Chemistry of zipping reactions in mesoporous carbon consisting of minimally stacked graphene layers.

The structural evolution of highly mesoporous templated carbons is examined from temperatures of 1173 to 2873 K to elucidate the optimal conditions for facilitating graphene-zipping reactions whilst minimizing graphene stacking processes. Mesoporous carbons comprising a few-layer graphene wall display excellent thermal stability up to 2073 K coupled with a nanoporous structure and three-dimensional framework. Nevertheless, advanced temperature-programmed desorption (TPD), X-ray diffraction, and Raman spectroscopy show graphene-zipping reactions occur at temperatures between 1173 and 1873 K. TPD analysis estimates zipping reactions lead to a 1100 fold increase in the average graphene-domain, affording the structure a superior chemical stability, electrochemical stability, and electrical conductivity, while increasing the bulk modulus of the framework. At above 2073 K, the carbon framework shows a loss of porosity due to the development of graphene-stacking structures. Thus, a temperature range between 1873 and 2073 K is preferable to balance the developed graphene domain size and high porosity. Utilizing a neutron pair distribution function and soft X-ray emission spectra, we prove that these highly mesoporous carbons already consist of a well-developed sp2-carbon network, and the property evolution is governed by the changes in the edge sites and stacked structures.

Study on the applicability of pressurized physically activated carbon as an adsorbent in adsorption heat pumps.

Activated carbon is a suitable adsorbent for adsorption heat pumps (AHPs) with ethanol refrigerants. Although chemically activated carbon with highly developed pore structures exhibits good ethanol adsorption, the associated high production costs inhibit its practical application as an AHP adsorbent. Moreover, although physical activation can produce inexpensive activated carbon, the limited pore development limits the ethanol uptake. Recently, we developed a pressurized physical activation method that can produce activated carbon with a well-developed pore structure and characteristic pore size distribution. In this study, we investigated the applicability of the pressurized physically activated carbon as an adsorbent in activated carbon-ethanol AHP systems. Because of the large number of pressurization-induced pores of appropriate size, the pressurized physically activated carbon showed effective ethanol uptake comparable with that of chemically activated carbon on a weight basis. Furthermore, on a volume basis, the pressurized physically activated carbon, with a high bulk density, showed much higher effective ethanol uptake than chemically activated carbon. These results confirm the potential of the pressurized physically activated carbon as a relatively inexpensive high-performance adsorbent for AHP systems with ethanol refrigerants.

Highly Chlorinated Polyvinyl Chloride as a Novel Precursor for Fibrous Carbon Material.

Pure, highly chlorinated polyvinyl chloride (CPVC), with a 63 wt % of chlorine, showed a unique-thermal-pyrolytic-phenomenon that meant it could be converted to carbon material through solid-phase carbonisation rather than liquid-phase carbonisation. The CPVC began to decompose at 270 °C, with a rapid loss in mass due to dehydrochlorination and novel aromatisation and polycondensation up to 400 °C. In this study, we attempted to prepare carbon fibre (CF) without oxidative stabilisation, using the aforementioned CPVC as a novel precursor. Through the processes of solution spinning and solid-state carbonisation, the spun CPVC fibre was directly converted to CF, with a carbonisation yield of 26.2 wt %. The CPVC-derived CF exhibited a relatively smooth surface; however, it still demonstrated a low mechanical performance. This was because the spun fibre was not stretched during the heat treatment. Tensile strength, Young's modulus and elongation values of 590 ± 84 MPa, 50 ± 8 GPa, and 1.2 ± 0.2%, respectively, were obtained from the CPVC spun fibre, with an average diameter of 19.4 µm, following carbonisation at 1600 °C for 5 min.

Shortening Stabilization Time Using Pressurized Air Flow in Manufacturing Mesophase Pitch-Based Carbon Fiber.

