Heat-treated Carbon Nanofibers Research Articles

Effect of Support Functionalization on Catalytic Direct Hydrogenation and Catalytic Transfer Hydrogenation of Muconic Acid to Adipic Acid

The liquid-phase hydrogenation of muconic acid (MA) to produce bio-adipic acid (AdA) is a prominent environmentally friendly chemical process, that can be achieved through two distinct methodologies: catalytic direct hydrogenation using molecular hydrogen (H2), or catalytic transfer hydrogenation utilizing a hydrogen donor. In this study, both approaches were explored, with formic acid (FA) selected as the hydrogen source for the latter method. Palladium-based catalysts were chosen for these processes. Metal’s nanoparticles (NPs) were supported on high-temperature heat-treated carbon nanofibers (HHT-CNFs) due to their known ability to enhance the stability of this metal catalyst. To assess the impact of support functionalization on catalyst stability, the HHT-CNFs were further functionalized with phosphorus and oxygen to obtain HHT-P and HHT-O, respectively. In the hydrogenation reaction, catalysts supported on functionalized supports exhibited higher catalytic activity and stability compared to Pd/HHT, reaching an AdA yield of about 80% in less than 2 h in batch reactor. The hydrogen-transfer process also yielded promising results, particularly with the 1%Pd/HHT-P catalyst. This work highlights the efficacy of support functionalization in improving catalyst performance, particularly when formic acid is used as a safer and more cost-effective hydrogen donor in the hydrogen-transfer process.

Bio-Adipic Acid Production from Muconic Acid Hydrogenation on Palladium-Transition Metal (Ni and Zn) Bimetallic Catalysts

The hydrogenation of muconic acid (MA) to bio-adipic acid (AdA) is one of the green chemical processes that has attracted the most interest in recent years. Indeed, MA can be readily obtained from biomass through fermentative processes. Here, we aimed to investigate the synergic effect of electronic promotion that the addition of a second metal, even in small quantities, can have on Pd-based catalyst, known for its low stability. Ni and Zn were taken into consideration and two different catalysts (1%Pd8Ni2/HHT and 1%Pd8Zn2/HHT) were synthetized by sol immobilization method and supported on high-temperature, heat-treated carbon nanofibers (HHT-CNFs) that are known to enhance the stability of palladium. The catalysts were tested in MA hydrogenation and thoroughly characterized by TEM, ICP, and XPS analysis to unveil the effect of the second metal. To solve the solubility issue and have a starting material as similar as feasible to the post-fermentation conditions of the biomass, sodium muconate salt was chosen as a substrate for the reaction. All of the synthetized bimetallic catalysts showed a higher activity than monometallic Pd and better stability during the recycling tests, pointing out that even a small amount of these two metals can increase the catalytic properties of monometallic Pd.

High-Performance Properties of an Aerospace Epoxy Resin Loaded with Carbon Nanofibers and Glycidyl Polyhedral Oligomeric Silsesquioxane

This paper proposes a new multifunctional flame retardant carbon nanofiber/glycidyl polyhedral oligomeric silsesquioxane (GPOSS) epoxy formulation specially designed for lightweight composite materials capable of fulfilling the ever-changing demands of the future aerospace industry. The multifunctional resin was designed to satisfy structural and functional requirements. In particular, this paper explores the advantages deriving from the combined use of GPOSS and CNFs (short carbon nanofibers) to obtain multifunctional resins. The multifunctional material was prepared by incorporating in the epoxy matrix heat-treated carbon nanofibers (CNFs) at the percentage of 0.5 wt% and GPOSS compound at 5 wt% in order to increase the mechanical performance, electrical conductivity, thermal stability and flame resistance property of the resulting nanocomposite. Dynamic mechanical analysis (DMA) shows that the values of the Storage Modulus (S.M.) of the resin alone and the resin containing solubilized GPOSS nanocages are almost similar in a wide range of temperatures (from 30 °C to 165 °C). The presence of CNFs, in the percentage of 0.5 wt%, determines an enhancement in the S.M. of 700 MPa from −30 °C to 180 °C with respect to the resin matrix and the resin/GPOSS systems. Hence, a value higher than 2700 MPa is detected from 30 °C to 110 °C. Furthermore, the electrical conductivity of the sample containing both GPOSS and CNFs reaches the value of 1.35 × 10−1 S/m, which is a very satisfying value to contrast the electrical insulating property of the epoxy systems. For the first time, TUNA tests have been performed on the formulation where the advantages of GPOSS and CNFs are combined. TUNA investigation highlights an electrically conductive network well distributed in the sample. The ignition time of the multifunctional nanocomposite is higher than that of the sample containing GPOSS alone of about 35%.

