The effect of pH on the functionalization of nylon fabric with carbon nanotubes

Single walled carbon nanotubes (SWCNTs) were dispersed in water and attached to nylon fabrics by a dip-drying procedure; scanning electron microscopy and Raman spectroscopy suggest the attachment of the SWCNTs. The electrical resistance of the functionalized fabrics is found to be pH-dependent, which is correlated with the quantity of SWCNTs dispersed in water at different values of pH. This can be further ascribed to the influence of the pK(a) of the acid (e.g., acetic acid in this study) used to tune pH. The acid may affect the dispersion of SWCNTs through two different mechanisms: (1) the free protons may protonate the amine and/or sulfonate group in the dye molecules, resulting in a variety of interactions among the dye molecules, SWCNTs and water molecules and (2) the resulting ions may increase the ionic strength of the solution, compressing the electric double layers of SWCNT colloids and thus impairing their stability. The former possibility is ruled out by data obtained using X-ray photoelectron spectroscopy, Raman spectroscopy, and ultraviolet-visible-near infrared spectroscopy; thus the latter is proposed to account for the experimental results. The colour strength of the functionalized fabrics increases with increasing pH, which is in agreement with their measured electrical properties.     

壳状碳纳米颗粒的制备和分散

利用高功率CO2连续激光照射C2H2,使之热解,成功制备了中空壳状碳纳米颗粒(CNSs),为增强其分散性,用王水对所制备的CNSs进行表面处理。利用TEM、XRD、FTIR以及Zeta电位测量等技术对CNSs和经化学处理后的碳纳米颗粒(T-CNSs)进行了对比分析。结果表明:CNSs壳层内碳原子呈石墨状规则排列;T-CNSs表面带有含氧的亲水官能团,使其很容易分散;化学处理没有改变CNSs的结构。     

Ester-functionalized single-walled carbon nanotubes via addition of haloformates

Herein, a versatile method to introduce ester functional groups to the surface of single-walled carbon nanotubes (SWCNTs) was defined. Ester-modified SWCNTs were prepared via the direct reaction of haloformates with reduced SWCNTs [(nBu–SWCNT ^n? ) Li _n ⁺ ] generated by n-butyl lithium. Ultraviolet–Visible–near infrared and Raman spectroscopy verified the evidence of covalent surface functionalization. Solubility of functionalized SWCNTs (f-SWCNTs) enhanced compared to purified SWCNTs. Gold tagging to positively charged SWCNTs displayed the presence and distribution of functional groups, confirming the conversion of esters into amides. f-SWCNTs were further characterized by thermo-gravimetric analysis coupled with mass spectrometry and fourier-transform infrared spectroscopy.     

Effect of temperature for synthesizing single-walled carbon nanotubes by catalytic chemical vapor deposition over Mo-Co-MgO catalyst

The influence of temperature on synthesizing single-walled carbon nanotubes (SWCNTs) by catalytic chemical vapor deposition of methane over Mo-Co-MgO catalyst was studied by Transmission Electron Microscope (TEM) and Raman scattering. The Mo-Co-MgO bimetallic catalyst was prepared by decomposing the mixture of magnesium nitrate, ammonium molybdate, citric acid, and cobalt nitrate. The results show that Mo-Co-MgO bimetallic catalyst is effective to synthesize SWCNTs. By using Mo-Co-MgO bimetallic catalyst, generation of SWCNTs even at 940 K was demonstrated. The optimum temperature of synthesizing SWCNTs over Mo-Co-MgO bimetallic catalyst may be about 1123 K. At 1123 K, the diameters of SWCNTs are in the range of 0.75–1.65 nm. The content of SWCNTs is increased with the increase of temperature below 1123 K and the carbon yield rate is also increased with the increase of synthesis temperature. Therefore, the amount of SWCNTs increases with the increase of temperature below 1123 K. However, above 1123 K, the content of SWCNTs is decreased with the increase of temperature; therefore, it is not effective to increase the amount of SWCNTs through increasing synthesis temperature above 1123 K.     