Oxidation-stabilization using pressurized air flows of 0.5 and 1.0 MPa could successfully shorten the total stabilization time to less than 60 min for manufacturing mesophase pitch-based carbon fibers without deteriorating mechanical performance. Notably, the carbonized fiber heat-treated at 1000 °C for 30 min, which was oxidative-stabilized at 260 °C without soaking time with a heating rate of 2.0 °C/min using 100 mL/min of pressurized air flow of 0.5 MPa (total stabilization time: 55 min), showed excellent tensile strength and Young's modulus of 3.4 and 177 GPa, respectively, which were higher than those of carbonized fiber oxidation-stabilized at 270 °C without soaking time with a heating rate of 0.5 °C/min using 100 mL/min of atmospheric air flow (total stabilization time: 300 min). Activation energies for oxidation reactions in stabilization using pressurized air flows were much lower than those of oxidation reactions using atmospheric air flow because of the higher oxidation diffusion from the outer surface into the center part of pitch fibers for the use of the pressurized air flows of 0.5 and 1.0 MPa than the atmospheric one. The higher oxygen diffusivities resulted in a more homogeneous distribution of oxygen weight uptake across the transverse section of mesophase pitch fibers, and allowed the improvement of the mechanical properties.

Calcination effect of borate-bearing hydroxyapatite on the mobility of borate.

Discharge from accidental nuclear power plants includes boric acid, which is used as a neutron absorbent in nuclear reactors. Co-precipitation of borate with hydroxyapatite (HAp), using Ca(OH)2, is known to be an effectively fast method for stabilization of borate as well as coexisting radioactive nuclides. To reduce bulky volume of solid residues after co-precipitation, calcination is necessary to investigate the chemical stability of targets. Calcination at 850°C resulted in the high crystalization of HAp with formation of xCaO·B2O3 as a by-phase in which x increased with a decrease in the borate contents. After calcination, the lattice parameter a of HAp showed a reentrant curve and c showed a convex curve with an increase in borate contents. A dissolution assay revealed that calcination sometimes increases the borate moiety and that the acceptable B contents in HAp are lower than 1.59mmol/g-calcined HAp. These results imply that during calcination of HAp, some borate is excluded to form the by-phase xCaO·B2O3, which is relatively insoluble in water, but some other fractions might be additionally emitted from the amorphous phase to weakly bind the calcined products.

Fast Water Relaxation through One-Dimensional Channels by Rapid Energy Transfer.

Water in carbon nanotubes is surrounded by hydrophobic carbon surfaces and shows anomalous structural and fast transport properties. However, the dynamics of water in hydrophobic nanospaces is only phenomenologically understood. In this study, water dynamics in hydrophobic carbon nanotubes is evaluated based on water relaxation using nuclear magnetic resonance spectroscopy and molecular dynamics simulations. Extremely fast relaxation (0.001 s) of water confined in carbon nanotubes of 1 nm in diameter on average is observed; the relaxation times of water confined in carbon nanotubes with an average diameter of 2 nm (0.40 s) is similar to that of bulk water (0.44 s). The extremely fast relaxation time of water confined in carbon nanotubes with an average diameter of 1 nm is a result of frequent energy transfer between water and carbon surfaces. Water relaxation in carbon nanotubes of average diameter 2 nm is slow because of the limited number of collisions between water molecules. The dynamics of interfacial water can therefore be controlled by varying the size of the hydrophobic nanospace.

Mechanism of boron uptake by hydrocalumite calcined at different temperatures.

Hydrocalumite (Ca-Al-layered double hydroxide (LDH)) was prepared and applied for the removal of borate. The properties of Ca-Al-LDH calcined at different temperatures were diverse, which affected the sorption density and mechanism of boron species. The sorption density increased with increase in calcined temperature and the sample calcined at 900°C (Ca-Al-LDH-900) showed the maximum sorption density in this work. The solid residues after sorption were characterized by (11)B NMR, (27)Al NMR, SEM, and XRD to investigate the sorption mechanism. Dissolution-reprecipitation was the main mechanism for sorption of borate in Ca-Al-LDH. For Ca-Al-LDH calcined at 300 and 500°C, regeneration occurred in a short time and the newly forming LDHs were decomposed to release Ca(2+) ions and formed ettringite with borate. Two stages occurred in the sorption of boron by Ca-Al-LDH calcined at 900°C. In the first stage, boron species adsorbed on the alumina gel resulting from the hydration of calcined products. In this stage, borate was included as an interlayer anion into the newly forming LDHs in the following stage, and then immobilized as HBO3(2-) into the interlayer, most the LDHs.

Sorption of H3BO3/B(OH)4⁻ on calcined LDHs including different divalent metals.

