Facile Fabrication of Eco‐Friendly Durable Superhydrophobic Material from Eggshell with Oil/Water Separation Property

Most superhydrophobic surfaces are fragile and even lose their functions under harsh conditions especially in outdoor applications. In this study, we have demonstrated a facile strategy for fabricating eco‐friendly and mechanical durable superhydrophobic material from eggshell. The as‐prepared superhydrophobic materials possess not only excellent self‐cleaning property and under oil superhydrophobicity, but also high‐efficient oil/water separation capability. More importantly, the obtained materials show outstanding and mechanical durable water repellency, which can maintain superhydrophobicity after 360 cm abrasion length of sandpaper. In addition, the materials also show durable superhydrophobic toward strong acidic/alkali solutions, UV irradiation, and water droplet impact, which demonstrates the outstanding chemical and environmental stability. This facile fabrication of the mechanical durable superhydrophobic materials and the utilization of daily garbage will provide the new ideas for engineering materials and accelerate the real application of the super‐repellent materials.

     

Robust Flower‐Like TiO2@Cotton Fabrics with Special Wettability for Effective Self‐Cleaning and Versatile Oil/Water Separation

Inspired by the hierarchical structure of the mastoid on the micrometer and nanometer scale and the waxy crystals of the mastoid on natural lotus surfaces, a facile one‐step hydrothermal strategy is developed to coat flower‐like hierarchical TiO₂ micro/nanoparticles onto cotton fabric substrates (TiO₂@Cotton). Furthermore, robust superhydrophobic TiO₂@Cotton surfaces are constructed by the combination of hierarchical structure creation and low surface energy material modification, which allows versatility for self‐cleaning, laundering durability, and oil/water separation. Compared with hydrophobic cotton fabric, the TiO₂@Cotton exhibits a superior antiwetting and self‐cleaning property with a contact angle (CA) lager than 160° and a sliding angle lower than 5°. The superhydrophobic TiO₂@Cotton shows excellent laundering durability against mechanical abrasion without an apparent reduction of the water contact angle. Moreover, the micro/nanoscale hierarchical structured cotton fabrics with special wettability are demonstrated to selectively collect oil from oil/water mixtures efficiently under various conditions (e.g., floating oil layer or underwater oil droplet or even oil/water mixtures). In addition, it is expected that this facile strategy can be widely used to construct multifunctional fabrics with excellent self‐cleaning, laundering durability, and oil/water separation. The work would also be helpful to design and develop new underwater superoleophobic/superoleophilic materials and microfluidic management devices.     

UV‐Resistant and Thermally Stable Superhydrophobic CeO2 Nanotubes with High Water Adhesion

A novel type of sticky superhydrophobic cerium dioxide (CeO₂) nanotube material is prepared by hydrothermal treatment without any chemical modification. A water droplet on the material surface shows a static water contact angle of about 157° but the water droplet is pinned on the material surface even when the material surface is turned upside down. Interestingly, the as‐prepared CeO₂ nanotube material displays durable superhydrophobicity and enhanced adhesion to water under ultraviolet (UV) light irradiation. Importantly, this change in water adhesion can be reversed by heat treatment to restore the original adhesive value of 20 µL. Further, the maximum volume of the water droplet adhered on the material surface of CeO₂ nanotubes can be regulated without loss of superhydrophobicity during the heating treatment/UV‐irradiation cycling. Meanwhile, the superhydrophobic CeO₂ nanotube material shows remarkable thermal stability even at temperatures as high as 450 °C, long‐term durability in chemical environment, and air‐storage and good resistance to oily contaminant. Finally, the potential application in no‐loss water transportation of this sticky superhydrophobic CeO₂ material is demonstrated.     

