Wetting of Graphene

Graphene, a remarkable 2D material, has attracted immense attention for its unique physical properties that make it ideal for a myriad of applications from electronics to biology. Fundamental to many such applications is the interaction of graphene with water, necessitating an understanding of wetting of graphene. Here, molecular dynamics simulations have been employed to understand two fundamental issues of water drop wetting on graphene: (a) the dynamics of graphene wetting and (b) wetting of graphene nanostructures. The first problem unravels that the wetting dynamics of nanodrops on graphene are exactly the same as on standard, non-2D (or non-layered) solids – this is an extremely important finding given the significant difference in the wetting statics of graphene with respect to standard solids stemming from graphene’s wetting translucency effect. This same effect, as shown in the second problem, interplays with roughness introduced by nanostructures to trigger graphene superhydrophobicity following a hitherto unknown route.

Graphene and Semicondutor or Metallic Nanoparticles for Energy Conversion

The purpose of the present PhD thesis is to investigate the properties of innovative nano- materials with respect to the conversion of renewable energies to electrical and chemical energy. The materials have been synthesized and characterized by means of a wide spectrum of morphological, compositional and photophysical techniques, in order to get an insight into the correlation between the properties of each material and the activity towards different energy conversion applications. Two main topics are addressed: in the first part of the thesis the light harvesting in pyrene functionalized silicon nanocrystals has been discussed, suggesting an original approach to suc- cessfully increase the absorption properties of these nanocrystals. The interaction of these nanocrystals was then studied, in order to give a deeper insight on the charge and energy extraction, preparing the way to implement SiNCs as active material in optoelectronic devices and photovoltaic cells. In addition to this, the luminescence of SiNCs has been exploited to increase the efficiency of conventional photovoltaic cells by means of two innovative architectures. Specifically, SiNCs has been used as luminescent downshifting layer in dye sensitized solar cells, and they were shown to be very promising light emitters in luminescent solar concentrators. The second part of the thesis was concerned on the production of hydrogen by platinum nanoparticles coupled to either electro-active or photo-active materials. Within this context, the electrocatalytic activity of platinum nanoparticles supported on exfoliated graphene has been studied, preparing an high-efficiency catalyst and disclosing the role of the exfoliation technique towards the catalytic activity. Furthermore, platinum nanoparticles have been synthesized within photoactive dendrimers, providing the first proof of concept of a dendrimer-based photocatalytic system for the hydrogen production where both sensitizer and catalyst are anchored to a single scaffold.

Synthesis of porous graphene/TiO2 by use of recycled graphite

Graphene-based nanomaterials are a kind of new technological materials with high interest for physicists, chemists and materials scientists. Graphene is a two-dimensional (2-D) sheet of carbon atoms in a hexagonal configuration with atoms bonded by sp2 bonds. These bonds and this electron configuration provides the extraordinary properties of graphene, such as very large surface area, a tunable band gap, high mechanical strength and high elasticity and thermal conductivity [1]. Graphene has also been investigated for preparation of composites with various semiconductors like TiO2, ZnO, CdS aiming at enhanced photocatalytic activity for their use for photochemical reaction as water splitting or CO2 to methanol conversion [2-3]. In this communication, the synthesis of porous graphene@TiO2 obtained from a powder graphite recycled, supplied by ECOPIBA, is presented. This graphite was exfoliated, using a nonionic surfactant (Triton X-100) and sonication. Titanium(IV) isopropoxide was used as TiO2 source. After removing the surfactant with a solution HCl/n-propanol, a porous solid is obtained with a specific area of 358 m2g-1. The solid was characterized by XRD, FTIR, XPS, EDX and TEM. Figure 1 shows the graphene 2D layer bonded with nanoparticles of TiO2. When a water suspension of this material is exposed with UV-vis radiation, water splitting reaction is carried out and H2/O2 bubbles are observed (Figure 2)

A novel graphene nanodots inlaid porous gold electrode for electrochemically controlled drug release

