VOCs自发吸附诱导固体表面润湿性转变的研究进展

安小龙; 付亚航; 孟可可; 王森; 刘鸣晔

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

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

功能表面及技术

VOCs自发吸附诱导固体表面润湿性转变的研究进展

安小龙, 付亚航, 孟可可^*, 王森, 刘鸣晔

作者信息 +

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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文章历史 +

摘要

吸附是一种广泛存在的自然现象,对材料的物理化学性质有着重要影响,其中,润湿性作为表征材料界面特性的关键指标,极易受到表面吸附行为的影响而发生改变。本文系统综述了挥发性有机物（VOCs）自发吸附导致固体表面亲水性下降以及向疏水性转变的研究进展。本文阐述了各种材料从亲水向疏水转变的动态演变过程,并且接触角随时间持续增大这一现象具有显著的材料与地域普遍性。同时,本文总结了引发这种润湿性转变的多重物理化学机理。研究证实,表面碳含量的逐步累积是核心因素。非极性碳氢键的主导地位、污染层的厚度演变以及表面微观形貌的重构,共同促成了该现象。本文探讨了润湿性转变的物理机理。早期研究提出了残余应力、缺陷演化和表面氧含量变化等解释。目前的主流共识是VOCs自发吸附降低了表面能。此外,本文还重点分析了水分子的竞争吸附这一核心微观机制。自然状态下的润湿性转变往往耗时较长,为了有效缩短这一周期,本文还整理了目前主流的加速吸附策略。深入理解吸附诱导润湿性转变的机制,对开发长期稳定的功能表面、设计自愈超疏水材料以及预测材料在实际环境中的性能演变具有重要意义,在自清洁、防腐蚀、减阻等领域具有广阔的应用前景。

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.

导出引用

安小龙, 付亚航, 孟可可, 王森, 刘鸣晔. VOCs自发吸附诱导固体表面润湿性转变的研究进展[J]. 表面技术. 2026, 55(20): 161-181

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

中图分类号： TB34

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