Creating a surface that is simultaneously amphiphobic in air and oleophobic in water is energy unfavorable. To overcome this counterintuitive scientific problem, we demonstrate a general approach for construction of environment-responsive coatings made of perfluorinated surfactant substituted polyelectrolyte multilayers (PEMs). Sum frequency generation (SFG) vibrational spectroscope indicates that in an air environment, the film coatings orderly protrude their hydrophobic perfluorinated tails into air to decrease surface energy, giving rise to amphiphobicity with water and hexadecane contact angles (CAs) of ∼114° and ∼65° respectively on flat substrates. When the coated substrates are placed in water, the coatings will undergo a reconfiguration, the perfluorinated chains of the coatings instantaneously migrate and embed themselves into the film bulk to optimize their surface energy, leaving hydrophilic portions and positively charged groups exposed at the film-water interface (confirmed by surface zeta potential, XPS and SFG), which leads to an underwater oleophobicity with hexadecane CA of ∼147°. By applying the coatings on roughed substrates, e.g., fabrics, both superamphiphobicity and underwater superoleophobicity were achieved with in-air water and hexadecane CAs of ∼155° and ∼152°, and underwater hexadecane CA of ∼169°, respectively. Moreover, the coatings with these special wettabilities exhibit a good self-healing performance upon both plasma-induced surface decomposition and salt treatment. These coatings may bring in new insights of surface wettability and offer great potential in self-cleaning, anti-oil-fouling both in air and water (especially for aquatic devices working in oil spill situations).

产生在空气中同时具有两亲性和在水中具有疏油性的表面是不利于能量的。为了克服这个与直觉相反的科学问题，我们展示了一种构造由全氟化表面活性剂取代的聚电解质多层（PEM）制成的环境响应性涂层的通用方法。总和频率产生（SFG）振动光谱仪表明，在空气环境中，薄膜涂层将其疏水性全氟化尾巴有序地突出到空气中以降低表面能，与水和十六烷的接触角（CAs）的两亲性约为114°和〜在平坦的基板上分别为65°。当将涂层的基材放在水中时，涂层将进行重新配置，涂层的全氟链瞬间迁移并嵌入到膜主体中以优化其表面能，从而使亲水部分和带正电荷的基团暴露在膜-水界面（由表面ζ电势，XPS和SFG确认），从而导致十六烷CA约为147°的水下疏油性。通过在粗糙的基材（例如织物）上施加涂料，分别在空气中的水和十六烷CA分别为155°和152°，以及水下十六烷CA分别为169°和19时都可以实现超疏油性和水下超疏油性。此外，具有这些特殊润湿性的涂料在等离子体诱导的表面分解和盐处理时均表现出良好的自修复性能。