Activated porous carbon nanofibers using Sn segregation for high-performance electrochemical capacitors

Activated porous carbon nanofibers (CNFs) with three different types of porous structures, which were controlled to contain 1, 4, and 8 wt% of Sn–poly(vinylpyrrolidone) (PVP) precursors in the core region and 7 wt% polyaniline (PAN)–PVP precursors in the shell region during electrospinning, were synthesized using a co-electrospinning technique with H₂-reduction. The formation mechanisms of activated porous CNF electrodes with the three different types of samples were demonstrated. The activated porous CNFs, for use as electrodes in high-performance electrochemical capacitors, have excellent capacitances (289.0 F/g at 10 mV/s), superior cycling stability, and high energy densities; these values are much better than those of the conventional CNFs. The improved capacitances of the activated porous CNFs are explained by the synergistic effect of the improved porous structures in the CNF electrodes and the formation of activated states on the CNF surfaces.     

Preparation and electrochemical properties of carbon nanofibers derived from polybenzimidazole/polyimide precursor blends

Carbon nanofibers (CNFs) were fabricated by thermal treatment of electrospun nanofibers obtained from precursor blends of polybenzimidazole (PBI) and Matrimid®. The microcarbon structures of CNFs obtained from PBI, and the 50:50 and 75:25 blends were studied using XRD and Raman spectra. Nitrogen adsorption/desorption measurements revealed that surface area and porosity of CNFs increased with an increase in Matrimid® content. Electrochemical performance of these CNF electrodes was studied for their application in energy storage devices. The CNFs from the PBI/Matrimid® (75:25)-precursor blend showed the lowest electrochemical impedance, and highest specific capacitance (111 F/g) and energy and power densities of 24 and 6 kW/kg, respectively. Steam activation and annealing further enhanced the performance resulting in a specific capacitance of 126 F/g, and energy and power densities of 49 and 7 kW/kg, respectively.     

Super growth of vertically-aligned carbon nanofibers and their field emission properties

We demonstrate a very efficient synthesis of vertically-aligned ultra-long carbon nanofibers (CNFs) with sharp tip ends using thermal chemical vapor deposition. Millimeter-scale CNFs with a diameter of less than 50 nm are readily grown on palladium thin film deposited Al₂O₃ substrate, which activate the conical stacking of graphitic platelets. The field emission performance of the as-grown CNFs is better than that of previous CNFs due to their extremely high aspect ratio and sharp tip angle. The CNF array gives the turn-on electric field of 0.9 V/μm, the maximum emission current density of 6.3 mA/cm² at 2 V/μm, and the field enhancement factor of 2585.     

Synthesis of electrically conducting composite adsorbents for wastewater treatment using adsorption & electrochemical regeneration

Electrically conducting adsorbent materials called Nyex™ 1000 & 2000 have already been reported with comparatively low adsorption capacity for various organic, biologically non-degradable and toxic compounds. Two composite adsorbents called CA₁ & CA₂ were synthesized using synthetic graphite-carbon black and expanded graphite-carbon black respectively. The aim of developing the new adsorbents was to increase the adsorption capacity along with good electrical properties. The developed adsorbents were characterized using N₂ adsorption for specific surface area, Boehm surface titration for surface chemistry, bed electrical conductivity, laser size analyzer for average particle size, and scanning electron microscope (SEM) for particle morphology and shape. Then both the composite adsorbents were tested for the adsorption of acid violet 17 followed by an electrochemical regeneration. The adsorption study revealed that both the adsorbents had almost similar kinetic behavior with a significant increase in adsorption capacity for acid violet 17 (300 & 26 mg g⁻¹ respectively) when compared with the adsorption capacity of previously developed electrically conducting materials called Nyex™ 1000 & 2000 (3.5 and 9 mg g⁻¹ respectively). The composite adsorbent CA₂ was successfully electrochemically regenerated by passing an electric charge of 138 C g⁻¹ at a current density of 14 mA cm⁻² for a treatment time of 60 min, whereas, the composite adsorbent CA₁ could not be regenerated successfully. The regeneration efficiencies of CA₂ were obtained at around 120% during five adsorption–regeneration cycles. The amount of actual charge passed of 138 C g⁻¹ for achieving 100% regeneration efficiency was found to be similar with stoichiometrically calculated amount of charge. The amount of electrical energy required to oxidize each mg of adsorbed acid violet onto CA₂ (24 J mg⁻¹) was found to be significantly lower to that of Nyex™ 1000 & 2000 adsorbents (52 J mg⁻¹ & 32 J mg⁻¹ respectively).     

