Mapping the Binding Energy of Layered Crystals to Macroscopic Observables.

Van der Waals (vdW) integration of two dimensional (2D) crystals into functional heterostructures emerges as a powerful tool to design new materials with fine-tuned physical properties at an unprecedented precision. The intermolecular forces governing the assembly of vdW heterostructures are investigated by first-principles models, yet translating the outcome of these models to macroscopic observables in layered crystals is missing. Establishing this connection is, therefore, crucial for ultimately designing advanced materials of choice-tailoring the composition to functional device properties. Herein, components from both vdW and non-vdW forces are integrated to build a comprehensive framework that can quantitatively describe the dynamics of these forces in action. Specifically, it is shown that the optical band gap of layered crystals possesses a peculiar ionic character that works as a quantitative indicator of non-vdW forces. Using these two components, it is then described why only a narrow range of exfoliation energies for this class of materials is observed. These findings unlock the microscopic origin of universal binding energy in layered crystals and provide a general protocol to identify and synthesize new crystals to regulate vdW coupling in the next generation of heterostructures.

Self-consistent dielectric functions of materials: Toward accurate computation of Casimir-van der Waals forces.

Research on theoretical calculation of Casimir-van der Waals (vdW) forces is characterized by a great number of inconsistencies and conflicting reports with widely differing results for many known materials, including water, contradicting experimental measurements. Despite its importance for conceptual advances in both fundamental aspects and practical applications, a universal framework for the accurate determination of Casimir-vdW forces is lacking. Here, we propose a universal theoretical platform for computing Casimir-vdW forces, accounting for the electronic dielectric constant, optical bandgap, density, and chemical composition. Using this methodology, we determine the dielectric function for 55 materials, over a wide range of photon energies, covering an extensive list of common metals, organic and inorganic semiconductors, and insulators. Internal consistency of the compiled data is validated using optical sum rules and Kramers-Kronig relations. We demonstrate that the calculated vdW forces based on these data match remarkably well with the experimentally measured vdW forces.

Silicon as a ubiquitous contaminant in graphene derivatives with significant impact on device performance.

Silicon-based impurities are ubiquitous in natural graphite. However, their role as a contaminant in exfoliated graphene and their influence on devices have been overlooked. Herein atomic resolution microscopy is used to highlight the existence of silicon-based contamination on various solution-processed graphene. We found these impurities are extremely persistent and thus utilising high purity graphite as a precursor is the only route to produce silicon-free graphene. These impurities are found to hamper the effective utilisation of graphene in whereby surface area is of paramount importance. When non-contaminated graphene is used to fabricate supercapacitor microelectrodes, a capacitance value closest to the predicted theoretical capacitance for graphene is obtained. We also demonstrate a versatile humidity sensor made from pure graphene oxide which achieves the highest sensitivity and the lowest limit of detection ever reported. Our findings constitute a vital milestone to achieve commercially viable and high performance graphene-based devices.

Processable 2D materials beyond graphene: MoS2 liquid crystals and fibres.

Herein, we show properly engineered MoS2 crystals can readily form liquid crystalline dispersions in water making them ideal candidates for large-scale manufacturing processes. The guideline provided here can serve as the basis to develop practical protocols to address the long-standing goal of large-scale manufacturing of 2D materials.

Superflexibility of graphene oxide.

Graphene oxide (GO), the main precursor of graphene-based materials made by solution processing, is known to be very stiff. Indeed, it has a Young's modulus comparable to steel, on the order of 300 GPa. Despite its very high stiffness, we show here that GO is superflexible. We quantitatively measure the GO bending rigidity by characterizing the flattening of thermal undulations in response to shear forces in solution. Characterizations are performed by the combination of synchrotron X-ray diffraction at small angles and in situ rheology (rheo-SAXS) experiments using the high X-ray flux of a synchrotron source. The bending modulus is found to be 1 kT, which is about two orders of magnitude lower than the bending rigidity of neat graphene. This superflexibility compares with the fluidity of self-assembled liquid bilayers. This behavior is discussed by considering the mechanisms at play in bending and stretching deformations of atomic monolayers. The superflexibility of GO is a unique feature to develop bendable electronics after reduction, films, coatings, and fibers. This unique combination of properties of GO allows for flexibility in processing and fabrication coupled with a robustness in the fabricated structure.

Self-Assembled Multifunctional Hybrids: Toward Developing High-Performance Graphene-Based Architectures for Energy Storage Devices.

