Multifunctional poly(2,5‐benzimidazole)/carbon nanotube composite films

The AB‐monomer, 3,4‐diaminobenzoic acid dihydrochloride, was recrystallized from an aqueous hydrochloric acid solution and used to synthesize high‐molecular‐weight poly(2,5‐benzimidazole) (ABPBI). ABPBI/carbon nanotube (CNT) composites were prepared via in situ polymerization of the AB‐monomer in the presence of single‐walled carbon nanotube (SWCNT) or multiwalled carbon nanotube (MWCNT) in a mildly acidic polyphosphoric acid. The ABPBI/SWCNT and ABPBI/MWCNT composites displayed good solubility in methanesulfonic acid and thus, uniform films could be cast. The morphology of these composite films was studied by X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The results showed that both types of CNTs were uniformly dispersed into the ABPBI matrix. Tensile properties of the composite films were significantly improved when compared with ABPBI, and their toughness (～200 MPa) was close to the nature's toughest spider silk (～215 MPa). The electrical conductivities of ABPBI/SWCNT and ABPBI/MWCNT composite films were 9.10 × 10^?5 and 2.53 × 10^?1 S/cm, respectively, whereas that of ABPBI film was 4.81 × 10^?6 S/cm. These values are ～19 and 52,700 times enhanced by the presence of SWCNT and MWCNT, respectively. Finally, without acid impregnation, the ABPBI film was nonconducting while the SWCNT‐ and MWCNT‐based composites were proton conducting with maximum conductivities of 0.018 and 0.017 S/cm, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1067–1078, 2010     

Polyelectrolyte‐Assisted Noncovalent Functionalization of Carbon Nanotubes with Ordered Self‐Assemblies of a Water‐Soluble Porphyrin

The self‐assembly and induced supramolecular chirality of meso‐tetrakis(4‐sulfonatophenyl)porphyrin (TSPP) on both single‐wall (SWCNT) and multiwall carbon nanotubes (MWCNT) are investigated. Under mild pH conditions (pH 3), TSPP forms aggregates when CNTs are dispersed in an aqueous solution containing positively charged polyelectrolytes such as poly‐L ‐lysine (PLL) or poly(allylamine hydrochloride) (PAH). Evidence for the geometry of the porphyrin aggregates is obtained from absorption spectra, whereby the fingerprints of J‐ and H‐aggregates are clearly seen only in the presence of smaller‐diameter nanotubes. J‐aggregates are better stabilized with PLL, whereas in the presence of PAH mainly H‐aggregates prevail. Excited‐state interactions within these nanohybrids are studied by steady‐state and time‐resolved fluorescence. The porphyrin emission intensity in the nanohybrid solution is significantly quenched compared to that of TSPP alone, and this implies strong electronic interaction between CNTs and porphyrin molecules. Fluorescence lifetime imaging microscopy (FLIM) further supports that porphyrin arrays are associated with the MWCNT sidewalls wrapped in PLL. In the case of the SWCNT hybrid, spherical structures associated with longer fluorescence lifetime appeared after one week, indicative of H‐aggregates of TSPP. The latter are the result of π–π stacking of porphyrin units on neighboring nanotubes facilitated by the strong tendency of these nanotubes to interact with each other. These results highlight the importance of optimum dimensions and surface‐area architectures of CNTs in the control/stability of the porphyrin aggregates with promising properties for light harvesting.     

