Adsorbents based on carbon microfibers and carbon nanofibers for the removal of phenol and lead from water

This paper describes the production, characteristics, and efficacy of carbon microfibers and carbon nanofibers for the removal of phenol and Pb(2+) from water by adsorption. The first adsorbent produced in the current investigation contained the ammonia (NH(3)) functionalized micron-sized activated carbon fibers (ACF). Alternatively, the second adsorbent consisted of a multiscale web of ACF/CNF, which was prepared by growing carbon nanofibers (CNFs) on activated ACFs via catalytic chemical vapor deposition (CVD) and sonication, which was conducted to remove catalytic particles from the CNF tips and open the pores of the CNFs. The two adsorbents prepared in the present study, ACF and ACF/CNF, were characterized by several analytical techniques, including SEM-EDX and FT-IR. Moreover, the chemical composition, BET surface area, and pore-size distribution of the materials were determined. The hierarchal web of carbon microfibers and nanofibers displayed a greater adsorption capacity for Pb(2+) than ACF. Interestingly, the adsorption capacity of ammonia (NH(3)) functionalized ACFs for phenol was somewhat larger than that of the multiscale ACF/CNF web. Difference in the adsorption capacity of the adsorbents was attributed to differences in the size of the solutes and their reactivity towards ACF and ACF/CNF. The results indicated that ACF-based materials were efficient adsorbents for the removal of inorganic and organic solutes from wastewater.     

Electrochemical capacitances of well-defined carbon surfaces

Reported is the capacitive behavior of homogeneous and well-defined surfaces of pristine carbon nanofibers (CNFs) and surface-modified CNFs. The capacitances of the well-defined CNFs were measured with cyclic voltammetry to correlate the surface structure with capacitance. Among the studied pristine CNFs, the edge surfaces of platelet CNFs (PCNF) and herringbone CNFs were more effective in capacitive charging than the basal plane surface of tubular CNF by a factor of 3-5. Graphitization of PCNF (GPCNF) changed the edge surface of PCNF into a domelike basal plane surface, and the corresponding capacitances decreased from 12.5 to 3.2 F/g. A chemical oxidation of the GPCNF, however, recovered a clear edge surface by removal of the curved basal planes to increase the capacitance to 5.6 F/g. The difference in the contribution of the edge surface and basal-plane surface to the capacitance of CNF was discussed in terms of the anisotropic conductivity of graphitic materials.     

Fast preparation of PtRu catalysts supported on carbon nanofibers by the microwave-polyol method and their application to fuel cells

PtRu alloy nanoparticles (24 +/- 1 wt %, Ru/Pt atomic ratios = 0.91-0.97) supported on carbon nanofibers (CNFs) were prepared within a few minutes by using a microwave-polyol method. Three types of CNFs with very different surface structures, such as platelet, herringbone, and tubular ones, were used as new carbon supports. The dependence of particles sizes and electrochemical properties on the structures of CNFs was examined. It was found that the methanol fuel cell activities of PtRu/CNF catalysts were in the order of platelet > tubular > herringbone. The methanol fuel cell activities of PtRu/CNFs measured at 60 degrees C were 1.7-3.0 times higher than that of a standard PtRu (29 wt %, Ru/Pt atomic ratio = 0.92) catalyst loaded on carbon black (Vulcan XC72R) support. The best electrocatalytic activity was obtained for the platelet CNF, which is characterized by its edge surface and high graphitization degree.     

Surface decoration and dispersibility of carbon nanofibers in aqueous surfactant solution

As a novel functional nanomaterial, the dispersion effect of carbon nanofibers (CNFs) has a significant influence on the application of CNFs in the composites. Two effective surfactants, methylcellulose (MC) and polycarboxylate superplasticizer, were used to analyze the dispersion of CNFs in aqueous solution. A method utilizing ultrasonic processing was employed to achieve a homogenous CNF suspension, and the dispersion effect was further characterized by the method of measuring ultraviolet absorbency (UV absorbency), zeta potential, surface tension and transmission electron microscopy (TEM) micrographs. The results show that the zeta potential and surface tension reach the saturation plateau at MC concentration and polycarboxylate superplasticizer concentration of about 0.4 and 0.8 g/L, respectively, which reflects that the optimum concentration ratio of MC to CNFs is 2: 1, and the optimum dispersing polycarboxylate superplasticizer to CNFs ratio of 4: 1 is required to achieve dispersions with maximum achievable dispersion of CNFs.     