One‐Step Preparation of Highly Durable Superhydrophobic Carbon Nanothorn Arrays

This study proposes a one‐step method for growing superhydrophobic carbon nanothorn arrays (NTAs) directly on various substrates. The fabricated carbon material (named methyl‐substituted graphdiyne (MGDY)) comprises sp and sp² carbons in a conjugated‐backbone form, as well as methyl groups introduced into the framework as hydrophobic‐enhanced functional groups. MGDY NTAs exhibit excellent hydrophobicity (contact angle ≥152°), substantial long‐period hydrophobic durability (the contact angle decreased by only 3.2% over 800 days), and acid/alkali tolerance. Owing to the enhanced durability and specific stability of carbon, a superhydrophobic interface can easily be constructed using MGDY NTAs, which can be applied to achieve successful long‐term metal‐corrosion protection and efficient oil–water separation.     

PVDF/SiO2/PDMS涂层超疏水纺织品性能

目的 针对普通纺织品材料防水性和防污性较差的问题,制备具有自清洁功能的超疏水涂层纺织品,并研究其性能.方法 以涤纶织物为基材,通过非溶剂诱导相分离法,使用聚偏氟乙烯和疏水纳米二氧化硅复合液在纺织品表面构筑微纳粗糙结构,采用聚二甲基硅氧烷对其进行疏水化处理,获得自清洁超疏水涂层纺织品.采用扫描电子显微镜、X射线能量散射光谱和视频光学接触角测量仪等对其结构和性能进行表征,并通过机械摩擦、洗涤、酸/碱/盐溶液浸渍和紫外光照等方法对其表面超疏水稳定性进行考察.结果 当聚偏氟乙烯质量分数为2％,疏水纳米二氧化硅质量分数为0.4％,聚二甲基硅氧烷质量分数为1％时,制备的纺织品的表面接触角可达(162.2°±0.8°),滚动角达(2.0°±0.4°),具有优异的超疏水自清洁效应;经72 h酸/碱/盐溶液浸渍、196 h紫外光照、2500次摩擦和120次家庭水洗后,其表面接触角仍大于150°,表现出优异的超疏水稳定性.结论 采用简便的非溶剂相分离法制备的涂层纺织品具有优异的自清洁性能,并且其超疏水性能具有机械耐久性和化学稳定性,有望应用于纺织材料包装领域.     

Laser‐Induced Graphene in Controlled Atmospheres: From Superhydrophilic to Superhydrophobic Surfaces

The modification of graphene‐based materials is an important topic in the field of materials research. This study aims to expand the range of properties for laser‐induced graphene (LIG), specifically to tune the hydrophobicity and hydrophilicity of the LIG surfaces. While LIG is normally prepared in the air, here, using selected gas atmospheres, a large change in the water contact angle on the as‐prepared LIG surfaces has been observed, from 0° (superhydrophilic) when using O₂ or air, to >150° (superhydrophobic) when using Ar or H₂. Characterization of the newly derived surfaces shows that the different wetting properties are due to the surface morphology and chemical composition of the LIG. Applications of the superhydrophobic LIG are shown in oil/water separation as well as anti‐icing surfaces, while the versatility of the controlled atmosphere chamber fabrication method is demonstrated through the improved microsupercapacitor performance generated from LIG films prepared in an O₂ atmosphere.     

Peanut Leaf Inspired Multifunctional Surfaces

Nature has long served as a source of inspiration for scientists and engineers to design and construct multifunctional artificial materials. The lotus and the peanut are two typical plants living in the aquatic and the arid (or semiarid) habitats, respectively, which have evolved different optimized solutions to survive. For the lotus leaf, an air layer is formed between its surface and water, exhibiting a discontinuous three‐phase contact line, which resulted in the low adhesive superhydrophobic self‐cleaning effect to avoid the leaf decomposition. In contrast to the lotus leaf, the peanut leaf shows high‐adhesive superhydrophobicity, arising from the formation of the quasi‐continuous and discontinuous three‐phase contact line at the microscale and nanoscale, respectively, which provides a new avenue for the fabrication of high adhesive superhydrophobic materials. Further, this high adhesive and superhydrophobic peanut leaf is proved to be efficient in fog capture. Inspired by the peanut leaf, multifunctional surfaces with structural similarity to the natural peanut leaf are prepared, exhibiting simultaneous superhydrophobicity and high adhesion towards water.     