A uniform graphene nanodots inlaid porous gold electrode was prepared via ion beam sputtering deposition (IBSD) and mild corrosion chemistry. HRTEM, SEM, AFM and XPS analyses revealed the successful fabrication of graphene nanodots inlaid porous gold electrode. The as-prepared porous electrode was used as π-orbital-rich drug loading platform to fabricate an electrochemically controlled drug release system with high performance. π-orbital-rich drugs with amino mioety, like doxorubicin (DOX) and tetracycline (TC), were loaded into the graphene nanodots inlaid porous gold electrode via non-covalent π-π stacking interaction. The amino groups in DOX and TC can be easily protonated at acidic medium to become positively-charged NH3(+), which allow these drug molecules to be desorbed from the porous electrode surface via electrostatic repulsion when positive potential is applied at the electrode. The drug loading and release experiment indicated that this graphene nanodots inlaid porous gold electrode can be used to conveniently and efficiently control the drug release electrochemically. Not only did our work provide a benign method to electrochemically controlled drug release via electrostatic repulsion process, it also enlighten the promising practical applications of micro electrode as a drug carrier for precisely and efficiently controlled drug release via embedding in the body.

Graphene nanodots encaged 3-D gold substrate as enzyme loading platform for the fabrication of high performance biosensors

Herein, a uniform three-dimensional (3-D) graphene nanodots-encaged porous gold electrode was prepared via ion beam sputtering deposition (IBSD) and mild corrosion chemistry for efficient enzyme electrode fabrication. Enzymes, like glucose oxidase and catalase, were modified with pyrene functionalities and then loaded into the graphene nanodots encaged porous gold electrode via non-covalent π-π stacking interaction between pyrene and graphene. The fabricated enzyme electrodes showed profound reusability and repeatability, high sensitivity, inherent selectivity and enhanced detection range. As for glucose analysis a broad linear range from 0.05 to 100 mM was obtained and the linear range for hydrogen peroxide was 0.005 to 4 mM. Detection limits of 30 μM for glucose and 1 μM for hydrogen peroxide were achieved (S/N = 3), respectively. These electrodes can be applied to analyze the clinical samples with reliable results. The formation mechanism and 3-D structure of the porous electrode were investigated using high resolution transmission electron microscope (HRTEM), atomic force microscopy (AFM), scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS). Most importantly, various other ideal biosensors can be fabricated using the same porous electrode and the same enzyme modification methodology.

Preparation of graphene oxide decorated Fe3O4@SiO2 nanocomposites with superior adsorption capacity and SERS detection for organic dyes

The fast detection and removal of organic dyes from contaminated water has become an urgent environmental issue due to their high toxicity, chemical stability, and low biodegradability. In this paper, we have developed graphene oxide decorated Fe3O4@SiO2 (Fe3O4@SiO2-GO) as a novel adsorbent aiming at the rapid adsorption and trace analysis of organic dyes followed by surface enhanced Raman scattering (SERS). The structure and morphology of the nanocomposites were characterized by transmission electron microscopy (TEM), Fourier infrared spectrometry (FT-IR), X-ray diffraction (XRD), and vibrating sample magnetometer (VSM). The obtained nanocomposites were used to adsorb methylene blue (MB) in aqueous solution based on π-π stacking interaction and electrostatic attraction between MB and GO, and the adsorption behaviors of MB were investigated. Moreover, the obtained nanocomposites with adsorbed dyes were separated from the solution and loaded with silver nanoparticles for SERS detection. These nanocomposites showed superior SERS sensitivity and the lowest detectable concentration was 1.0 × 10-7 M.

Rheological behaviours of graphene oxide reinforced cement composite

Graphene oxide (GO) offers great potential as nanoscale reinforcement for cementitious material. In this work, the rheological behaviours of the GO-cement composite were investigated for the first time. It was found that the workability of cement paste (w/c=0.5) is significantly decreased with the addition of 0.02wt% GO sheets. The rheology tests results show that the GO sheets greatly increase the yield stress and viscosity of the cement paste. It is also found that the yield stress and viscosity of the GO-cement composite increase with increasing size of GO sheets. The reduction of workability is undesirable for the application of the novel GO-cement composite. Therefore, further research works are needed to improve the workability of the composite.