Tailored SWCNT functionalization optimized for compatibility with epoxy matrices

We have modified single walled carbon nanotubes (SWCNTs) with well defined matrix-based architectures to improve interface interaction in SWCNT/epoxy composites. The hardener and two pre-synthesized oligomers containing epoxy and hardener moieties were covalently attached to the SWCNT walls by in?situ diazonium or carboxylic coupling reactions. In this way, SWCNTs bearing amine or epoxide-terminated fragments of different molecular weights, which resemble the chemical structure of the cured resin, were synthesized. A combination of characterization techniques such as Raman and infrared absorption (FTIR) spectroscopy, elemental analysis and coupled thermogravimetry-FTIR spectroscopy were used to identify both the functional groups and degree of functionalization of SWCNTs synthesized by the laser ablation and arc-discharge methods. Depending on the type of reaction employed for the chemical functionalization and the molecular weight of the attached fragment, it was possible to control the degree of functionalization and the electronic properties of the functionalized SWCNTs. Improved dispersion of SWCNTs in the epoxy matrix was achieved by direct integration without using solvents, as observed from optical microscopy and rheology measurements of the SWCNT/epoxy mixtures. Composite materials using these fillers are expected to exhibit improved properties while preserving the thermosetting architecture.     

A general route to efficient functionalization of silicon quantum dots for high-performance fluorescent probes

A general technique for efficient surface modification of silicon nanocrystals is highly desirable for the development of silicon quantum dots (SiQDs) as fluorescent probes for biological applications. Herein, a facile microwave-assisted hydrosilylation process for the preparation of stable SiQDs in a single step is presented. FTIR spectroscopy indicates that molecules with various terminal functionalities, such as alcohol, alkyl groups, and carboxylic acid, are grafted successfully onto the surface of silicon nanocrystals. The dispersibility of such SiQDs is clearly dependent on the terminal functional groups of the grafted molecules. In addition, the as-prepared SiQDs show excellent cell compatibility, photoluminescence properties, and stability, and their use as long-term intracellular fluorescent probes is also demonstrated. It is envisaged that this facile and effective method for the stabilization and functionalization of SiQDs with tailored wetting and chemical properties will enable wide application of SiQDs in a number of areas.     

Decoration of single-walled carbon nanotubes with Pt nanoparticles from an organometallic precursor

Carbon nanotubes (CNTs) are nanomaterials of high interest due to their unique structural, electrical, and mechanical properties. Carbon materials have been widely employed to support metallic nanoparticles for catalysis and electrochemical applications. In this work, we investigated the synthesis of platinum nanoparticles generated from the complex Pt₂(dba)₃ (tris(dibenzylideneacetone) diplatinum) and stabilized with a long alkyl chain amine, hexadecylamine (HDA) and supported on functionalized single-walled carbon nanotubes (SWCNTs). High resolution transmission electron microscopy (HRTEM) studies revealed isolated Pt nanoparticles (2?C3 nm) on SWCNTs. Powder X-ray diffraction (XRD) was used to assess the structure of Pt nanoparticles dispersed on SWCNTs assigned to Pt face-centered cubic (fcc). Additionally, infrared Fourier transform spectroscopy confirmed the presence of the stabilizer at the surface of the Pt nanoparticles even after the purification step and functional groups at the surface of pre-treated SWCNTs. This synthetic method may be an alternative route to prepare small size Pt nanoparticles supported on functionalized SWCNTs.     

