Wetting‐Induced Climbing for Transferring Interfacially Assembled Large‐Area Ultrathin Pristine Graphene Film

Owing to inherent 2D structure, marvelous mechanical, electrical, and thermal properties, graphene has great potential as a macroscopic thin film for surface coating, composite, flexible electrode, and sensor. Nevertheless, the production of large‐area graphene‐based thin film from pristine graphene dispersion is severely impeded by its poor solution processability. In this study, a robust wetting‐induced climbing strategy is reported for transferring the interfacially assembled large‐area ultrathin pristine graphene film. This strategy can quickly convert solvent‐exfoliated pristine graphene dispersion into ultrathin graphene film on various substrates with different materials (glass, metal, plastics, and cloth), shapes (film, fiber, and bulk), and hydrophobic/hydrophilic patterns. It is also applicable to nanoparticles, nanofibers, and other exfoliated 2D nanomaterials for fabricating large‐area ultrathin films. Alternate climbing of different ultrathin nanomaterial films allows a layer‐by‐layer transfer, forming a well‐ordered layered composite film with the integration of multiple pristine nanomaterials at nanometer scale. This powerful strategy would greatly promote the development of solvent‐exfoliated pristine nanomaterials from dispersions to macroscopic thin film materials.     

Polymeric Graphene Bulk Materials with a 3D Cross‐Linked Monolithic Graphene Network

Although many great potential applications are proposed for graphene, till now none are yet realized as a stellar application. The most challenging issue for such practical applications is to figure out how to prepare graphene bulk materials while maintaining the unique two‐dimensional (2D) structure and the many excellent properties of graphene sheets. Herein, such polymeric graphene bulk materials containing three‐dimensional (3D) cross‐linked networks with graphene sheets as the building unit are reviewed. The theoretical research on various proposed structures of graphene bulk materials is summarized first. Then, the synthesis or fabrication of these graphene materials is described, which comprises mainly two approaches: chemical vapor deposition and cross‐linking using graphene oxide directly. Finally, some exotic and exciting potential applications of these graphene bulk materials are presented.     

Fabrication of Millimeter‐Scale,Single‐Crystal One‐Third‐Hydrogenated Graphene with Anisotropic Electronic Properties

Periodically hydrogenated graphene is predicted to form new kinds of crystalline 2D materials such as graphane, graphone, and 2D C_xH_y, which exhibit unique electronic properties. Controlled synthesis of periodically hydrogenated graphene is needed for fundamental research and possible electronic applications. Only small patches of such materials have been grown so far, while the experimental fabrication of large‐scale, periodically hydrogenated graphene has remained challenging. In the present work, large‐scale, periodically hydrogenated graphene is fabricated on Ru(0001). The as‐fabricated hydrogenated graphene is highly ordered, with a √3 × √3/R30° period relative to the pristine graphene. As the ratio of hydrogen and carbon is 1:3, the periodically hydrogenated graphene is named “one‐third‐hydrogenated graphene” (OTHG). The area of OTHG is up to 16 mm². Density functional theory calculations demonstrate that the OTHG has two deformed Dirac cones along one high‐symmetry direction and a finite energy gap along the other directions at the Fermi energy, indicating strong anisotropic electrical properties. An efficient method is thus provided to produce large‐scale crystalline functionalized graphene with specially desired properties.     

The Antibacterial Applications of Graphene and Its Derivatives

Graphene materials have unique structures and outstanding thermal, optical, mechanical and electronic properties. In the last decade, these materials have attracted substantial interest in the field of nanomaterials, with applications ranging from biosensors to biomedicine. Among these applications, great advances have been made in the field of antibacterial agents. Here, recent advancements in the use of graphene and its derivatives as antibacterial agents are reviewed. Graphene is used in three forms: the pristine form; mixed with other antibacterial agents, such as Ag and chitosan; or with a base material, such as poly (N‐vinylcarbazole) (PVK) and poly (lactic acid) (PLA). The main mechanisms proposed to explain the antibacterial behaviors of graphene and its derivatives are the membrane stress hypothesis, the oxidative stress hypothesis, the entrapment hypothesis, the electron transfer hypothesis and the photothermal hypothesis. This review describes contributions to improving these promising materials for antibacterial applications.     

