Electrospinning of poly(trimethylene terephthalate)/carbon nanotube composites

Poly(trimethylene terephthalate) (PTT) nanocomposites containing carbon nanotubes (CNTs) with different surface structure and aspect ratio were prepared by melt compounding for electrospinning. The dispersion state of the CNTs in the composites was then examined utilizing rheology tools. The results show that carboxylic surface functionalized CNTs present better dispersion in the matrix than hydroxy surface functionalized CNTs because the former has stronger affinity to the PTT. Besides surface functionalization, the aspect ratio of CNTs is also vital to their final dispersion. The CNTs with lower aspect ratio are dispersed as individuals or small bundles while those with higher aspect ratio are dispersed mainly as flocs with large hydrodynamic radius, showing higher effective volume fraction. The presence of CNTs has a large influence on the morphologies of electrospun fiber and on the appearances of CNTs in the fibers. In the presence of CNTs with lower aspect ratio, continuous composite fibers are obtained. But the structure of those continuous fibers highly depends on the surface group of CNTs. Carboxylic surface functionalized CNTs are well embedded by the PTT and oriented along the fiber axis during electrospinning, leading to bead-free and uniform fiber morphology; while hydroxy surface functionalized CNTs show tortuous conformations with less orientation in the fibers, and as a result, the obtained fibers show beaded and misshaped morphologies. In the case of higher aspect ratio, however, the CNTs prefer to exist as entanglements or knots in the streamlines, and thereby only beaded or even uncontinuous fibers are obtained. Therefore, the formation and fiber morphology of PTT/CNT composite fibers obtained by electrospinning strongly depend on the surface functional groups of the CNTs, as well as on the CNT structure.     

Molecular dynamics simulation study of the structural characteristics of water molecules confined in functionalized carbon nanotubes

Molecular dynamics (MD) simulations were performed to study the structural properties of water molecules confined in functionalized carbon nanotubes (CNTs). Four CNTs, two armchair-type (6, 6), (7, 7) and two zigzag-type (10, 0), (12, 0) CNTs, representing different helicities and different diameters, were chosen and functionalized at their open ends by the hydrophilic -COOH and the hydrophobic -CH3 groups. The structural properties of water molecules inside the functionalized CNTs, including the orientation distributions of dipole moment and O-H bonds, the length of the single-file water chain, and the average number of hydrogen bonds, were analyzed during a process of simulations. MD simulation results in this work showed that the -CH3 functional groups exert little special effects on the structural properties of water molecules. It is mainly due to the relatively small size of the -CH3 group and its hydrophobic nature, which is consistent with hydrophobic CNTs. For CNTs functionalized by -COOH groups, the configurations of -COOH groups, incurvature or excurvature, determine whether water molecules can enter the CNTs. The incurvature or excurvature configurations of -COOH groups are the results of synergy effects of the CNTs' helicity and diameter and control the flow direction of water molecules in CNTs.     

Tuning periodicity of polymer-decorated carbon nanotubes

Carbon nanotube (CNT) is one of the most extensively investigated nanomaterials. Patterning soft matter such as liquid crystals and polymers on CNTs could potentially enable various applications for CNTs. We have demonstrated that controlled polymer crystallization using CNTs as the 1D nucleation sites can lead to periodically functionalized CNTs. Here we show that selected crystalline block copolymers can be periodically decorated along CNTs. This facile technique opens a gateway to periodic patterning on 1-D nanomaterials.     

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.     

Morphology,rheological and crystallization behavior in non-covalently functionalized carbon nanotube reinforced poly(butylene succinate) nanocomposites with low percolation threshold

Multi-walled carbon nanotubes (CNTs) were non-covalently functionalized by surface wrapping of poly(sodium 4-styrenesulfonate) (PSS) with the aid of ultrasound. The functionalized CNTs were incorporated into poly(butylene succinate) (PBS) through solution coagulation to fabricate CNTs filled PBS nanocomposites. The morphologies of the PBS/CNT nanocomposites were studied by scanning electron microscope (SEM) and transmission electron microscope (TEM), and the effect of loading of functionalized CNT on the rheological behavior, electrical conductivity and mechanical properties of the nanocomposites was investigated systemically. SEM observation indicates that functionalized CNTs dispersed in PBS matrix without obvious aggregation and showed good interfacial adhesion with the PBS phase. TEM observation reveals that a CNT network was formed when the loading of CNTs increased from 0.1 to 0.3 wt%. Rheological investigation indicates the formation of a CNT network with a percolation threshold of only 0.3 wt%. Significant improvement in electrical conductivity occurred at CNT loading of 0.3 wt%, with the value of electrical conductivity increasing by six orders of magnitude compared to neat PBS. Differential scanning calorimetry indicates that the melt crystallization temperature of PBS was improved by ∼14 °C with addition of only 0.05 wt% functionalized CNTs. Tensile tests indicate that both the yield strength and Young's modulus of PBS were apparently reinforced by incorporation of functionalized CNTs, while the elongation at break was reduced gradually.     