Photochemical modification of single-walled carbon nanotubes using HPHMP photoinitiator for enhanced organic solvent dispersion

Photochemical modification of single-walled carbon nanotubes (SWCNTs) was carried out by covalent attachment of 2-propanol-2-yl radicals on the surface of SWCNTs, which were engendered by the photolysis of 1-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (HPHMP) under ultraviolet (UV) light. Pristine single-walled carbon nanotubes (p-SWCNTs) were dispersed in acetone along with HPHMP photoinitiator. After that, the mixture was irradiated by UV light to generate the free radicals which were introduced onto the surface of SWCNTs. The modification of SWCNTs was supported by UV/visible spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, thermal gravimetric analysis–mass spectrometry (TGA–MS), and transmission electron microscopy (TEM). UV/visible results revealed the loss of van Hove singularities due to covalent modification. The modification was further verified by FT-IR showing the signals at 3421 and 1100 cm⁻¹ due to stretching and bending of O–H group, respectively. Moreover, other peaks at 2927 and 2858 cm⁻¹ indicated the asymmetric and symmetric stretching modes of aliphatic C–H bond, respectively. Raman spectra illustrated that the intensity ratio of the tangential mode to the disorder mode (I _G/I _D), for modified SWCNTs (F-SWCNTs), decreased nearly four times than p-SWCNTs. TGA–MS also evidenced the signal corresponding to m/z 59 at 400 °C indicating the presence of 2-propanol-2-yl groups. TEM and dispersibility data demonstrated that the sidewall modification detached the bundled structure, enhanced the dispersion in common organic solvents and retained the original size of SWCNTs without hefty modification, which could cut or damage the nanotubes.     

Carbon nanotubes with hydrophilic surfaces produced by a wet-mechanochemical reaction with potassium hydroxide using ethanol as solvent

Multi-walled carbon nanotubes (MWCNTs) were treated by a simple wet-mechanochemical reaction with potassium hydroxide using ethanol as solvent to enhance their dispersibility. Fourier transmission infrared spectroscopy measurements show that the non-reactive surfaces of MWCNTs were modified directly by multiple hydroxyl groups. The products, defined as MWCNTols, are highly soluble in water and other polar solvents. Different microstructures of linear, swirl, and ring shapes have been observed in MWCNTol sheets. The formation mechanism has been investigated and MWCNTol length was proposed as the key factor affecting the observed microstructures.     

Effect of cutting and functionalization of single-walled carbon nanotubes on their dispersion behaviors

Cutting of single-walled carbon nanotubes (SWCNTs) and their modification with poly (ethylene glycol) and polystyrene were successfully performed through a treatment of the SWCNTs with piranha solutions and monoamine terminated polymers. The shortening and functionalization of SWCNTs were confirmed through size exclusion chromatography and Raman spectroscopy observations. The shortened SWCNTs exhibited more aggregated morphology than as-prepared SWCNTs in scanning electron microscope and atomic force microscope observations. Cutting and functionalization of SWCNTs with different polymer chains effectively tailored their dispersion behaviors in solvents. Polystyrene composite films exhibited improved transparency employing shortened SWCNTs, suggesting that the size of SWCNTs are critical factors in controlling the transparency of polymer composite films.     

Application of response surface methodology with a Box–Behnken design for struvite precipitation

Struvite crystals were precipitated by the reaction of magnesium chloride hexahydrate and ammonium dihydrogen phosphate using different concentrations of citric acid as the additive (100, 300, and 500 ppm). The structure, morphology, functional groups and particle size of the crystals were evaluated experimentally by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy (FTIR) and particle size analysis. The experimental results demonstrated that citric acid exerted a significant influence on the struvite precipitation and the crystal morphology changed from rod-like to tubular shaped with a larger size and hollow bodies. The average particle size changed from 17.60 to 33.60 μm with increasing citric acid concentration. The results of FTIR suggested that the citric acid adsorbed on the crystal surface. Following the characterization of the crystals prepared using different concentrations of citric acid, the response surface methodology coupled with Box-Behnken design were applied as a statistical tool to determine the effects of the key parameters affecting the precipitation process (temperature, pH and additive concentration) on the responses (namely, particle size and specific cake resistance of struvite). Second-order polynomial equations for both responses were improved to correlate the parameters. Analysis of variance (ANOVA) showed a significant quadratic regression model with high coefficients of the determination values. The optimum conditions for particle size were found to be 60 °C, pH 8 and 500 ppm additive concentration.     

