Modeling ferrocene reactions and iron nanoparticle formation: Application to CVD synthesis of carbon nanotubes

This paper presents a practically useful model that can predict the formation process and the growth rate of iron nanoparticles from ferrocene. There is a strong need to create such a model that can help improve the process of carbon nanotube (CNT) production by chemical vapor deposition (CVD) and flame synthesis methods. This study serves this purpose. A simple reaction mechanism between ferrocene and hydrogen was proposed based on experimental and theoretical studies conducted by other researchers; then the method of moments with interpolative closure (MOMIC) was applied to compute the size distribution of iron particles. MOMIC was found to reproduce the result of a sectional method with better accuracy than a lognormal method. We simulated the isothermal decomposition of ferrocene and the consequent formation of iron particles with MOMIC; the computed diameter of iron particles agreed reasonably well with experimental data. Analytical solutions for particle diameter were obtained as a function of residence time, assuming monodisperse particles and a constant collision frequency function. They compared very well to the numerical prediction by a monodisperse model and reasonably well to that by MOMIC, suggesting the analytical solutions to be a simple first approximation in assessing the performance of CVD and flame synthesis methods of producing CNTs.     

An electrochemical study for corrosion inhibition of iron by some organic phosphonium chloride derivatives in acid media

The inhibiting action of (chloromethyl) triphenyl phosphonium chloride (CTP), tetraphenyl phosphonum chloride (TP), triphenyl phosphine oxide (TPO), triphenyl (phenylmethyl) phosphonium chloride (TPM) and triphenyl phosphine (TPP) on the corrosion of iron in 1 M HCl solution was studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Experimental results revealed that CTP, TP, TPO, and TPM act as inhibitors for iron in acid environments, while TPP is an accelerator. These compounds are mixed-type inhibitors and the inhibition efficiency increased with increasing concentrations. Equivalent circuits of the investigated systems are suggested.     

Purification of carbon nanotubes grown by thermal CVD

We show the results of a set of purifications on carbon nanotubes (CNT) by acid and basic treatments. CNTs were obtained by thermal decomposition of camphor at 850 °C in a CVD growth system, by means of a growth process catalyzed by iron clusters originating from the addition of ferrocene in the precursors mixture. The purification procedures involved HNO₃, H₂SO₄, HSO₃Cl and NaOH for different process temperatures.As-grown CNTs showed a consistent presence of metal catalyst (about 6 wt%), evidenced by TGA. The purification treatments led to a certain amount of opening of the CNT tips, with a consequent loss of metal catalyst encapsulated in tips. This is also confirmed by BET analysis, which showed an increase of the surface area density of CNT after the purification.FT-IR and XPS revealed the presence of carboxylic groups on the CNT surface chemically modified by the harsh environment of the purification process.Among the various treatments that have been tested, the 1:3 solution of nitric and sulphuric acid was the most effective in modifying the CNT surface and inducing the formation of functional groups.     

Toxicological effects of multi-wall carbon nanotubes in rats

The aim of this study was to evaluate the lung toxicity of multi-wall carbon nanotubes (MWCNTs). The present work exposed MWCNTs into the rats in intratracheal instillation administration modes. We systematically studied the distribution of nanoparticles in vivo, target organs and time-effects of nanotoxicity, dose-effects of nanotoxicity, etc. These results indicate that under the conditions of this test, pulmonary exposures to MWCNTs in rats by intratracheal instillation produced a series of multiple lesions in a dose-dependent and time-dependent manner, evidence of a foreign tissue body reaction.     

The effect of process variables on the characteristics of carbon nanotubes obtained by spray pyrolysis

A simple spray pyrolysis setup is used to grow multi-walled carbon nanotubes (MWCNTs), from a ferrocene solution in benzene as precursor. The effects of process variables such as growth temperature, position of the aerosol generator and position in the reactor where the sample was formed were investigated. These variables have a strong influence on the graphitization degree, homogeneity, diameter and alignment of the nanotubes, as observed by TEM, SEM, XRD and Raman spectroscopy. Vertically aligned MWCNT arrays with high density were obtained in large areas (10 × 10 mm²), with high yield (2.1 mg cm⁻²) and at a growth rate at 1.43 μm min⁻¹, by a suitable choice of the experimental conditions.     

