- [Show abstract] [Hide abstract] ABSTRACT: Shortly after the discovery of fullerenes, many researchers pointed out that carbon nanotubes could be considered as elongated fullerenes. However, the detailed formation mechanism for both structures has been a topic of debate for several years, and consequently it has been difficult to draw a clear connection between the two systems. While the synthesis conditions appear to be different for both fullerenes and nanotubes, here, we demonstrate that it is highly likely that, at an initial growth stage, single-walled carbon nanotubes begin to grow from a hemisphere-like fullerene cap. More importantly, by analysing the minimum-energy path, it is shown that the insertion of C2 fragments drives the transformation of this fullerene cap into an elongated structure that leads to the formation of very short carbon nanotubes. This article is part of the themed issue Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene. © 2016 The Author(s) Published by the Royal Society. All rights reserved.
- [Show abstract] [Hide abstract] ABSTRACT: The present study aims at developing a silicon/soft-carbon nanohybrid material for high performance lithium-ion battery (LIB). It is composed of micronized silicon coated with so-called “soft-carbon” dispersed in soft-carbon matrix at nanometer level. This material is characterized with abundant nanosized voids with diameter of ca. 70 nm and hard bulk skeletal structure. It exhibited a long cycle life of 163 charging and discharging cycles with a large capacity of 850 mAh/g and retention rate up to 90% of the initial capacity in a half cell with Li-metal counter electrode. For this new material, the volume expansion ratio was 6.9% at a capacity level of 1100 mAh/g. This electrode capacity is approximately three times larger than that of graphite-based electrode currently used in LIB. Furthermore, this electrode retained 80.9% of its capacity at 250 cycles in a full cell with a LiCoO2 counter electrode. Addition of 5 wt % fluoroethylene carbonate (FEC) to the electrolyte improved the retention up to 81.3% after 300 cycles. These results demonstrate the usefulness and high possibility of this material as the negative electrode of LIB.
- [Show abstract] [Hide abstract] ABSTRACT: As a novel and efficient surface analysis technique, graphene-enhanced Raman scattering (GERS) has attracted increasing research attention in recent years. In particular, chemically doped graphene exhibits improved GERS effects when compared with pristine graphene for certain dyes, and it can be used to efficiently detect trace amounts of molecules. However, the GERS mechanism remains an open question. We present a comprehensive study on the GERS effect of pristine graphene and nitrogen-doped graphene. By controlling nitrogen doping, the Fermi level (EF) of graphene shifts, and if this shift aligns with the lowest unoccupied molecular orbital (LUMO) of a molecule, charge transfer is enhanced, thus significantly amplifying the molecule’s vibrational Raman modes. We confirmed these findings using different organic fluorescent molecules: rhodamine B, crystal violet, and methylene blue. The Raman signals from these dye molecules can be detected even for concentrations as low as 10−11 M, thus providing outstanding molecular sensing capabilities. To explain our results, these nitrogen-doped graphene-molecule systems were modeled using dispersion-corrected density functional theory. Furthermore, we demonstrated that it is possible to determine the gaps between the highest occupied and the lowest unoccupied molecular orbitals (HOMO-LUMO) of different molecules when different laser excitations are used. Our simulated Raman spectra of the molecules also suggest that the measured Raman shifts come from the dyes that have an extra electron. This work demonstrates that nitrogen-doped graphene has enormous potential as a substrate when detecting low concentrations of molecules and could also allow for an effective identification of their HOMO-LUMO gaps.
- [Show abstract] [Hide abstract] ABSTRACT: High surface area graphene monoliths consist mainly of single graphene layers wider than 10 nm. The interlayer porosity of high temperature treated nanoporous graphene monoliths with tuned intergraphene layer structures is evaluated by hybrid analysis of Ar adsorption at 87 K, N2 adsorption at 77 K, high resolution transmission electron microscopic observation, and small-angle X-ray scattering (SAXS) measurements. SAXS analysis results in surface areas that are 1.4 and 4.5 times larger than those evaluated by Ar adsorption for graphene monoliths nontreated and treated at 2273 K, respectively. A distorted graphene sheet structure model is proposed for the high surface area graphene monoliths on the basis of the hybrid analysis.
- [Show abstract] [Hide abstract] ABSTRACT: Linear carbon chains (LCCs) consisting of sp-hybridized carbon atoms are considered a fascinating 1D system and could be used in the fabrication of the next-generation molecular devices because of its ideal linear atomic nature. A large portion of long LCCs inside multi-walled carbon nanotubes (MWCNTs) were synthesized by atmospheric arc discharge in the presence of boron. Closed-end growth of MWCNTs in the arc process is suggested as a critical condition for the simultaneous growth of LCCs within the inner cores of carbon nanotubes. The strong Raman line around 1850 cm−1 was used to characterize the degree of filling as well as their structural stability under high temperature thermal treatments. We observed a distinctive change in the electrical conductivity of the MWCNT assembly before and after the disappearance of LCCs due to the expected strong coupling interaction between the LCCs and the innermost tube. This work demonstrates for the first time the enhanced effect of confined linear carbon chains on the overall electrical conductivity of MWCNT assemblies.