Electronic Property Modification of Single‐Walled Carbon Nanotubes by Encapsulation of Sulfur‐Terminated Graphene Nanoribbons

The use of carbon nanotubes (CNTs) as cylindrical reactor vessels has become a viable means for synthesizing graphene nanoribbons (GNRs). While previous studies demonstrated that the size and edge structure of the as‐produced GNRs are strongly dependent on the diameter of the tubes and the nature of the precursor, the atomic interactions between GNRs and surrounding CNTs and their effect on the electronic properties of the overall system are not well understood. Here, it is shown that the functional terminations of the GNR edges can have a strong influence on the electronic structure of the system. Analysis of SWCNTs before and after the insertion of sulfur‐terminated GNRs suggests a metallization of the majority of semiconducting SWCNTs. This is indicated by changes in the radial breathing modes and the D and G band Raman features, as well as UV–vis–NIR absorption spectra. The variation in resonance conditions of the nanotubes following GNR insertion make direct (n,m) assignment by Raman spectroscopy difficult. Thus, density functional theory calculations of representative GNR/SWCNT systems are performed. The results confirm significant changes in the band structure, including the development of a metallic state in the semiconducting SWCNTs due to sulfur/tube interactions. The GNR‐induced metallization of semiconducting SWCNTs may offer a means of controlling the electronic properties of bulk CNT samples and eliminate the need for a physical separation of semiconducting and metallic tubes.     

羟基磷灰石的表面改性及其对聚乳酸基多孔支架性能的影响

分别采用柠檬酸和硬脂酸对纳米羟基磷灰石（n-HA）进行表面处理,并利用TGA、FTIR、XPS等研究了不同改性剂的改性效果,发现柠檬酸和硬脂酸能够成功接枝在n-HA表面,但硬脂酸的接枝率更高。将柠檬酸改性的n-HA与聚乳酸（PLA）共混制备复合材料,通过SEM观察发现,制备的n-HA/PLA复合材料在n-HA粉体添加量不超过20wt%时,经处理后的n-HA粉体在基体中分散均匀,两相界面处结合紧密。同时研究了n-HA/PLA复合材料制备多孔骨支架的3D打印成型工艺,并测试了其力学性能,结果表明,采用熔融沉积3D打印技术制备的支架有良好的压缩模量,但达到10%形变时所承受的压缩强度与PLA相比仍然有一定差距。     

Biodegradation of Single‐Walled Carbon Nanotubes by Eosinophil Peroxidase

Eosinophil peroxidase (EPO) is one of the major oxidant‐producing enzymes during inflammatory states in the human lung. The degradation of single‐walled carbon nanotubes (SWCNTs) upon incubation with human EPO and H₂O₂ is reported. Biodegradation of SWCNTs is higher in the presence of NaBr, but neither EPO alone nor H₂O₂ alone caused the degradation of nanotubes. Molecular modeling reveals two binding sites for SWCNTs on EPO, one located at the proximal side (same side as the catalytic site) and the other on the distal side of EPO. The oxidized groups on SWCNTs in both cases are stabilized by electrostatic interactions with positively charged residues. Biodegradation of SWCNTs can also be executed in an ex vivo culture system using primary murine eosinophils stimulated to undergo degranulation. Biodegradation is proven by a range of methods including transmission electron microscopy, UV‐visible‐NIR spectroscopy, Raman spectroscopy, and confocal Raman imaging. Thus, human EPO (in vitro) and ex vivo activated eosinophils mediate biodegradation of SWCNTs: an observation that is relevant to pulmonary responses to these materials.     

Effect of silane modification on CNTs/silica composites fabricated by a non-firing process to enhance interfacial property and dispersibility

Carbon nanotube/ceramic composites have been in the spotlight thanks to their excellent properties. Sintering is the vital part of ceramics fabrication in terms of reliability, however sintering the carbon nanotube (CNT) based ceramic composites is a challenging task. In this study, interfacial bonding of silane functionalized CNT with silica ceramic is investigated by a non-firing sintering process. CNTs are first treated by a mixed acid with the aid of a silane 3-aminopropyl triethoxysilane (APTES), which improves the chemical bonding and dispersibility of CNT in ceramic bodies. The extent of APTES chemical functionalization and mechanical property of CNT/silica ceramic composites are characterized using Raman spectrometer, FT-IR analysis, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and three-point bending strength measurement. Results show that composites are successfully prepared without sintering with stable CNT-silica interface, superior dispersibility, and good mechanical properties.     

