Bioinspired Controllable Electro‐Chemomechanical Coloration Films

Coloration materials and devices with broad manipulatable color spectra and precisely controllable capability are highly pursued in various applications, such as camouflage engineering, optical sensors, anticounterfeiting technology, real‐time monitoring, and so on. For achieving the goals, in the present work, a conceptually novel bioinspired coloration film is demonstrated using nanoscale amorphous silicon (a‐Si) layer deposited on a reflective metal substrate. With precisely manipulating the reversible lithiation/delithiation behaviors, such coloration films enable to present consecutively tunable chromogenic property in a broad visible band, since the simultaneous changes in both chemical components and film thickness upon electrochemical processes substantially vary the conditions of destructive interference. Accordingly, the corresponding model based on electro‐chemomechanical coupling effects confirms the coloration mechanism induced by thickness and intrinsic properties (refraction index and optical absorptivity). Additionally, such coloration films also suggest universal design ability, namely tailoring the coloration spectra via simply changing film thicknesses and metal substrates. Thus, the results promise a versatile strategy for fabricating advanced coloration materials and devices that are pursued in specular reflection, sensing, anticounterfeiting, labels, displaying, and sensors.     

Bioinspired,Stimuli‐Responsive,Multifunctional Superhydrophobic Surface with Directional Wetting,Adhesion, and Transport of Water

A novel smart stimuli responsive surface can be fabricated by the subsequent self‐assembly of the graphene monolayer and the TiO₂ nanofilm on various substrates, that is, fabrics, Si wafers, and polymer thin films. Multiscale application property can be achieved from the interfacial interaction between the hierarchical graphene/TiO₂ surface structure and the underlying substrate. The smart surface possesses superhydrophobic property as a result of its hierarchical micro‐ to nanoscale structural roughness. Upon manipulating the UV induced hydrophilic conversion of TiO₂ on graphene/TiO₂ surface, smart surface features, such as tunable adhesiveness, wettability, and directional water transport, can be easily obtained. The existence of graphene indeed enhances the electron–hole pair separation efficiency of the photo‐active TiO₂, as the time required for the TiO₂ superhydrophilic conversion is largely reduced. Multifunctional characteristics, such as gas sensing, droplet manipulation, and self‐cleaning, are achieved on the smart surface as a result of its robust superhydrophobicity, tunable wettability, and high photo‐catalytic activity. It is also revealed that the superhydrophilic conversion of TiO₂ is possibly caused by the atomic rearrangement of TiO₂ under UV radiation, as a structural transformation from {101} to {001} is observed after the UV treatment.     

Bioinspired Graphene Oxide Membranes with Dual Transport Mechanisms for Precise Molecular Separation

The implementation of membrane technology to replace or combine with energy‐intensive cryogenic distillation for precise separation of ethylene/ethane mixture proves an extremely important yet highly challenging task. Inspired by the hierarchical structure and facilitated gas transport of biological membranes, a highly selective ethylene/ethane separation membrane is explored through the fixation of a silver ion carrier and the impregnation of ionic liquid within 2D nanochannels of graphene oxide laminate, where plenty of ethylene‐permeating in‐plane nano‐wrinkles and ethylene‐facilitated plane‐to‐plane nanochannels are constructed. By virtue of synergistic effects of molecular sieving and carrier‐facilitated transport, an unprecedented combination of high ethylene permeance (72.5 GPU) and superhigh ethylene/ethane selectivity (215) is achieved, out‐performing currently reported advanced membranes. Moreover, molecular dynamics simulations verify a favorable membrane nanostructure for fast and selective transport of ethylene molecules. This bioinspired approach with dual transport mechanisms may open novel avenues to the design of high‐performance membranes for precise molecular separation.     

Self‐Healing Reduced Graphene Oxide Films by Supersonic Kinetic Spraying

The industrial scale application of graphene and other functional materials in the field of electronics has been limited by inherent defects, and the lack of simple deposition methods. A simple spray deposition method is developed that uses a supersonic air jet for a commercially available reduced graphene oxide (r‐GO) suspension. The r‐GO flakes are used as received, which are pre‐annealed and pre‐hydrazine‐treated, and do not undergo any post‐treatment. A part of the considerable kinetic energy of the r‐GO flakes entrained by the supersonic jet is used in stretching the flakes upon impact with the substrate. The resulting “frozen elastic strains” heal the defects (topological defects, namely Stone‐Wales defect and C₂ vacancies) in the r‐GO flakes, which is reflected in the reduced ratio of the intensities of the D and G bands in the deposited film. The defects can also be regenerated by annealing.     