Emerging Applications of Superhydrophilic‐Superhydrophobic Micropatterns

Water on superhydrophilic surfaces spreads or is absorbed very quickly, and exhibits water contact angles close to zero. We encounter superhydrophilic materials in our daily life (e.g., paper, sponges, textiles) and they are also ubiquitous in nature (e.g., plant and tree leaves, Nepenthes pitcher plant). On the other hand, water on completely non‐wettable, superhydrophobic surfaces forms spherical droplets and rolls off the surface easily. One of the most well‐known examples of a superhydrophobic surface is the lotus leaf. Creating novel superhydrophobic surfaces has led to exciting new properties such as complete water repellency, self‐cleaning, separation of oil and water, and antibiofouling. However, combining these two extreme states of superhydrophilicity and superhydrophobicity on the same surface in precise two‐dimensional micropatterns opens exciting new functionalities and possibilities in a wide variety of applications from cell, droplet, and hydrogel microarrays for screening to surface tension confined microchannels for separation and diagnostic devices. In this Progress Report, we briefly describe the methods for fabricating superhydrophilic‐superhydrophobic patterns and highlight some of the newer and emerging applications of these patterned substrates that are currently being explored. We also give an outlook on current and future applications that would benefit from using such superhydrophilic‐superhydrophobic micropatterns.     

Highly Stretchable Superhydrophobic Composite Coating Based on Self‐Adaptive Deformation of Hierarchical Structures

With the rapid development of stretchable electronics, functional textiles, and flexible sensors, water‐proof protection materials are required to be built on various highly flexible substrates. However, maintaining the antiwetting of superhydrophobic surface under stretching is still a big challenge since the hierarchical structures at hybridized micro‐nanoscales are easily damaged following large deformation of the substrates. This study reports a highly stretchable and mechanically stable superhydrophobic surface prepared by a facile spray coating of carbon black/polybutadiene elastomeric composite on a rubber substrate followed by thermal curing. The resulting composite coating can maintain its superhydrophobic property (water contact angle ≈170° and sliding angle <4°) at an extremely large stretching strain of up to 1000% and can withstand 1000 stretching–releasing cycles without losing its superhydrophobic property. Furthermore, the experimental observation and modeling analysis reveal that the stable superhydrophobic properties of the composite coating are attributed to the unique self‐adaptive deformation ability of 3D hierarchical roughness of the composite coating, which delays the Cassie–Wenzel transition of surface wetting. In addition, it is first observed that the damaged coating can automatically recover its superhydrophobicity via a simple stretching treatment without incorporating additional hydrophobic materials.     

Silver‐Quantum‐Dot‐Modified MoO3 and MnO2 Paper‐Like Freestanding Films for Flexible Solid‐State Asymmetric Supercapacitors

Free‐standing paper‐like thin‐film electrodes have great potential to boost next‐generation power sources with highly flexible, ultrathin, and lightweight requirements. In this work, silver‐quantum‐dot‐ (2–5 nm) modified transition metal oxide (including MoO₃ and MnO₂) paper‐like electrodes are developed for energy storage applications. Benefitting from the ohmic contact at the interfaces between silver quantum dots and MoO₃ nanobelts (or MnO₂ nanowires) and the binder‐free nature and 0D/1D/2D nanostructured 3D network of the fabricated electrodes, substantial improvements on the electrical conductivity, efficient ionic diffusion, and areal capacitances of the hybrid nanostructure electrodes are observed. With this proposed strategy, the constructed asymmetric supercapacitors, with Ag quantum dots/MoO₃ “paper” as anode, Ag quantum dots/MnO₂ “paper” as cathode, and neutral Na₂SO₄/polyvinyl alcohol hydrogel as electrolyte, exhibit significantly enhanced energy and power densities in comparison with those of the supercapacitors without modification of Ag quantum dots on electrodes; present excellent cycling stability at different current densities and good flexibility under various bending states; offer possibilities as high‐performance power sources with low cost, high safety, and environmental friendly properties.     