电感耦合等离子体对HDPE粉体的表面处理

用搅拌式电感耦合等离子体反应器对高密度聚乙烯（HDPE）粉体进行表面处理,采用水接触角、红外光谱（FT-IR）和X射线光电子能谱（XPS）对等离子体处理前后HDPE粉体的水接触角、表面成分的变化进行分析。实验结果表明,随着等离子体处理时间延长和放电功率增加,水接触角减小。在功率100W处理30min后,水接触角从处理前...     

Fabrication and electrochemical behavior of vertically-aligned carbon nanotube electrodes covalently attached to p-type silicon via a thioester linkage

Vertically-aligned single-walled carbon nanotubes (SWCNTs) (VACNTs) are becoming increasingly recognized due to their fast electron transfer rates. However, the chemistry available for further functionalizing these electrodes is limited. Here we describe a new approach to the fabrication of VACNTs. SWCNTs were covalently attached to a p-type silicon (100) (Si) wafer surface using a thioester linkage in which the nanotubes were firstly acid treated and then, in the presence of a hydroxylated Si wafer surface, reacted with phosphorus pentasulfide (a mild electrophilic catalyst). The novel nanostructure was characterized using atomic force microscopy (AFM) showing vertical alignment with FTIR spectroscopy indicating pendant thiocarboxylic acid groups for further reaction. In addition, electrochemical properties using cyclic voltammetry indicate that the electrodes have excellent electrochemical properties with an electron transfer rate of 2.98 × 10^? 3 cm s^? 1.     

Synthesis of mesitylene-based polyamine dendrimer for functionalisation of single-walled carbon nanotubes

We have synthesised first generation (G1) of mesitylene-based polyamine dendrimer by following the convergent approach. The polyamine dendrimer was characterised by the usual spectroscopic techniques including liquid chromatography coupled with mass spectrometry. To develop polycationic functionalised carbon nanotubes (f-CNTs) as advanced systems for the delivery of nucleic acid, we attached G1 polyamine dendrimer onto the surface of single-walled CNTs (SWCNTs). The f-SWCNTs were characterised by thermogravimetric analysis and transmission electron microscopy. The nanotubes after functionalisation with polyamine dendrimer showed good dispersibility in highly polar solvents.     

Combined electron microscopy and spectroscopy characterization of as-received,acid purified,and oxidized HiPCO single-wall carbon nanotubes

Single-wall carbon nanotubes (SWCNTs) are very important materials due to their combination of unique structure, dimension, strength, chemical stability, and electronic properties. Nevertheless, SWCNTs from commercial sources usually contain several impurities, which are usually removed by a purification process that includes reflux in acids and strong oxidation. This strong chemical procedure may alter the nanotube properties and it is thus important to control the extent of functionalization and oxidation during the purification procedure. In this report, we provide a comprehensive study of the structure and physical composition of SWCNTs during each step of the purification process. Techniques such as Raman spectroscopy, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy and Infrared spectroscopy were used to track the SWCNTs structure, in terms of length and diameter distribution, and surface chemical modifications during each purification stage.     

XANES study of phenylalanine and glycine adsorption on single-walled carbon nanotubes

We applied X-ray absorption near edge structure (XANES) spectroscopy to investigate the adsorption of amino acids (phenylalanine and glycine) onto single-walled carbon nanotubes (SWCNTs). The adsorption of amino acids has been confirmed by XANES analysis. Moreover, a clear energy shift of the C 1s to π_C=O? peak for glycine adsorbed on SWCNTs has been identified and assigned to the interaction between the amino acid and SWCNTs. The experimental data confirm the capability of the XANES spectroscopy as a powerful tool to characterize fine structural details at the interface of complex bio-systems.