A new Raman metric for the characterisation of graphene oxide and its derivatives

Raman spectroscopy is among the primary techniques for the characterisation of graphene materials, as it provides insights into the quality of measured graphenes including their structure and conductivity as well as the presence of dopants. However, our ability to draw conclusions based on such spectra is limited by a lack of understanding regarding the origins of the peaks. Consequently, traditional characterisation techniques, which estimate the quality of the graphene material using the intensity ratio between the D and the G peaks, are unreliable for both GO and rGO. Herein we reanalyse the Raman spectra of graphenes and show that traditional methods rely upon an apparent G peak which is in fact a superposition of the G and D' peaks. We use this understanding to develop a new Raman characterisation method for graphenes that considers the D' peak by using its overtone the 2D'. We demonstrate the superiority and consistency of this method for calculating the oxygen content of graphenes, and use the relationship between the D' peak and graphene quality to define three regimes. This has important implications for purification techniques because, once GO is reduced beyond a critical threshold, further reduction offers limited gain in conductivity.

Compositional effects of large graphene oxide sheets on the spinnability and properties of polyurethane composite fibers

Recent advances in wearable electronics, technical textiles, and wearable strain sensing devices have resulted in extensive research on stretchable electrically conductive fibers. Addressing these areas require the development of efficient fiber processing methodologies that do not compromise the mechanical properties of the polymer (typically an elastomer) when nanomaterials are added as conductive fillers. It is highly desirable that the addition of conductive fillers provides not only electrical conductivity, but that these fillers also enhance the stiffness, strength, stretchability, and toughness of the polymer. Here, the compatibility of polyurethane (PU) and graphene oxide (GO) is utilized for the study of the properties of elastomeric conductive fibers prepared by wet-spinning. The GO-reinforced PU fibers demonstrate outstanding mechanical properties with a 200-fold and a threefold enhancement in Young's modulus and toughness, respectively. Postspinning thermal annealing of the fibers results in electrically conductive fibers with a low percolation threshold (≈0.37 wt% GO). An investigation into optimized fiber's electromechanical behavior reveals linear strain sensing abilities up to 70%. Results presented here provide practical insights on how to simultaneously maintain or improve electrical, mechanical, and electromechanical properties in conductive elastomer fibers.

Towards the knittability of graphene oxide fibres

Recent developments in graphene oxide fibre (GO) processing include exciting demonstrations of hand woven textile structures. However, it is uncertain whether the fibres produced can meet the processing requirements of conventional textile manufacturing. This work reports for the first time the production of highly flexible and tough GO fibres that can be knitted using textile machinery. The GO fibres are made by using a dry-jet wet-spinning method, which allows drawing of the spinning solution (the GO dispersion) in several stages of the fibre spinning process. The coagulation composition and spinning conditions are evaluated in detail, which led to the production of densely packed fibres with near-circular cross-sections and highly ordered GO domains. The results are knittable GO fibres with Young's modulus of ~7.9 GPa, tensile strength of ~135.8 MPa, breaking strain of ~5.9%, and toughness of ~5.7 MJ m(-3). The combination of suitable spinning method, coagulation composition, and spinning conditions led to GO fibres with remarkable toughness; the key factor in their successful knitting. This work highlights important progress in realising the full potential of GO fibres as a new class of textile.

N-doped pierced graphene microparticles as a highly active electrocatalyst for li-air batteries

In this work we report a novel scalable strategy to prepare a lithium-air battery electrode from 3D Ndoped pierced graphene microparticles (N-PGM) with highly active performance. This approach has combined the merits of spray drying technology and the hard template method. The pierced structured graphene microparticles were characterized physically and electrochemically. An x-ray
photoelectron spectrometer and Raman spectra have revealed that the novel structure possesses a higher N-doping level than conventional graphene without the pierced structure. A much higher BET surface area was also achieved for the N-PGMthan the conventional N-doped graphene microparticles (N-GM). Cyclic voltammetry indicated that the lithium-air battery with the N-PGM electrode has a better utilization for the graphene mass and a higher void volume for Li2O2 formation than that of theN-GMelectrode. N-PGMalso exhibits improved decomposition kinetics for Li oxide
species yielded in the cathodic reaction. Charge and discharge measurements showed that theN-PGM lithium-air battery achieved an improved specific capacity and an enhanced cycle performance than when anN-GMelectrode is used.