Charge Transport in Polycrystalline Graphene: Challenges and Opportunities

Graphene has attracted significant interest both for exploring fundamental science and for a wide range of technological applications. Chemical vapor deposition (CVD) is currently the only working approach to grow graphene at wafer scale, which is required for industrial applications. Unfortunately, CVD graphene is intrinsically polycrystalline, with pristine graphene grains stitched together by disordered grain boundaries, which can be either a blessing or a curse. On the one hand, grain boundaries are expected to degrade the electrical and mechanical properties of polycrystalline graphene, rendering the material undesirable for many applications. On the other hand, they exhibit an increased chemical reactivity, suggesting their potential application to sensing or as templates for synthesis of one‐dimensional materials. Therefore, it is important to gain a deeper understanding of the structure and properties of graphene grain boundaries. Here, we review experimental progress on identification and electrical and chemical characterization of graphene grain boundaries. We use numerical simulations and transport measurements to demonstrate that electrical properties and chemical modification of graphene grain boundaries are strongly correlated. This not only provides guidelines for the improvement of graphene devices, but also opens a new research area of engineering graphene grain boundaries for highly sensitive electro‐biochemical devices.     

Electron Transfer Directed Antibacterial Properties of Graphene Oxide on Metals

Nanomaterials such as silver nanoparticles and graphene‐based composites are known to exhibit biocidal activities. However, interactions with surrounding medium or supporting substrates can significantly influence this activity. Here, it is shown that superior antimicrobial properties of natural shellac‐derived graphene oxide (GO) coatings is obtained on metallic films, such as Zn, Ni, Sn, and steel. It is also found that such activities are directly correlated to the electrical conductivity of the GO‐metal systems; the higher the conductivity the better is the antibacterial activity. GO‐metal substrate interactions serve as an efficient electron sink for the bacterial respiratory pathway, where electrons modify oxygen containing functional groups on GO surfaces to generate reactive oxygen species (ROS). A concerted effect of nonoxidative electron transfer mechanism and consequent ROS mediated oxidative stress to the bacteria result in an enhanced antimicrobial action of naturally derived GO‐metal films. The lack of germicidal effect in exposed cells for GO supported on electrically nonconductive substrates such as glass corroborates the above hypothesis. The results can lead to new GO coated antibacterial metal surfaces important for environmental and biomedical applications.     

Advances in Biomimetic and Nanostructured Biohybrid Materials

The rapid increase of interest in the field of biohybrid and biomimetic materials that exhibit improved structural and functional properties is attracting more and more researchers from life science, materials science, and nanoscience. Concomitant results offer valuable opportunities for applications that involve disciplines dealing with engineering, biotechnology, medicine and pharmacy, agriculture, nanotechnology, and others. In the current contribution we collect recent illustrative examples of assemblies between materials of biological origin and inorganic solids of different characteristics (texture, structure, and particle size). We introduce here a general overview on strategies for the preparation and conformation of biohybrids, the synergistic effects that determine the final properties of these materials, and their diverse applications, which cover areas as different as tissue engineering, drug delivery systems, biosensing devices, biocatalysis, green nanocomposites, etc.     

Vertical ZnO Nanotube Transistor on a Graphene Film for Flexible Inorganic Electronics

The bottom‐up integration of a 1D–2D hybrid semiconductor nanostructure into a vertical field‐effect transistor (VFET) for use in flexible inorganic electronics is reported. Zinc oxide (ZnO) nanotubes on graphene film is used as an example. The VFET is fabricated by growing position‐ and dimension‐controlled single crystal ZnO nanotubes vertically on a large graphene film. The graphene film, which acts as the substrate, provides a bottom electrical contact to the nanotubes. Due to the high quality of the single crystal ZnO nanotubes and the unique 1D device structure, the fabricated VFET exhibits excellent electrical characteristics. For example, it has a small subthreshold swing of 110 mV dec^?1, a high I_max/I_min ratio of 10⁶, and a transconductance of 170 nS µm^?1. The electrical characteristics of the nanotube VFETs are validated using 3D transport simulations. Furthermore, the nanotube VFETs fabricated on graphene films can be easily transferred onto flexible plastic substrates. The resulting components are reliable, exhibit high performance, and do not degrade significantly during testing.     