Pd–Au Bimetallic Catalysts for the Hydrogenation of Muconic Acid to Bio-Adipic Acid

The hydrogenation reaction of muconic acid, produced from biomass using fermentative processes, to bio-adipic acid is one of the most appealing green emerging chemical process. This reaction can be promoted by catalysts based on a metal belonging to the platinum group, and the use of a second metal can preserve and increase their activity. Pd–Au bimetallic nanoparticle samples supported on high-temperature, heat-treated carbon nanofibers were prepared using the sol immobilization method, changing the Pd–Au molar ratio. These catalysts were characterized by TEM, STEM, and XPS analysis and tested in a batch reactor pressurized with hydrogen, where muconic acid dissolved in water was converted to adipic acid. The synthesized Pd–Au bimetallic catalysts showed higher activity than monometallic Au and Pd material and better stability during the recycling tests. Moreover, the selectivity toward the mono-unsaturated changed by decreasing the Pd/Au molar ratio: the higher the amount of gold, the higher the selectivity toward the intermediates.

Cyclic Voltammetry Characterization of Au, Pd, and AuPd Nanoparticles Supported on Different Carbon Nanofibers

Three types of carbon nanofibers (pyrolytically stripped carbon nanofibers (PS), low-temperature heat treated carbon nanofibers (LHT), and high-temperature heat treated carbon nanofibers (HHT)) with different graphitization degrees and surface chemistry have been used as support for Au, Pd, or bimetallic AuPd alloy nanoparticles (NPs). The carbon supports have been characterized using Raman, X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV). Moreover, the morphology of the metal nanoparticles was investigated using transmission electron microscopy (TEM) and CV. The different properties of the carbon-based supports (particularly the graphitization degree) yield different electrochemical behaviors, in terms of potential window widths and electrocatalytic effects. Comparing the electrochemical behavior of monometallic Au and Pd and bimetallic AuPd, it is possible to observe the interaction of the two metals when alloyed. Moreover, we demonstrate that carbon surface has a strong effect on the electrochemical stability of AuPd nanoparticles. By tuning the Au-Pd nanoparticles’ morphology and modulating the surface chemistry of the carbon support, it is possible to obtain materials characterized by novel electrochemical properties. This aspect makes them good candidates to be conveniently applied in different fields.

The effect of filler aspect ratio on the electromagnetic properties of carbon-nanofibers reinforced composites

The effect of filler aspect ratio on the electromagnetic properties of epoxy-amine resin reinforced with carbon nanofibers is here investigated. A heat treatment at 2500 °C of carbon nanofibers seems to increase their aspect ratio with respect to as-received ones most likely due to a lowering of structural defects and the improvement of the graphene layers within the dixie cup conformation. These morphological differences revealed by Raman's spectroscopy and scanning electron microscopy analyses may be responsible for the different electrical properties of the resulting composites. The DC characterization of the nanofilled material highlights an higher electrical conductivity and a lower electrical percolation threshold for the heat-treated carbon nanofibers based composites. In fact, the electrical conductivity is about 0.107 S/m and 1.36 × 10−3 S/m for the nanocomposites reinforced with heat-treated and as received fibers, respectively, at 1 wt. % of nanofiller loading, while the electrical percolation threshold falls in the range [0.05–0.32]wt. % for the first nanocomposites and above 0.64 wt. % for the latter. Moreover, also a different frequency response is observed since the critical frequency, which is indicative of the transition from a resistive to a capacitive-type behaviour, shifts forward of about one decade at the same filler loading. The experimental results are supported by theoretical and simulation studies focused on the role of the filler aspect ratio on the electrical properties of the nanocomposites.

Polarized wave electromagnetic shielding of anisotropic carbon nanomodifier-based LLDPE composites

The polarized wave electromagnetic shielding (EM SE) of nanocomposites containing 10 vol% of carbon nanomodifiers in a semicrystalline matrix is reported. Heat-treated carbon nanofibers, Pyrograf® III PR-19 heat treatment (HT) and multiwalled carbon nanotubes (MWNT) HT were dispersed in a linear low-density polyethylene matrix to produce flow-induced orientation of the nanomodifiers in the spun microfilaments. Consequently, the electrical conductivity of the resulting nanocomposites exhibited anisotropic behavior due to the nanomodifier orientation. The in-plane conductivity in the longitudinal direction (PR-19 HT comp.: ∼0.02 S/m; MWNT HT comp.: ∼3 S/m) was at least an order of magnitude higher than that along the transverse direction. As measured with a rectangular waveguide (WR510, 1.45–2.2 GHz), the PR-19 HT- and MWNT HT-oriented nanocomposites (1-mm thick) displayed EM SE values of 0.7 dB and 3.0 dB, respectively, when the nanomodifiers were transversely oriented with the polarized electric field. In contrast, when the orientation of the nanomodifiers was parallel with the field, EM SE values of 3.2 and 9.0 dB were obtained, respectively. The higher EM SE values are consistent with high conductivities observed in the direction of preferred orientation of the modifiers. POLYM. ENG. SCI., 55:299–307, 2015. © 2014 Society of Plastics Engineers