Catalytic functions of Mo/Ni/MgO in the synthesis of thin carbon nanotubes

The functions and structures of Mo/Ni/MgO catalysts in the synthesis of carbon nanotubes (CNTs) have been investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Thin 2-5-walled CNTs with high purities (over 90%) have been successfully synthesized by catalytic decomposition of CH(4) over Mo/Ni/MgO catalysts at 1073 K. It has been found that the yield of CNTs as well as the outer diameter or thickness correlates well with the contents of these three elements. The three components Mo, Ni, and MgO are all necessary to synthesize the thin CNTs at high yields since no catalytic activity was observed for CNT synthesis when one of these components was not present. The outer diameter of the CNTs increases from 4 to 13 nm and the thickness of graphene layers also increases with increasing Mo content at a fixed Ni content, while the inner diameter stays at 2-3 nm regardless of their contents. Furthermore, the average outer diameter is in good agreement with the average particle size of metal catalyst. That is, the thickness or the outer diameter can be controlled by selecting the composition of the Mo/Ni/MgO catalysts. XRD analyses have shown that Mo and Ni form a Mo-Ni alloy before CNT synthesis, while the Mo-Ni alloy phase is separated into Mo carbide and Ni. These alloy particles are supported on MgO cubic particles 15-20 nm in width. It has been found that only small Mo-Ni alloy particles 2-16 nm in size catalyze CNT synthesis, with larger particles over 15 nm exhibiting no activity. Mo carbide and Ni should play different roles in the synthesis of the thin CNTs, in which Ni is responsible for the dissociation of CH(4) into carbon and Mo(2)C works as a carbon reservoir.     

Curvature‐dependent adsorption of water inside and outside armchair carbon nanotubes

The curvature dependence of the physisorption properties of a water molecule inside and outside an armchair carbon nanotube (CNT) is investigated by an incremental density‐fitting local coupled cluster treatment with single and double excitations and perturbative triples (DF‐LCCSD(T)) study. Our results show that a water molecule outside and inside (n, n) CNTs (n = 4, 5, 6, 7, 8, 10) is stabilized by electron correlation. The adsorption energy of water inside CNTs decreases quickly with the decrease of curvature (increase of radius) and the configuration with the oxygen pointing toward the CNT wall is the most stable one. However, when the water molecule is adsorbed outside the CNT, the adsorption energy varies only slightly with the curvature and the configuration with hydrogens pointing toward the CNT wall is the most stable one. We also use the DF‐LCCSD(T) results to parameterize Lennard‐Jones (LJ) force fields for the interaction of water both with the inner and outer sides of CNTs and with graphene representing the zero curvature limit. It is not possible to reproduce all DF‐LCCSD(T) results for water inside and outside CNTs of different curvature by a single set of LJ parameters, but two sets have to be used instead. Each of the two resulting sets can reproduce three out of four minima of the effective potential curves reasonably well. These LJ models are then used to calculate the water adsorption energies of larger CNTs, approaching the graphene limit, thus bridging the gap between CNTs of increasing radius and flat graphene sheets. © 2016 Wiley Periodicals, Inc.     

Controlled growth of well-aligned carbon nanotubes with large diameters

Well-aligned carbon nanotubes (CNTs) with large diameters (25–200 nm) were synthesized by pyrolysis of iron(II) phthalocyanine. The outer diameter up to 218.5 nm and the length of the well-aligned CNTs can be systematically controlled by varying the growth time. A tube-in-tube nano-structure with large and small diameters of 176 and 16.7 nm, respectively, was found. The grain sizes of the iron catalyst play an important role in controlling the CNT diameters. These results are of great importance to design new aligned CNT-based electron field emitters in the potential application of panel displays.     

纳米受限下溶质水化结构的分子模拟

利用分子动力学模拟研究了五种不同种类的溶质分子(K+, Mg2+, Cl-, K-和K0)在直径为0.60-1.28 nm的纳米碳管内的水化结构. 模拟结果揭示了单电荷溶质、双电荷溶质和中性溶质在受限条件下具有不同的水化行为. 单价溶质的配位数只有在直径不大于0.73 nm的纳米碳管内才会明显减少. 和带有电荷的溶质不同, 中性溶质的配位数对纳米碳管直径的改变非常敏感, 并且随着管径的减小而迅速减少. 模拟结果还表明带单价正电荷的溶质(K+)第一配位层水分子的取向结构会随着纳米碳管直径的改变发生变化, 而其他溶质配位层取向结构在本文所涉及的纳米碳管内都几乎和体相中一致. 在直径大于1.0 nm的纳米碳管中, K+的配位层取向结构有序度随着管径的减小而单调下降, 但是在直径小于1.0 nm的纳米碳管中, 随着碳管管径的减小而迅速上升. 在两个最窄的纳米碳管内, 其结构有度甚至高于体相. 双电荷溶质的水化结构在本文所研究的碳管直径范围内和体相完全一致, 即使在直径只有0.6 nm的碳管内也无任何改变.     