LDHs with different divalent metals (Zn-LDH, Mg-LDH and Ca-LDH) have been synthesized and produced calcined LDHs (Zn-CLDH, Mg-CLDH and Ca-CLDH) for borate removal. Based on XRD, SEM, BET, (27)Al NMR, CO2-TPD, and (11)B NMR, detailed characterization of different CLDHs before and after reaction with the boron species was systematically performed. The surface area, basicity and the particle charge of the different CLDHs, which are related to the hydration and regeneration, were markably influenced by the nature of the divalent metals. Transformation of crystal phases and the types of boron species adsorbed by the different CLDHs varied as time changed. The regeneration of Ca-CLDH required the shortest time. However, Ca-LDH decomposed to release Ca(2+) ions, forming ettringite with borate. Zn-CLDH also rapidly transformed into Zn-LDH. During this reconstruction, B(OH)4(-) was intercalated into the interlayer of Zn-LDHs, which is the predominant mechanism of borate removal by Zn-CLDH. Increase in the initial pH caused a competition between borate and OH(-) so that the removal efficiency of borate by Zn-CLDH decreased. For Mg-CLDH, surface complexation and electrostatic attraction were included in the first stage, immobilizing boric acid into Mg(OH)2 and attracting borate as interlayer anionic species into the new forming Mg-LDHs in the second stage.

Two-dimensional materials as emulsion stabilizers: interfacial thermodynamics and molecular barrier properties.

A new application for two-dimensional (2D) materials is emulsification, where they can serve as ultrathin platelike interfacial stabilizers in two-liquid systems. We present a first detailed thermodynamic analysis of atomically thin 2D materials at organic-aqueous liquid-liquid interfaces and derive expressions for the transfer free energies of emulsion stabilization that account for material geometry, van der Waals transparency or opacity, and variable hydrophobicity. High mass potency is shown to be an intrinsic property of the 2D geometry, which at the atomically thin limit places every atom in contact with both liquid phases, resulting in unit atom efficiency. The thermodynamic model successfully predicts that graphene oxide but not pristine graphene has a favorable hydrophobic-hydrophilic balance for oil-water emulsion stabilization. Multilayer tiling is predicted to occur by the passivation of droplet surface patches left uncovered by packing inefficiencies in the first monolayer, and complete multilayer coverage is confirmed by cryogenic scanning electron microscopy. The molecular barrier function of graphene interfacial films causes a significant suppression of dispersed-phase evaporation rates with potential applications in controlled release. Finally, these emulsions can be used as templates for creating solid graphene foams or graphene microsacks filled with lipophilic cargos. Emerging 2D materials are promising as dispersants or emulsifiers where high mass potency and multifunctional properties are desired.

Toward an effective adsorbent for polar pollutants: formaldehyde adsorption by activated carbon.

Due to increasing concerns about environmental pollutants, the development of an effective adsorbent or sensitive sensor has been pursued in recent years. Diverse porous materials have been selected as promising candidates for detecting and removing harmful materials, but the most appropriate pore structure and surface functional groups, both important factors for effective adsorbency, have not yet been fully elucidated. In particular, there is limited information relating to the use of activated carbon materials for effective adsorbent of specific pollutants. Here, the pore structure and surface functionality of polyacrylonitrile-based activated carbon fibers were investigated to develop an efficient adsorbent for polar pollutants. The effect of pore structure and surface functional groups on removal capability was investigated. The activated carbons with higher nitrogen content show a great ability to absorb formaldehyde because of their increased affinity with polar pollutants. In particular, nitrogen functional groups that neighbor oxygen atoms play an important role in maximizing adsorption capability. However, because there is also a similar increase in water affinity in adsorbents with polar functional groups, there is a considerable decrease in adsorption ability under humid conditions because of preferential adsorption of water to adsorbents. Therefore, it can be concluded that pore structures, surface functional groups and the water affinity of any adsorbent should be considered together to develop an effective and practical adsorbent for polar pollutants. These studies can provide vital information for developing porous materials for efficient adsorbents, especially for polar pollutants.

Synthesis of silicon monoxide-pyrolytic carbon-carbon nanofiber composites and their hybridization with natural graphite as a means of improving the anodic performance of lithium-ion batteries.