基于皮秒激光的超疏水镍铝青铜合金表面的制备

利用皮秒激光器在镍铝青铜合金表面制备了具有不同微观形貌的微纳米复合结构,再通过硬脂酸进行表面修饰。采用扫描电镜和X射线衍射仪等表征了所得表面的形貌和化学成分。研究结果表明,经皮秒激光加工和硬脂酸修饰后,表面的接触角都达到150°以上。不同的脉冲能量密度下,试样表面的微观形貌和润湿性不同。随着脉冲能量密度的增大,修饰后的试样表面的滚动角逐渐减小,当脉冲能量密度为6.85 J/cm^2时,滚动角减小到7°,随着脉冲能量密度的进一步增加,滚动角又逐渐增大。耐蚀性测试结果表明:超疏水镍铝青铜合金表面具有更好的耐腐蚀性能。采用优化的工艺参数可以在镍铝青铜合金上加工出超疏水表面,有助于提高其耐腐蚀性能。     

Functional Free‐Standing Graphene Honeycomb Films

Fabricating free‐standing, three‐dimensional (3D) ordered porous graphene structure can service a wide range of functional materials such as environmentally friendly materials for antibacterial medical applications and efficient solar harvesting devices. A scalable solution processable strategy is developed to create such free‐standing hierarchical porous structures composed of functionalized graphene sheets via an “on water spreading” method. The free‐standing film shows a large area uniform honeycomb structure and can be transferred onto any substrate of interest. The graphene‐based free‐standing honeycomb films exhibit superior broad spectrum antibacterial activity as confirmed using green fluorescent protein labeled Pseudomonas aeruginosa PAO1 and Escherichia coli as model pathogens. Functional nanoparticles such as titanium dioxide (TiO₂) nanoparticles can be easily introduced into conductive graphene‐based scaffolds by premixing. The formed composite honeycomb film electrode shows a fast, stable, and completely reversible photocurrent response accompanying each switch‐on and switch‐off event. The graphene‐based honeycomb scaffold enhances the light‐harvesting efficiency and improves the photoelectric conversion behavior; the photocurrent of the composite film is about two times as high as that of the pure TiO₂ film electrode. Such composite porous films combining remarkably good electrochemical performance of graphene, a large electrode/electrolyte contact area, and excellent stability during the photo‐conversion process hold promise for further applications in water treatment and solar energy conversion.     

Bioinspired Multifunctional Foam with Self‐Cleaning and Oil/Water Separation

Oil/water separation is a worldwide challenge. Learning from nature provides a promising approach for the construction of functional materials with oil/water separation. In this contribution, inspired by superhydrophobic self‐cleaning lotus leaves and porous biomaterials, a facile method is proposed to fabricate polyurethane foam with simultaneous superhydrophobicity and superoleophilicity. Due to its low density, light weight, and superhydrophobicity, the as‐prepared foam can float easily on water. Furthermore, the foam demonstrates super‐repellency towards corrosive liquids, self‐cleaning, and oil/water separation properties, possessing multifunction integration. We expect that this low‐cost process can be readily and widely adopted for the design of multifunctional foams for large‐area oil‐spill cleanup.     

空间整形飞秒激光图案化加工氧化石墨烯

氧化石墨烯(GO)是结构中含有部分含氧官能团的石墨烯衍生物,通过加热、化学反应和激光诱导等方法,该材料可以被还原。激光辐照可以诱导一定区域内的GO发生还原反应,具有灵活、区域选择性良好、无需特殊环境等优点。提出了一种基于空间整形的飞秒激光图案化加工GO的方法,即空间整形激光辐照法,分别采用空间整形激光辐照法和激光逐点扫描法在GO上加工图案,并对加工结果进行表征和对比,分析了辐照时间、激光通量等参数对加工结果的影响。结果表明空间整形激光辐照法可以图案化加工GO并使加工区域的GO被还原,从而提高图案化加工效率,且该方法具有良好的可重复性和图案灵活性,在制备GO基底的微电路、微器件方面具有应用潜力。     

Structured Reduced Graphene Oxide/Polymer Composites for Ultra‐Efficient Electromagnetic Interference Shielding

A high‐performance electromagnetic interference shielding composite based on reduced graphene oxide (rGO) and polystyrene (PS) is realized via high‐pressure solid‐phase compression molding. Superior shielding effectiveness of 45.1 dB, the highest value among rGO based polymer composite, is achieved with only 3.47 vol% rGO loading owning to multi‐facet segregated architecture with rGO selectively located on the boundaries among PS multi‐facets. This special architecture not only provides many interfaces to absorb the electromagnetic waves, but also dramatically reduces the loading of rGO by confining the rGO at the interfaces. Moreover, the mechanical strength of the segregated composite is dramatically enhanced using high pressure at 350 MPa, overcoming the major disadvantage of the composite made by conventional‐pressure (5 MPa). The composite prepared by the higher pressure shows 94% and 40% increment in compressive strength and compressive modulus, respectively. These results demonstrate a promising method to fabricate an economical, robust, and highly efficient EMI shielding material.     

