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.

[1]  Claire J. Carmalt,et al.  Robust self-cleaning surfaces that function when exposed to either air or oil , 2015, Science.

[2]  Zhiqun Lin,et al.  Surface-treated TiO2 nanoparticles for dye-sensitized solar cells with remarkably enhanced performance. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[3]  H. Fuchs,et al.  Controllable wettability and adhesion on bioinspired multifunctional TiO2 nanostructure surfaces for liquid manipulation , 2014 .

[4]  Doris Vollmer,et al.  Candle Soot as a Template for a Transparent Robust Superamphiphobic Coating , 2012, Science.

[5]  Tong Lin,et al.  Photoreactive azido-containing silica nanoparticle/polycation multilayers: durable superhydrophobic coating on cotton fabrics. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[6]  Jie Zhu,et al.  Fabrication of condensate microdrop self-propelling porous films of cerium oxide nanoparticles on copper surfaces. , 2015, Angewandte Chemie.

[7]  Wei-min Liu,et al.  Extreme wettability and tunable adhesion: biomimicking beyond nature? , 2012 .

[8]  Hongzheng Chen,et al.  Superhydrophobic cotton fabrics prepared by sol–gel coating of TiO2 and surface hydrophobization , 2008, Science and technology of advanced materials.

[9]  Lan Sun,et al.  Inorganic-modified semiconductor TiO2 nanotube arrays for photocatalysis , 2014 .

[10]  T. Darmanin,et al.  Superhydrophobic Surfaces by Electrochemical Processes , 2013, Advanced materials.

[11]  Guojun Liu,et al.  Simple approach towards fabrication of highly durable and robust superhydrophobic cotton fabric from functional diblock copolymer , 2013 .

[12]  R. Khajavi,et al.  Fabrication of superhydrophobic polymethylsilsesquioxane nanostructures on cotton textiles by a solution-immersion process. , 2011, Journal of colloid and interface science.

[13]  Naiqing Zhang,et al.  Designing heterogeneous chemical composition on hierarchical structured copper substrates for the fabrication of superhydrophobic surfaces with controlled adhesion. , 2013, ACS applied materials & interfaces.

[14]  H. Erbil,et al.  Transformation of a Simple Plastic into a Superhydrophobic Surface , 2003, Science.

[15]  Xiaotao Zhu,et al.  Robust and durable superhydrophobic cotton fabrics for oil/water separation. , 2013, ACS applied materials & interfaces.

[16]  H. Fuchs,et al.  In Situ Surface‐Modification‐Induced Superhydrophobic Patterns with Reversible Wettability and Adhesion , 2013, Advanced materials.

[17]  Chaoxia Wang,et al.  Surface Deposition on Cellulose Substrate via Cationic SiO2/TiO2 Hybrid Sol for Transfer Printing Using Disperse Dye , 2013 .

[18]  Xiaotao Zhu,et al.  A novel superhydrophobic bulk material , 2012 .

[19]  H. Fuchs,et al.  Multifunctional superamphiphobic TiO2 nanostructure surfaces with facile wettability and adhesion engineering. , 2014, Small.

[20]  Tong Lin,et al.  Superphobicity/philicity Janus Fabrics with Switchable, Spontaneous, Directional Transport Ability to Water and Oil Fluids , 2013, Scientific Reports.

[21]  W. Daoud,et al.  Photostable self-cleaning cotton by a copper(II) porphyrin/TiO2 visible-light photocatalytic system. , 2013, ACS applied materials & interfaces.

[22]  A. Fujishima,et al.  TiO2 photocatalysis and related surface phenomena , 2008 .

[23]  Yuekun Lai,et al.  Robust superhydrophobic TiO2@fabrics for UV shielding, self-cleaning and oil–water separation , 2015 .

[24]  M. Xue,et al.  Tunable water adhesion on titanium oxide surfaces with different surface structures. , 2012, ACS applied materials & interfaces.

[25]  Neelesh A. Patankar,et al.  Stabilization of Leidenfrost vapour layer by textured superhydrophobic surfaces , 2012, Nature.

[26]  B. Ding,et al.  Gravity driven separation of emulsified oil–water mixtures utilizing in situ polymerized superhydrophobic and superoleophilic nanofibrous membranes , 2013 .

[27]  Lei Wu,et al.  Mimic nature, beyond nature: facile synthesis of durable superhydrophobic textiles using organosilanes. , 2013, Journal of materials chemistry. B.

[28]  Feng Shi,et al.  A pH-responsive smart surface for the continuous separation of oil/water/oil ternary mixtures , 2014 .

[29]  Cai‐Feng Wang,et al.  Versatile superhydrophobic and photocatalytic films generated from TiO2–SiO2@PDMS and their applications on fabrics , 2014 .

[30]  Yang Yu,et al.  Laundering Durability of Superhydrophobic Cotton Fabric , 2010, Advanced materials.

[31]  Jianzhong Ma,et al.  Long-lived superhydrophobic surfaces , 2013 .

[32]  Ke-Qin Zhang,et al.  Multifunctional TiO2‐Based Particles: The Effect of Fluorination Degree and Liquid Surface Tension on Wetting Behavior , 2015 .

[33]  U. Farooq,et al.  Bioinspired underwater superoleophobic surface with ultralow oil-adhesion achieved by femtosecond laser microfabrication , 2014 .

[34]  Akira Fujishima,et al.  Bio-inspired titanium dioxide materials with special wettability and their applications. , 2014, Chemical reviews.

[35]  Jianzhong Ma,et al.  Washable and wear-resistant superhydrophobic surfaces with self-cleaning property by chemical etching of fibers and hydrophobization. , 2014, ACS applied materials & interfaces.