Nanocomposite Elastomeric Biomaterials for Myocardial Tissue Engineering Using Embryonic Stem Cell‐derived Cardiomyocytes

Regeneration or repair of the damaged myocardium requires different strategies including engineered constructs for more efficient cell delivery. This study was undertaken to examine the potential of a new nanostructured elastomer to deliver embryonic stem cell‐derived cardiomyocytes (ESC‐CM) to an infarcted area of the myocardium. Engineered materials were biocompatible, mechanically stable, and elastomeric nanocomposites serving as substrates for delivery of ESC‐CM and as a left ventricular support device in myocardial regeneration strategies. Materials investigated were soft and strong poly(aliphatic/aromatic‐ester) multiblock thermoplastic elastomers with poly(ethylene terephthalate) (PET) hard segments and dimerized fatty acid, i.e., dilinoleic acid (DLA) soft segments, respectively, with and without addition of 0.2 wt% TiO₂ nanoparticles to form nanocomposites. The PET/DLA‐TiO₂ nanocomposite exhibited over 8 MPa tensile strength and 900% elongation at break. Addition of TiO₂ nanoparticles significantly altered surface roughness and enhanced adhesion and spreading of ESC‐CM derived from mouse and human embryonic stem cells. The newly developed materials did not affect the functional activity of spontaneously beating hESC‐CM, as demonstrated by unaltered rate of their beating, and the cells continued to demonstrate contractile activity on the materials for more than two months in culture (the longest time tested). Quantitative proliferation and survival assays using fibroblasts confirmed the ability of the new materials to support cells as well as or better than the present commercial‐type thermoplastic elastomer analog. The results indicate that PET/DLA and PET/DLA‐TiO₂ are promising candidates for the manufacture of engineered patches to deliver ESC‐CMs.     

Contactless Spin Switch Sensing by Chemo-Electric Gating of Graphene

Direct electrical probing of molecular materials is often impaired by their insulating nature. Here, graphene is interfaced with single crystals of a molecular spin crossover complex, [Fe(bapbpy)(NCS)₂], to electrically detect phase transitions in the molecular crystal through the variation of graphene resistance. Contactless sensing is achieved by separating the crystal from graphene with an insulating polymer spacer. Next to mechanical effects, which influence the conductivity of the graphene sheet but can be minimized by using a thicker spacer, a Dirac point shift in graphene is observed experimentally upon spin crossover. As confirmed by computational modeling, this Dirac point shift is due to the phase-dependent electrostatic potential generated by the crystal inside the graphene sheet. This effect, named as chemo-electric gating, suggests that molecular materials may serve as substrates for designing graphene-based electronic devices. Chemo-electric gating, thus, opens up new possibilities to electrically probe chemical and physical processes in molecular materials in a contactless fashion, from a large distance, which can enhance their use in technological applications, for example, as sensors.     

Multifunctional Cellular Materials Based on 2D Nanomaterials: Prospects and Challenges

Recent advances in emerging 2D nanomaterial‐based cellular materials (2D‐CMs) open up new opportunities for the development of next generation cellular solids with exceptional properties. Herein, an overview of the current research status of 2D‐CMs is provided and their future opportunities are highlighted. First, the unique features of 2D nanomaterials are introduced to illustrate why these nanoscale building blocks are promising for the development of novel cellular materials and what the new features of 2D nanoscale building blocks can offer when compared to their 0D and 1D counterparts. An in‐depth discussion on the structure–property relationships of 2D‐CMs is then provided, and the remarkable functions that can be achieved by engineering their cellular architecture are highlighted. Additionally, the use of 2D‐CMs to tackle key challenges in different practical applications is demonstrated. In conclusion, a personal perspective on the challenges and future research directions of 2D‐CMs is given.     

Direct Growth of Highly Stable Patterned Graphene on Dielectric Insulators using a Surface‐Adhered Solid Carbon Source

A novel method is described for the direct growth of patterned graphene on dielectric substrates by chemical vapor deposition (CVD) in the presence of Cu vapor and using a solid aromatic carbon source, 1,2,3,4‐tetraphenylnapthalene (TPN), as the precursor. The UV/O₃ treatment of the TPN film both crosslinks TPN and results in a strong interaction between the substrate and the TPN that prevents complete sublimation of the carbon source from the substrate during CVD. Substrate‐adhered crosslinked TPN is successfully converted to graphene on the substrate without any organic contamination. The graphene synthesized by this method shows excellent mechanical and chemical stability. This process also enables the simultaneous patterning of graphene materials, which can thus be used as transparent electrodes for electronic devices. The proposed method for the synthesis directly on substrates of patterned graphene is expected to have wide applications in organic and soft hybrid electronics.     