纳米碳纤维的表面性质和微结构对氧还原催化活性的影响

采用超声处理的方法分别对管式纳米碳纤维(t-CNF)和鱼骨式纳米碳纤维(f-CNF)进行了表面化学处理. XPS结果表明, 在混酸(浓硫酸+浓硝酸)和氨水中进行超声化学处理可以在CNF表面分别引入含氧官能团和含氮官能团. 电化学测试结果表明, 2种不同微结构CNF的氧还原催化活性都遵循相同的趋势, 即CNF-P相似文献   

In situ synthesis of Pt/carbon nanofiber nanocomposites with enhanced electrocatalytic activity toward methanol oxidation

Pt/carbon nanofiber (Pt/CNF) nanocomposites were facilely synthesized by the reduction of hexachloroplatinic acid (H(2)PtCl(6)) using formic acid (HCOOH) in aqueous solution containing electrospun carbon nanofibers at room temperature. The obtained Pt/CNF nanocomposites were characterized by TEM and EDX. The Pt nanoparticles could in situ grow on the surface of CNFs with small particle size, high loading density, and uniform dispersion by adjusting the concentration of H(2)PtCl(6) precursor. The electrocatalytic activities of the Pt/CNF nanocomposites were also studied. These Pt/CNF nanocomposites exhibited higher electrocatalytic activity toward methanol oxidation reaction compared with commercial E-TEK Pt/C catalyst. The results presented may offer a new approach to facilely synthesize direct methanol fuel cells (DMFCs) catalyst with enhanced electrocatalytic activity and low cost.     

Ruthenium Nanoparticles on Nano‐Level‐Controlled Carbon Supports as Highly Effective Catalysts for Arene Hydrogenation

The reaction of three types of carbon nanofibers (CNFs; platelet: CNF‐P, tubular: CNF‐T, herringbone: CNF‐H) with [Ru₃(CO)₁₂] in toluene heated at reflux provided the corresponding CNF‐supported ruthenium nanoparticles, Ru/CNFs (Ru content=1.1–3.8 wt %). TEM studies of these Ru/CNFs revealed that size‐controlled Ru nanoparticles (2–4 nm) exist on the CNFs, and that their location was dependent on the surface nanostructures of the CNFs: on the edge of the graphite layers (CNF‐P), in the tubes and on the surface (CNF‐T), and between the layers and on the edge (CNF‐H). Among these Ru/CNFs, Ru/CNF‐P showed excellent catalytic activity towards hydrogenation of toluene with high reproducibility; the reaction proceeded without leaching of the Ru species, and the catalyst was reusable. The total turnover number of the five recycling experiments for toluene hydrogenation reached over 180 000 (mol toluene) (mol Ru)^?1. Ru/CNF‐P was also effective for the hydrogenation of functionalized benzene derivatives and pyridine. Hydrogenolysis of benzylic C? O and C? N bonds has not yet been observed. Use of poly(ethylene glycol)s (PEGs) as a solvent made possible the biphasic catalytic hydrogenation of toluene. After the reaction, the methylcyclohexane formed was separated by decantation without contamination of the ruthenium species and PEG. The insoluble PEG phase containing all of the Ru/CNF was recoverable and reusable as the catalyst without loss of activity.     

Thin, bendable electrodes consisting of porous carbon nanofibers via the electrospinning of polyacrylonitrile containing tetraethoxy orthosilicate for supercapacitor

In the present study, electrically conducting carbon nanofiber (CNF) mats were produced by incorporating tetraethoxy orthosilicate (TEOS) into polyacrylonitrile (PAN) via electrospinning. A simple thermal treatment was applied to the electrospun nanofibers to create ultramicropores that could accommodate a large number of ions were formed on the surface of the CNFs, removing the need for a time-consuming activation step. The Si/CNF composites showed high capacitance and energy/power density values due to the formation of ultramicropores and the introduction of heteroatoms.     

