A comparative study of single-walled carbon nanotube purification techniques using Raman spectroscopy

Raman spectroscopy has been utilized to show the increase of single-walled carbon nanotubes (SWCNTs) content in commercial grade samples synthesized by the chemical vapour deposition (CVD) technique with a minimization of impurities using both hydrochloric acid treatment and surfactant purification. Surfactant purification methods proved to be the most effective, resulting in a three-fold increase in the percentage of SWCNTs present in the purified product as determined by Raman spectroscopy.     

A multimodal spectrometer for Raman scattering and near-infrared absorption measurement

Raman and infrared (IR) spectroscopy are complementary spectroscopic techniques. However, measurement of Raman and IR spectra are commonly carried out on separate instruments. A dispersive system that enables both Raman spectroscopy and NIR spectroscopy was designed, built, and tested. The prototype system measures spectral ranges of 2600–300 cm⁻¹ and 752–987 nm for Raman and NIR channels, respectively. A wavelength accuracy better than 0.6 nm and spectral resolution better than 1 nm (14.4 cm⁻¹ for Raman channel) could be achieved with our configuration. The linearity of spectral response was better than 99.8%. The intensity stability of the instrument was found to be 0.7% and 0.4% for Raman and NIR channels, respectively. The performance of the instrument was evaluated using binary aqueous solutions of ethanol and ovalbumin. It was found that ethanol concentrations (2–10%) could be predicted with a root mean squared error of prediction (RMSEP) of 0.45% using Raman peak height at 882.2 cm⁻¹. Quantification of ovalbumin concentration (8–16 g/L) in aqueous solutions and in denatured states yielded RMSEP values of 1.05 g/L and 0.74 g/L, respectively. Using concentration as external perturbation in two-dimensional correlation spectroscopy (2DCOS), heterospectral correlation analysis revealed the relationship between NIR and Raman spectra.     

Dispersion and orientation of single-walled carbon nanotubes in a chromonic liquid crystal

A post-synthesis alignment of individual single-walled carbon nanotubes (SWCNTs) is desirable for translating their unique anisotropic properties to a macroscopic scale. Here, we demonstrate excellent dispersion, orientation and concomitant-polarised photoluminescence of SWCNTs in a nematic chromonic liquid crystal. The methods to obtain stable suspension are described, and order parameters of the liquid crystal matrix and of the nanotubes are measured independently.     

Characteristics of the Raman spectra of single-walled carbon nanotube bundles under electrochemical potential control

Resonant Raman scattering spectra of single-walled carbon nanotube–sodium dodecyl sulfate (SWNT–SDS) bundles adsorbed on Au electrodes have been investigated in aqueous electrolytes. Raman intensities of the radial breathing mode (RBM) with 785-nm laser excitation were monitored at different electrode potentials between −0.5 and +0.8 V relative to the SCE. Six resolved RBM peaks assignable to different diameter tubes all decreased in intensity when the electrode was positively biased, because of depletion of valence-band electrons associated with resonant excitation. The attenuation occurred at more positive potentials for narrower-diameter tubes with higher RBM frequencies consistent with their larger bandgaps. The results suggest the Fermi level is equilibrated in bundled SWNTs in contrast with the large Fermi-level shifts reported for isolated SWNTs.     

Bare gold nanoparticles mediated surface-enhanced Raman spectroscopic determination and quantification of carboxylated single-walled carbon nanotubes

The paper proposes a simple and portable approach for the surface enhanced Raman scattering (SERS) spectroscopy in situ determination of carboxylated single walled carbon nanotubes (SWNTs) in river water samples. The method is based on the subsequent microfiltration of a bare gold nanoparticles solution and the water sample containing soluble carbon nanotubes by using a home-made filtration device with a small filtration diameter. An acetate cellulose membrane with a pore size of 0.2 μm first traps gold nanoparticles to form the SERS-active substrate and then concentrates the carbon nanotubes. The measured SERS intensity data were closely fit with a Langmuir isotherm. A portable Raman spectrometer was employed to measure SERS spectra, which enables in situ determination of SWNTs in river waters. The limit of detection was 10 μg L⁻¹. The precision, for a 10 mg L⁻¹ concentration of carbon nanotubes, is 1.19% intra-membrane and 10.5% inter-membrane.     

Production of single-walled carbon nanotubes from methane over Co-Mo/MgO nanocatalyst:A comparative study of fixed and fluidized bed reactors

In this study,the performances of fixed and fluidized bed reactors in the production of single-walled carbon nanotubes(SWNTs)have been investigated.In both reactors,single-walled carbon nanotubes were grown by catalytic chemical vapor decomposition(CCVD)of methane over Co-Mo/MgO nanocatalyst under two different operating conditions.The synthesized samples were characterized by TEM,TGA and Raman spectroscopy.It is found that the performance of a fluidized bed in the synthesis of carbon nanotubes is much better than that of a fixed bed.The quality of carbon nanotubes obtained from the fluidized bed was significantly higher than that from the fixed bed and the former one with the ID/IG ratio of 0.11 while the latter one with the ID/IG ratio of 0.71.Also,the yield of SWNTs in the fluidized bed was 92 wt%,while it was 78 wt%in the fixed bed.These advantages of fluidized bed reactors for the synthesis of carbon nanotubes can be attributed to more available space for the growth of carbon nanotubes and more uniform temperature and concentration profiles.     