Biohybrid Microtube Swimmers Driven by Single Captured Bacteria

Bacteria biohybrids employ the motility and power of swimming bacteria to carry and maneuver microscale particles. They have the potential to perform microdrug and cargo delivery in vivo, but have been limited by poor design, reduced swimming capabilities, and impeded functionality. To address these challenge, motile Escherichia coli are captured inside electropolymerized microtubes, exhibiting the first report of a bacteria microswimmer that does not utilize a spherical particle chassis. Single bacterium becomes partially trapped within the tube and becomes a bioengine to push the microtube though biological media. Microtubes are modified with “smart” material properties for motion control, including a bacteria‐attractant polydopamine inner layer, addition of magnetic components for external guidance, and a biochemical kill trigger to cease bacterium swimming on demand. Swimming dynamics of the bacteria biohybrid are quantified by comparing “length of protrusion” of bacteria from the microtubes with respect to changes in angular autocorrelation and swimmer mean squared displacement. The multifunctional microtubular swimmers present a new generation of biocompatible micromotors toward future microbiorobots and minimally invasive medical applications.     

Ball‐Mill‐Exfoliated Graphene: Tunable Electrochemistry and Phenol Sensing

A simple wet ball‐milling method for exfoliating pristine graphite to graphene nanosheets is proposed. The surfactant of cetyltrimethyl ammonium bromide is utilized to greatly improve the exfoliation efficiency of graphene nanosheets. Variation of the ball‐milling time is an efficient way to control the size and thickness of graphene nanosheets, as well as the level of edge defects. With an increase of ball‐milling time, superior electrochemical reactivity is imparted owing to enlarged active area and increased catalytic ability. The obtained graphene nanosheets are sensitive for electrochemical oxidation of phenols (e.g., hydroquinone, p‐chlorophenol, and p‐nitrophenol), and thus qualified for the simultaneous sensing of trace level of phenols. The detection limits of simultaneous monitoring of hydroquinone, p‐chlorophenol, and p‐nitrophenol are as low as 0.017, 0.024, and 0.42 mg L^?1, respectively. The proposed strategy thus opens up a new way to tune electrochemistry of graphene materials as well as to design their new applications.     

One‐Step Formation of a Single Atomic‐Layer Transistor by the Selective Fluorination of a Graphene Film

In this study, the scalable and one‐step fabrication of single atomic‐layer transistors is demonstrated by the selective fluorination of graphene using a low‐damage CF₄ plasma treatment, where the generated F‐radicals preferentially fluorinated the graphene at low temperature (<200 °C) while defect formation was suppressed by screening out the effect of ion damage. The chemical structure of the C–F bonds is well correlated with their optical and electrical properties in fluorinated graphene, as determined by X‐ray photoelectron spectroscopy, Raman spectroscopy, and optical and electrical characterizations. The electrical conductivity of the resultant fluorinated graphene (F‐graphene) was demonstrated to be in the range between 1.6 kΩ/sq and 1 MΩ/sq by adjusting the stoichiometric ratio of C/F in the range between 27.4 and 5.6, respectively. Moreover, a unique heterojunction structure of semi‐metal/semiconductor/insulator can be directly formed in a single layer of graphene using a one‐step fluorination process by introducing a Au thin‐film as a buffer layer. With this heterojunction structure, it would be possible to fabricate transistors in a single graphene film via a one‐step fluorination process, in which pristine graphene, partial F‐graphene, and highly F‐graphene serve as the source/drain contacts, the channel, and the channel isolation in a transistor, respectively. The demonstrated graphene transistor exhibits an on‐off ratio above 10, which is 3‐fold higher than that of devices made from pristine graphene. This efficient transistor fabrication method produces electrical heterojunctions of graphene over a large area and with selective patterning, providing the potential for the integration of electronics down to the single atomic‐layer scale.     

Direct Growth of Ultrafast Transparent Single‐Layer Graphene Defoggers

The idea flat surface, superb thermal conductivity and excellent optical transmittance of single‐layer graphene promise tremendous potential for graphene as a material for transparent defoggers. However, the resistance of defoggers made from conventional transferred graphene increases sharply once both sides of the film are covered by water molecules which, in turn, leads to a temperature drop that is inefficient for fog removal. Here, the direct growth of large‐area and continuous graphene films on quartz is reported, and the first practical single‐layer graphene defogger is fabricated. The advantages of this single‐layer graphene defogger lie in its ultrafast defogging time for relatively low input voltages and excellent defogging robustness. It can completely remove fog within 6 s when supplied a safe voltage of 32 V. No visible changes in the full defogging time after 50 defogging cycles are observed. This outstanding performance is attributed to the strong interaction forces between the graphene films and the substrates, which prevents the permeation of water molecules. These directly grown transparent graphene defoggers are expected to have excellent prospects in various applications such as anti‐fog glasses, auto window and mirror defogging.     

