Synthesis of Fe/Fe3C nanoparticles encapsulated in nitrogen-doped carbon with single-source molecular precursor for the oxygen reduction reaction

Ammonium ferric citrate (AFC) was used as a single-source molecular precursor to prepare Fe/Fe₃C nanoparticles encapsulated in nitrogen-doped carbon by pyrolysis in Ar atmosphere followed by acid-leaching. Comparative studies, using citric acid and ferric citrate as the precursors, indicated that the ammonia and ferric ion in AFC and the pyrolysis temperature affected the composition of iron species and the properties of carbon in AFC-derived materials. Above the pyrolysis temperature of 600 °C, the iron species were Fe/Fe₃C, and the carbon had a hollow graphitic nanoshell structure in AFC-derived materials. The specific surface area and content of nitrogen element decreased with increasing pyrolysis temperature. The AFC-derived material pyrolyzed at 600 °C had the optimal graphitization degree, specific surface area (489 m² g⁻¹) and content of nitrogen (1.8 wt.%), thus resulted in the greatest activity for oxygen reduction reaction among the AFC-derived materials pyrolyzed at different temperatures. The AFC-derived material pyrolyzed at 600 °C exhibited improved methanol-resistance ability compared with Pt/C catalyst.     

Preparation and one-step activation of microporous carbon nanofibers for use as supercapacitor electrodes

Microporous carbon nanofibers were prepared by electrospinning from resole-type phenolic resin, followed by one-step activation. KOH was utilized to tune the fiber diameter and improve porous texture. By adjusting KOH content in the spinning solution, the fiber diameter could be controlled in the range of 252–666 nm and the microporous volume and specific surface area could be greatly improved. The electrochemical measurements in 6 M KOH aqueous solution showed that the microporous carbon nanofibers possessed high specific capacitance, considerable rate performance, and superior specific surface capacitance to conventional microporous carbons. The maximal specific capacitance of 256 F g⁻¹ and high specific surface capacitance of 0.51 F m⁻² were achieved at 0.2 A g⁻¹. Furthermore, the specific capacitance could still remain 170 F g⁻¹ at 20 A g⁻¹ with the retention of 67%. Analysis showed that the high specific surface capacitance of the resultant carbons was mainly attributed to optimized pore size (0.7–1.2 nm) and the excellent rate performance should be principally due to the reduced ion transportation distance derived from the nanometer-scaled fibers.     

Polystyrene-based carbon spheres as electrode for electrochemical capacitors

A series of carbon spheres with various porous texture parameters were prepared from polystyrene-based macroreticular resin spheres by carbonization and activation. The as-prepared carbon spheres had a maximum specific surface area of 996 m² g^?1, total pore volume of 1.34 cm³ g^?1 and average pore size of 5.39 nm. Moreover, these carbon spheres showed a mesopore size distributed mainly in about 40 nm. A high specific capacitance of 153 F g^?1 for carbon sphere by carbonization, 164 F g^?1 for carbon sphere by activation for 1 h and 182 F g^?1 for carbon sphere by activation for 2 h can be obtained. Moreover, a specific energy between 2.3 and 5.1 Wh kg^?1 for these carbon spheres can be obtained in 6 mol L^?1 KOH electrolyte.     

Tubular graphene nanoribbons with attached manganese oxide nanoparticles for use as electrodes in high-performance supercapacitors

Graphene nanoribbons (GNRs) with tubular shaped thin graphene layers were prepared by partially longitudinal unzipping of vapor-grown carbon nanofibers (VGCFs) using a simple solution-based oxidative process. The GNR sample has a similar layered structure to graphene oxide (GO), which could be readily dispersed in isopropyl alcohol to facilitate electrophoretic deposition (EPD). GO could be converted to graphene after heat treatment at 300 °C. The multilayer GNR electrode pillared with open-ended graphene tubes showed a higher capacitance than graphene flake and pristine VGCF electrodes, primarily due to the significantly increased surface area accessible to electrolyte ions. A GNR electrode with attached MnO₂ nanoparticles was prepared by EPD method in the presence of hydrated manganese nitrate. The specific capacitance of GNR electrode with attached MnO₂ could reach 266 F g⁻¹, much higher than that of GNR electrode (88 F g⁻¹) at a discharge current of 1 A g⁻¹. The hydrophilic MnO₂ nanoparticles attached to GNRs could act as a redox center and nanospacer to allow the storage of extra capacitance.     