H2 adsorption on Ag‐nanocluster/single‐walled carbon nanotube composites: A molecular dynamics study on the effects of nanocluster size,diameter, and chirality of nanotube

The H₂ physisorption on Ag_N (with N = 32, 108, 256, 500, and 864)/carbon nanotube (CNT; in armchair and zigzag structures with diameters between 0.54 and 2.98 nm) composites were studied by molecular dynamic simulation to investigate the effect of nanocluster size, diameter, and chirality of nanotube on the adsorption phenomena. The calculations indicate that the effects of nanocluster properties are more important than those of the nanotube, in such a way that increase of nanocluster size, decreases the H₂ adsorption. Also, the diameter and chirality of CNTs have considerable influence on the adsorption phenomena. As the diameter of nanotube is increased, the amount of adsorption is decreased. Moreover, H₂ molecules have more tendencies to those nanoclusters located on the armchair nanotubes than the zigzag ones. Another important result is the reversibility of H₂ adsorption on these materials in which the structure of composite in vacuum and after reduction of H₂ pressure to zero, is not changed, considerably. © 2015 Wiley Periodicals, Inc.     

A density functional theory study of van der Waals interaction in carbon nanotubes

In this article, we investigate the effect of van der Waals force in zigzag carbon nanotubes (CNTs) including single-wall CNT (SWCNT) and double-walled CNT (DWCNT) structures with several interaction configurations. The solid-state density functional theory is employed to calculate the geometric optimization, normal mode frequencies, and IR and Raman spectra with the periodic boundary condition. For SWCNTs, we find that the Raman intensity is not affected by the tube diameter or the electronic structure. The IR absorption, however, increases with the tube diameter. We find that the close metallicity of the electronic structure has a significant impact on the IR simulations. When the van der Waals force is applied outside the CNTs at a distance longer than 3.0, the effect on Raman spectra is minimal but some effects can still be confirmed by IR absorption. When the van der Waals force acts inside the CNTs, the effect on the spectrum can be observed, especially at a distance of 2.8 Å, both IR and Raman can be significantly enhanced in many modes.     

The preparation of PZS-OH/CNT composite and its adsorption of U(VI) in aqueous solutions

In this paper, polycyclotriphosphazene coated carbon nanotubes (PZS-OH/CNT) composite material has been synthesized via a facial method. The prepared PZS-OH/CNT was characterized by FTIR, BET, zeta potential and SEM. The material was investigated as an adsorbent for the adsorption towards U(VI) from aqueous solutions. Several parameters like solution pH, contact time and temperature were used to evaluate the sorption efficiency. The results indicated that the adsorption capacity of uranium on PZS-OH/CNT was improved from 41.48 mg g⁻¹ for CNT to 338.98 mg g⁻¹ due to the presence of functional groups on PZS-OH/CNT. The U(VI) sorption on PZS-OH/CNT was well fitted to the Langmuir adsorption isotherm and pseudo-second kinetics models. The thermodynamic parameters (ΔH, ΔS and ΔG) showed the U(VI) adsorption on CNT and PZS-OH/CNT was endothermic and spontaneous in nature.

     

Adsorption of U(VI) onto kaolin studied by batch method

Adsorption of U(VI) on purified kaolin was studied by batch methods under ambient conditions, including contact time, pH, fulvic acid, etc. Three kinetic models were used to model the kinetic adsorption which was very well described by the pseudo-second-order rate equation, and the activation energy of adsorption was 52.20 kJ/mol. The Freundlich and Dubinin–Radushkevich models fitted the experimental data better than the Langmuir model for the adsorption and desorption isotherms. The thermodynamic parameters indicated that the adsorption of U(VI) on kaolin was an endothermic and spontaneous process.     