Dual‐Layer Superamphiphobic/Superhydrophobic‐Oleophilic Nanofibrous Membranes with Unidirectional Oil‐Transport Ability and Strengthened Oil–Water Separation Performance

Thin porous membranes with unidirectional oil‐transport capacity offer great opportunities for intelligent manipulation of oil fluids and development of advanced membrane technologies. However, directional oil‐transport membranes and their unique membrane properties have seldom been reported in research literature. Here, it is proven that a dual‐layer nanofibrous membrane comprising a layer of superamphiphobic nanofibers and a layer of superhydrophobic oleophilic nanofibers has an unexpected directional oil‐transport ability, but is highly superhydrophobic to liquid water. This novel fibrous membrane is prepared by a layered electrospinning technique using poly(vinylidene fluoride‐hexafluoropropylene) (PVDF‐HFP), PVDP‐HFP containing well‐dispersed FD‐POSS (fluorinated decyl polyhedral oligomeric silsesquioxanes), and FAS (fluorinated alkyl silane) as materials. The directional oil‐transport is selective only to oil fluids with a surface tension in the range of 23.8–34.0 mN m^–1. By using a mixture of diesel and water, it is further proven that this dual‐layer nanofibrous membrane has a higher diesel–water separation ability than the single‐layer nanofiber membranes. This novel nanofibrous membrane and the incredible oil‐transport ability may lead to the development of intelligent membrane materials and advanced oil–water separation technologies for diverse applications in daily life and industry.     

A Robust and Cost‐Effective Superhydrophobic Graphene Foam for Efficient Oil and Organic Solvent Recovery

Water pollution caused by chemical reagent leaking, industrial wastewater discharging, and crude oil spills has raised global concerns on environmental sustainability, calling for high‐performance absorbent materials for effective treatments. However, low‐cost materials capable of effectively separating oils and organic solvents from water with a high adsorption capacity and good recyclability are rare on the market. Here, a cost‐effective method is reported to fabricate high‐performance graphene modified absorbents through the facile thermal reduction of graphene oxide on the skeletons of melamine foam. By integrating the high porosity, superior elasticity, and mechanical stability of raw sponge with the chemical stability and hydrophobicity of graphene sheets, the as‐fabricated graphene foam not only possesses a rough and superhydrophobic surface, but also exhibits an excellent adsorption performance and extraordinary recyclability for various oils and organic solvents. It is worth mentioning that the superhydrophobic surface also endows the graphene foam with an excellent efficiency for oil/water separation. More importantly, the cost‐effective fabrication method without involving expensive raw materials and sophisticated equipment permits a scale‐up of the graphene foam for pollution disposal. All these features make the graphene foam an ideal candidate for removal and collection of oils and organic solvents from water.     

Lubrication mechanisms of C‐MoS2‐Fe2O3 (Fe3O4) nano‐composite lubricants at the rubbing interfaces of non‐copper coated solid wires against the contact tube

Graphite‐MoS₂‐Fe₂O₃ (Fe₃O₄) nano‐composite lubricating coatings were prepared on the surfaces of non‐copper coated solid wires by a mechanical coating technique. The tribological behaviours of graphite‐MoS₂‐Fe₂O₃ (Fe₃O₄) coatings at the rubbing interfaces of welding wires against the contact tube were investigated. The results demonstrate that the lubricating properties of graphite‐Fe₃O₄ coatings outperform the lubricating properties of graphite‐Fe₂O₃ coatings. The anti‐wear performance of the contact tube is strengthened with increasing nano‐MoS₂ contents. Layers of protective tribofilms are formed at the rubbing interfaces of welding wires against a contact tube by tribochemical reaction among lubricants. The tribofilms are composed of FeO, MoO₃ and FeMoO₄ with excellent lubricating properties. They can avoid direct contact of welding wires against the contact tube, thus decreasing contact tube wear. With the transition of the contact tube wear from mild to severe, the dominant wear mechanisms of contact tube change from fatigue peeling and oxidative wear to abrasive wear and arc ablation.     