The production of porosity in carbon nanofibers by the catalytic action of Ni nanoparticles in low temperature activation

Carbon nanofibers (CNFs) containing Ni nanoparticles were synthesized by carbonization of electrospun polyacrylonitrile nanofibers containing NiCl₂ followed by low-temperature activation (∼325 °C) in an oxygen atmosphere. The surface area of activated CNFs with 0.11 wt.% of the Ni oxide nanoparticles was 654 m²/g with increasing nanopores, which is significantly higher than the value for pure CNFs (30 m²/g). It was confirmed that the addition of trace amounts of Ni nanoparticles effectively produces a porous structure due to their catalytic role, which can increase the specific adsorption capacity of the activated CNFs without structural deformation.     

Transmission electron microscopy study of the microstructure of carbon/carbon composites reinforced with in situ grown carbon nanofibers

Introduction of carbon nanofibers (CNFs) into carbon/carbon (C/C) composites is an effective method to improve the mechanical properties of C/C composites. In situ grown CNFs reinforced C/C composites as well as conventional C/C composites without CNFs were fabricated by chemical vapor infiltration. Transmission electron microscopy investigations indicate that the entangled CNFs (30–120 nm) formed interlocking networks on the surface of carbon fibers (CFs). Moreover, a thin high-textured (HT) pyrocarbon (PyC) layer (～20 nm) was deposited on the surface of CFs during the growth of CNFs. We find the microstructure of C/C composites depends strongly on the local distribution density (LDD) of CNFs. In regions of low CNF LDD, a triple-layer structure was formed. The inner layer (attached to CF) is HT PyC (～20 nm), the middle layer (150–200 nm) is composed of HT PyC coated CNFs (HT/CNFs) and medium-textured PyC, and the outmost layer (several microns) is composed of HT/CNFs and micropores. In regions of high CNF LDD, a double-layer structure was formed. The inner layer is HT PyC (～20 nm), and the outer layer is composed of HT/CNFs, isotropic PyC and nanopores. However, only medium-textured PyC and micropores were found in the matrix of the conventional C/C composites.     

Kinetically controlled synthesis of carbon nanofibers with different morphologies by catalytic CO disproportionation over iron catalyst

Carbon nanofibers (CNFs) were synthesized by CO disproportionation on iron catalyst at CO concentration between 58.3% and 75.0%, H₂ concentration between 8.3% and 25.0% and reaction temperature between 833 and 913 K. The time-depending rate of CNFs growth as a function of time was determined by an on-line mass spectrometer and the morphologies of all CNFs products were observed by electronic microscopy. Not only the CNFs growth rate but also the morphology of the grown CNFs were shown to vary with the three operating variables. SEM and TEM images showed that the three-dimensional morphologies of the CNFs were twist, helical or straight and an interesting relationship between the maximal growth rate and the morphology was observed. When the growth rate was between 0.8 and 0.9 mmol/(s gcat), the CNFs were twist. As the growth rate increased to 1.0 mmol/(s gcat), more helical nanofibers appeared. Straight nanofibers were produced when the growth rate reached the level of 1.2 mmol/(s gcat). Finally when the rate of CNFs growth was high at 1.8 mmol/(s gcat), the absolute majority of the solid products was amorphous carbon coexisting with some short and thick nanofibers. Under different operating conditions, the crystal faces of the catalysts had different anisotropy properties for carbon deposition, thus producing CNFs with different morphologies.     

Desirable electrical and mechanical properties of continuous hybrid nano-scale carbon fibers containing highly aligned multi-walled carbon nanotubes

The continuous highly aligned hybrid carbon nanofibers (CNFs) with different content of acid-oxidized multi-walled carbon nanotubes (MWCNTs) were fabricated through electrospinning of polyacrylonitrile (PAN) followed by a series of heat treatments under tensile force. The effects of MWCNTs on the micro-morphology, the degree of orientation and ordered crystalline structure of the resulting nanofibers were analyzed quantitatively by diversified structural characterization techniques. The orientation of PAN molecule chains and the graphitization degree in carbonized nanofibers were distinctly improved through the addition of MWCNTs. The electrical conductivity of the hybrid CNFs with 3 wt% MWCNTs reached 26 S/cm along the fiber direction due to the ordered alignment of MWCNTs and nanofibers. The reinforcing effect of hybrid CNFs in epoxy composites was also revealed. An enhancement of 46.3% in Young’s modulus of epoxy composites was manifested by adding 5 wt% hybrid CNFs mentioned above. At the same time, the storage modulus of hybrid CNF/epoxy composites was significantly higher than that of pristine epoxy and CNF/epoxy composites not containing MWCNTs, and the performance gap became greater under the high temperature regions. It is believed that such a continuous hybrid CNF can be used as effective multifunctional reinforcement in polymer matrix composites.     

