Liquid phase exfoliation and interfacial assembly of two-dimensional nanomaterials

Liquid phase exfoliation (LPE) has been demonstrated to be a powerful and versatile technique for scalable production of two-dimensional (2D) nanomaterials, such as graphene and molybdenum disulfide (MoS2) which allows for their processing into a wide range of structures. LPE can be understood in terms of the chemical physics of the interactions of the liquid with the nanosheets. Here, it is shown that the prototypical solvent for LPE of 2D materials, N-methyl- 2-pyrrolidone, undergoes chemical modification during exfoliation which gives rise to increased absorption and photoluminescence, making it particularly unsuitable for dispersion of photoluminescent nanomaterials such as MoS2. A subsequent study identifies the influence of solvent properties on the exfoliation process and presents a model which allows for consistent size selection of few-layer nanosheets from any chosen solvent. Using this understanding, applications-driven solvent selection can be used to identify alternative solvents which facilitate processing of liquid-exfoliated nanosheets into composite and thin film structures. This approach allows for exfoliation into water-immiscible solvents to enable assembly of liquid-exfoliated 2D materials can be assembled at the interface between two immiscible liquids as solid-stabilised emulsions where the nanosheets act as both stabiliser and functional material. An understanding of the chemical physics of these emulsions is developed in terms of surface energies which allows for both measurement of the surface properties of the stabilising nanosheets and design of emulsions for potential applications as inks, composites, sensors and energy storage devices. In addition, Langmuir deposition can be used to assemble densely-packed ultrathin films at the air/water interface. This method is used to prepare few-layer MoS2 nanosheet networks, which exhibit interesting spectroscopic properties. Furthermore, these films exhibit high conductivity which is attributed to doping by nanosheet edges. The combination of nanoscale film thickness and increased conductivity highlights their potential for optoelectronic devices. As such, this study demonstrates that, through understanding of exfoliation and size selection, interfacial assembly represents a promising approach for realisation of functional composites and thin films, enabled by ultra-thin interfacial films of 2D nanosheets

Understanding solvent spreading for Langmuir deposition of nanomaterial films: a Hansen solubility parameter approach

In order to prepare high-quality Langmuir films of two-dimensional materials it is important to select a solvent optimized for both exfoliation and spreading at the air-water interface. Whilst it is generally accepted that exfoliation and stabilisation of two-dimensional materials is well-described using the Hansen solubility parameter theory, a complementary description of solvent spreading behaviour is lacking. To this end we develop an understanding of solvent spreading using a Hansen solubility parameter framework. Our model accurately predicts the behaviour of both water-immiscible and water-miscible solvents in Langmuir film formation experiments. We demonstrate that spreading behaviour can be modified by controlling the surface pressure of the subphase using an amphiphilic species and accordingly utilise this approach to determine the maximum spreading pressure for a selection of solvents. Ultimately, by building on this understanding we open up additional routes to optimize the preparation of Langmuir films of two-dimensional materials and other nanoparticles

Functional liquid structures by emulsification of graphene and other two-dimensional nanomaterials

Pickering emulsions stabilised with nanomaterials provide routes to a range of functional macroscopic assemblies. We demonstrate the formation and properties of water-in-oil emulsions prepared through liquid-phase exfoliation of graphene. Due to the functional nature of the stabiliser, the emulsions exhibit conductivity due to inter-particle tunnelling. We demonstrate a strain sensing application with a large gauge factor of ~40; the highest reported in a liquid. Our methodology can be applied to other two-dimensional layered materials opening up applications such as energy storage materials, and flexible and printable electronics

Triply bonded pancake π-dimers stabilized by tetravalent actinides

Aromatic π-stacking is a weakly attractive, noncovalent interaction often found in biological macromolecules and synthetic supramolecular chemistry. The weak nondirectional nature of π-stacking can present challenges in the design of materials owing to their weak, nondirectional nature. However, when aromatic π-systems contain an unpaired electron, stronger attraction involving face-to-face π-orbital overlap is possible, resulting in covalent so-called “pancake” bonds. Two-electron, multicenter single pancake bonds are well known, whereas four-electron double pancake bonds are rare. Higher-order pancake bonds have been predicted, but experimental systems are unknown. Here, we show that six-electron triple pancake bonds can be synthesized by a 3-fold reduction of hexaazatrinaphthylene (HAN) and subsequent stacking of the [HAN]3– triradicals. Our analysis reveals a multicenter covalent triple pancake bond consisting of a σ-orbital and two equivalent π-orbitals. An electrostatic stabilizing role is established for the tetravalent thorium and uranium ions in these systems. We also show that the electronic absorption spectrum of the triple pancake bonds closely matches computational predictions, providing experimental verification of these unique interactions. The discovery of conductivity in thin films of triply bonded π-dimers presents new opportunities for the discovery of single-component molecular conductors and other spin-based molecular materials