Single-walled carbon nanotube-facilitated dispersion of particulate TiO2 on ZrO2 ceramic membrane filters

We report that SWCNTs substantially improve the uniformity and coverage of TiO2 coatings on porous ZrO2 ceramic membrane filters. The ZrO2 filters were dip coated with 100 nm anatase TiO2, TiO2/SWCNT composites, a TiO2+SWCNT mixture, and a TiO2/MWCNT composite at pH 3, 5, and 8. Whereas the TiO2+SWCNT mixture and the TiO2/MWCNT composite promote better coverage and less clumping than TiO2 alone, the TiO2/SWCNT composite forms a complete uniform coating without cracking at pH 5 ( approximately 100% coverage). A combination of chemical and electrostatic effects between TiO2 and SWCNTs forming the composite as well as between the composite and the ZrO2 surface explains these observations.     

Adsorption of benzene,toluene, ethylbenzene and p-xylene by NaOCl-oxidized carbon nanotubes

Multiwalled carbon nanotubes (CNTs) were oxidized by sodium hypochlorite (NaOCl) solution and were employed as adsorbents to study their characterizations and adsorption performance of benzene, toluene, ethylbenzene and p-xylene (abbreviated as BTEX) in an aqueous solution. The physicochemical properties of CNTs such as purity, structure and surface nature were greatly improved after oxidation, which significantly enhanced BTEX adsorption capacity. The adsorption capacity of CNT(NaOCl) increased with contact time and initial adsorbate concentration, but changed insignificantly with solution ionic strength and pH. A comparative study on the BTEX adsorption revealed that the CNT(NaOCl) had better BTEX adsorption as compared to CNTs and granular activated carbon. This suggests that the CNT(NaOCl) are efficient BTEX adsorbents and that they possess good potential for BTEX removal in wastewater treatment.     

Adsorption kinetics and equilibrium modeling of cesium on copper ferrocyanide

The copper ferrocyanide (CuFC) prepared in this study was characterized using X-ray diffraction and scanning election microscopy. The distribution of particle sizes of the CuFC suspension was determined. The adsorption kinetics data were evaluated for an intraparticle diffusion model, a pseudo-first order model and a pseudo-second order model at temperatures of 288, 298 and 308 K, respectively. It was found that the adsorption process of Cs⁺ on CuFC was best described by a pseudo-second order kinetic model, with a correlation coefficient (R ²) equal to 1.000, and the adsorption rate constant increased with increasing temperature. This result indicated that chemisorptions took place during the adsorption process. The adsorption equilibrium data fit well to the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. The mean adsorption energy (E) between 11 and 13 kJ/mol at different temperatures indicated that ion exchange was the main mechanism during the adsorption process. Thermodynamic parameters were also evaluated during the adsorption. The values of the standard Gibbs free energy change (ΔG ^o) and standard enthalpy change (ΔH ^o) suggested that the adsorption was a spontaneous and endothermic process. The distribution coefficient (K _d) was more than 2.94 × 10⁶ mL/g when the pH of solution was between 2.6 and 10.9, and the initial Cs⁺ concentration was 100 μg/L. The existence of K⁺ and Na⁺ did not affect the adsorption of Cs⁺ on CuFC when the concentration of K⁺ and Na⁺ in the solution was below 20 and 1,000 mg/L, respectively.     

Adsorption of trace thorium(IV) from aqueous solution by mono-modified β-cyclodextrin polyrotaxane using response surface methodology (RSM)

The adsorption of thorium(IV) was studied using a novel supramolecular polyrotaxane based on β-cyclodextrin derivatives. The effects of pH, contact time, Th(IV) initial concentration and adsorbents dosage on the adsorption of thorium(IV) by polyrotaxane were optimized using Box–Behnken design of response surface methodology. Analysis of variance and correlation coefficients showed that the predicted model was consistent with the experimental data well. The adsorption best fitted to the Langmuir model indicated that the adsorption process happened on homogeneous surface. The thermodynamic parameters (?G ⁰ < 0, ?H ⁰ > 0, ?S ⁰ > 0) demonstrated that the adsorption of Th(IV) ions onto polyrotaxane was spontaneous and endothermic.     