The intermediate frequency modes of single- and double-walled carbon nanotubes: a Raman spectroscopic and in situ Raman spectroelectrochemical study

The intermediate frequency modes (IFM) of single-walled carbon nanotubes (SWCNTs) and double-walled carbon nanotubes (DWCNTs) were analyzed by Raman spectroscopy and in situ Raman spectroelectrochemistry. The inner and outer tubes of DWCNTs manifested themselves as distinct bands in the IFM region. This confirmed the diameter dependence of IFM frequencies. Furthermore, the analysis of inner tubes of DWCNTs allowed a more-precise assignment of the bands in the IFM region to features intrinsic for carbon nanotubes. Although the inner tubes in DWCNTs are assumed to be structurally perfect, the role of defects on IFM was discussed. The dependence of IFM on electrochemical charging was also studied. In situ spectroelectrochemical data provide a means to distinguish the bands of the outer and inner tubes.     

Application of single-walled carbon nanotube body to unique emitter: a first-principles study

The field emission characteristics of the body for single-walled carbon nanotubes (SWNTs) are investigated by use of the first-principles calculations. We find that field emission property, chemical stability and binding energy of the tube body with the practical diameter are less sensitive to the tube diameter, morphology, and conductive characteristic, and conclude the emission features of the body film: consistence in emission sites, uniformity in emission energy distribution, predictability in emission effects and high emission stability, which are similar to those of graphite sheet or diamond film. These unique features guarantee the tube body to be applicable to flat panel displays with the same picture quality, cylindrical cathode and linear emitter.     

A hyaluronic acid dispersed carbon nanotube electrode used for a mediatorless NADH sensing and biosensing

A biocompatible nanocomposite consisting of single-walled carbon nanotubes (CNTs) dispersed in a hyaluronic acid (HA) was investigated as a sensing platform for a mediatorless electrochemical detection of NADH. The device was characterised by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and extensively by electrochemistry. CNT-HA bionanocomposite showed more reversible electrochemistry, higher short-term stability of NADH sensing and higher selectivity of NADH detection compared to frequently used CNT-CHI (chitosan) modified GCE. Finally the performance of the sensor modified by CNT-HA was tested in a batch and flow injection analysis (FIA) mode of operation with basic characteristics revealed. The NADH sensor exhibits a good long-term operational stability (95% of the original sensitivity after 22 h of continuous operation). Subsequently a d-sorbitol biosensor based on such a nanoscale built interface was prepared and characterised with a d-sorbitol dehydrogenase used as a biocatalyst.     

Characterization of the chemical interaction between single-walled carbon nanotubes and titanium dioxide nanoparticles by thermogravimetric analyses and resonance Raman spectroscopy

Raman spectroscopy is a powerful technique that is used to characterize or observe alterations in the structure or properties of carbon nanotubes and its composites. This method can provide information about electronic changes or quantify them. We used Raman spectroscopy to study the chemical and electronic changes in a composite formed by titanium dioxide nanoparticles and single-walled carbon nanotubes. This composite was characterized by scanning electron microscopy to investigate the morphology and by thermogravimetric analyses to assess the thermal stability of the isolated carbon nanotubes as compared with the nanotubes by titanium dioxide nanoparticles. The Raman results showed that the modification of the nanotubes with the TiO₂ nanoparticles generates a new material with different structure of the nanotubes, resulting in a decrease in defects. The charge transfer from the TiO₂ nanoparticles to the nanotubes alters the electronic properties of both moieties in the hybrid material. The interaction between the nanotubes and nanoparticles decreases the CC bound order of the nanotubes and decreases their thermal stability.     

碳纳米管修饰碳纤维超微圆柱电极的研制与应用

制作了碳纳米管修饰碳纤维组合电极(EUME-CNT),研究了木犀草素在EUME-CNT上的电化学行为,并且通过优化测定参数,建立了木犀草素的电化学分析方法。检出限达到4×10-7mol/L,线性范围为6×10-7~1×10-5mol/L。     

Preparation and application of surface enhanced Raman scattering substrate synthesized from single walled carbon nanotubes and silver nanoparticlesEI北大核心CSCD