Dispersion of acid-treated carbon nanofibers into gel matrices prepared by the sol-gel method

1-Naphthol has been used as an in-situ fluorescent probe to characterize the dispersibility of carbon nanofibers (CNFs) into the sol-gel matrix of silicon alkoxide. The ion-pair fluorescence of 1-naphthol was found in the gel dispersing acid-treated CNFs instead of 1Lb fluorescence, which was preferred in the low polar gel matrix. This indicates that 1-naphthol easily interacts with oxidized groups present on the surface of the acid-treated CNFs due to the high dispersibility of the CNFs into the gel matrix. The oxidized groups on the CNF surface are useful for preventing self-assembly and/or aggregation of the CNFs in the gel matrix.     

Electrochemistry of perfluorinated fullerenes: the case of three isomers of C60F36

1-Naphthol has been used as an in situ fluorescent probe to characterize the surface physicochemical properties of carbon nanofibers (CNFs). The fluorescence of 1-naphthol adsorbed on untreated CNFs originates from the ¹L_b state and its peaks are shifted by the polarity of the surrounding media, indicating that there is a relatively non-polar area on the CNF surface. 1-Naphthol interacting with oxidized sites on the surface of nitric acid-treated CNFs exhibited an ion-pair fluorescence. This shows that there are some functional groups, interacting with 1-naphthol, on the treated CNF surface. The surface physicochemical properties of the CNFs can be characterized by this fluorescent probe.     

The acquirement of desirable dielectric properties of carbon nanofiber composites based on the controlled crystallization

This study focused on uncovering the relationship among nanofiller, crystallization behavior, and dielectric property of polymer composites. The effects of carbon nanofibers (CNFs) and heat treatment on the crystalline structures and dielectric properties of the semi‐crystalline polymers were analyzed by using high density polyethylene (HDPE) as a matrix, which is a representative of non‐polar polymer and contains only one crystal structure. The experimental results showed that the degree of crystallinity, size distribution of crystallity, and relative amount of different crystal planes in the HDPE matrix were changing due to the addition of CNFs. With the increase of CNF loading, the dielectric constant, dielectric loss and AC conductivity of the HDPE composites were increased, presenting a typical percolation characteristic, and the dependence of the dielectric constant on frequency became more obvious. All kinds of electronic transmission, polarization effect, and relaxation behaviors in CNF/HDPE composite system were deeply analyzed. After heat treatment, the degree of crystallinity of HDPE composites was decreased with the enhanced cooling rate. For the CNF/HDPE composites with nanofiller content slightly higher than the percolation threshold, the significant increase of the dielectric constant and the dramatical reduction of the dielectric loss over a wide frequency range were realized simultaneously through rapid cooling treatment. The research indicated that a general commercial polymer material with excellent dielectric properties, which exhibited a high dielectric constant and a low dielectric loss, can be obtained by a simple technical approach different from traditional fabrication method of threshold composites.     

Chemoselective Hydrogenation of Functionalized Nitroarenes and Imines by Using Carbon Nanofiber‐Supported Iridium Nanoparticles

The reaction of three types of carbon nanofibers (CNFs; platelet: CNF‐P, tubular: CNF‐T, herringbone: CNF‐H) with Ir₄(CO)₁₂ in mesitylene at 165 °C provided the corresponding CNF‐supported iridium nanoparticles, Ir/CNFs (Ir content=2.3–2.6 wt. %). Transmission electron microscopy (TEM) studies of these Ir/CNF samples revealed that size‐controlled Ir nanoparticles (average particle size of 1.1–1.5 nm) existed on the CNFs. Among the three Ir/CNF samples, Ir/CNF‐T showed an excellent catalytic activity and chemoselectivity towards hydrogenation of functionalized nitroarenes and imines; the corresponding aniline derivatives were obtained with high turnover numbers at ambient temperature under 10 atm of H₂, and the catalyst is reusable. Ir/CNF‐T was also effective for the reductive N‐alkylation of anilines with carbonyl compounds.     