The synthesis of multi-walled carbon nanotubes (MWNTs) by catalytic pyrolysis of the phenol-formaldehyde resins

A series of carbon nanomaterials, particularly multi-walled carbon nanotubes (MWNT), are obtained as products from catalytic pyrolysis of the cross-linked phenol-formaldehyde resins with different ferrocene under inert atmosphere. The morphology and structure of the samples were evaluated by TEM and XRD techniques. CNTs morphology is dependent on the iron nanoparticles and their forms (Fe, Fe₃C) resulted from ferrocene decomposition. The amount of nanotubes increases with iron content released from ferrocene catalyst during the pyrolysis process. Fe₃C nanoparticles drive the nucleation and the growth of carbon nanotubes during the pyrolysis process. Long (up to microns) well-defined MWNTs with small defects, ropes and disordered carbon are representatives in the pyrolyzed resins composition.     

Magnetic properties of multiwalled carbon nanotubes as a function of acid treatment

We investigate the electronic properties of multiwalled carbon nanotubes both before and after acid treatment with concentrated sulphuric and nitric acids. Magnetic susceptibility measurements were performed using a SQUID magnetometer and show that there is a considerable enhancement in the density of states at the Fermi level. The data shows that the diamagnetic influence from the graphitic nanotubes dominates. We experimentally observe, after acid treatment, that the diamagnetic susceptibility remains unchanged at 5 K but notably decreases at 77 K. We propose the acid treatment has increased the Van Vleck paramagnetic contribution lowering the diamagnetic response from the π-electron orbital magnetisation. The Van Vleck paramagnetic contribution is finite-temperature dependent with a diminishing contribution at higher fields.     

Characterization of iron surface modified by 2-mercaptobenzothiazole self-assembled monolayers

A self-assembled monolayer of 2-mercaptobenzothiazole (MBT) adsorbed on the iron surface was prepared. The films were characterized by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared reflection spectroscopy (FT-IR) and scanning electron microscopy (SEM). Besides, the microcalorimetry method was utilized to study the self-assembled process on iron surface and the adsorption mechanism was discussed from the power-time curve. The results indicated that MBT was able to form a film spontaneously on iron surface and the presence of it could protect iron from corrosion effectively. However, the assembling time and the concentration influence the protection efficiency. Quantum chemical calculations, according to which adsorption mechanism was discussed, could explain the experimental results to some extent.     

Short time synthesis of high quality carbon nanotubes with high rates by CVD of methane on continuously emerged iron nanoparticles

We report the variation of yield and quality of carbon nanotubes (CNTs) grown by chemical vapor deposition (CVD) of methane on iron oxide-MgO at 900-1000 °C for 1-60 min. The catalyst was prepared by impregnation of MgO powder with iron nitrate, dried, and calcined at 300 °C. As calcined and unreduced catalyst in quartz reactor was brought to the synthesis temperature in helium flow in a few minutes, and then the flow was switched to methane. The iron oxide was reduced to iron nanoparticles in methane, while the CNTs were growing.TEM micrographs, in accordance with Raman RBM peaks, indicate the formation of mostly single wall carbon nanotubes of about 1.0 nm size. High quality CNTs with I_G/I_D Raman peak ratio of 14.5 are formed in the first minute of CNTs synthesis with the highest rate. Both the rate and quality of CNTs degrades with increasing CNTs synthesis time. Also CNTs quality sharply declines with temperature in the range of 900-1000 °C, while the CNTs yield passes through a maximum at 950 °C. About the same CNTs lengths are formed for the whole range of the synthesis times. A model of continuous emergence of iron nanoparticle seeds for CNTs synthesis may explain the data. The data can also provide information for continuous production of CNTs in a fluidized bed reactor.     

Growth of carbon nanotubes by Fe-catalyzed chemical vapor processes on silicon-based substrates

In this paper, a site-selective catalytic chemical vapor deposition synthesis of carbon nanotubes on silicon-based substrates has been developed in order to get horizontally oriented nanotubes for field effect transistors and other electronic devices. Properly micro-fabricated silicon oxide and polysilicon structures have been used as substrates. Iron nanoparticles have been obtained both from a thin Fe film evaporated by e-gun and from iron nitrate solutions accurately dispersed on the substrates. Single-walled nanotubes with diameters as small as 1 nm, bridging polysilicon and silicon dioxide “pillars”, have been grown. The morphology and structure of CNTs have been characterized by SEM, AFM and Raman spectroscopy.     