Water chain encapsulated in carbon nanotube revealed by density functional theory

The noncovalent interactions between encapsulated water chains and single‐walled carbon nanotube (SWCNT) are studied using a self‐consistent charge density functional tight binding method with dispersion correction. The most interesting and important feature we observe is the diameter shrinking of CNTs when water chains are confined inside SWCNT. The diameter shrinking of CNTs can be suggested to the original of the van der Waals and H‐π interaction between water chains and CNTs. The calculated Raman spectra show the interactions between SWCNTs and water chains probably give rise to a kind of “mode hardening effect,” which agrees with the diameter shrinking of CNTs when water chains are confined inside SWCNT. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011.     

FIB-SEM imaging of carbon nanotubes in mouse lung tissue

Ultrastructural characterisation is important for understanding carbon nanotube (CNT) toxicity and how the CNTs interact with cells and tissues. The standard method for this involves using transmission electron microscopy (TEM). However, in particular, the sample preparation, using a microtome to cut thin sample sections for TEM, can be challenging for investigation of regions with agglomerations of large and stiff CNTs because the CNTs cut with difficulty. As a consequence, the sectioning diamond knife may be damaged and the uncut CNTs are left protruding from the embedded block surface excluding them from TEM analysis. To provide an alternative to ultramicrotomy and subsequent TEM imaging, we studied focused ion beam scanning electron microscopy (FIB-SEM) of CNTs in the lungs of mice, and we evaluated the applicability of the method compared to TEM. FIB-SEM can provide serial section volume imaging not easily obtained with TEM, but it is time-consuming to locate CNTs in the tissue. We demonstrate that protruding CNTs after ultramicrotomy can be used to locate the region of interest, and we present FIB-SEM images of CNTs in lung tissue. FIB-SEM imaging was applied to lung tissue from mice which had been intratracheally instilled with two different multiwalled CNTs; one being short and thin, and the other longer and thicker. FIB-SEM was found to be most suitable for detection of the large CNTs (Ø ca. 70 nm), and to be well suited for studying CNT agglomerates in biological samples which is challenging using standard TEM techniques.

Density functional and molecular docking studies towards investigating the role of single-wall carbon nanotubes as nanocarrier for loading and delivery of pyrazinamide antitubercular drug onto pncA protein

The potential biomedical application of carbon nanotubes (CNTs) pertinent to drug delivery is highly manifested considering the remarkable electronic and structural properties exhibited by CNT. To simulate the interaction of nanomaterials with biomolecular systems, we have performed density functional calculations on the interaction of pyrazinamide (PZA) drug with functionalized single-wall CNT (fSWCNT) as a function of nanotube chirality and length using two different approaches of covalent functionalization, followed by docking simulation of fSWCNT with pncA protein. The functionalization of pristine SWCNT facilitates in enhancing the reactivity of the nanotubes and formation of such type of nanotube-drug conjugate is thermodynamically feasible. Docking studies predict the plausible binding mechanism and suggests that PZA loaded fSWCNT facilitates in the target specific binding of PZA within the protein following a lock and key mechanism. Interestingly, no major structural deformation in the protein was observed after binding with CNT and the interaction between ligand and receptor is mainly hydrophobic in nature. We anticipate that these findings may provide new routes towards the drug delivery mechanism by CNTs with long term practical implications in tuberculosis chemotherapy.     