By hydrothermal synthesis, silver nanoparticles (AgNPs) arranged on single-walled carbon nanotubes (SWCNTs) uniformly, and a SiO2/CNTs/AgNPs surface enhanced Raman scattering (SERS) substrate with composite open structure was prepared. The synthesized SiO2/CNTs/AgNPs were characterized by transmission electron microscopy (TEM. Using rhodamine 6G(R6G) as the probe molecule, the enhancement factor (EF) was 1.23×108, and the standard deviation was 2.31. Taking the phenol red, a common water pollutant, as the practical sample, the concentration of phenol red in the range of 1×10-4 -1×10-10 mol/L had a great exponential fitting relationship with its Raman signal intensity at 1153 cm-1 and 1441 cm-1, and the correlation coefficient (R2) was 0.99991. The substrate can realize the qualitative and quantitative detection of practical samples. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Vibrational and electrical investigations of a uniaxially stretched polystyrene/carbon nanotube composite

Multiwall carbon nanotube (MWCNT)/polystyrene (PS) composite materials were prepared in the absence and in the presence of a surfactant. TEM analysis reveals the formation of chains made of several nanotubes tied up together upon application of the surfactant while an almost random distribution is observed without any treatment. These nanotubes are seen to be highly oriented in the uniaxially stretched composite. It is shown that the presence of the surfactant and the alignment reduce electrical conductivity while polymer chain orientation remains insensitive to these parameters.     

Polyglycerol-derived amphiphiles for the solubilization of single-walled carbon nanotubes in water: a structure-property study

A series of nonionic amphiphiles derived from polyglycerol dendrons were studied for their ability to solubilize and isolate single-walled carbon nanotubes. The amphiphiles possessed differently sized polar head groups, hydrophobic tail units, and various aromatic and non-aromatic groups between the head and tail groups. Absorbance analysis revealed that amphiphiles with anchor groups derived from pyrene were far inferior to those that possessed simple linear aliphatic tail groups. Absorbance and near-infrared fluorescence analyses revealed a weak dependence on the dendron size of the head group, but a strong positive trend in suspended nanotube density and fluorescence intensity for amphiphiles with longer tail units. Variations in the moieties linking the head and tail groups led to a range of effects on the suspensions, with linkers imparting flexibility and a bent shape that gave improved performance overall. This was illustrated most dramatically by a pair of benzamide-containing amphiphiles, the para isomer of which showed evidence in the fluorescence data of increased nanotube aggregate formation when compared with the meta isomer. In addition, statistical AFM was used to illustrate more directly the microscopic differences between amphiphiles that were effective at nanotube bundle disruption and those that were not.     

A study of DFT and surface enhanced Raman scattering in silver colloids for thymine

The vibrational spectrum of crystal thymine is calculated by density functional theory (DFT) at the B3LYP complex function. Considering the effect of intermolecular H-bonds, we add two water molecules that can form H-bonds with the CO and NH groups of thymine. The experimental spectra of normal Raman of thymine in solid state and surface enhanced Raman (SERS) of thymine adsorbed in silver colloids are presented in this study. The calculated Raman spectrum of thymine by DFT is in agreement with the experimental result of normal Raman spectrum. The appearance of new bands of thymine in SERS shows that molecules of thymine are adsorbed in the surface of silver nanoparticles with a perpendicular orientation through an oxygen atom (O7).     

A Raman spectroscopic study of the morphological structure of the polyethylenes

The method described by Strobl and Hagedorn to analyze the Raman spectrum internal modes of semi-crystalline polyethylene has been applied to a set of selected polyethylene samples crystallized under controlled conditions. The crystallite structure can be described in terms of the relative amounts of the crystalline orthorhombic phase, the liquid-like amorphous phase and the interfacial region. The dependence of the level of crystallinity on molecular weight and crystallization conditions is very similar to that found by other methods. However, this method allows for the quantitative determination of the interfacial content which becomes significant for molecular weights greater than about 1×10⁵ for linear polyethylene fractions, and for all the branched samples and copolymers. The degree of crystallinity determined from density measurements is equal to the sum of the crystallinity and interfacial content obtained from the Raman analysis while enthalpy of fusion measurements yield values which are equal to just the crystallinity content. The difference between the level of crystallinity obtained from density and enthalpy of fusion is thus found to be primarily due to interfacial contributions.Dedicated to Prof. Dr. F. H. Müller     

Real-time assessment of carbon nanotube alignment in a polymer matrix under an applied electric field via polarized Raman spectroscopy

A technique has been developed utilizing polarized Raman spectroscopy to measure alignment of carbon nanotubes in situ in a polymer matrix under an applied electric field. Previous studies of alignment have been restricted to optically transparent solvents or polymerized specimens that prevent accurate analyses of alignment dynamics in polymers. The effects of electric field strength on the degree of alignment and the time to achieve an aligned state are discussed. The use of in situ, real-time polarized Raman spectroscopy provides a non-invasive technique for assessing carbon nanotube alignment, which can assist in determining processing conditions to improve the mechanical and electrical properties of aligned nanocomposites.