RESUMEN

Functional materials with under-liquid dual superlyophobicity have generated a great deal of concern from researchers due to their switchable separation ability oil-water mixtures and emulsions. Conceptually, under-liquid dual superlyophobicity is a Cassie state achievable under-liquid through the synergy of an under-liquid double lyophobic surface and the construction of a highly rough surface. However, obtaining an under-liquid dual superlyophobic surface remains difficult due to its thermodynamic contradiction and complex surface composition. Herein, we successfully prepared a functional coating by modifying the mixture of cellulose nanocrystals (CNCs) and nano-TiO2 with perfluorooctanoic acid (PFOA) via a simple method, then obtained a polyester fiber membrane with under-liquid dual superlyophobicity by roll coating method. The surface wettability of the polyester (PET) membrane was altered, transforming it from the original under-water oleophobic/under-oil superhydrophilic state to the under-water superoleophobic/under-oil superhydrophobic state after coated. The resulting membrane was applied to separate oil and water on-demand. The coated PET membrane exhibited high separation efficiency (>99 %) and high separation flux, effectively separating immiscible oil-water systems as well as oil-in-water and water-in-oil emulsions. The coated PET membrane also demonstrated the ability to perform alternate separation of oil-water mixtures through wetting, washing, and rewetting cycles, with repeated processes up to 10 times without significant reduction in separation efficiency. Furthermore, compared with the previous works, our approach offers a simpler and more convenient method for constructing under-liquid dual superlyophobic surface, making it more suitable for continuous corporate production. This study may provide inspiration for the production and application in large-scale of under-liquid dual superlyophobic membranes.

Asunto(s)

Fabaceae , Nanopartículas , Celulosa , Poliésteres , Termodinámica

RESUMEN

The smart membrane with under-liquid dual superlyophobicity, which can achieve on-demand separation of oil/water emulsions only by simple liquid pre-wetting, is of essential value for the treatment of complicated real oil/water systems. Here, we first fabricated a stable suspension of imine-linked covalent organic framework nanospheres (TPB-DMTP-COF), and subsequently fabricated COF functionalized smart membranes with under-liquid dual superlyophobicity by immersing polyacrylonitrile-based (PAN-based) membranes into TPB-DMTP-COF nanosphere suspension. Accordingly, effective switchable separation of both oil-in-water and water-in-oil emulsions by TPB-DMTP-COF/PAN membranes can be achieved by employing pre-wetting processes (both the oil contact angle under water and the water contact angle under oil are over 150°). Specifically, the separation flux and the separation efficiency are higher than 1200 L/m2‧h and 98.0 %, and 2100 L/m2‧h and 97.4 % for the surfactant-stabilized oil-in-water and water-in-oil emulsions, respectively. Furthermore, the ultralow adhesions in liquid contributed to the outstanding reusability and antifouling resistance of the prepared TPB-DMTP-COF/PAN membranes. This work provides a feasible approach for fabricating a smart membrane with under-liquid dual superlyophobicity for oily wastewater treatment.

RESUMEN

Surfaces with unusual under-liquid dual superlyophobicity are attractive on account of their widespread applications, but their development remains difficult due to thermodynamic contradiction. Additionally, these surfaces may suffer from limited antifouling ability, which has restricted their practical applications. Herein, we report a successful in situ growth of a hybrid zeolitic imidazolate framework-8 and zinc oxide nanorod on a porous poly(vinylidene fluoride) membrane (ZIF-8@ZnO-PPVDF) and its application as a self-cleaning switchable barrier material in rapid filtration for emulsified oily wastewater. The novel ZIF-8@ZnO-PPVDF exhibits superior mechanical strength, reversible under-liquid dual superlyophobicity, photocatalytic self-cleaning property, and an effective alternate separation capacity toward both oil-in-water (O/W) and water-in-oil (W/O) emulsions with ultrahigh fluxes and efficiencies (>99%). By simply using a "bait-hook-eliminate" method to separate the O/W emulsions containing soluble organic pollutants, we demonstrate that the ZIF-8@ZnO-PPVDF can achieve stable separation fluxes over 600 L m-2 h-1 with high efficiencies and be completely/nondestructively regenerated by visible-light irradiation after each cycle. This study would demonstrate a new approach to prepare an under-liquid dual superlyophobic revivable membrane for various applications.

RESUMEN

Surfaces with under-water superoleophobicity or under-oil superhydrophobicity have attractive features due to their widespread applications. However, it is difficult to achieve under-liquid dual superlyophobic surfaces, that is, under-oil superhydrophobicity and under-water superoleophobicity coexistence, due to the thermodynamic contradiction. Herein, we report an approach to obtain the under-liquid dual superlyophobic surface through conformational transitions of surface self-assembled molecules. Preferential exposure of either hydrophobic or hydrophilic moieties of the hydroxythiol (HS(CH2)nOH, where n is the number of methylene groups) self-assembled monolayers to the surrounding solvent (water or oil) can be used to manipulate macroscopic wettability. In water, the surfaces modified with different hydroxythiols exhibit under-water superoleophobicity because of the exposure of hydroxyl groups. In contrast, surface wettability to water is affected by molecular orientation in oil, and the surface transits from under-oil superhydrophilicity to superhydrophobicity when n ≥ 4. This surface design can amplify the molecular-level conformational transition to the change of macroscopic surface wettability. Furthermore, on-demand oil/water separation relying on the under-liquid dual superlyophobicity is successfully demonstrated. This work may be useful in developing the materials with opposite superwettability.