Exposing {001} Crystal Plane on Hexagonal Ni‐MOF with Surface‐Grown Cross‐Linked Mesh‐Structures for Electrochemical Energy Storage

Hexagonal nickel‐organic framework (Ni‐MOF) [Ni(NO₃)₂·6H₂O, 1,3,5‐benzenetricarboxylic acid, 4‐4′‐bipyridine] is fabricated through a one‐step solvothermal method. The {001} crystal plane is exposed to the largest hexagonal surface, which is an ideal structure for electron transport and ion diffusion. Compared with the surrounding rectangular crystal surface, the ion diffusion length through the {001} crystal plane is the shortest. In addition, the cross‐linked porous mesh structures growing on the {001} crystal plane strengthen the mixing with conductive carbon, inducing preferable conductivity, as well as increasing the area of ion contact and the number of active sites. These advantages enable the hexagonal Ni‐MOF to exhibit excellent electrochemical performance as supercapacitor electrode materials. In a three‐electrode cell, specific capacitance of hexagonal Ni‐MOF in the 3.0 m KOH electrolyte is 977.04 F g^?1 and remains at the initial value of 92.34% after 5,000 cycles. When the hexagonal Ni‐MOF and activated carbon are assembled into aqueous devices, the electrochemical performance remains effective.     

A Phase‐Separation Route to Synthesize Porous CNTs with Excellent Stability for Na+ Storage

Porous carbon nanotubes (CNTs) are obtained by removing MoO₂ nanoparticles from MoO₂@C core@shell nanofibers which are synthesized by phase‐segregation via a single‐needle electrospinning method. The specific surface area of porous CNTs is 502.9 m² g^?1, and many oxygen‐containing functional groups (C? OH, C?O) are present. As anodes for sodium‐ion batteries, the porous CNT electrode displays excellent rate performance and cycling stability (110 mA h g^?1 after 1200 cycles at 5 A g^?1). Those high properties can be attributed to the porous structure and surface modification to steadily store Na⁺ with high capacity. The work provides a facile and broadly applicable way to fabricate the porous CNTs and their composites for batteries, catalysts, and fuel cells.     

Bioinspired Mechanically Robust Metal‐Based Water Repellent Surface Enabled by Scalable Construction of a Flexible Coral‐Reef‐Like Architecture

Mechanical robustness is a central concern for moving artificial superhydrophobic surfaces to application practices. It is believed that bulk hydrophilic materials cannot be use to construct micro/nanoarchitectures for superhydrophobicity since abrasion‐induced exposure of hydrophilic surfaces leads to remarkable degradation of water repellency. To address this challenge, the robust mechanical durability of a superhydrophobic surface with metal (hydrophilic) textures, through scalable construction of a flexible coral‐reef‐like hierarchical architecture on various substrates including metals, glasses, and ceramics, is demonstrated. Discontinuous coral‐reef‐like Cu architecture is built by solid‐state spraying commercial electrolytic Cu particles (15–65 µm) at supersonic particle velocities. Subsequent flame oxidation is applied to introduce a porous hard surface oxide layer. Owing to the unique combination of the flexible coral‐reef‐like architecture and self‐similar manner of the fluorinated hard oxide surface layer, the coating surface retains its water repellency with an extremely low roll‐off angle (<2°) after cyclic sand‐paper abrasion, mechanical bending, sand‐grit erosion, knife‐scratching, and heavy loading of simulated acid rain droplets. Strong adhesion to glass, ceramics, and metals up to 34 MPa can be achieved without using adhesive. The results show that the present superhydrophobic coating can have wide outdoor applications for self‐cleaning and corrosion protection of metal parts.     

Bio-inspired design of a transparent TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite gel coating with adjustable wettability

Although the superhydrophobicity and transparence are generally two contradictory characters as the roughness factor, it is literature abundant for achieving both of these two purposes. To our knowledge, the integration multipurpose (transparent, superhydrophobic, superhydrophilic, underwater superoleophobicity, anti-fogging, and photo-controllable ability) in one has not been reported so far and these are vital for their promising applications in various aspects which can attract broad attention from scholars to engineers. In this work, we are successful to bio-inspired design of a kind versatile transparent nanocoating with superhydrophobic or superhydrophilic/underwater superoleophobic properties. The TiO₂/SiO₂ nanocoatings can be transformed from superhydrophobicity into superhydrophilicity and underwater superoleophobicity after heat treatment (450 °C and 2 h). If it was coated on conductive glass, the electrical conductivity was impervious, while the wettability can be manipulated. Importantly, both these superhydrophobic and superhydrophilic TiO₂/SiO₂ composite nanocoatings were endowed with photo-induced self-cleaning nature and these antifouling coatings could prolong their service life.     

