Selective suspension of single layer graphene mechanochemically exfoliated from carbon nanofibres

This paper presents the first report of the successful ball-milling exfoliation of graphitic filaments （GANF~ carbon nanofibres） into single layer graphene. The addition of small amounts of solvent during the milling process makes it possible to enhance the intercalation of the exfoliating agent （melamine） between the graphene layers, thus promoting exceptional exfoliation. Advantage has also been taken of the fact that the Hansen solubility parameters of graphene are different from those of carbon fibres, which allows single and few-layer graphene to be suspended in a particular solvent, thus discriminating them from poorly exfoliated carbon nanofibres.     

Clean transfer of graphene on Pt foils mediated by a carbon monoxide intercalation process

Noble metals such as Pt are a perfect substrate for the catalytic growth of monolayer graphene. However, the requirements of the subsequent transfer process are not compatible with the traditional etching method. In this work, we find that the interaction of graphene with Pt foil can be weakened through the intercalation of carbon monoxide （CO） under ambient pressure. This intercalation process occurs on both hexagonal-shape graphene islands and irregular graphene patches on changing the CO partial pressure from 0 to 0.6 MPa, as observed by scanning electron microscopy （SEM）, Raman spectroscopy and X-ray photoemission spectroscopy. We demonstrate that, on a practical timescale, the intercalation ratio is proportional to the partial pressure of CO. Furthermore, we develop a clean transfer method of CO-intercalated graphene with water as a peeling agent. We show that this method enables the transfer of tens of micrometer-scale graphene patches onto SiO2/Si, which are free from metal or oxide particle contamination. This transfer method should be a significant step towards the dean transfer of graphene, as well as the recydable use of noble metal substrates.     

A graphene-based surface plasmon sensor

We present the application of graphene as a plasmon sensor. It was found that the electronic transport of chemical vapor deposition CVD-synthesized graphene is sensitive to surface plasmons generated by the illumination of metal nanoparticles. The observed change in electronic conduction can be up to seven times larger than the intrinsic photoresponse of graphene. A study of the mechanism revealed local field-assisted oxygen desorption induced by surface plasmons to be the cause of this intriguing behavior. A detailed investigation of the wavelength and spacing dependence of the plasmon-graphene coupling proves that graphene can be used as a sensitive, high resolution electronic plasmon detector. This finding shows the potential of devices exploiting the novel properties of graphene and surface plasmons.      

Anomalous moire pattern of graphene investigated by scanning tunneling microscopy： Evidence of graphene growth on oxidized Cu（111）

The growth of graphene on oriented （111） copper films has been achieved by atmospheric pressure chemical vapor deposition. The structural properties of as-produced graphene have been investigated by scanning tunneling microscopy. Anomalous moir6 superstructures composed of well-defined linear periodic modulations have been observed. We report here on comprehensive and detailed studies of these particular moir6 patterns present in the graphene topography revealing that, in certain conditions, the growth can occur on the oxygen-induced reconstructed copper surface and not directly on the oriented （111） copper film as expected.     

Terahertz graphene optics

The magnitude of the optical sheet conductance of single-layer graphene is universal, and equal to e ²/4? (where 2??? = h (the Planck constant)). As the optical frequency decreases, the conductivity decreases. However, at some frequency in the THz range, the conductivity increases again, eventually reaching the DC value, where the magnitude of the DC sheet conductance generally displays a sample- and doping-dependent value between ??e ²/h and 100 e ²/h. Thus, the THz range is predicted to be a non-trivial region of the spectrum for electron transport in graphene, and may have interesting technological applications. In this paper, we present the first frequency domain measurements of the absolute value of multilayer graphene (MLG) and single-layer graphene (SLG) sheet conductivity and transparency from DC to 1 THz, and establish a firm foundation for future THz applications of graphene.      