Gas phase oxidation as a tool to introduce oxygen containing groups on metal-loaded carbon nanofibers

Oxygen containing groups were introduced, onto carbon nanofibers (CNFs) that were previously loaded with palladium, using HNO₃ vapor. Using traditional liquid-phase oxidations this is not possible due to severe metal leaching. For the samples oxidized using HNO₃ vapor temperature programmed desorption and X-ray photoelectron spectroscopy revealed the presence of two major classes of oxygen containing groups, i.e. carboxylic acid groups which are thermally stable up to 300 °C and less acidic (e.g. phenol) and basic groups which were stable up to 700 °C. The amount of acidic oxygen containing groups introduced by this gas-phase treatment ranged from 0.1 to 0.3 mmol/g, as determined by titration. The latter amount is comparable to that introduced by traditional liquid-phase treatment in 65% HNO₃ on bare CNFs. Transmission electron microscopy and H₂-chemisorption measurements show a gradual increase of the average metal particle size from 2.1 nm for the starting Pd/CNF to 4.5 nm for Pd/CNF treated for 75 h in HNO₃ vapor indicating that the extent of sintering with gas-phase treatment is limited. Elemental analysis showed that no leaching occurred upon gas-phase oxidation, whereas 90% of the metal was lost with a liquid-phase reflux HNO₃ treatment.     

Preparation of porous carbon nanofibers derived from graphene oxide/polyacrylonitrile composites as electrochemical electrode materials

Porous carbon nanofibers (CNFs) derived from graphene oxide (GO) were prepared from the carbonization of electrospun polyacrylonitrile nanofibers with up to 15 wt.% GO at 1200 °C, followed by a low-temperature activation. The activated CNFs with reduced GOs (r-GO) revealed a specific surface area and adsorption capacity of 631 m²/g and 191.2 F/g, respectively, which are significantly higher than those of pure CNFs (16 m²/g and 3.1 F/g). It is believed that rough interfaces between r-GO and CNFs introduce oxygen pathways during activation, help to produce large amounts of all types of pores compared to pure activated CNFs.     

Superoleophobic and conductive carbon nanofiber/fluoropolymer composite films

A solution-based, large-area coating procedure is developed to produce conductive polymer composite films consisting of hollow-core carbon nanofibers (CNFs) and a fluoroacrylic co-polymer available as a water-based dispersion. CNFs (100 nm dia., length ～130 μm) were dispersed by sonication in a formic acid/acetone co-solvent system, which enabled colloidal stability and direct blending of the CNFs and aqueous fluoroacrylic dispersions in the absence of surfactants. The dispersions were sprayed on smooth and microtextured surfaces, thus forming conformal coatings after drying. Nanostructured composite films of different degrees of oil and water repellency were fabricated by varying the concentration of CNFs. The effect of substrate texture and CNF content on oil/water repellency was studied. Water and oil static contact angles (CAs) ranged from 98° to 164° and from 61° to 164°, respectively. Some coatings with the highest water/oil CAs displayed self-cleaning behavior (droplet roll-off angles <10°). Inherent conductivity of the composite films ranged from 63 to 940 S/m at CNF concentrations from 10 to 60 wt.%, respectively. Replacement of the long CNFs with shorter solid-core carbon nanowhiskers (150 nm dia., length 6–8 μm) produced stable fluoropolymer–nanowhisker dispersions, which were ink-jetted to generate hydrophobic, conductive, printed line patterns with a feature size ～100 μm.     

Biomimetic synthesis and characterization of carbon nanofiber/hydroxyapatite composite scaffolds

Three dimensional electrospun carbon nanofiber (CNF)/hydroxyapatite (HAp) composites were biomimetically synthesized in simulated body fluid (SBF). The CNFs with diameter of ∼250 nm were first fabricated from electrospun polyacrylonitrile precursor nanofibers by stabilization at 280 °C for 2 h, followed by carbonization at 1200 °C. The morphology, structure and water contact angle (WCA) of the CNFs and CNF/HAp composites were characterized. The pristine CNFs were hydrophobic with a WCA of 139.6°, resulting in the HAp growth only on the very outer layer fibers of the CNF mat. Treatment in NaOH aq. solutions introduced carboxylic groups onto the CNFs surfaces, and hence making the CNFs hydrophilic. In the SBF, the surface activated CNFs bonded with Ca²⁺ to form nuclei, which then easily induced the growth of HAp crystals on the CNFs throughout the CNF mat. The fracture strength of the CNF/HAp composite with a CNF content of 41.3% reached 67.3 MPa. Such CNF/HAp composites with strong interfacial bondings and high mechanical strength can be potentially useful in the field of bone tissue engineering.     