原子吸收法（氘灯扣背景）快速测定磷酸中微量铅,铁

本文研究了磷酸中铅、铁的测定方法，并讨论了磷酸产生的背景干扰和背景吸收校正，获得满意的结果。其回收率为９２．７％－１０６．５％，测量精度小于１１．４３％。     

Deposition of silver nanoparticles on carbon nanotube by chemical reduction method: Evaluation of surface,thermal and optical properties

Silver was stabilized on multi-walled carbon nanotubes (MWCNTs) by chemical-reduction technique using N,N-dimethylformamide (DMF) as a reducing agent. The influence of silver on the performance of carbon nanotubes (CNTs) was investigated by employing Fourier-transform infrared spectra (FTIR), Raman spectroscopy (RAS), thermal gravimetric analysis (TGA), zeta potential measurement, scanning electron microscope (SEM), electron dispersive X-ray spectrometer (EDX), transmission electron microscopy (TEM), and reflectance spectroscopy (RS). FTIR as well as RS methods evidenced the synthesis procedure using chemical reduction method was successful. Performing TGA of the samples under oxygen atmosphere demonstrated that the silver nanoparticles (Ag NPs) generated on MWCNTs surface can decrease the thermal stability of the particles by the catalytic oxidation of CNTs. In contrary, the thermal stability of the MWCNTs has improved under nitrogen atmosphere. EDX results showed the presence of Ag, Au and Co on the surface of deposited sample. The synthesised silver multi-walled carbon nanotubes (Ag–MWCNTs) were found to have higher UV reflection activity compared with untreated particles. The Ag–CNTs can be used in producing anti-UV composites.     

Enhanced electrical and mass transfer characteristics of acid-treated carbon nanotubes for capacitive deionization

Capacitive deionization (CDI) has attracted significant attention for the next generation water treatment due to its low energy consumption and environment friendly properties in comparison to widely established methods. For CDI technology to move forward, however, the development of carbon electrodes having superb electrosorption behavior is essential. In this study, we demonstrate the functionalization of carbon nanotubes (CNTs) via acid treatment shows enhanced electrochemical characteristics and effectively improves the wettability of the acid-treated CNTs (a-CNTs) via the addition of oxygen functional groups, leading to a higher electric double layer capacitance. Furthermore, defect formation in a-CNTs increases the conductivity and decreases the mass transfer resistance during CDI operation. CDI measurements confirmed a 270% increase in performance of a-CNTs in contrast to pristine CNTs (p-CNTs), attributable to the improved characteristics outlined above.     

A novel continuous process for synthesis of carbon nanotubes using iron floating catalyst and MgO particles for CVD of methane in a fluidized bed reactor

A novel continuous process is used for production of carbon nanotubes (CNTs) by catalytic chemical vapor deposition (CVD) of methane on iron floating catalyst in situ deposited on MgO in a fluidized bed reactor. In the hot zone of the reactor, sublimed ferrocene vapors were contacted with MgO powder fluidized by methane feed to produce Fe/MgO catalyst in situ. An annular tube was used to enhance the ferrocene and MgO contacting efficiency. Multi-wall as well as single-wall CNTs was grown on the Fe/MgO catalyst while falling down the reactor. The CNTs were continuously collected at the bottom of the reactor, only when MgO powder was used. The annular tube enhanced the contacting efficiency and improved both the quality and quantity of CNTs.The SEM and TEM micrographs of the products reveal that the CNTs are mostly entangled bundles with diameters of about 10-20 nm. Raman spectra show that the CNTs have low amount of amorphous/defected carbon with I_G/I_D ratios as high as 10.2 for synthesis at 900 °C. The RBM Raman peaks indicate formation of single-walled carbon nanotubes (SWNTs) of 1.0-1.2 nm diameter.     