Adsorption of Reactive Blue 4 dye from water solutions by carbon nanotubes: experiment and theory

Multi-walled and single-walled carbon nanotubes were used as nanoadsorbents for the successful removal of Reactive Blue 4 textile dye from aqueous solutions. The adsorbents were characterised by infrared and Raman spectroscopy, N(2) adsorption/desorption isotherms and scanning and transmission electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium isotherms at 298-323 K was fixed at 4 hours for both adsorbents. The general order kinetic model provided the best fit to the experimental data compared with pseudo-first order and pseudo-second order kinetic adsorption models. For Reactive Blue 4 dye, the equilibrium data (298 to 323 K) were best fitted to the Liu isotherm model. The maximum sorption capacity for adsorption of the dye occurred at 323 K, attaining values of 502.5 and 567.7 mg g(-1) for MWCNT and SWCNT, respectively. Simulated dyehouse effluents were used to check the applicability of the proposed nanoadsorbents for effluent treatment (removal of 99.89% and 99.98%, for MWCNT and SWCNT, respectively). The interaction of Reactive Blue 4 textile dye with single-walled carbon nanotubes (SWCNTs) was investigated using first principles calculations based on density functional theory. Results from ab initio calculations indicated that Reactive Blue 4 textile dye could be adsorbed on SWCNT through an electrostatic interaction; these results are in agreement with the experimental predictions.     

A study of the factors affecting the adsorption of cobalt ions onto Pakistani coal powder from solutions

Large deposits of coal are abundantly available in Pakistan. An attempt has been made to check its efficacy for the cobalt ions from aqueous solutions in order to exploit the locally available naturally occurring cheaper material for the decontamination/removal of metal ions from nuclear and industrial effluents. The adsorption behavior of cobalt ions on coal powder has been studied as a function of various physicochemical parameters i.e., stirring speed, shaking time, pH, concentration of cobalt ions, temperature, etc. Conditions for the uptake of cobalt ions were established. Adsorption dynamics models such as intra-particle diffusion model, pseudo-first order kinetic model (Lagergren’s equation) and pseudo-second order kinetic model were applied to the adsorption data to elucidate the adsorption process and its mechanism. Results reveal that the adsorption mechanism is predominantly diffusion and both intra-particle and boundary layer diffusion seem significant in the rate controlling step. The adsorption process is best accounted for using pseudo second order kinetic model and the overall rate of adsorption process appears to be controlled by more than one step, namely the external mass transfer and intra-particle diffusion mechanism. The existence of two slopes in the Freundlich plot also confirms the surface diffusion and intra-particle diffusion modes of adsorption. The Langmuir isotherm equation was obeyed well in the whole range of cobalt ions concentration with high value of correlation coefficient (r ²  = 0.999). The adsorption energy (E _a) calculated from D–R isotherm was 6.756 kJ/mol indicating physical nature of adsorption. The adsorption of cobalt ions increased with the increase of temperature and thermodynamic parameters such as ΔH, ΔS and ΔG were calculated. Results suggested that the cobalt ions adsorption on coal powder is endothermic (ΔH 33.90 kJ/mol) and spontaneous (negative ΔG values) process. The adsorption of other metal ions on coal powder was studied at optimized condition for cobalt ions to check its selectivity. Consequently, cobalt ions can be removed from Zr, Ru Eu, Er, Sm, Gd, Dy, Ce, U, and Th ions, where as Cs, Cr and Sr ions reduces the adsorption of cobalt ions by co-adsorption and their reducing affect is in the order of Sr > Cr > Cs.     

不同直径碳纳米管的抗电化学氧化性

本文比较了由化学气相沉积法制备的不同直径(在100 nm以内)的多壁碳纳米管(CNT)的抗电化学氧化性.将CNT电极于1.2 V(vs.RHE)下电氧化120 h,记录氧化电流~时间变化曲线;X射线光电子能谱(XPS)分析氧化前后CNT的表面化学组成.结果表明,随着CNT直径的减小,其氧化电流降低,但其中以为10~20 nm的CNT电极氧化电流最小,表面氧的增量也最小,即被氧化的程度最低,抗电化学氧化性最强.根据不同直径CNT的缺陷位、不定型碳的丰度和碳原子的应力能,分析了其抗电化学氧化性差异的原因.