- [Show abstract] [Hide abstract] ABSTRACT: Double- and triple-walled carbon nanotubes (DWNTs and TWNTs) consist of coaxially-nested two and three single-walled carbon nanotubes (SWNTs).They act as the geometrical bridge between SWNTs and multi-walled carbon nanotubes (MWNTs), providing an ideal model for studying the coupling interactions between different shells in MWNTs. Within this context, this article comprehensively reviews various synthetic routes of DWNTs' and TWNTs' production, such as arc discharge, catalytic chemical vapor deposition and thermal annealing of pea pods (i.e., SWNTs encapsulating fullerenes). Their structural features, as well as promising applications and future perspectives are also discussed.
- [Show abstract] [Hide abstract] ABSTRACT: Efficient water desalination constitutes a major challenge for the next years and reverse osmosis membranes will play a key role to achieve this target. In this work, a high-performance reverse osmosis nanocomposite membrane was prepared by interfacial polymerization in presence of multiwalled carbon nanotubes. The effect of carbon nanotubes on the chlorine resistance, antifouling and desalination performance of the nanocomposite membranes was studied. We found that the addition of carbon nanotubes not only improved the membrane performance in terms of flow and antifouling, but also inhibited the chlorine degradation of these membranes. Several reports have acknowledged the benefits of adding carbon nanotubes to aromatic PA nanocomposite membranes, but little attention has been paid to the mechanisms related to the improvement of flow rate, selectivity and chlorine tolerance. We carried out a comprehensive study of the chemical and physical effects of carbon nanotubes on the fully crosslinked polyamide network. The chemical structure, chlorine resistance and membrane degradation was studied by several analytical techniques, permeation and fouling studies, whereas the microstructure of the nanocomposite was studied by small and wide angle X-ray scattering, high resolution transmission electron microscopy, and molecular dynamics. We found that the addition of the nanotube affects the interfacial polymerization, resulting in a polymer network with smaller pore size and higher sodium and chlorine rejection. We simulated the hydration of the membrane in seawater and found that the radial distribution function of water confined in the pores of the nanocomposite membrane exhibited smaller clusters of water molecules, thus suggesting a dense membrane structure. We analysed the network mobility and found that the nanotube provides mechanical stability to the polymer matrix. This study presents solid evidence towards more efficient and robust reverse osmosis membranes using carbon nanotubes as mechanical reinforcing and chlorine protection additive.
- [Show abstract] [Hide abstract] ABSTRACT: Ultrathin, flexible and highly water-permeable nanostructured carbon (NC)-based membranes are formed on porous polymer supports by plasma high-power impulse magnetron sputtering in order to fabricate carbon-based membranes for water desalination. The carbon membranes are produced at room temperature using mixtures of argon (Ar), nitrogen (N2) and methane (CH4) as precursors, and this procedure constitutes a simple solvent-free, waste-free scalable process. Structural characterization, molecular simulation, water permeation and salt rejection assessments are used to correlate the performance and membrane structure. Molecular simulations indicate that nitrogen doping on the carbon-based membranes drastically modifies the pore distribution and avoids the formation of clustered regions of high-density carbons. The optimum NC-based membrane has up to 96% salt rejection rate for 0.2 wt% NaCl saline water, with high water permeability ca. 25 l m−2 h−1 MPa−1. The NC-based membranes as active layers for desalination membranes exhibit attractive characteristics which render them a potential alternative to current polymeric technology used in reverse osmosis processes.
Dataset: Supplementary Information
- [Show abstract] [Hide abstract] ABSTRACT: Large efforts have been made over the last 40 years to increase the mechanical strength of polyacrylonitrile (PAN)-based carbon fibers (CFs) using a variety of chemical or physical protocols. In this paper, we report a new method to increase CFs mechanical strength using a slow heating rate during the carbonization process. This new approach increases both the carbon sp3 bonding and the number of nitrogen atoms with quaternary bonding in the hexagonal carbon network. Theoretical calculations support a crosslinking model promoted by the interstitial carbon atoms located in the graphitic interlayer spaces. The improvement in mechanical performance by a controlled crosslinking between the carbon hexagonal layers of the PAN based CFs is a new concept that can contribute further in the tailoring of CFs performance based on the understanding of their microstructure down to the atomic scale.
- [Show abstract] [Hide abstract] ABSTRACT: Three-dimensional (3D), porous monoliths with high electrical and thermal conductivities were produced by using unmodified multi-walled carbon nanotubes (CNTs) and polyacrylonitrile (PAN) as the entire elements through a template-free thermally induced phase separation approach. Multi-walled CNTs in the PAN/CNT monoliths were fully dispersed and as a result, interconnected CNT networks with high uniformity were established. The average value of the porosity, surface area, electrical conductivity, thermal conductivity and mechanical strength were found to be 90%, 210m2/g, 2.7S/cm, 0.148W/(m.K) and 1.1 MPa, respectively, for a 3D porous PAN/CNT monolith sample with a 33 wt% CNT loading. This new class of the CNT based monolith opens up new possibilities for various practical applications.