An XANES study on the modification of single‐walled carbon nanotubes by nitric acid

X‐ray absorption near‐edge structure (XANES) spectroscopy has been applied to identify the modification process of single‐walled carbon nanotubes (SWCNTs) treated by nitric acid. The carboxyl groups created by the nitric acid treatment have been found to be formed on both the carbonaceous fragments and the side walls of SWCNTs. The carbonaceous fragments could be removed by a following washing treatment with sodium hydroxide. XANES spectra indicate that carbonaceous fragments are the result of the synthesis process and/or of the nitric acid treatment. Tube walls of SWCNTs are weakly oxidized by the nitric acid treatment although, after removing carbonaceous fragments, a direct oxidation process of SWCNTs is observed. Experimental data address the removal of carbonaceous fragments on SWCNTs as an efficient method for side‐wall modification of a SWCNT.     

Evidence of Verwey transition in iron- and iron oxide-encapsulated carbon nanotubes

Magnetization measurements in two different samples of iron- and iron oxide-encapsulated carbon nanotubes are presented. The samples showed coercivity smaller than 1 kOe. The dependence of the coercivity with the temperature has an abrupt change at temperatures close to 125 K. In this temperature the ZFC and FC magnetization curves also present an abrupt change. This effect is attributed to a Verwey transition.     

Field emission characteristics of screen-printed carbon nanotubes cold cathode by hydrogen plasma treatment

Selective plasma etching and hydrogen plasma treatment were introduced in turn to improve field emission characteristics of screen-printed carbon nanotubes (CNTs) cold cathode, which was prepared by using slurry of mixture of multi-wall CNTs, organic vehicles and inorganic binder, i.e. silicon dioxide sol. The results show that selective plasma etching process could effectively remove parts of surface inorganic vehicle (SiO₂) layer and expose more smooth and clean CNTs on cathode surface, which could significantly decrease the operating field of CNTs cathode. There are some nanoparticles emerging on the out of CNTs wall after hydrogen plasma treatment, which are equivalent to increase field emission point of cathode. At the same time, these nanoparticles can increase the local electric field of CNTs, which can decrease operating voltage of CNTs cathode and improve uniformity field emission.     

Synthesis and characterization of graphenated carbon nanotubes on IONPs using acetylene by chemical vapor deposition method

The graphenated carbon nanotubes (G-CNTs) were synthesized on monodisperse spherical iron oxide nanoparticles (IONPs) using acetylene as carbon precursor by simple chemical vapor deposition method. The reaction parameters such as temperature and flow of carbon source were optimized in order to achieve G-CNTs with excellent quality and quantity. Transmission electron microscopy (TEM) clearly illustrated that the graphene flakes are forming along the whole length on CNTs. The degree of graphitization was revealed by X-ray diffraction (XRD) analysis and Raman spectroscopic techniques. The intensity of D to G value was less than one which confirms the obtained G-CNTs have high degree of graphitization. The optimum reaction temperature for the IONPs to form metallic clusters which in turn lead to the formation of G-CNTs with high carbon deposition yield is at 900 °C. The TEM shows the CNTs diameter is 50 nm with foiled graphene flakes of diameter around 70 nm. Our results advocate for IONPs as a promising catalytic template for quantitative and qualitative productivity of nanohybrid G-CNTs. The produced G-CNTs with high degree of graphitization might be an ideal candidate for nanoelectronic application like super capacitors and so on.     

Protection of iron corrosion by stearic acid and stearic imidazoline self-assembled monolayers

A type of stearic imidazoline (IM) inhibitor was prepared using stearic acid (SA) and diethylenetriamine (DETA) as raw materials. The monolayers of IM and SA were assembled on the iron surface. The electrochemical characterization of stearic acid (SA) and stearic imidazoline (IM) on an oxide free iron surface had been studied. The monolayers of IM inhibitor were characterized by electrochemical impedance spectroscopy (EIS), electrochemical polarization curves, double layer capacitance, X-ray photoelectron spectroscopy (XPS) and molecular simulation. The results of electrochemical studies had illustrated that the inhibition efficiency of IM was higher than SA. XPS showed that the IM molecules adsorbed on the iron surface. The molecular simulation calculations showed that the IM molecules were tilted at an angle on the iron surface.