Concept: Carbon forms
Carbon exhibits a large number of allotropes and its phase behaviour is still subject to significant uncertainty and intensive research. The hexagonal form of diamond, also known as lonsdaleite, was discovered in the Canyon Diablo meteorite where its formation was attributed to the extreme conditions experienced during the impact. However, it has recently been claimed that lonsdaleite does not exist as a well-defined material but is instead defective cubic diamond formed under high pressure and high temperature conditions. Here we report the synthesis of almost pure lonsdaleite in a diamond anvil cell at 100 GPa and 400 °C. The nanocrystalline material was recovered at ambient and analysed using diffraction and high resolution electron microscopy. We propose that the transformation is the result of intense radial plastic flow under compression in the diamond anvil cell, which lowers the energy barrier by “locking in” favourable stackings of graphene sheets. This strain induced transformation of the graphitic planes of the precursor to hexagonal diamond is supported by first principles calculations of transformation pathways and explains why the new phase is found in an annular region. Our findings establish that high purity lonsdaleite is readily formed under strain and hence does not require meteoritic impacts.
A new sandwich-type impedimetric immunosensor based on functionalized graphene oxide nanosheets with a high ratio of horseradish peroxidase (HRP) and detection antibody was developed for the detection of carcinoembryonic antigen (CEA) by coupling with enzymatic biocatalytic precipitation of 4-chloro-1-naphthol (4-CN) on the captured antibody-modified glassy carbon electrode. Two molecular tags (with and without the graphene oxide nanosheets) were investigated for the detection of CEA and improved analytical features were acquired with the graphene-based labeling. With the labeling method, the performance and factors influencing the properties of the impedimetric immunosensors were also studied and evaluated. Under the optimal conditions, the dynamic concentration range of the impedimetric immunosensors spanned from 1.0pgmL(-1) to 80ngmL(-1) CEA with a detection limit (LOD) of 0.64pgmL(-1). Intra- and inter-assay coefficients of variation were less than 7.5% and 11%, respectively. Additionally, the methodology was evaluated for CEA analysis of 10 clinical serum samples and 5 diluted serum samples, receiving in a good accordance with the results obtained by the impedimetric immunoassay and the commercialized electrochemiluminescent method.
Graphene has shown much promise as an organic electronic material but, despite recent achievements in the production of few-layer graphene, the quantitative exfoliation of graphite into pristine single-layer graphene has remained one of the main challenges in developing practical devices. Recently, reduced graphene oxide has been recognized as a non-feasible alternative to graphene owing to variable defect types and levels, and attention is turning towards reliable methods for the high-throughput exfoliation of graphite. Here we report that microwave irradiation of graphite suspended in molecularly engineered oligomeric ionic liquids allows for ultrahigh-efficiency exfoliation (93% yield) with a high selectivity (95%) towards ‘single-layer’ graphene (that is, with thicknesses <1 nm) in a short processing time (30 minutes). The isolated graphene sheets show negligible structural deterioration. They are also readily redispersible in oligomeric ionic liquids up to ~100 mg ml(-1), and form physical gels in which an anisotropic orientation of graphene sheets, once induced by a magnetic field, is maintained.
Graphene oxide film is made of stacked graphene layers with chemical functionalities and we report that plasticity in the film can be engineered by strain rate tuning. The deformation behavior and plasticity of such functionalized layered systems is dominated by shear slip between individual layers and interaction between functional groups. Stress-strain behavior and theoretical models suggest that the deformation is strongly strain rate dependent and undergoes brittle to ductile transition with decreasing strain rate.
Rapid variations of the environmental energy caused by ultrashort laser pulses have induced phase transitions in carbon allotropes, therefore bringing the promise of revealing new carbon phases. Here, by exposing polycrystalline graphite to 25 fs laser pulses at 4 J/cm(2) fluence under standard air atmosphere, we demonstrated the synthesis of translucent micrometer-sized structures carrying diamond-like and onion-like carbon phases. Texturized domains of the diamond phase were also identified. Concerning different synthesized carbon forms, pulse superposition and singularities of the thermodynamical process, we pinpoint the synthesis mechanism by the laser-induced subsequent products energetically evolving to attain the diamond-like phase.
Carbon-based electronics is a promising alternative to traditional silicon-based electronics as it could enable faster, smaller and cheaper transistors, interconnects and memory devices. However, the development of carbon-based memory devices has been hampered either by the complex fabrication methods of crystalline carbon allotropes or by poor performance. Here we present an oxygenated amorphous carbon (a-COx) produced by physical vapour deposition that has several properties in common with graphite oxide. Moreover, its simple fabrication method ensures excellent reproducibility and tuning of its properties. Memory devices based on a-COx exhibit outstanding non-volatile resistive memory performance, such as switching times on the order of 10 ns and cycling endurance in excess of 10(4) times. A detailed investigation of the pristine, SET and RESET states indicates a switching mechanism based on the electrochemical redox reaction of carbon. These results suggest that a-COx could play a key role in non-volatile memory technology and carbon-based electronics.
