molecular interactions
governed by surface chemistry and environmental conditions, thereby controlling
macroscopic performance. Recent advances in chemical modulation strategies have
enabled precise control over the structure and functionality of these films through
approaches such as surface functionalization, molecular adsorption, and
development of stimuli-responsive systems. This review presents a comprehensive
overview of the mechanisms underlying interfacial film formation, including
adsorption, self-assembly, and film growth dynamics, along with the key
thermodynamic and kinetic considerations. Emphasis is placed on both covalent

and non-covalent modification strategies, including pH-, ionic strength-, and redox-
responsive systems, which provide tunable and adaptive interfacial behaviors. The

stability of the interfacial films was critically examined in terms of mechanical
integrity, chemical resistance, and long-term durability under varying
environmental conditions. Advanced characterization techniques and
computational modelling approaches are discussed for their ability to provide
molecular-level insights into the structure–property relationships. Furthermore, the
functional implications of chemically modulated interfacial films have been
explored across a wide range of applications, including tribology, corrosion
protection, electrochemical systems, biomedical devices, and industrial processes.
Finally, emerging trends, current challenges, and future research directions are

highlighted, focusing on the development of adaptive, durable, and high-
performance interfacial systems.