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.     

Preparation of sulfur-doped microporous carbons for the storage of hydrogen and carbon dioxide

Structurally well ordered, sulfur-doped microporous carbon materials have been successfully prepared by a nanocasting method using zeolite EMC-2 as a hard template. The carbon materials exhibited well-resolved diffraction peaks in powder XRD patterns and ordered micropore channels in TEM images. Adjusting the synthesis conditions, carbons possess a tunable sulfur content in the range of 1.3–6.6 wt.%, a surface area of 729–1627 m² g^?1 and a pore volume of 0.60–0.90 cm³ g^?1. A significant proportion of the porosity in the carbons (up to 82% and 63% for surface area and pore volume, respectively) is contributed by micropores. The sulfur-doped microporous carbons exhibit isosteric heat of hydrogen adsorption up to 9.2 kJ mol^?1 and a high hydrogen uptake density of 14.3 × 10^?3 mmol m^?2 at ?196 °C and 20 bar, one of the highest ever observed for nanoporous carbons. They also show a high CO₂ adsorption energy up to 59 kJ mol^?1 at lower coverages (with 22 kJ mol^?1 at higher CO₂ coverages), the highest ever reported for any porous carbon materials and one of the highest amongst all the porous materials. These findings suggest that S-doped microporous carbons are potential promising adsorbents for hydrogen and CO₂.     

Discovery of effective solvents for platelet-type graphite nanofibers

The dispersibility of platelet-type graphite nanofibers (PGNFs), an archetype of carbon material with a surface dominated by graphitic edge planes, has been measured in 28 solvents and rationalized on the basis of solvent surface tension and Hansen solubility parameters. Successful solvents possess surface tensions of ∼25–35 mJ m⁻² and substantial values of the hydrogen-bonding Hansen parameter (δ_H ∼ 14–16 MPa^1/2), and many of them are alcohols, such as 1-butanol, ethanol or cyclohexanol. Such result is mainly attributed to the fact that the PGNF edge planes are decorated with oxygen functional groups. The dispersion behavior of the nanofibers could be changed to that typically exhibited by carbon nanotubes and graphene by means of a high temperature annealing that converted their surface edge planes to curved basal planes.     

Robust growth of herringbone carbon nanofibers on layered double hydroxide derived catalysts and their applications as anodes for Li-ion batteries

Herringbone carbon nanofibers (CNFs) were efficiently produced by chemical vapor deposition on Ni nanoparticles derived from layered double hydroxide (LDH) precursors. The as-obtained CNFs with a diameter ranging from 40 to 60 nm demonstrated herringbone morphologies when they grew on Ni/Al LDH derived catalysts both in the fixed-bed and fluidized-bed reactor. The Ni/Mg/Al, Ni/Cu/Al, as well as Ni/Mo/Mg/Al catalysts were also effective to grow herringbone CNFs. The diameter and specific surface area of the as-obtained CNFs highly depended on the catalyst composition and the growth temperature. When CNFs were grown at 550 °C on Ni/Al catalyst, the as-obtained products had an outer diameter of ca. 50 nm and a specific surface area of 242 m² g⁻¹, possessed a discharge capacity of 330 mAh g⁻¹ as the electrode in a two-electrode coin-type cell. With the increase of the surface area, the discharge capacity increased at a rate of 0.90 mAh cm⁻², while the initial coulombic efficiency decreased gradually on nanocarbon anodes. This is attributed to the fact that CNFs with higher surface area afford smaller sp² carbon layer that facilitated more Li ions to extract from the anodes.     

Low cost preparation of high thermal conductivity carbon blocks with ultra-high anisotropy from a commercial graphite paper

A carbon block with ultra-high anisotropy was produced from a commercial graphite paper as the thermal reinforcement and a thermosetting phenolic resin as the binder. Hot-pressing at a maximum temperature of 200 °C was used to densify and integrate the graphite paper stacks. It has been found that the graphite paper blocks have high thermal conductivities in the paper direction and low ones perpendicular. An anisotropy of 98.8% and a thermal conductivity of 197.8 W m^?1 K^?1 in the paper direction were achieved when the density was 1.1 g cm^?3. The thermal conductivity increased to 284.8 W m^?1 K^?1 with a decrease of anisotropy to 98.3% with a density of 1.56 g cm^?3.     