There are increasing demands of more sensitive sensors for monitoring potential hazards in real water that may cause serious problems to human health. Herein, we report the development of a non-enzymatic nitrite sensor using nanocomposite of reduced graphene oxide decorated with silver nanoparticle (Ag-rGO). First, Ag-rGO nanocomposite was synthesized using a facile and cost-effective microwave-assisted approach. Then, as-synthesized Ag-rGO nanocomposite was used to modify glassy carbon electrode (GCE) and applied for the sensitive and selective detection of nitrite in the aqueous medium with increasing concentration of nitrite. Under optimized conditions, sensor achieved high sensitive response (18.4 μA/μM·cm2) in a wide linear range (0.1-120 μM), low limit of detection (∼0.012 μM), and good selectivity using differential pulse voltammograms (DPV). The applicability of fabricated non-enzymatic nitrite sensor was checked in real sample with satisfactory results.
Owing to their very high thermal conductivity as well as large surface-to-volume ratio, graphene-based films/papers have been proposed as promising candidates of lightweight thermal interface materials and lateral heat spreaders. In this work, we study the cross-plane (<i>c</i>-axis) thermal conductivity (<i>k<sub>c</sub></i>) and diffusivity (<i>α</i><sub><i>c</i></sub>) of two typical graphene-based papers, which are partially reduced graphene paper (PRGP) and graphene oxide paper (GOP), and compare their thermal properties with highly-reduced graphene paper (GP) and graphite. The determined <i>α<sub>c</sub></i> of PRGP varies from (1.02 ± 0.09) × 10<sup>-7</sup> m<sup>2</sup>/s at 295 K to (2.31 ±0.18) × 10<sup>-7</sup> m<sup>2</sup>/s at 12 K. This low <i>α<sub>c</sub></i> is mainly attributed to the strong phonon scattering at the grain boundaries and defect centers due to the small grain sizes and high-level defects. For GOP, <i>α<sub>c</sub></i> varies from (1.52 ± 0.05) × 10<sup>-7</sup> m<sup>2</sup>/s at 295 K to (2.28 ±0.08) × 10<sup>-7</sup> m<sup>2</sup>/s at 12.5 K. The cross-plane thermal transport of GOP is attributed to the high density of functional groups between carbon layers which provide weak thermal transport tunnels across the layers in the absence of direct energy coupling among layers. This work sheds light on the understanding and optimizing of nanostructure of graphene-based paper-like materials for desired thermal performance.
Although graphene technology has reached technology readiness level 9 and hydrogen fuel has been identified as a viable futuristic energy resource, pristine atomic layers such as graphene are found to be inactive towards the hydrogen evolution reaction (HER). Enhancing the intrinsic catalytic activity of a material and increasing its number of active sites by nanostructuring are two strategies in novel catalyst development. Here, electrocatalytically inert graphene (G) and hexagonal boron nitride (hBN) are made active for the HER by forming van der Waals (vdW) heterostructures via vertical stacking. The HER studies are conducted using defect free shear exfoliated graphite and hBN modified glassy carbon electrodes via layer by layer sequential stacking. The G/hBN stacking pattern (AA, AB, and AB') and stacking sequence (G/hBN or hBN/G) have been found to play important roles in the HER activity. Enhancement in the intrinsic activity of graphene by the formation of G/hBN vdW stacks has been further confirmed with thermally reduced graphene oxide and hBN based structures. Tunability in the HER performance of the G/hBN vdW stack is also confirmed via a three-dimensional rGO/hBN electrode. HER active sites in the G/hBN vdW structures are then mapped using density functional theory calculations, and an atomistic interpretation has been identified.
We report a facile and cost-effective approach to develop self-standing reduced Graphene Oxide (rGO) film based optical sensor and its low-temperature performance analysis where midgap defect states play a key role in tuning the crucial sensor parameters. Graphite oxide (GO) is produced by modified Hummers' method and reduced thermally at 250 °C for 1 h in Argon atmosphere to obtain rGO. Self-standing rGO film is prepared via vacuum filtration. The developed film is characterized by HRTEM, FESEM, Raman, and XRD techniques. The developed sensor exhibits highest sensitivity towards 635 nm illumination wavelength, irrespective of the operating temperature. For a given excitation wavelength, photoresponse study at low temperature (123K-303K) reveals inverse relationship between sensitivity and operating temperature. Highest sensitivity of 49.2% is obtained at 123 K for 635 nm laser at power density of 1.4 mW/mm2. Unlike sensitivity, response- and recovery-time demonstrate directly proportional dependence with operating temperature. Power dependent studies establish linear relation between power-density and sensitivity, and a safe limit beyond which sample heating prolongs the recovery time. Wavelength-dependent studies shows that proposed sensor can efficiently operate from visible to near NIR region. To the best of our knowledge such rGO based optical sensor performance at low temperature had not been reported earlier.