Regulating Cellular Behavior on Few‐Layer Reduced Graphene Oxide Films with Well‐Controlled Reduction States

Understanding the effect of graphene on cellular behavior is important for enabling a range of new biological and biomedical applications. However, due to the complexity of cell responses and graphene surface states, regulating cellular behaviors on graphene or its derivatives is still a great challenge. To address this challenge we have developed a novel, facile route to regulate the cellular behaviors on few‐layer reduced graphene oxide (FRGO) films by controlling the reduction states of graphene oxide. Our results indicate that the surface oxygen content of FRGO has a strong influence on cellular behavior, with the best performance for cell attachment, proliferation and phenotype being obtained in moderately reduced FRGO. Cell performance decreased significantly as the FRGO was highly reduced. Moderate performance was found in non‐reduced pure graphene oxide and control glass slides. Our results highlight the important role of surface physicochemical characteristics of graphene and its derivatives in their interactions with biocomponents, and may have great potential in enabling the utility of graphene based materials in various biomedical and bioelectronic applications.     

Emulsifier‐Free Graphene Dispersions with High Graphene Content for Printed Electronics and Freestanding Graphene Films

A novel and highly versatile synthetic route for the production of functionalized graphene dispersions in water, acetone, and isopropanol (IPA), which exhibit long‐term stability and are easy to scale up, is reported. Both graphene functionalization (wherein the oxygen content can be varied from 4 to 16 wt%) and dispersion are achieved by the thermal reduction of graphite oxide, followed by a high‐pressure homogenization (HPH) process. For the first time, binders, dispersing agents, and reducing agents are not required to produce either dilute or highly concentrated dispersions of single graphene sheets with a graphene content of up to 15 g L^?1. High graphene content is essential for the successful printing of graphene dispersions by 3D microextrusion. Free‐standing graphene films and micropatterned graphene materials are successfully prepared using this method. Due to the absence of toxic reducing agents, the graphene exhibits no cytotoxicity and is biocompatible. Furthermore, the electrical conductivity of graphene is significantly improved by the absence of binders. Flexible microarrays can be printed on different substrates, producing microarrays that are mechanically stable and can be bent several times without affecting electrical conductivity.     

Self‐Assembling TiO2 Nanorods on Large Graphene Oxide Sheets at a Two‐Phase Interface and Their Anti‐Recombination in Photocatalytic Applications

TiO₂ nanorods are self‐assembled on the graphene oxide (GO) sheets at the water/toluene interface. The self‐assembled GO–TiO₂ nanorod composites (GO–TiO₂ NRCs) can be dispersed in water. The effective anchoring of TiO₂ nanorods on the whole GO sheets is confirmed by transmission electron microscopy (TEM), X‐ray diffraction (XRD), Fourier transform IR spectroscopy (FTIR), and thermogravimetric analysis (TGA). The significant increase of photocatalytic activity is confirmed by the degradation of methylene blue (MB) under UV light irridiation. The large enhancement of photocatalytic activity is caused by the effective charge anti‐recombination and the effective absorption of MB on GO. The effective charge transfer from TiO₂ to GO sheets is confirmed by the significant photoluminescence quenching of TiO₂ nanorods, which can effectively prevent the charge recombination during photocatalytic process. The effective absorption of MB on GO is confirmed by the UV‐vis spectra. The degradation rate of MB in the second cycle is faster than that in the first cycle because of the reduction of GO under UV light irradiation.     

Ultrafast Fabrication of Covalently Cross‐linked Multifunctional Graphene Oxide Monoliths

Stable graphene oxide monoliths (GOMs) have been fabricated by exploiting epoxy groups on the surface of graphene oxide (GO) in a ring opening reaction with amine groups of poly(oxypropylene) diamines (D₄₀₀). This method can rapidly form covalently bonded GOM with D₄₀₀ within 60 s. FTIR and XPS analyses confirm the formation of covalent C‐N bonds. Investigation of the GOM formation mechanism reveals that the interaction of GO with a diamine cross‐linker can result in 3 different GO assemblies depending on the ratio of D₄₀₀ to GO, which have been proven both by experiment and molecular dynamics calculations. Moreover, XRD results indicate that the interspacial distance between GO sheets can be tuned by varying the diamine chain length and concentration. We demonstrate that the resulting GOM can be moulded into various shapes and behaves like an elastic hydrogel. The fabricated GOM is non‐cyctotoxic to L929 cell lines indicating a potential for biomedical applications. It could also be readily converted to graphene monolith upon thermal treatment. This new rapid and facile method to prepare covalently cross‐linked GOM may open the door to the synthesis and application of next generation multifunctional 3D graphene structures.     