Graphene-wrapped polyaniline nanofibers as electrode materials for organic supercapacitors

Graphene-wrapped polyaniline nanofibers were prepared by assembly of negatively charged graphene oxide with positively charged aqueous dispersible polyaniline nanofibers in an aqueous dispersion, followed by the reduction of the graphene oxide. The hybrid material with a graphene oxide loading of 9.1 wt.% displayed a high specific capacitance of over 250 F g⁻¹ in a 1 M Et₄N⁺·BF₄⁻/propylene carbonate electrolyte, a 39.7% increase compared with pristine polyaniline nanofibers. A significant improvement in long-term cycle life was also realized. The hybrid exhibited an initial specific capacitance of 236 F g⁻¹, which remained as high as 173.3 F g⁻¹ over 1000 cycles, or a 26.3% decrease, much better than that for pure polyaniline nanofibers. An asymmetric supercapacitor based on this hybrid material and activated carbon was assembled. An energy density of 19.5 W h kg⁻¹ at a power density of 738.95 W kg⁻¹ was obtained for the cell under an operating voltage window of 2 V.     

Microwave-assisted sol–gel synthesis of alpha alumina nanopowder and study of the rheological behavior

In the present work, alpha alumina nanopowder was synthesized via a sol–gel route. After preparation of bohemite (AlOOH) sol, carbon black was added and the resultant sol was dried and calcined in microwave furnace for 10 min. XRD results showed that alpha alumina was the only crystalline phase with specific surface area, mean diameter and crystallite size of 51 m² g^?1, 100 and 25 nm, respectively. Rheological measurements revealed that the optimal content of Tiron at pH=10 is 1 and 0.1 g per 100 g nano- and micron-alumina (1.5 m² g^?1), respectively. Furthermore, the optimum solid content of the slips was determined as 35–45 and 70 wt.% for nano- and micron-alumina, respectively.     

Graphitic carbon nitride nanosheet-assisted preparation of N-enriched mesoporous carbon nanofibers with improved capacitive performance

N-enriched mesoporous carbon nanofibers (NMCNFs) were prepared by an electrospinning technique using graphitic carbon nitride (g-C₃N₄) nanosheets both as sacrificial template and N-doping source. The resultant NMCNF film has a high N-doping level of 8.6 wt% and a high specific surface area of 554 m² g⁻¹. When directly used as the electrode material for supercapacitor, the free-standing NMPCNF film shows a significantly improved capacitive performance including a higher specific capacitance (220 F g⁻¹ at 0.2 A g⁻¹) and a better rate capability (∼70% retention at 20 A g⁻¹) than those of microporous carbon nanofiber film prepared using the same process without using g-C₃N₄ nanosheets (145 F g⁻¹ at 0.2 A g⁻¹ and ∼45% retention at 20 A g⁻¹). Moreover, the NMCNFs show superior stability with only a ∼3% decrease of its initial capacitance after 1000 cycles at a high current density of 10 A g⁻¹. More significantly, the energy density of a symmetrical supercapacitor (SC) based on the NMPCNF film can reach 12.5 Wh kg⁻¹ at a power density of 72 W kg⁻¹.     

Nitrogen-doped porous carbons through KOH activation with superior performance in supercapacitors

A series of nitrogen-doped porous carbons are prepared through KOH activation of a nonporous nitrogen-enriched carbon which is synthesized by pyrolysis of the polymerized ethylenediamine and carbon tetrachloride. The porosity and nitrogen content of the nitrogen-doped porous carbons depend strongly on the weight ratio of KOH/carbon. As the weight ratio of KOH/carbon increases from 0.5 to 2, the specific surface area increases from 521 to 1913 m² g⁻¹, while the nitrogen content decreases from 10.8 to 1.1 wt.%. The nitrogen-doped porous carbon prepared with a moderate KOH/carbon weight ratio of 1, which possesses a balanced specific surface area (1463 m² g⁻¹) and nitrogen content (3.3 wt.%), exhibits the largest specific capacitance of 363 F g⁻¹ at a current density of 0.1 A g⁻¹ in 1 M H₂SO₄ aqueous electrolyte, attributed to the co-contribution of double-layer capacitance and pseudocapacitance. Moreover, it shows excellent rate capability (182 F g⁻¹ remained at 20 A g⁻¹) and good cycling stability (97% capacitance retention over 5000 cycles), making it a promising electrode material for supercapacitors.     