Continuous wafer-scale graphene on cubic-SiC（O01）

The atomic and electronic structure of graphene synthesized on commercially available cubic-SiC（001）/Si（001） wafers have been studied by low energy electron microscopy （LEEM）, scanning tunneling microscopy （STM）, low energy electron diffraction （LEED）, and angle resolved photoelectron spectroscopy （ARPES）. LEEM and STM data prove the wafer-scale continuity and uniform thickness of the graphene overlayer on SIC（001）. LEEM, STM and ARPES studies reveal that the graphene overlayer on SIC（001） consists of only a few monolayers with physical properties of quasi-freestanding graphene. Atomically resolved STM and micro-LEED data show that the top graphene layer consists of nanometer-sized domains with four different lattice orientations connected through the 〈110〉-directed boundaries. ARPES studies reveal the typical electron spectrum of graphene with the Dirac points close to the Fermi level. Thus, the use of technologically relevant SiC（001）/Si（001） wafers for graphene fabrication repre-sents a realistic way of bridging the gap between the outstanding properties of graphene and their applications.     

Weak mismatch epitaxy and structural Feedback in graphene growth on copper foil

Graphene growth by low-pressure chemical vapor deposition on low cost copper foils shows great promise for large scale applications. It is known that the local crystallography of the foil influences the graphene growth rate. Here we find an epitaxial relationship between graphene and copper foil. Interfacial restructuring between graphene and copper drives the formation of (n10) facets on what is otherwise a mostly Cu(100) surface, and the facets in turn influence the graphene orientations from the onset of growth. Angle resolved photoemission shows that the electronic structure of the graphene is decoupled from the copper indicating a weak interaction between them. Despite this, two preferred orientations of graphene are found, ±8° from the Cu[010] direction, creating a non-uniform distribution of graphene grain boundary misorientation angles. Comparison with the model system of graphene growth on single crystal Cu(110) indicates that this orientational alignment is due to mismatch epitaxy. Despite the differences in symmetry the orientation of the graphene is defined by that of the copper. We expect these observations to not only have importance for controlling and understanding the growth process for graphene on copper, but also to have wider implications for the growth of two-dimensional materials on low cost metal substrates.      

Atomically smooth ultrathin films of topological insulator Sb2Te3

The growth and characterization of single-crystalline thin films of topological insulators (TIs) is an important step towards their possible applications. Using in situ scanning tunneling microscopy (STM) and angle-resolved photoemission spectroscopy (ARPES), we show that moderately thick Sb₂Te₃ films grown layer-by-layer by molecular beam epitaxy (MBE) on Si(111) are atomically smooth, single-crystalline, and intrinsically insulating. Furthermore, these films were found to exhibit a robust TI electronic structure with their Fermi energy lying within the energy gap of the bulk that intersects only the Dirac cone of the surface states. Depositing Cs in situ moves the Fermi energy of the Sb₂Te₃ films without changing the electronic band structure, as predicted by theory. We found that the TI behavior is preserved in Sb2Te3 films down to five quintuple layers (QLs).      

Electron-electron interactions in monolayer graphene quantum capacitors

We demonstrate the effects of electron-electron （e-e） interactions in monolayer graphene quantum capacitors. Ultrathin yttrium oxide showed excellent per-formance as the dielectric layer in top-gate device geometry. The structure and dielectric constant of the yttrium oxide layers have been carefully studied. The inverse compressibility retrieved from the quantum capacitance agreed fairly well with the theoretical predictions for the e--e interactions in monolayer graphene at different temperatures. We found that electron-hole puddles played a significant role in the low-density carrier region in graphene. By considering the temperature-dependent charge fluctuation, we established a model to explain the round-off effect originating from the e-e interactions in monolayer graphene near the Dirac point.     

Enhanced π-π interactions between a C60 fullerene and a buckle bend on a double-walled carbon nanotube

In situ low-voltage aberration corrected transmission electron microscopy (TEM) observations of the dynamic entrapment of a C₆₀ molecule in the saddle of a bent double-walled carbon nanotube is presented. The fullerene interaction is non-covalent, suggesting that enhanced π-π interactions (van der Waals forces) are responsible. Classical molecular dynamics calculations confirm that the increased interaction area associated with a buckle is sufficient to trap a fullerene. Moreover, they show hopping behavior in agreement with our experimental observations. Our findings further our understanding of carbon nanostructure interactions, which are important in the rapidly developing field of low-voltage aberration corrected TEM and nano-carbon device fabrication.      