Carbon nanotube-nucleobase hybrids: nanorings from uracil-modified single-walled carbon nanotubes

Single‐walled carbon nanotubes (SWCNTs) have been covalently functionalized with uracil nucleobase. The hybrids have been characterized by using complementary spectroscopic and microscopic techniques including solid‐state NMR spectroscopy. The uracil‐functionalized SWCNTs are able to self‐assemble into regular nanorings with a diameter of 50–70 nm, as observed by AFM and TEM. AFM shows that the rings do not have a consistent height and thickness, which indicates that they may be formed by separate bundles of CNTs. The simplest model for the nanoring formation likely involves two bundles of CNTs interacting with each other via uracil–uracil base‐pairing at both CNT ends. These nanorings can be envisaged for the development of advanced electronic circuits.     

Pt 纳米颗粒在聚二甲基二烯丙基氯化铵功能化碳纳米管上的自发沉积及其对甲醇的电氧化性能

利用聚二甲基二烯丙基氯化铵(PDDA)非共价修饰的碳纳米管(CNTs)与PtCl₆^2-之间的自发氧化还原作用, 制备了Pt 纳米颗粒(Pt NPs)/CNTs-PDDA复合催化剂. PDDA在该催化剂中具有三种作用: (1) 作为金属前驱体PtCl₆^2-还原为Pt NPs 的还原剂; (2) 作为原位产生的Pt NPs 的稳定剂; (3) 在CNTs 表面形成保护膜抑制CNTs 在甲醇电催化氧化过程中的腐蚀. 采用傅里叶变换红外(FTIR)光谱、热重分析和拉曼光谱对CNTs-PDDA进行了表征, 表明PDDA通过π-π作用已成功覆盖在CNTs 表面, 并且修饰过程没有导致CNTs 结构的破坏. 采用透射电子显微镜(TEM)对Pt NPs/CNTs-PDDA 催化剂进行了表征, 结果表明, Pt NPs 均匀地分散在CNTs上, 平均粒径约2 nm, 且粒径分布范围窄. 用循环伏安法、计时电流法进一步考察了Pt NPs/CNTs-PDDA催化剂在酸性介质中对甲醇的电催化氧化的性能. 电化学测试结果表明, 与原始CNTs 负载的Pt NPs催化剂相比,Pt NPs/CNTs-PDDA催化剂具有更高的电化学活性表面积、电催化质量比活性和稳定性.     

Carbon nanotubes for in vivo cancer nanotechnology

The latest progress of using carbon nanotubes (CNTs) for in vivo cancer nanotechnology is reviewed. CNTs can be functionalized by either covalent or non-covalent chemistry to produce functional bioconjugates for many in vivo applications. In vivo behaviors and toxicology studies of CNTs are summarized, suggesting no significant toxicity of well functionalized CNTs to the treated mice. Owing to their unique chemical and physical properties, CNTs, especially single-walled carbon nanotubes (SWNTs), have been widely used for various modalities of in vivo cancer treatment and imaging. Future development of CNT-based nanomedicine may bring novel opportunities to cancer diagnosis and therapy.     

Chitosan‐Functionalized Carbon Nanotubes as Support for the High Dispersion of PtRu Nanoparticles and their Electrocatalytic Oxidation of Methanol

Carbon nanotubes (CNTs) were non‐covalently functionalized with chitosan (Chit) and then employed as the support for PtRu nanoparticles. The functionalization was carried out at room temperature without the use of corrosive acids, thereby preserving the integrity and the electronic conductivity of the CNTs. Transmission electron microscopy reveals that PtRu nanoparticles were highly dispersed on the surface of Chit‐functionalized CNTs (CNT‐Chit) with small particle‐size. Cyclic voltammetry studies indicated that the PtRu nanoparticle/CNT‐Chit nanohybrids have a higher electrochemical surface area, electrocatalytic performance, and stability towards methanol oxidation compared to PtRu nanoparticles supported on the pristine CNTs.     