耐腐蚀超疏水铜网的制备及其在油水分离中的应用

针对目前超疏水材料耐腐蚀差的问题,制备一种耐腐蚀的超疏水铜网,并应用于油水混合物的分离。将十八胺修饰的多壁碳纳米管与有机硅改性的水性聚氨酯相结合,喷涂到铜网制备了具有鸟巢状结构的铜基超疏水表面。结果表明,该表面呈现对水高的接触角162°和对油极低接触角0°。另外,可对石油醚/水、四氯化碳/水、甲苯/水、己烷/水、煤油/水等油水混合物高效分离,分离效率均大于93.79%,且具有良好的可循环使用性。耐腐蚀性测试结果表明,该超疏水表面分别在1mol/L的NaOH,HCl,NaCl溶液中浸泡24h后,仍可保持超疏水特性,具有优异的耐腐蚀性能。     

Bimetal‐Organic‐Framework Derivation of Ball‐Cactus‐Like Ni‐Sn‐P@C‐CNT as Long‐Cycle Anode for Lithium Ion Battery

Metal phosphides are a new class of potential high‐capacity anodes for lithium ion batteries, but their short cycle life is the critical problem to hinder its practical application. A unique ball‐cactus‐like microsphere of carbon coated NiP₂/Ni₃Sn₄ with deep‐rooted carbon nanotubes (Ni‐Sn‐P@C‐CNT) is demonstrated in this work to solve this problem. Bimetal‐organic‐frameworks (BMOFs, Ni‐Sn‐BTC, BTC refers to 1,3,5‐benzenetricarboxylic acid) are formed by a two‐step uniform microwave‐assisted irradiation approach and used as the precursor to grow Ni‐Sn@C‐CNT, Ni‐Sn‐P@C‐CNT, yolk–shell Ni‐Sn@C, and Ni‐Sn‐P@C. The uniform carbon overlayer is formed by the decomposition of organic ligands from MOFs and small CNTs are deeply rooted in Ni‐Sn‐P@C microsphere due to the in situ catalysis effect of Ni‐Sn. Among these potential anode materials, the Ni‐Sn‐P@C‐CNT is found to be a promising anode with best electrochemical properties. It exhibits a large reversible capacity of 704 mA h g^?1 after 200 cycles at 100 mA g^?1 and excellent high‐rate cycling performance (a stable capacity of 504 mA h g^?1 retained after 800 cycles at 1 A g^?1). These good electrochemical properties are mainly ascribed to the unique 3D mesoporous structure design along with dual active components showing synergistic electrochemical activity within different voltage windows.     

Ultrathin Molybdenum Dioxide Nanosheets as Uniform and Reusable Surface‐Enhanced Raman Spectroscopy Substrates with High Sensitivity

Metal oxides have advantages over the traditional noble metals to be used as substrate materials for surface‐enhanced Raman spectroscopy (SERS) with low cost, versatility, and biocompatibility, but their enhancement factors are generally quite low with a poor limit of detection. Here, ultrathin molybdenum dioxide (MoO₂) nanosheets synthesized by chemical vapor deposition demonstrated in large area are used as SERS substrates with superior signal uniformity in the whole area with a limit of detectable concentration down to 4 × 10^?8m and enhancement factor up to 2.1 × 10⁵, exceeding that of 2D materials and comparable to that of noble metal films. More practically important, the planar MoO₂ substrate is more robust than noble metals and shows excellent reusability and uniformity, which is usually prohibited for nanostructured or nanoparticle‐based metal oxide substrates. The enhancement is mainly attributed to the surface plasmon resonance effect as evidenced by the first principle calculations and UV–vis absorption spectroscopy characterization, which can be further increased by decreasing the thickness of the MoO₂ nanosheets. The overall superior performance makes the MoO₂ nanosheets an ideal substrate for practical SERS applications.