Novel composites of silicon monoxide, pyrolytic carbon and carbon nanofiber (SiO/PyC/CNF) were hybridized with natural graphite (NG) as a means of improving the anodic performance of Li-ion batteries. Samples were made with hybridization levels of 10-30 wt% of NG exhibited excellent cyclability with a discharge capacity of 389-522 mAh g(-1) in a Li-ion battery system. SiO/PyC/CNF composite hybrids showed better cyclability than other carbon composites containing SiO/PyC and SiO/CNF. These hybridization effects were attributed to the lower contact resistance of SiO/PyC/CNF in the electrode. The internal spaces created throughout the SiO/PyC/CNF composite and their effect on material dispersion in the hybridized electrodes may have prevented electrode damage by relieving tensions induced by the expansion of SiO particles in the electrode over the course of repeated charge and discharge processes.

Structure and electrochemical applications of boron-doped graphitized carbon nanofibers.

Boron-doped graphitized carbon nanofibers (CNFs) were prepared by optimizing CNFs preparation, surface treatment, graphitization and boron-added graphitization. The interlayer spacing (d002) of the boron-doped graphitized CNFs reached 3.356 Å, similar to that of single-crystal graphite. Special platelet CNFs (PCNFs), for which d002 is less than 3.400 Å, were selected for further heat treatment. The first heat treatment of PCNFs at 2800 °C yielded a d002 between 3.357 and 3.365 Å. Successive nitric acid treatment and a second heat treatment with boric acid reduced d002 to 3.356 Å. The resulting boron-doped PCNFs exhibited a high discharge capacity of 338 mAh g⁻¹ between 0 and 0.5 V versus Li/Li⁺ and 368 mAh g⁻¹ between 0 and 1.5 V versus Li/Li⁺. The first-cycle Coulombic efficiency was also enhanced to 71-80%. Such capacity is comparable to that of natural graphite under the same charge/discharge conditions. The boron-doped PCNFs also exhibited improved rate performance with twice the capacity of boron-doped natural graphite at a discharge rate of 5 C.

High magnetic field solid-state NMR analyses by combining MAS, MQ-MAS, homo-nuclear and hetero-nuclear correlation experiments.

A general strategy of structural analysis of alumina silicate by combining various solid-state NMR measurements such as single pulse, multi-quantum magic angle spinning, double-quantum homo-nuclear correlation under magic angle spinning (DQ-MAS), and cross-polarization hetero-nuclear correlation (CP-HETCOR) was evaluated with the aid of high magnetic field NMR (800 MHz for (1) H Larmor frequency) by using anorthite as a model material. The high magnetic field greatly enhanced resolution of (27) Al in single pulse, DQ-MAS, and even in triple-quantum magic angle spinning NMR spectra. The spatial proximities through dipolar couplings were probed by the DQ-MAS methods for homo-nuclear correlations between both (27) Al-(27) Al and (29) Si-(29) Si and by CP-HETCOR for hetero-nuclear correlations between (27) Al-(29) Si in the anorthite framework. By combining various NMR methodologies, we elucidated detailed spatial correlations among various aluminum and silicon species in anorthite that was hard to be determined using conventional analytical methods at low magnetic field. Moreover, the presented approach is applicable to analyze other alumina-silicate minerals.

Graphitization behaviour of chemically derived graphene sheets.

Graphene sheets were prepared via chemical reduction of graphite oxides and then graphitized at 2800 °C. The structure changes from pristine graphite to graphitized graphene sheets were monitored using X-ray diffraction and Raman spectroscopy. It was found that the graphitized graphene sheets exhibited relatively low degree of graphitization and high level of structural defects. XPS spectra revealed that oxygen functionalities could be completely eliminated after graphitization. Morphology observations indicated that graphitization could induce the coalescence and connection of the crumpled graphene agglomerations into compressed grains. The connections included the joint of graphitic sheets along the c-axis with van der Waals force between graphitic sheets and the joint of sheets in the in-plane with covalent bond between carbon atoms. New structures such as the formation of loop at the tip of graphene sheets and the formation of 3D concentric graphene nanoparticles occurred in the graphitized graphene sheets, as a result of self-organization to achieve their lowest potential energy. Our findings should provide some experimental implications for understanding of graphitization behaviour and thermal stability of strictly 2D graphene monolayers.

Partially unzipped carbon nanotubes as a superior catalyst support for PEM fuel cells.