Ultrasensitive strain gauges enabled by graphene-stabilized silicone emulsions

Here, an approach is presented to incorporate graphene nanosheets into a silicone rubber matrix via solid stabilization of oil‐in‐water emulsions. These emulsions can be cured into discrete, graphene‐coated silicone balls or continuous, elastomeric films by controlling the degree of coalescence. The electromechanical properties of the resulting composites as a function of interdiffusion time and graphene loading level are characterized. With conductivities approaching 1 S m−1, elongation to break up to 160%, and a gauge factor of ≈20 in the low‐strain linear regime, small strains such as pulse can be accurately measured. At higher strains, the electromechanical response exhibits a robust exponential dependence, allowing accurate readout for higher strain movements such as chest motion and joint bending. The exponential gauge factor is found to be ≈20, independent of loading level and valid up to 80% strain; this consistent performance is due to the emulsion‐templated microstructure of the composites. The robust behavior may facilitate high‐strain sensing in the nonlinear regime using nanocomposites, where relative resistance change values in excess of 107 enable highly accurate bodily motion monitoring

Surfactant-free liquid-exfoliated copper hydroxide nanocuboids for non-enzymatic electrochemical glucose detection

To facilitate printable sensing solutions particles need to be suspended and stabilised in a liquid medium. Hansen parameters were used to identify that alcohol–water blends are ideal for stabilising colloidal copper hydroxide in dispersion. The suspended material can be further separated in various size fractions with a distinct cuboid geometry which was verified using atomic force microscopy. This facilitates the development of Raman spectroscopic metrics for determining particle sizes. This aspect ratio is related to the anisotropic crystal structure of the bulk crystallites. As the size of the nanocuboids decreases electrochemical sensitivity of the material increases due to an increase in specific surface area. Electrochemical glucose sensitivity was investigated using both cyclic voltammetry and chronoamperometry. The sensitivity is noted to saturate with film thickness. The electrochemical response of 253 mA M−1 cm−2 up to 0.1 mM and 120 mA cm−2 up to 0.6 mM allow for calibration of potential devices. These results indicate suitability for use as a glucose sensor and, due to the surfactant-free, low boiling point solvent approach used to exfoliate the nanocuboids, it is an ideal candidate for printable solutions. The ease of processing will also allow this material to be integrated in composite films for improved functionality in future devices

Localised strain and doping of 2D materials

There is a growing interest in 2D materials-based devices as the replacement for established materials, such as silicon and metal oxides in microelectronics and sensing, respectively. However, the atomically thin nature of 2D materials makes them susceptible to slight variations caused by their immediate environment, inducing doping and strain, which can vary between, and even microscopically within, devices. One of the misapprehensions for using 2D materials is the consideration of unanimous intrinsic properties over different support surfaces. The interfacial interaction, intrinsic structural disorder and external strain modulate the properties of 2D materials and govern the device performance. The understanding, measurement and control of these factors are thus one of the significant challenges for the adoption of 2D materials in industrial electronics, sensing, and polymer composites. This topical review provides a comprehensive overview of the effect of strain-induced lattice deformation and its relationship with physical and electronic properties. Using the example of graphene and MoS2 (as the prototypical 2D semiconductor), we rationalise the importance of scanning probe techniques and Raman spectroscopy to elucidate strain and doping in 2D materials. These effects can be directly and accurately characterised through Raman shifts in a non-destructive manner. A generalised model has been presented that deconvolutes the intertwined relationship between strain and doping in graphene and MoS2 that could apply to other members of the 2D materials family. The emerging field of straintronics is presented, where the controlled application of strain over 2D materials induces tuneable physical and electronic properties. These perspectives highlight practical considerations for strain engineering and related microelectromechanical applications

Mid-infrared electrochromics enabled by intraband modulation in carbon nanotube networks

Tuneable infrared properties, such as transparency and emissivity, are highly desirable for a range of applications, including thermal windows and emissive cooling. Here, we demonstrate the use of carbon nanotube networks spray-deposited onto an ionic liquid-infused membrane to fabricate devices with electrochromic modulation in the mid-infrared spectrum, facilitating control of emissivity and apparent temperature. Such modulation is enabled by intraband transitions in unsorted single-walled carbon nanotube networks, allowing the use of scalable nanotube inks for printed devices. These devices are optimized by varying film thickness and sheet resistance, demonstrating the emissivity modulation (from ∼0.5 to ∼0.2). These devices and the understanding thereof open the door to selection criteria for infrared electrochromic materials based on the relationship between band structure, electrochemistry, and optothermal properties to enable the development of solution-processable large-area coatings for widespread thermal management applications

Charge Transfer Hybrids of Graphene Oxide and the Intrinsically Microporous Polymer PIM-1

Nanohybrid materials based on nanoparticles of the intrinsically microporous polymer PIM-1 and graphene oxide (GO) are prepared from aqueous dispersions with a re-precipitation method, resulting in the surface of the GO sheets being decorated with nanoparticles of PIM-1. The significant blueshift in fluorescence signals for the GO/PIM-1 nanohybrids indicates modification of the optoelectronic properties of the PIM-1 in the presence of the GO due to their strong interactions. The stiffening in the Raman G peak of GO (by nearly 6 cm^{-1}) further indicates p-doping of the GO in the presence of PIM. Kelvin probe force microscopy (KPFM) and electrochemical reduction measurements of the nanohybrids provide direct evidence for charge transfer between the PIM-1 nanoparticles and the GO nanosheets. These observations will be of importance for future applications of GO-PIM-1 nanohybrids as substrates and promoters in catalysis and sensing