The prospect of developing multifunctional flexible three-dimensional (3D) architectures based on integrative chemistry for lightweight, foldable, yet robust, electronic components that can turn the many promises of graphene-based devices into reality is an exciting direction that has yet to be explored. Herein, inspired by nature, we demonstrate that through a simple, yet novel solvophobic self-assembly processing approach, nacre-mimicking, layer-by-layer grown, hybrid composite materials (consisting of graphene oxide, carbon nanotubes, and conducting polymers) can be made that can incorporate many of the exciting attributes of graphene into real world materials. The as-produced, self-assembled 3D multifunctional architectures were found to be flexible, yet mechanically robust and tough (Young's modulus in excess of 26.1 GPa, tensile strength of around 252 MPa, and toughness of 7.3 MJ m(-3)), and exhibited high native electrical conductivity (38700 S m(-1)) and unrivalled volumetric capacitance values (761 F cm(-3)) with excellent cyclability and rate performance.

High-performance multifunctional graphene yarns: toward wearable all-carbon energy storage textiles.

The successful commercialization of smart wearable garments is hindered by the lack of fully integrated carbon-based energy storage devices into smart wearables. Since electrodes are the active components that determine the performance of energy storage systems, it is important to rationally design and engineer hierarchical architectures atboth the nano- and macroscale that can enjoy all of the necessary requirements for a perfect electrode. Here we demonstrate a large-scale flexible fabrication of highly porous high-performance multifunctional graphene oxide (GO) and rGO fibers and yarns by taking advantage of the intrinsic soft self-assembly behavior of ultralarge graphene oxide liquid crystalline dispersions. The produced yarns, which are the only practical form of these architectures for real-life device applications, were found to be mechanically robust (Young's modulus in excess of 29 GPa) and exhibited high native electrical conductivity (2508 ± 632 S m(-1)) and exceptionally high specific surface area (2605 m(2) g(-1) before reduction and 2210 m(2) g(-1) after reduction). Furthermore, the highly porous nature of these architectures enabled us to translate the superior electrochemical properties of individual graphene sheets into practical everyday use devices with complex geometrical architectures. The as-prepared final architectures exhibited an open network structure with a continuous ion transport network, resulting in unrivaled charge storage capacity (409 F g(-1) at 1 A g(-1)) and rate capability (56 F g(-1) at 100 A g(-1)) while maintaining their strong flexible nature.

Organic solvent-based graphene oxide liquid crystals: a facile route toward the next generation of self-assembled layer-by-layer multifunctional 3D architectures.

We introduce soft self-assembly of ultralarge liquid crystalline (LC) graphene oxide (GO) sheets in a wide range of organic solvents overcoming the practical limitations imposed on LC GO processing in water. This expands the number of known solvents which can support amphiphilic self-assembly to ethanol, acetone, tetrahydrofuran, N-dimethylformamide, N-cyclohexyl-2-pyrrolidone, and a number of other organic solvents, many of which were not known to afford solvophobic self-assembly prior to this report. The LC behavior of the as-prepared GO sheets in organic solvents has enabled us to disperse and organize substantial amounts of aggregate-free single-walled carbon nanotubes (SWNTs, up to 10 wt %) without compromise in LC properties. The as-prepared LC GO-SWNT dispersions were employed to achieve self-assembled layer-by-layer multifunctional 3D hybrid architectures comprising SWNTs and GO with unrivalled superior mechanical properties (Young's modulus in excess of 50 GPa and tensile strength of more than 500 MPa).

Enhancement of the electrochemical capacitance of TiO2 nanotube arrays through controlled phase transformation of anatase to rutile.

Here, we report the fabrication of self-organized titania (TiO(2)) nanotube array supercapacitor electrodes through controlled phase transformation of TiO(2), with aerial capacitances as high as 2.6 mF cm(-2), which far exceeds the values so far reported in the literature. The role of phase transformation in the electrochemical charge-discharge behaviour of nanocrystalline TiO(2) nanotubes is investigated and discussed in detail. The ease of synthesis and the exceptional electrochemical properties make these nanotube arrays an alternative candidate for use in energy storage devices.

A highly ordered titania nanotube array as a supercapacitor electrode.

We report the synthesis of self-organized titania nanotubes and nanocrystalline titania powders employing an alternative and novel approach. Integrating these nanostructures in a binder-free working electrode improved the capacitance up to 911 µF cm(-2), which is around one to two orders of magnitude higher than the conventional electric double layer capacitors.