Research Progress on Wettability Transition of Solid Surfaces Induced by Spontaneous Adsorption of VOCs

AN Xiaolong; FU Yahang; MENG Keke; WANG Sen; LIU Mingye

doi:10.16490/j.cnki.issn.1001-3660.2026.20.013

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Surface Technology ›› 2026, Vol. 55 ›› Issue (20) : 161-181. DOI: 10.16490/j.cnki.issn.1001-3660.2026.20.013

Functional Surfaces and Technology

Research Progress on Wettability Transition of Solid Surfaces Induced by Spontaneous Adsorption of VOCs

AN Xiaolong, FU Yahang, MENG Keke^*, WANG Sen, LIU Mingye

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Abstract

This comprehensive review clarifies the dynamic physicochemical mechanisms driving the adsorption-induced decrease in surface hydrophilicity and the subsequent transition toward a hydrophobic state caused by volatile organic compounds (VOCs). Unlike previous claims attributing intrinsic hydrophobicity to materials like rare-earth oxides, cross-regional and cross-material analyses demonstrate that this transition is a universal environmental phenomenon. Its fundamental driving force is carbon accumulation, rather than the intrinsic properties of materials or specific geographical climates.
The evolution of surface chemistry has been quantitatively tracked in current research through the extensive use of advanced surface analysis techniques, including X-ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR). The sustained accumulation of non-polar C—C and C—H bonds is widely regarded as the main driver for the decrease in surface energy. For example, following 30 days of exposure to ambient air, XPS analysis demonstrates an increase in the C/Cu atomic ratio of copper coatings from 2.27 to 5.25. Meanwhile, ToF-SIMS has detected specific short- and medium-chain hydrocarbon ions that construct a complex adsorption network between nanoparticles. Ellipsometry measurements have verified the rapid initial formation of these contamination layers, recording the development of an adsorption layer 0.5 to 0.6 nm thick on highly oriented pyrolytic graphite (HOPG) within just 30 minutes. Macroscopically, this manifests as a dramatic change in contact angles. For example, 2D materials such as freshly prepared graphene on copper surge from an initial 44° to approximately 80° within 24 hours, while pristine CeO₂ films transition from a superhydrophilic state of 6° to a stable 96° over 1 000 hours. Morphologically, atomic force microscopy (AFM) reveals that VOC adsorption not only produces a smoothing effect by filling surface nanogaps, but also generates distinct and robust stripe-like 2D domains along the armchair direction of the HOPG lattice, namely the structures that are fundamentally distinct from the fragile, zigzag-aligned stripes formed by competitive water molecules.
Various transition mechanisms are critically evaluated in this work, determining that the synergistic interaction between chemical and physical adsorption serves as the current mainstream mechanistic model. According to a proposed multistage state model, high-energy defect surfaces are first hydroxylated, after which the polar hydroxyl groups are progressively substituted by non-polar hydrocarbon chains. Under ambient conditions, VOCs such as short-chain carboxylic acids undergo acid-base condensation reactions with surface hydroxyls via their carboxyl groups, forming an anchored chemisorbed layer. This adsorbed layer promotes subsequent physisorption through dispersion forces, thereby constructing a robust, low-surface-energy film. Notably, this transition is strongly modulated by competitive adsorption, where atmospheric moisture rapidly occupies active sites via hydrogen bonding, significantly hindering the adsorption of VOCs.
To overcome the inherently sluggish kinetics of the natural aging process which can span from weeks to months, this review systematically presents several acceleration strategies and their underlying physical mechanisms. Thermal treatment (e.g., at 200 ℃ for 6 hours) significantly enhances the Brownian motion of molecules and reduces the adsorption activation energy, elevating the contact angle to over 130°. A high-vacuum environment (10^-4 Pa) accelerates this process by reducing competitive airborne molecules, allowing residual non-polar VOCs to chemisorb rapidly and achieve extreme superhydrophobicity within 120 minutes. Surface texturing, such as the synthesis of silver nanoparticle-decorated silicon nanowires, expands the specific surface area to 22.192 m²/g, introducing a spatial confinement effect to capture and enrich VOCs at the solid-liquid interface. In addition, the review highlights innovative external field interventions: electromagnetic induction heating alters the local electronic environment by weakening metal-oxygen bonds. Meanwhile, ultrasonic irradiation triggers cavitation effects and piezoelectric polarization (reducing the adsorption energy to -9.6 eV in PVDF-HFP). Collectively, these methods enhance the adsorption rate by several orders of magnitude. Furthermore, an applied external electric field can predictably modulate the adsorption energy through the second-order Stark effect.
A profound understanding of the mechanisms underlying adsorption-induced wettability transitions is of great significance for developing long-term stable functional surfaces, designing self-healing superhydrophobic materials, and predicting the performance evolution of materials in real-world environments. Furthermore, it holds broad application prospects in fields such as self-cleaning, anti-corrosion, and drag reduction.

Key words

wettability transition / solid surfaces / VOCs adsorption / hydrophobicity / surface contamination

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AN Xiaolong, FU Yahang, MENG Keke, WANG Sen, LIU Mingye. Research Progress on Wettability Transition of Solid Surfaces Induced by Spontaneous Adsorption of VOCs[J]. Surface Technology. 2026, 55(20): 161-181

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