Tearing Graphene Sheets From Adhesive Substrates Produces Tapered Nanoribbons

Graphene is a truly two‐dimensional atomic crystal with exceptional electronic and mechanical properties. Whereas conventional bulk and thin‐film materials have been studied extensively, the key mechanical properties of graphene, such as tearing and cracking, remain unknown, partly due to its two‐dimensional nature and ultimate single‐atom‐layer thickness, which result in the breakdown of conventional material models. By combining first‐principles ReaxFF molecular dynamics and experimental studies, a bottom‐up investigation of the tearing of graphene sheets from adhesive substrates is reported, including the discovery of the formation of tapered graphene nanoribbons. Through a careful analysis of the underlying molecular rupture mechanisms, it is shown that the resulting nanoribbon geometry is controlled by both the graphene–substrate adhesion energy and by the number of torn graphene layers. By considering graphene as a model material for a broader class of two‐dimensional atomic crystals, these results provide fundamental insights into the tearing and cracking mechanisms of highly confined nanomaterials.     

Morphology and performance of graphene layers on as-grown and transferred substrates

Graphene’s excellent physical, electrical, mechanical and passivating properties are revolutionizing the world of nanotechnology. In its beginning, graphene was only used as the conductive channel in metal-oxide-semiconductor field-effect transistors and as metallic electrode in capacitors, but the development of chemical vapor deposited graphene on metal catalysts, together with an ingenious process to transfer it to arbitrary substrates extended the use of graphene to many other applications. The main problem of this methodology is to get a good adhesion between the graphene and the target substrate that ensures both protection and interaction. In this paper, we analyze the capability of graphene to adapt to underlying simple and complex substrates. We observe the important adhesion differences depending on the graphene thickness and the target substrate roughness. We take advantage of graphene coatings to protect different materials from high current densities, mechanical frictions and oxidation. The findings and prototypes here designed may open the way to extend the use of graphene as protective coating.     

Chemically Integrated Inorganic‐Graphene Two‐Dimensional Hybrid Materials for Flexible Energy Storage Devices

State‐of‐the‐art energy storage devices are capable of delivering reasonably high energy density (lithium ion batteries) or high power density (supercapacitors). There is an increasing need for these power sources with not only superior electrochemical performance, but also exceptional flexibility. Graphene has come on to the scene and advancements are being made in integration of various electrochemically active compounds onto graphene or its derivatives so as to utilize their flexibility. Many innovative synthesis techniques have led to novel graphene‐based hybrid two‐dimensional nanostructures. Here, the chemically integrated inorganic‐graphene hybrid two‐dimensional materials and their applications for energy storage devices are examined. First, the synthesis and characterization of different kinds of inorganic‐graphene hybrid nanostructures are summarized, and then the most relevant applications of inorganic‐graphene hybrid materials in flexible energy storage devices are reviewed. The general design rules of using graphene‐based hybrid 2D materials for energy storage devices and their current limitations and future potential to advance energy storage technologies are also discussed.     

Photoluminescence Architectures for Disease Diagnosis: From Graphene to Thin‐Layer Transition Metal Dichalcogenides and Oxides

Ever since the discovery of graphene, increasing efforts have been devoted to the use of this stellar material as well as the development of other graphene‐like materials such as thin‐layer transition metal dichalcogenides and oxides (TMD/Os) for a variety of applications. Because of their large surface area and unique optical properties, these two‐dimensional materials with a size ranging from the micro‐ to the nanoscale have been employed as the substrate to construct photoluminescence architectures for disease diagnosis as well as theranostics. These architectures are built through the simple self‐assembly of labeled biomolecular probes with the substrate material, leading to signal quenching. Upon the specific interaction of the architecture with a target biomarker, the signal can be spontaneously restored in a reversible manner. Meanwhile, by co‐loading therapeutic agents and employing the inherent photo‐thermal properties of the material substrates, a combined disease imaging and therapy (theranostics) can be achieved. This review highlights the latest advances in the construction and application of graphene and TMD/O based thin‐layer material composites for single‐target and multiplexed detection of a variety of biomarkers and theranostics. These versatile material architectures, owing to their ease in preparation, low cost and flexibility in functionalization, provide promising tools for both basic biochemical research and clinical applications.