Strongly Anisotropic Thermal Conductivity of Free‐Standing Reduced Graphene Oxide Films Annealed at High Temperature

Thermal conductivity of free‐standing reduced graphene oxide films subjected to a high‐temperature treatment of up to 1000 °C is investigated. It is found that the high‐temperature annealing dramatically increases the in‐plane thermal conductivity, K, of the films from ≈3 to ≈61 W m^?1 K^?1 at room temperature. The cross‐plane thermal conductivity, K_⊥, reveals an interesting opposite trend of decreasing to a very small value of ≈0.09 W m^?1 K^?1 in the reduced graphene oxide films annealed at 1000 °C. The obtained films demonstrate an exceptionally strong anisotropy of the thermal conductivity, K/K_⊥ ≈ 675, which is substantially larger even than in the high‐quality graphite. The electrical resistivity of the annealed films reduces to 1–19 Ω □^?1. The observed modifications of the in‐plane and cross‐plane thermal conductivity components resulting in an unusual K/K_⊥ anisotropy are explained theoretically. The theoretical analysis suggests that K can reach as high as ≈500 W m^?1 K^?1 with the increase in the sp² domain size and further reduction of the oxygen content. The strongly anisotropic heat conduction properties of these films can be useful for applications in thermal management.     

Self‐Healing Graphene Oxide Based Functional Architectures Triggered by Moisture

Self‐healing materials are capable of spontaneously repairing themselves at damaging sites without additional adhesives. They are important functional materials with wide applications in actuators, shape memorizing materials, smart coatings, and medical treatments, etc. Herein, this study reports the self‐healing of graphene oxide (GO) functional architectures and devices with the assistance of moisture. These GO architectures can completely restore their mechanical‐performance (e.g., compressibility, flexibility, and strength) after healing their broken sites using a little amount of water moisture. On the basis of this effective moisture‐triggered self‐healing process, this study develops GO smart actuators (e.g., bendable actuator, biomimetic walker, rotatable fiber motor) and sensors with self‐healing ability. This work provides a new pathway for the development of self‐healing materials for their applications in multidimensional spaces and functional devices.     

The Elastic Properties and Plastic Behavior of Two‐Dimensional Polymer Structures Fabricated by Laser Interference Lithography

The elastic and plastic properties within a two‐dimensional polymer (SU8) structure with sixfold symmetry fabricated via interference lithography are presented. There is a nonuniform spatial distribution in the elastic modulus, with a higher elastic modulus obtained for nodes (brightest regions in the laser interference pattern) and a lower elastic modulus for beams (darkest regions in the laser interference pattern) of the photopatterned films. We suggest that such a nonuniformity and unusual plastic behavior are related to the variable material properties “imprinted” by the interference pattern.     

Two‐Dimensional Nanostructured Materials for Gas Sensing

Two‐dimensional (2D) nanostructures are highly attractive for fabricating nanodevices due to their high surface‐to‐volume ratio and good compatibility with device design. In recent years 2D nanostructures of various materials including metal oxides, graphene, metal dichalcogenides, phosphorene, BN and MXenes, have demonstrated significant potential for gas sensors. This review aims to provide the most recent advancements in utilization of various 2D nanomaterials for gas sensing. The common methods for the preparation of 2D nanostructures are briefly summarized first. The focus is then placed on the sensing performances provided by devices integrating 2D nanostructures. Strategies for optimizing the sensing features are also discussed. By combining both the experimental results and the theoretical studies available, structure‐properties correlations are discussed. The conclusion gives some perspectives on the open challenges and future prospects for engineering advanced 2D nanostructures for high‐performance gas sensors devices.     

High‐Performance Monolayer MoS2 Films at the Wafer Scale by Two‐Step Growth

To realize multifunctional devices at the wafer scale, the growth process of monolayer (ML) 2D semiconductors must meet two key requirements: 1) growth of continuous and homogeneous ML film at the wafer scale and 2) controllable tuning of the properties of the ML film. However, there is still no growth method available that fulfills both of these criteria. Here, the first report is presented on the preparation of continuous and uniform ML MoS₂ films through a two‐step process at the wafer scale. Unlike in previous ML MoS₂ film growth processes, the ML MoS₂ film can be uniformly modulated across the wafer in terms of material structure and composition, exciton state, and electronic transport performance. A significant result is that the high‐quality wafer‐scale ML MoS₂ films realize superior electronic performance compared to reported two‐step‐grown films, and it even matches or exceeds reported ML MoS₂ films prepared by other processes. The transistor performance of the optimized ML film achieves a field effect mobility of 10 to 30 cm² V^?1 s^?1, an on/off current ratio of about 10⁷, and hysteresis as low as 0.4 V.