Influence of wet oxidation of herringbone carbon nanofibers on the pseudocapacitance effect

Herringbone carbon nanofibers (CNFs) were treated with concentrated HNO₃ and a mixture of diluted HNO₃/H₂SO₄ to obtain a series of oxygen enriched CNF with different oxygen group distribution, but with a similar porous texture. Oxygen functional groups were determined by X-ray photoelectron spectroscopy. CNFs with a very high relative concentration of carbonyl and/or quinone groups and hydroxyl groups were obtained by adjusting the suitable temperature and time of oxidation with HNO₃ and HNO₃/H₂SO₄, respectively. The electrochemical behavior of the samples was studied in three- and two-electrode cells. The performance of oxidized CNFs-based supercapacitors working in 1 mol L⁻¹ H₂SO₄ and 6 mol L⁻¹ KOH was analyzed using cyclic voltammetry and galvanostatic charging/discharging. The specific capacitance of the oxidized CNFs was more than twice enhanced in acidic and alkaline media compared to the pristine CNFs due to the pseudocapacitance effect. It was revealed that not only quinone groups but also hydroxyl groups contribute into the overall capacitance through the pseudocapacitance effect. With increasing surface concentration of the CO and C–OH groups, the capacitance values increase for the capacitors operating in both media.     

Evidence for atomically dispersed Pd in catalysts supported on carbon nanofibers

The state of palladium deposited on carbon nanofibers (CNFs) with stacked structure in 0.04–0.5 wt% concentration was studied by XRD, electron microscopy and EXAFS. Palladium was found to exist as single atoms attached to CNF in the samples with Pd concentration 0.2 wt% or less. Most probable location of Pd atoms according to EXAFS data was analysed using quantum-chemical calculation.     

Fabrication of magnetic polybenzoxazine-based carbon nanofibers with Fe3O4 inclusions with a hierarchical porous structure for water treatment

Hierarchical porous, magnetic Fe₃O₄@carbon nanofibers (Fe₃O₄@CNFs) based on polybenzoxazine precursors have been synthesized by a combination of electrospinning and in situ polymerization. The benzoxazine monomers could easily form thermosetting nanofibers by in situ ring-opening polymerization and subsequently be converted into CNFs by carbonization. The resultant fibers with an average diameter of 130 nm are comprised of carbon fibers with embedded Fe₃O₄ nanocrystals, and could have a high surface area of 1885 m² g^?1 and a porosity of 2.3 cm³ g^?1. Quantitative pore size distribution and fractal analysis were used to investigate the hierarchical porous structure using N₂ adsorption and synchrotron radiation small-angle X-ray scattering measurements. The role of precursor composition and activation process for the effects of the porous structure is discussed, and a plausible correlation between surface fractal dimension and porous parameter is proposed. The Fe₃O₄@CNFs exhibit efficient adsorption for organic dyes in water and excellent magnetic separation performance, suggesting their use as a promising adsorbent for water treatment, and also provided new insight into the design and development of a carbon nanomaterial based on a polybenzoxazine precursor.     

Carbon nanoflake growth from carbon nanotubes by hot filament chemical vapor deposition

We report the growth of carbon nanoflakes (CNFs) on Si substrate by the hot filament chemical vapor deposition without the substrate bias or the catalyst. CNFs were grown using the single wall carbon nanotubes and the multiwall carbon nanotubes as the nucleation center, in the Ar-rich CH₄–H₂–Ar precursor gas mixture with 1% CH₄, at the chamber pressure and the substrate temperature of 7.5 Torr and 840 °C, respectively. In the H₂-rich condition, CNF synthesis failed due to severe etch-removal of carbon nanotubes (CNTs) while it was successful at the optimized Ar-rich condition. Other forms of carbon such as nano-diamond or mesoporous carbon failed to serve as the nucleation centers for the CNF growth. We proposed a mechanism of the CNF synthesis from the CNTs, which involved the initial unzipping of CNTs by atomic hydrogen and subsequent nucleation and growth of CNFs from the unzipped portion of the graphene layers.     