The direct architecture of carbon fiber‐carbon nanofiber hierarchical reinforcements for superior interfacial properties of CF/epoxy composites

A simple and efficient chemical method was developed to graft directly carbon nanofibers (CNFs) onto carbon fiber (CF) surface to construct a CF‐CNF hierarchical reinforcing structure. The grafted CF reinforcements via covalent ester linkage at low temperature without any usage of dendrimer or catalyst was investigated by FTIR, X‐ray photoelectron spectroscopy, Raman, scanning electron microscopy, atomic force microscopy, dynamic contact angle analysis, and single fiber tensile testing. The results indicated that the CNFs with high density could effectively increase the polarity, wettability, and roughness of the CF surface. Simultaneous enhancements of the interfacial shear strength, flexural strength, and dynamic mechanical properties as well as the tensile strength of CFs were achieved, for an increase of 75.8%, 21.9%, 21.7%, and 0.5%, respectively. We believe the facile and effective method may provide a novel and promising interface design strategy for next‐generation advanced composite structures.     

Effect of cellulose nanofibers on induced polymerization of aniline and formation of nanostructured conducting composite

Cellulose nanofibers (CNFs), derived from the most abundant and renewable biopolymer, are known as natural one-dimensional nanomaterials because of their high aspect ratio. CNFs also are rich in hydroxyl groups, offering opportunities for functionalization toward development of high-value nanostructured composites. Herein, CNFs were extracted from poplar wood powder by chemical pretreatment combined with high-intensity ultrasonication, and then coated with polyaniline (PANI) through in situ polymerization. The PANI-coated CNFs formed nanostructured frameworks around PANI, thereby conferring the CNF/PANI composite with stability and higher charge transport. The optimum PANI content to achieve maximum conductivity of CNF/PANI composites was determined. The morphology, crystall structure, chemical composition, and conductivity of the samples were characterized by transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and four-point probe method, respectivily. Our results demonstrated that CNFs can be effective as a template for a flexible and stable conducting polymer to form higher-order nanostructures.     

Enhanced Conductivity and mechanical properties of polyimide based nanocomposite materials with carbon nanofibers via carbonization of electrospun polyimide fibers

Carbon nanofibers (CNF) have been obtained by the thermal treatment of the electrospun polyimide fibers in our present work. The carbon structure and surface morphology of the as-received CNFs were investigated using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Investigations of the nanocomposite materials fabricated using these CNFs as conductive fillers and polyimide as matrix show that the presence of CNFs can improve both the mechanical and electrical properties of the material. The conductivity of the nanocomposite films increases with increases in the CNF content and a percolation threshold of about 6.3 vol % (0.0785 in weight fraction) is calculated according to percolation theory.     

Cellulose nanofibril-reinforced biodegradable polymer composites obtained via a Pickering emulsion approach

Preparation of cellulose nanofibril (CNF)-reinforced, biodegradable polymer composites is challenging in that it’s hard to achieve good dispersion of the hydrophilic cellulose fibers in a hydrophobic polymer matrix. In this work, we developed a surfactant-free and efficient process to prepare CNF-reinforced poly (lactic acid) (PLA) composites from an aqueous dichloromethane Pickering emulsion self-emulsified by CNFs. CNF/PLA composites of homogeneous dispersion were obtained upon evaporation of CH₂Cl₂, filtration, drying and hot-pressing. Differential scanning calorimetry measurement revealed an enhanced crystallization capacity of the CNF/PLA composites. Thermogravimetric analysis indicated an increase of onset degradation temperature. The composites displayed an enhanced storage modulus compared with neat PLA throughout the testing temperature range, and especially in the high-temperature region (>70 °C). Enhancements of the flexural modulus and strength were also achieved.     