[36]  Sindy K. Y. Tang,et al.  Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity , 2011, Nature.

[37]  Jianmao Yang,et al.  Amphiphobic fluorinated polyurethane composite microfibrous membranes with robust waterproof and breathable performances , 2013 .

[38]  Yihe Zhang,et al.  A facile method to fabricate functionally integrated devices for oil/water separation. , 2015, Nanoscale.

[39]  G. Armatas,et al.  Mesoporous Au–TiO2 nanoparticle assemblies as efficient catalysts for the chemoselective reduction of nitro compounds , 2013 .

[40]  Linfan Li,et al.  Laundering durability of photocatalyzed self-cleaning cotton fabric with TiO₂ nanoparticles covalently immobilized. , 2013, ACS applied materials & interfaces.

[41]  T. Darmanin,et al.  Chemical and physical pathways for the preparation of superoleophobic surfaces and related wetting theories. , 2014, Chemical reviews.

[42]  Jin Zhai,et al.  Directional water collection on wetted spider silk , 2010, Nature.

[43]  B. Ding,et al.  Superwetting hierarchical porous silica nanofibrous membranes for oil/water microemulsion separation. , 2014, Nanoscale.

[44]  Lei Wu,et al.  Facile preparation of durable and robust superhydrophobic textiles by dip coating in nanocomposite solution of organosilanes. , 2013, Chemical communications.

[45]  A. Welle,et al.  Surface Patterning via Thiol‐Yne Click Chemistry: An Extremely Fast and Versatile Approach to Superhydrophilic‐Superhydrophobic Micropatterns , 2014 .

[46]  Shu Yang,et al.  Transparent and Superamphiphobic Surfaces from One‐Step Spray Coating of Stringed Silica Nanoparticle/Sol Solutions , 2014 .

[47]  David Reinhoudt,et al.  What do we need for a superhydrophobic surface? A review on the recent progress in the preparation of superhydrophobic surfaces. , 2007, Chemical Society reviews.

[48]  H. Fuchs,et al.  Bioinspired patterning with extreme wettability contrast on TiO2 nanotube array surface: a versatile platform for biomedical applications. , 2013, Small.

[49]  Tong Lin,et al.  Robust, superamphiphobic fabric with multiple self-healing ability against both physical and chemical damages. , 2013, ACS applied materials & interfaces.

[50]  Jin Zhai,et al.  Bioinspired super-antiwetting interfaces with special liquid-solid adhesion. , 2010, Accounts of chemical research.

[51]  Bin Ding,et al.  In situ polymerized superhydrophobic and superoleophilic nanofibrous membranes for gravity driven oil-water separation. , 2013, Nanoscale.

[52]  Tong Lin,et al.  Superstrong, Chemically Stable, Superamphiphobic Fabrics from Particle‐Free Polymer Coatings , 2015 .

[53]  Bharat Bhushan,et al.  Self-cleaning efficiency of artificial superhydrophobic surfaces. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[54]  L. Gerhardt,et al.  A Simple, One‐Step Approach to Durable and Robust Superhydrophobic Textiles , 2008 .

[55]  Suobo Zhang,et al.  Fabrication of superhydrophobic cellulose-based materials through a solution-immersion process. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[56]  W. Daoud,et al.  Superhydrophobic and photocatalytic self-cleaning cotton , 2014 .

[57]  Lei Jiang,et al.  Designing Superhydrophobic Porous Nanostructures with Tunable Water Adhesion , 2009 .

[58]  Q. Lu,et al.  Transparent, thermally and mechanically stable superhydrophobic coating prepared by an electrochemical template strategy , 2015 .

[59]  H. Fuchs,et al.  Bioinspired TiO2 Nanostructure Films with Special Wettability and Adhesion for Droplets Manipulation and Patterning , 2013, Scientific Reports.

[60]  Mei Li,et al.  Reversible Switching of Water‐Droplet Adhesion on a Superhydrophobic Polythiophene Surface , 2014 .

[61]  Gareth H. McKinley,et al.  Fabrics with Tunable Oleophobicity , 2009 .

[62]  P. Levkin,et al.  Emerging Applications of Superhydrophilic‐Superhydrophobic Micropatterns , 2013, Advanced materials.

[63]  Olli Ikkala,et al.  Switchable Static and Dynamic Self-Assembly of Magnetic Droplets on Superhydrophobic Surfaces , 2013, Science.

[64]  H. Habermeier,et al.  Linking Atomic Structure and Local Chemistry at Manganese‐Segregated Antiphase Boundaries in ZrO2–La2/3Sr1/3MnO3 Thin Films , 2015 .

[65]  Zhiguang Guo,et al.  Biomimetic superoleophobic surfaces: focusing on their fabrication and applications , 2015 .

[66]  Naiqing Zhang,et al.  pH-induced reversible wetting transition between the underwater superoleophilicity and superoleophobicity. , 2014, ACS applied materials & interfaces.

[67]  J. Mano,et al.  Combinatorial on-chip study of miniaturized 3D porous scaffolds using a patterned superhydrophobic platform. , 2013, Small.

[68]  U. Farooq,et al.  Reversible Underwater Lossless Oil Droplet Transportation , 2015 .

[69]  Tong Lin,et al.  Robust, electro-conductive, self-healing superamphiphobic fabric prepared by one-step vapour-phase polymerisation of poly(3,4-ethylenedioxythiophene) in the presence of fluorinated decyl polyhedral oligomeric silsesquioxane and fluorinated alkyl silane , 2013 .