Direct Electrochemistry and Electrocatalysis of Hemoglobin in Nafion/Carbon Nanochip Film on Glassy Carbon Electrode

The use of heat treated carbon nanofibers, known as carbon nanochips (CNCs) for the studies of the direct electrochemistry and electrocatalytic properties of heme proteins, is demonstrated. A glassy carbon electrode (GCE) was modified with CNCs, and hemoglobin (Hb) was immobilized on the modified electrode surface by casting a film of Hb. Nafion was employed to fix the CNCs and Hb tightly on the surface of the GCE. The modified electrode was characterized by scanning electron microscopy. Ultraviolet-visible and Fourier transform infrared spectroscopy showed that Hb immobilized in the CNC film remained in its native structure. Electrochemical impedance spectroscopy and cyclic voltammetry (CV) were employed for electrochemical studies. The results showed that the presence of CNCs in the film can greatly enhance the electrochemical response of Hb. A pair of well-defined reversible CV peaks was observed, and the formal potential of the heme Fe(III)/Fe(II) redox couple was found to be -253 mV [vs Ag/AgCl (saturated KCl)]. The apparent heterogeneous electron-transfer rate constant (k(s)) was estimated as 2.54 s(-1). The modified electrode showed excellent electrocatalytic behavior to hydrogen peroxide (H(2)O(2)), trichloroacetic acid, and sodium nitrite. H(2)O(2) had a linear current response from 0.5 to 30 microM (R(2) = 0.9997; n = 5) with a detection limit of 0.05 microM when the signal-to-noise ratio was 3 and the apparent Michaelis-Menten constant (K(m)(app)) was 21.55 microM. These values suggest that CNCs are the best matrix described so far for the development of biosensors, far superior to untreated carbon nanofibers. The direct immobilization of proteins onto the surface of CNCs is shown to be a highly efficient method for the development of a new class of very sensitive, stable, and reproducible electrochemical biosensors.

Understanding the Dielectric Properties of Heat-Treated Carbon Nanofibers at Terahertz Frequencies: a New Perspective on the Catalytic Activity of Structured Carbonaceous Materials

Terahertz time domain spectroscopy (THz-TDS) has been used to study the electrical and optical properties of a series of carbon nanofibers (CNFs) that have undergone different heat treatments. The ...

The graphitization of carbon nanofibers produced by the catalytic decomposition of natural gas

Fishbone carbon nanofibers (CNFs) were produced by methane decomposition in a fluidized bed reactor using nickel–copper based catalysts that were prepared with different promoters (SiO 2, Al 2O 3, TiO 2, MgO). The CNFs were subjected to heat treatment (HT) in the temperature range 2400–2800 °C to explore their ability to graphitize. The influence of treatment temperature and CNF metal content on the structural and textural parameters of the resulting heat treated carbon nanofibers was studied. More-ordering was achieved in CNFs containing Si and Ti because of the catalytic effect of these metals. Since titanium carbide appeared after the HT, the formation of graphitic material by carbide decomposition seems to be a plausible mechanism to explain the catalytic graphitization of the CNFs. A parallel evolution of the structural and textural properties of the nanofibers during HT was found, suggesting that a decrease of the specific surface area is caused by the removal of structural defects and an increase of crystallite size.

Nanoscale Weibull Statistics for Nanofibers and Nanotubes

In this paper a modification of the classical Weibull statistics is applied to nanostructures. A comparison is presented of “nanoscale” versus classical Weibull statistics in treating recent experimental results on the fracture strength of C nanofibers and nanotubes, and WS2 nanotubes. “Nanoscale” Weibull moduli of 3.8 for electrospun and then heat-treated carbon nanofibers, 2.7 for arc-discharge synthesized multiwalled carbon nanotubes, 1.8 for chemical vapor deposited multiwalled carbon nanotubes, and 3.0 for multiwalled WS2 nanotubes, are deduced.

Hydrogen storage in heat-treated carbon nanofibers prepared by the vertical floating catalyst method

Hydrogen storage in carbon nanofibers (CNFs) prepared by the floating catalyst method is investigated. The pristine CNF materials are subjected to several heat treatments under different temperatures with the protection of Ar for 2 h to get favorable structure and adsorption surface. These treatments improved the graphitization degree and surface activity of the CNFs effectively. At last these materials can absorb ∼4 wt.% of hydrogen at room temperature under ∼10 MPa. The effect of the surface functional groups on the adsorption performance of the CNFs is highlighted.