Fabrication of electronspun porous CeO2 nanofibers with large surface area for pollutants removal

The porous CeO₂ nanofibers with diameter of 100–140 nm were successfully synthesized by single-capillary electrospinning of a Ce(NO₃)₃·6H₂O/PVP precursor solution, followed by calcination. The preparation parameters, including solution parameters and process parameters, affecting the spinnability and the morphology of nanofibers were investigated and discussed systematically. And the effects of different calcination temperatures on the microstructure CeO₂ nanofibers were also studied. A plausible mechanism was proposed to explain the formation process of the CeO₂ nanofibers. The N₂ adsorption-desorption isotherm analysis showed that the specific surface area and average pore size of the nanofibers were 195.75 g/m² and 2.4 nm, respectively. Moreover, as absorbent, the porous CeO₂ nanofibers adsorbed the MO effectively. The adsorption experiment indicated that the adsorption process can be divided into two stages, including quick adsorption and gradual adsorption. And the adsorption capacities were not only determined by the specific surface area, but closely related to the pore size. Finally, the adsorption data were modeled by the pseudo-first-order and pseudo-second-order kinetics equations. The results showed that the pseudo-second order kinetics could best describe the adsorption of MO onto the porous CeO₂ nanofibers.     

Thermal conductivity of individual carbon nanofibers

In the present paper, we present results of thermal conductivity measurements in commercially-available, chemical vapor deposition grown, heat-treated and non-heat-treated individual carbon nanofibers (CNFs). The thermal conductivity measurements are made using the T-type probe experimental configuration using a Wollaston wire probe inside a high resolution scanning electron microscope. The results show a significant increase in the thermal conductivity of CNFs that are annealed at 2800 °C for 20 h when compared with the non-heat-treated CNF samples. When adjusted for thermal contact resistance, the highest measured thermal conductivity is 449 ± 39 W/m-K. The average thermal conductivity of the heat-treated samples is 163 W/m-K, while the average thermal conductivity of the non-heat-treated samples is 4.6 W/m-K. The results demonstrate the importance of the quality of the CNFs, in particular their heat treatment (high temperature annealing), in controlling their thermal conductivity for thermal management applications.     

Comparative study of the structure and microstructure of PAN-based nano- and micro-carbon fibers

The work presents results on the manufacture and comparative assessment of the structure and microstructure parameters of polyacrylonitrile polymer (PAN)-based carbon nano- and micro-fibers. Using the same polymer solution, PAN nano- and microfibers were obtained. The PAN nanofibers were obtained by electrospinning, and microfibers were spun using the conventional solution-spinning method. The PAN-based fiber precursors were annealed to 1000 °C, 2000 °C and to 2800 °C. Using X-ray diffraction and Raman spectroscopy, the structural and microstructural parameters of both types of carbon fibers were examined. The morphology of PAN nanofibers and carbon nanofibers (CNF) were studied by SEM. Both types of ex-PAN carbon fibers (nano and micro) have similar the c-axis spacing (d₀₀₂) values and crystallite sizes after heat treatment to 2000 °C presenting turbostratic structure. HR-TEM images of low temperature CNF show uniform microstructure with the misoriented small carbon crystallites along the fiber axis. The ratio of the integrated intensities of the D and G peaks for carbon nanofibers after heat treatment at 2000 °C was distinctly higher in comparison to carbon microfibers (CF). After additional annealing the fibers to 2800 °C a better structural ordering show CNF. The crystallite sizes (L_c, L_a) in CNF were distinctly higher in comparison to the crystallites in CF. CF consist of two carbon components, whereas CNF contain three carbon components varying in structural and microstructural parameters. One of carbon phases in CNF was found to have the interlayer spacing close to graphite, i.e. d₀₀₂=0.335 nm.     

Biofunctionalization of carbon nanofiber tips for scanning probe microscopy using thin Au coating and immobilized biorecognition molecules

Individual carbon nanofibers (CNFs) synthesized on the apices of tetrahedral-type Si cantilever tips via argon-ion (Ar⁺) bombardment, i.e., CNF-tipped scanning probe microscopy (SPM) probes, were sputter coated with a Au film without undergoing any obvious deformations. Indentations made using the Au-coated CNF tips showed that the buckling force of the tips increased with the thickness of the Au film. The CNF tip coated with a thin Au film less than approximately 8 nm in thickness elastically buckled when subjected to mechanical deflection, which was similar to the bare CNF tips. After annealing the Au-coated CNF-tipped SPM probes, we biofunctionalized them by immobilizing thiol-derivatized, single-stranded DNA (ssDNA) molecules, used as representative biorecognition molecules, on the Au(1 1 1)-coated surfaces. The ability of the immobilized ssDNA molecules to bind with complimentary RNA targets was confirmed via field-emission scanning electron microscopy and energy-dispersive X-ray spectroscopy-based analysis of quantum dots bound to the ssDNA/RNA hybrids formed on the surfaces of the biofunctionalized CNF-tipped SPM probes.