- [Show abstract] [Hide abstract] ABSTRACT: The pulsed laser deposition method was used to decorate appropriately single wall carbon nanotubes (SWCNTs) with PbS quantum dots (QDs), leading to the formation of a novel class of SWCNTs/PbS-QDs nanohybrids (NHs), without resorting to any ligand engineering and/or surface functionalization. The number of laser ablation pulses (NLp) was used to control the average size of the PbS-QDs and their coverage on the SWCNTs’ surface. Photoconductive (PC) devices fabricated from these SWCNTs/PbS-QDs NHs have shown a significantly enhanced photoresponse, which is found to be PbS-QD size dependent. Wavelength-resolved photocurrent measurements revealed a strong photoconductivity of the NHs in the UV-visible region, which is shown to be due to multiple exciton generation (MEG) in the PbS-QDs. For the 6.5 nm-diameter PbS-QDs (with a bandgap (Eg) = 0.86 eV), the MEG contribution of the NHs based PC devices was shown to lead to a normalized internal quantum efficiency in excess of 300% for photon energies ≥4.5Eg. While the lowest MEG threshold in our NHs based PC devices is found to be of ~2.5Eg, the MEG efficiency reaches values as high as 0.9 ± 0.1.
Dataset: Supplementary Information
- [Show abstract] [Hide abstract] ABSTRACT: This work aims to enhance resin reinforcing performance and thermal resistance through the innovative use of multi-walled carbon nanotubes (MWCNTs) for advanced material applications. The new method, which relied on MWCNT disentanglement under high shear stress, produced resin matrix nanocomposites. The MWCNT/resin nanocomposites showed improved stiffness without significant flexibility loss and did not flow above 160 °C. These dramatic improvements may result from the formation of a three-dimensional structure at the MWCNT/resin interface.
- [Show abstract] [Hide abstract] ABSTRACT: Vapor sensors are easily fabricated onto alumina substrates using foils of silver-decorated nitrogen-doped multiwalled carbon nanotubes (CN X-MWNTs-Ag) as active sensing material. The vapor sensors are tested using carbon disulfide, acetone, ethanol, and chloroform vapors. The CN X-MWNTs are produced by chemical vapor deposition process and then decorated with 14 nm Ag nanoparticles (Ag-NPs). The samples are characterized using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. Our results demonstrate that Ag-decorated CN X-MWNTs exhibit a better response and sensitivity when compared with pristine CN X-MWNTs based sensors, making them promising candidates for air-pollutants environmental monitoring. The temperature effect on the sensor performance is also studied; we found that the detection mechanism could be tuned from physisorption, at room temperature, to chemisorption at higher working temperature. Finally, first-principles density functional calculations are carried out to understand the interactions between the systems involved in the sensors, finding good agreement between experimental results and the theoretical approach.
- [Show abstract] [Hide abstract] ABSTRACT: We used engine oil-water emulsion as a model produced water to evaluate the oil sorption properties of exfoliated graphite (EG) and showed that 100mg/L of oil in emulsion can be reduced to a concentration of a 0.1-few mg/L using as-received commercially available EG and surface modified EG subjected to an additional oxidation treatment. Oil at a concentration of less than 15mg/L, the standard of typical water treatment processes. Although EG also sorbs water, it sorbs oil preferentially and the oil concentration of the sorbed phase in EG was estimated to be about 200 times that of the initial untreated emulsion. The sorption mechanism was discussed with the aid of the ab-initio relaxation calculation and classical molecular dynamics (MD) simulation for n-Hexane (C6H14) adsorption on graphene. When EG was incorporated with micron-size iron particles, the oil sorbed EG was found to be effectively recovered from emulsion by using magnetic field. The oil concentration in emulsion treated with EG was able to reduce down to the level comparable to that achieved by nanofiltration (NF) or reverse osmosis (RO) membrane treatment. We concluded that EG from natural graphite can effectively remove oil component during the treatment of emulsion and exhibits high potential for practical use.
- [Show abstract] [Hide abstract] ABSTRACT: Heteroatom doping is an efficient way to modify the chemical and electronic properties of graphene. In particular, boron doping is expected to induce a p-type (boron)-conducting behavior to pristine (nondoped) graphene, which could lead to diverse applications. However, the experimental progress on atomic scale visualization and sensing properties of large-area boron-doped graphene (BG) sheets is still very scarce. This work describes the controlled growth of centimeter size, high-crystallinity BG sheets. Scanning tunneling microscopy and spectroscopy are used to visualize the atomic structure and the local density of states around boron dopants. It is confirmed that BG behaves as a p-type conductor and a unique croissant-like feature is frequently observed within the BG lattice, which is caused by the presence of boron-carbon trimers embedded within the hexagonal lattice. More interestingly, it is demonstrated for the first time that BG exhibits unique sensing capabilities when detecting toxic gases, such as NO2 and NH3, being able to detect extremely low concentrations (e.g., parts per trillion, parts per billion). This work envisions that other attractive applications could now be explored based on as-synthesized BG.
Nissin Kogyo Co., Ltd.
Shonai, Nagano, Japan
- • Division of Electrical and Electronic Engineering
- • Faculty of Engineering