Partially unzipped carbon nanotubes prepared by strong oxidation and thermal expansion of carbon nanotubes were explored as an advanced catalyst support for PEM fuel cells. The unique hybrid structure of 1D nanotube and 2D double-side graphene resulted in an outstanding electrocatalytic performance.

Fabrication of uniform graphene discs via transversal cutting of carbon nanofibers.

The graphene discs with well-defined shape are successfully fabricated using a simple oxidation and exfoliation process of high-crystalline carbon nanofibers (CNFs). To control the shapes of graphene discs, two different types of CNFs (platelet and herringbone-type) are used as starting materials. The CNFs are formed by the perpendicular stacking of graphene discs, resulting in free edges on the external surface and ready access to interlay spaces. Interestingly, the diameter and shape of the graphene discs can be controlled by selectively designing the morphology of starting materials and optimizing the cutting method. In addition, a mechanical reduction method for oxidized graphene discs is also proposed in order to combine the high recovery of π-conjugated electronic structure with the solution processability of graphene discs. The reduced graphene discs can be formed without any additives, such as reducing agent, and are highly dispersed in different solvents with a high content of graphene discs. This novel strategy offers great possibility for fabricating various graphene-based nanomaterials with rational nanostructure design.

Histological assessments for toxicity and functionalization-dependent biodistribution of carbon nanohorns.

Single-walled carbon nanohorns (SWNHs) intravenously administered to mice did not show severe toxicity during a 26-week test period, which was confirmed by normal gross appearance, normal weight gain and the lack of abnormality in the tissues on histological observations of the mice. SWNH biodistribution was influenced by chemical functionalization. Accumulation of SWNH in the lungs reduced as SWNH hydrophilicity increased; however, the most hydrophilic SWNHs modified with bovine serum albumin (BSA) were most likely to be trapped in the lungs, suggesting that the BSA moiety enhanced macrophage phagocytosis in the lungs. Clearance of some of the hydrophobic SWNHs from the lungs was observed, the mechanism of which is briefly discussed.

Highly efficient field emission from carbon nanotube-nanohorn hybrids prepared by chemical vapor deposition.

Electrically conductive carbon nanotubes (CNTs) with high aspect ratios emit electrons at low electric fields, thus applications to large-area field emission (FE) devices with CNT cathodes are attractive to save energy consumption. However, the poor dispersion and easy bundling properties of CNTs in solvents have hindered this progress. We have solved these problems by growing single-walled CNTs (SWNTs) on single-walled carbon nanohorn (SWNH) aggregates that have spherical forms with ca. 100-nm diameters. In the obtained SWNT-SWNH hybrids (NTNHs), the SWNTs diameters were 1-1.7 nm and the bundle diameters became almost uniform, that is, less than 10 nm, since the SWNTs were separated by SWNH aggregates. We also confirmed that a large-area FE device with NTNH cathodes made by screen printing was highly and homogeneously bright, suggesting the success of the hybrid strategy.

Preparation of nitrogen-doped graphene sheets by a combined chemical and hydrothermal reduction of graphene oxide.

Nitrogen-doped graphene sheets were prepared through a hydrothermal reduction of colloidal dispersions of graphite oxide in the presence of hydrazine and ammonia at pH of 10. The effect of hydrothermal temperature on the structure, morphology, and surface chemistry of as-prepared graphene sheets were investigated though XRD, N(2) adsorption, solid-state (13)C NMR, SEM, TEM, and XPS characterizations. Oxygen reduction and nitrogen doping were achieved simultaneously under the hydrothermal reaction. Up to 5% nitrogen-doped graphene sheets with slightly wrinkled and folded feature were obtained at the relative low hydrothermal temperature. With the increase of hydrothermal temperature, the nitrogen content decreased slightly and more pyridinic N incorporated into the graphene network. Meanwhile, a jellyfish-like graphene structure was formed by self-organization of graphene sheets at the hydrothermal temperature of 160 °C. Further increase of the temperature to 200 °C, graphene sheets could self-aggregate into agglomerate particles but still contained doping level of 4 wt % N. The unique hydrothermal environment should play an important role in the nitrogen doping and the jellyfish-like graphene formation. This simple hydrothermal method could provide the synthesis of nitrogen-doped graphene sheets in large scale for various practical applications.