Metal intercalation-induced selective adatom mass transport on graphene

Recent experiments indicate that metal intercalation is a very effective method to manipulate the graphene-adatom interaction and control metal nanostructure formation on graphene. A key question is mass transport, i.e., how atoms deposited uniformly on graphene populate different areas depending on the local intercalation. Using first-principles calculations, we show that partially intercalated graphene, with a mixture of intercalated and pristine areas, can induce an alternating electric field because of the spatial variations in electron doping, and thus, an oscillatory electrostatic potential. This alternating field can change normal stochastic adatom diffusion to biased diffusion, leading to selective mass transport and consequent nucleation, on either the intercalated or pristine areas, depending on the charge state of the adatoms.

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Microwave synthesis of large few-layer graphene sheets in aqueous solution of ammonia

Few-layer graphene (FLG) sheets with sizes exceeding several micrometers have been synthesized by exfoliation of expanded graphite in aqueous solution of ammonia under microwave irradiation, with an overall yield approaching 8 wt.%. Transmission electron microscopy (in bright-field and dark-field modes) together with electron diffraction patterns and atomic force microscopy confirmed that this graphene material consisted mostly of mono-, bi- or few-layer graphene (less than ten layers). The high degree of surface reduction was confirmed by X-ray photoelectron and infrared spectroscopies. In addition, the high stability of the FLG in the liquid medium facilitates the deposition of the graphene material onto several substrates via low-cost solution-phase processing techniques, opening the way to subsequent applications of the material.      

Solution-processable graphene mesh transparent electrodes for organic solar cells

Graphene mesh electrodes (GMEs) with good conductivity and transparency have been fabricated by the standard industrial photolithography and O₂ plasma etching process using graphene solutions. Organic photovoltaic (OPV) cells using GMEs as the transparent electrodes with a blend of poly-(3-hexylthiophene)/phenyl-C₆₁-butyric acid methyl ester (P3HT/PC₆₁BM) as the active layer have been fabricated and exhibit a power conversion efficiency (PCE) of 2.04%, the highest PCE for solution-processed graphene transparent electrode-based solar cells reported to date.      

Light-controlled synthesis of uniform platinum nanodendrites with markedly enhanced electrocatalytic activity

We report a fast in situ seeding approach based on zinc（II） porphyrin （ZnP） under white light irradiation, leading to uniform spherical platinum nanodendrites with tunable sizes. The platinum nanodendrites exhibit significantly improved electrocatalytic activities toward oxygen reduction reaction （ORR） and methanol oxidation reaction （MOR） compared with commercial platinum black.     

Raman scattering study of the phonon dispersion in twisted bilayer graphene

Bilayer graphene with a twist angle θ between the layers generates a superlattice structure known as a Moiré pattern. This superlattice provides a θ-dependent q wavevector that activates phonons in the interior of the Brillouin zone. Here we show that this superlattice-induced Raman scattering can be used to probe the phonon dispersion in twisted bilayer graphene (tBLG). The effect reported here is different from the widely studied double-resonance in graphene-related materials in many aspects, and despite the absence of stacking order in tBLG, layer breathing vibrations (namely ZO’ phonons) are observed.      

Elastic properties of hybrid graphene/boron nitride monolayer

Recently, hybridized monolayers consisting of hexagonal boron nitride (h-BN) phases inside a graphene layer have been synthesized and shown to be an effective way of opening band gap in graphene monolayers (Ci et?al. in Nat Mater 9(5):430–435, 2010). In this paper, we report a first-principles density functional theory study of the h-BN domain size effect on the elastic properties of graphene/boron nitride hybrid monolayers (h-BNC). We found that both in-plane stiffness and longitudinal sound velocity of h-BNC linearly decrease with h-BN concentration. Our results could be used for the design of future graphene-based nanodevices of surface acoustic wave sensors and waveguides.     