Functionalized N-doped interconnected carbon nanofibers as an anode material for sodium-ion storage with excellent performance

The electrochemical performance of sodium-ion battery was improved by using functionalized interconnected N-doped carbon nanofibers (FN-CNFs) as the anode. The material was synthesized with polypyrrole as precursor by a simple method. The FN-CNF electrode exhibits excellent rate capability and cycling stability, delivering a capacity of 134.2 mAh g⁻¹ at a high current density of 200 mA g⁻¹ after 200 cycles and retains a capacity of 73 mAh g⁻¹ even at an extremely high current density of 20 A g⁻¹. The superior performance can be attributed to N-doped sites and functionalized groups, which are capable of capturing sodium ions rapidly and reversibly through surface adsorption and surface redox reactions.     

Mesoporous carbon nanofibers with large cage-like pores activated by tin dioxide and their use in supercapacitor and catalyst support

The mesoporous carbon nanofibers (MCFs) with large cage-like pores have been fabricated by thermally treating electrospun fibers of polyvinyl alcohol containing tin compound. During the process, tin oxide is reduced to melting tin and the carbon is activated to form the porous carbon. The results of X-ray diffraction and transmission electron microscopy at different temperatures show that particles of SnO₂ (∼1.9 nm) exist in the fibers at 300 °C while mixtures of Sn and SnO with rod-like shapes appear in the matrix when the fibers are heated at 400 °C, and that Sn migrates to the surface of fibers and pores are formed in the fibers at higher temperature. Specific surface area of MCFs can reach 800 m² g⁻¹ and the average diameter of interior pores is about 10.3 nm while the entrance pores are small. The specific capacitance of MCFs is 105 F g⁻¹ and the fabricated symmetrical capacitors exhibit high-rate capacitive properties and excellent stability, Pt nanoparticles which can be densely loaded on MCFs exhibit relatively high activity and stability toward electro-oxidation of methanol, which indicate that MCFs may be used as electrodes for high-rate energy storage and support for catalyst. This approach may be extended to prepare other porous carbon materials.     

The influence of the carbon precursor,carbon feed rate and helium gas flow rate on the synthesis of fullerenes from carbon powder in an entrained flow 3-phase AC plasma reactor operating at atmospheric pressure

We studied an entrained flow 3-phase AC plasma reactor operating at atmospheric pressure with helium for the synthesis of fullerenes from different carbon powder precursors through an evaporation–condensation process. A parametric study focusing on gas flow rate and carbon powder feed rate was carried out using three commercial carbon materials: Y50A acetylene black from SN2A, E 250 carbon black from TIMCAL, and KS 4 graphite powder from TIMCAL. This study revealed a strong dependence of these parameters with fullerene yield and rate of fullerene production. It also revealed the key role of the carbon black purity. The best results were obtained using acetylene black Y50 A, for which a rate of fullerene production of the order of 17 g h^?1 corresponding to a 480 g h^?1 carbon feed rate at 3.6% fullerene content (C60 + C70) were obtained. The specific energy input defined as the plasma power related to carbon precursor feed rate and rate of fullerene production were estimated to 0.039 kWh g^?1 and 1.11 kWh g^?1 respectively.     

The production of hypocrellin colorants by submerged cultivation of the medicinal fungus Shiraia bambusicola

Hypocrellin production using submerged cultivation of the medicinal fungus Shiraia bambusicola revealed that both glucose and (NH₄)₂SO₄ were optimal carbon and nitrogen sources. Hypocrellin production increased with increasing initial glucose concentration within the range of 10–50 g l^?1 and (NH₄)₂SO₄ concentration in the range of 1–2 g l^?1. The effects of carbon and nitrogen concentration were optimized using central composite experimental design and response surface analysis; maximum hypocrellin production (196.94 ± 6.93 mg l^?1) was achieved using 45.7 g l^?1 glucose and 1.93 g l^?1 (NH₄)₂SO₄.     

Equilibrium and kinetic studies for removal of malachite green from aqueous solution by a low cost activated carbon

A low cost activated carbon was synthesized from coconut coir and was applied for the removal of malachite green (MG) from its aqueous solutions. Characterization of the adsorbent was carried out and BET surface area of the adsorbent was found to be 205.27 m²/g. The process of removal of MG was better governed by second order kinetics with a rate constant of 0.21 g mg^?1 min^?1 at 323 K. The coefficient of mass transfer was found to be 3.70 × 10^?5 cm s^?1. The value of ΔG° was found to be negative indicating feasibility and spontaneity of the adsorption process.