Achieving very high fraction of β-crystal PVDF and PVDF/CNF composites and their effect on AC conductivity and microstructure through a stretching process

It is well known that the ferroelectric performance of poly (vinylidene fluoride) (PVDF) is caused by its β-crystal structure, which can be efficiently induced through a stretching process applied to the PVDF. Though numerous PVDF nanocomposites have been reported on, there is still a lack of studies on how the stretching process affects the phase transformation in PVDF nanocomposites. In this study, the effects of stretching on the crystalline structures and alternating current (AC) conductivity of PVDF nanocomposites with different concentrations (up to 5.0 wt.%) of CNFs were investigated. Results revealed that the stretching process is not only an effective approach to produce β-crystal from pure PVDF, but also for CNF/PVDF composites. The extremely high phase transformation from α- to β-crystal (?96%) is maintained for the nanocomposites with above 1.0 wt.% CNFs. The AC conductivity of CNF/PVDF composites remarkably decreases when the resultant percolation threshold is raised from 1.0 to 4.2 wt.% CNFs after stretching. This is attributed to the reduced crystallinity induced by the phase transformation from α- to β-PVDF as well as the CNF re-orientation.     

Effect of carbon nanofiber microstructure on oxygen reduction activity of supported palladium electrocatalyst

Palladium electrocatalysts supported on carbon nanofibers (CNFs) with controlled microstructure or on activated carbon (AC) are prepared, and the effects of the carbon materials microstructure on the oxygen reduction reaction (ORR) properties of the electrocatalysts are investigated. The physical properties of the CNFs with different microstructure, i.e. platelet CNF (p-CNF) and fish-bone CNF (f-CNF), are characterized by high resolution transmission electron microscope and N₂ physisorption. From cyclic voltammetric studies, it is found that Pd/p-CNF and Pd/f-CNF are more active than Pd/AC. The effects of CNF microstructure on the ORR activities of Pd/f-CNF and Pd/p-CNF are discussed. The p-CNF has a higher ratio of edge atoms to basal atoms, and therefore Pd/p-CNF has more positive ORR onset reduction potential and ORR peak potential than Pd/f-CNF. The supports also have influences on the reaction process. The ORR is surface reaction controlled when Pd/AC is used, while it becomes diffusion control when Pd/f-CNF is used.     

Direct current electrodeposition of carbon nanofibers in DMF

Carbon nanofibers (CNFs) were electrodeposited on indium tin oxide (ITO) electrodes by using a DC electric field from N,N′-dimethylformamide (DMF). An improved dispersion of CNFs has been found in DMF solution compared to ethanol and acetonenitrile. After treated by concentrated H₂SO₄/HNO₃, CNFs were dispersed uniformly and stably in DMF. During the electrodeposition process, CNFs moved towards anode indicating the negative charge of the nanofibers. Effects of electric field strength, CNF concentration in the suspension, and the solvents used for CNF dispersion were examined on the deposition nature of CNFs.     

In-Vitro Cytotoxicity Study: Cell Viability and Cell Morphology of Carbon Nanofibrous Scaffold/Hydroxyapatite Nanocomposites

Electrospun carbon nanofibers (CNFs), which were modified with hydroxyapatite, were fabricated to be used as a substrate for bone cell proliferation. The CNFs were derived from electrospun polyacrylonitrile (PAN) nanofibers after two steps of heat treatment: stabilization and carbonization. Carbon nanofibrous (CNF)/hydroxyapatite (HA) nanocomposites were prepared by two different methods; one of them being modification during electrospinning (CNF-8HA) and the second method being hydrothermal modification after carbonization (CNF-8HA; hydrothermally) to be used as a platform for bone tissue engineering. The biological investigations were performed using in-vitro cell counting, WST cell viability and cell morphology after three and seven days. L929 mouse fibroblasts were found to be more viable on the hydrothermally-modified CNF scaffolds than on the unmodified CNF scaffolds. The biological characterizations of the synthesized CNF/HA nanofibrous composites indicated higher capability of bone regeneration.