Composites of graphene and encapsulated silicon for practically viable high-performance lithium-ion batteries

A facile and scalable approach to synthesize silicon composite anodes has been developed by encapsulating Si particles via in situ polymerization and carbonization of phloroglucinol-formaldehyde gel, followed by incorporation of graphene nanoplatelets. As a result of its structural integrity, high packing density and an intimate electrical contact consolidated by the conductive networks, the composite anode yielded excellent electrochemical performance in terms of charge storage capability, cycling life and coulombic efficiency. A half cell achieved reversible capacities of 1,600 mAh·g^?1 and 1,000 mAh·g^?1 at 0.5 A·g^?1 and 2.1 A·g^?1, respectively, while retaining more than 70% of the initial capacities over 1,000 cycles. Complete lithium-ion pouch cells coupling the anode with a lithium metal oxide cathode demonstrated excellent cycling performance and energy output, representing significant advance in developing Si-based electrode for practical application in high-performance lithium-ion batteries.      

Nitrogen-doped graphene supported Pd@PdO core-shell clusters for C-C coupling reactions

The introduction of nitrogen significantly decreases the metal particle size and improves the performance of metal-based graphene-supported catalysts. In this work, the density functional theory is used to understand the interaction between nitrogen-doped graphene and Pd@PdO clusters. Experiments show that small size Pd@PdO clusters （1-2 nm） can be grown uniformly on nitrogen-doped graphene sheets by a facile oxidation-reduction method. The nanoscale interaction relationship between nitrogen-doped graphene and Pd@PdO clusters is investigated through X-ray photoelectron spectroscopy （XPS） and X-ray absorption spectra （XAS）. The composite catalysts are applied in Suzuki-Miyaura reactions giving high yields and good structural stability. These results have potential impact in design and optimization of future high performance catalyst materials for cross coupling reactions.     

Simultaneous N-intercalation and N-doping of epitaxial graphene on 6H-SiC(0001) through thermal reactions with ammonia

Surface functionalization of epitaxial graphene overlayers on 6H-SiC(0001) has been attempted through thermal reactions in NH₃. X-ray photoelectron spectroscopy and micro-region low energy electron diffraction results show that a significant amount of N is present at the NH₃-treated graphene surface, which results in strong band bending at the SiC surface as well as decoupling of the graphene overlayers from the substrate. The majority of the surface N species can be removed by annealing in vacuum up to 850 °C, weakening the surface band bending and resuming the strong coupling of graphene with the SiC surface. The desorbed N atoms can be attributed to the intercalated species between graphene and SiC. Low temperature scanning tunneling spectroscopy and density functional theory simulations confirm the presence of N dopants in the graphene lattice, which are in the form of graphitic substitution and can be stable above 850 °C. This is the first report of simultaneous N intercalation and N doping of epitaxial graphene overlayers on SiC, and it may be employed to alter the surface physical and chemical properties of epitaxial graphene overlayers.      

Solvent-dependent evolution of cyclic penta-twinned rhodium icosahedral nanocrystals and their enhanced catalytic properties

Cyclic penta-twinned noble metal nanocrystals exhibit promising properties due to their unique geometric and electronic structures. However, the controlled synthesis of cyclic penta-twinned nanostructures, especially of noble metals with a high cohesive energy (e.g., Rh), is very difficult, and the corresponding growth mechanism is not fully understood. Herein, we report a facile one-pot hydrothermal approach for the synthesis of cyclic penta-twinned Rh icosahedral nanocrystals. It was found that apart from regulating the surface free energy by changing the concentration or category of the capping agents, the solvent might influence the adsorption ability of the surfactant on the Rh crystal surface, which results in a change in the surface free energy and thus allows the formation of Rh cyclic penta-twinned nanostructures. In addition, due to their unique electronic and geometric structures, the Rh icosahedral nanocrystals exhibit superior catalytic activity and stability for the electrooxidation of ethanol as compared to single-crystal Rh tetrahedral nanocrystals and commercial Rh black.

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