Theoretical study of quantum capacitance and associated delay in armchair-edge graphene nanoribbons

This work presents a comprehensive investigation of the quantum capacitance and the associated effects on the carrier transit delay in armchair-edge graphene nanoribbons (A-GNRs) based on semi-analytical method. We emphasize on the realistic analysis of bandgap with taking edge effects into account by means of modified tight binding (TB) model. The results show that the edge effects have significant influence in defining the bandgap which is a necessary input in the accurate analyses of capacitance. The quantum capacitance is discussed in both nondegenerate (low gate voltage) and degenerate (high gate voltage) regimes. We observe that the classical capacitance limits the total gate (external) capacitance in the degenerate regime, whereas, quantum capacitance limits the external gate capacitance in the nondegenerate regime. The influence of gate capacitances on the gate delay is studied extensively to demonstrate the optimization of switching time. Moreover, the high-field behavior of a GNR is studied in the degenerate and nondegenerate regimes. We find that a smaller intrinsic capacitance appears in the channel due to high velocity carrier, which limits the quantum capacitance and thus limit the gate delay. Such detail analysis of GNRs considering a realistic model would be useful for the optimized design of GNR-based nanoelectronic devices.

Superhydrophobic and superoleophilic micro-wrinkled reduced graphene oxide as a highly portable and recyclable oil sorbent.

The potential of superhydrophobic and superoleophilic microwrinkled reduced graphene oxide (MWrGO) structures is here demonstrated for oil spill cleanup. The impact of the thickness of MWrGO films on the sorption performance of three different oils was investigated. Water contact angles across the MWrGO surfaces were found to exceed 150°, while oil could be easily absorbed by the microwrinkled structures of MWrGO within seconds after contact. Although the oil surface diffusion rate was not found to be dependent on the thickness of the graphene oxide films, the oil sorption capacity was the largest with the thinner MWrGO films due to the high surface area resulting from their fine surface texture. Furthermore, the composite films can be repeatedly used for at least 20 oil sorption-removal cycles without any notable loss in selectivity and uptake capacity. These MWrGO/elastomer composite films could be applied as a potential candidate material for future oil spill cleanup.

High-performance multifunctional graphene-PLGA fibers: toward biomimetic and conducting 3D scaffolds

The development of electrically conducting fibers based on known cytocompatible materials is of interest to those engaged in tissue regeneration using electrical stimulation. Herein, it is demonstrated that with the aid of rheological insights, optimized formulations of graphene containing spinnable poly(lactic-co-glycolic acid) (PLGA) dopes can be made possible. This helps extend the general understanding of the mechanics involved in order to deliberately translate the intrinsic superior electrical and mechanical properties of solution-processed graphene into the design process and practical fiber architectural engineering. The as-produced fibers are found to exhibit excellent electrical conductivity and electrochemical performance, good mechanical properties, and cellular affinity. At the highest loading of graphene (24.3 wt%), the conductivity of as-prepared fibers is as high as 150 S m-1 (more than two orders of magnitude higher than the highest conductivity achieved for any type of nanocarbon-PLGA composite fibers) reported previously. Moreover, the Young's modulus and tensile strength of the base fiber are enhanced 647- and 59-folds, respectively, through addition of graphene.

Fabrication of graphene foam supported carbon nanotube/polyaniline hybrids for high-performance supercapacitor applications

A large-scale, high-powered energy storage system is crucial for addressing the energy problem. The development of high-performance materials is a key issue in realizing the grid-scale applications of energy-storage devices. In this work, we describe a simple and scalable method for fabricating hybrids (graphenepyrrole/ carbon nanotube-polyaniline (GPCP)) using graphene foam as the supporting template. Graphene-pyrrole (G-Py) aerogels are prepared via a green hydrothermal route from two-dimensional materials such as graphene sheets, while a carbon nanotube/polyaniline (CNT/PANI) composite dispersion is obtained via the in situ polymerization method. The functional nanohybrid materials of GPCP can be assembled by simply dipping the prepared G-py aerogels into the CNT/PANI dispersion. The morphology of the obtained GPCP is investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which revealed that the CNT/PANI was uniformly deposited onto the surfaces of the graphene. The as-synthesized GPCP maintains its original three-dimensional hierarchical porous architecture, which favors the diffusion of the electrolyte ions into the inner region of the active materials. Such hybrid materials exhibit significant specific capacitance of up to 350 F g^-1, making them promising in large-scale energy-storage device applications.