Thermal stability of functionalized carbon nanotubes studied by in-situ transmission electron microscopy

The thermal stability of funtionalized carbon nanotubes (CNTs) has been studied experimentally by direct in-situ observations using a heating stage in a transmission electron microscope, from room temperature (RT) to about 1000 °C. It was found that the thermal stability of the functionalized CNTs was significantly reduced during the in-situ heating process. Their average diameter dramatically expanded from RT to about 500 °C, and then tended to be stable until about 1000 °C. The X-ray energy dispersive spectroscopy analysis suggested that the diameter expansion was associated with coalescence of the carbon structure instead of deposition with additional foreign elements during the heating process.     

Noncovalent modification of carbon nanotubes by conjugated polymer: A theoretical study

The energetic and optical properties of (n, n) carbon nanotubes (CNTs) for n = 3–11 noncovalently modified with poly(phenylenethynylene) (PPE) were studied using a density‐functional tight‐binding method. The binding energies between the PPE and (n, n) CNTs were found increasing with the diameter increase for n ≤ 9 and then decreasing due to steric hindrance effect. It was verified that the binding is due to π–π interaction and van der Waals attraction, with very small charge transfers involved. Significant blue shifts in the absorption and fluorescent spectra of the PPE upon interacting with the CNTs were revealed in the calculation, which are responsible to the optical “quenching” observed in experiment. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

直径大于2nm的(15, 15)碳纳米管的仿生生物改性及其脱盐行为的分子模拟

模仿水通道蛋白结构在直径大于2 nm的(15, 15)的碳纳米管内壁添加不同数量的―NH₃⁺和―COO^-,并结合端口改性建立连续的碳纳米管膜模型,利用分子动力学模拟方法研究了水以及Na⁺和Cl^-在碳纳米管中的通量、密度分布和离子进入碳纳米管的平均力势。结果表明,在200 MPa压力下,对碳纳米管进行内壁和端口改性可以在保持较高水通量基础上显著提高碳纳米管的截盐作用。当在(15, 15)碳纳米管内壁添加5对―COO^-和―NH₃⁺基团或内壁添加4对―COO^-和―NH₃⁺且端口添加1对时, Cl^-截盐率可达到100%, Na⁺的截盐率达到88%。改性(15, 15)碳纳米管的最小水通量仍是未改性(8, 8)碳纳米管的4.6倍。     

Effect of CNT incorporation on PAN/PPy nanofibers synthesized by electrospinning method

In this study, carbon nanotubes (CNTs) added polyacrylonitrile/polypyrrole (PAN/PPy) electrospun nanofibers were produced. Average diameters of the nanofibers were measured as 268 and 153 nm for 10 and 25 wt% of PPy contents, respectively. A relatively higher strain to failure values (23.3%) were observed for the low PPy content. When as-grown CNTs (1 and 4 wt%) were added into the PAN/PPy blends, disordered nanofibers were observed to form within the microstructure. To improve the interfacial properties of CNTs/PAN/PPy composites, CNTs were functionalized with H₂SO₄/HNO₃/HCl solution. The functionalized CNTs were well dispersed within the nanofibers and aligned along the direction of nanofibers. Therefore, beads formation on nanofibers decreased. The impedance of the nanofibers was found to decrease with the PPy content and CNT addition. These nanofibers had a great potential to be used as an electrochemical actuator or a tissue engineering scaffold.     

氮气热处理对CNTs-LaNi5电极电化学性能的影响

研究了碳纳米管(CNTs)氮气热处理后结构的变化, 以及热处理温度对CNTs-LaNi5电极电化学性能的影响. CNTs热处理后, 管壁变薄, 层数变少, 管的外径减小, 更有利于氢气的吸附和脱附. 将碳纳米管与LaNi5储氢合金按质量比1:10混合, 制作成CNTs-LaNi5电极. 800 ℃时CNTs-LaNi5电极的储氢性能最好, 最大容量为519.1 mAh•g-1, 相应的平台电压高达1.19 V. 在500～600 ℃范围内, 随着温度升高, 放电容量有较大幅度的增加; 在600～800 ℃范围内, 随着温度升高, 放电容量有较小幅度的增加; 但到900 ℃时, 放电容量反而下降. 由此可见, CNTs的热处理温度对CNTs-LaNi5电极的电化学储氢性能有着较大的影响. 纯LaNi5电极的放电容量仅为265.6 mAh•g-1, 平台电压仅为0.83 V. 添加了碳纳米管的CNTs-LaNi5电极的电化学活性高于纯LaNi5电极.     

Introduction of Multiple Hydrogen Bonding for Enhanced Mechanical Performance of Polymer-Carbon Nanotube Composites

Due to their outstanding mechanical properties and high aspect ratios, carbon nanotubes (CNTs) are envisioned as attractive nanofillers in polymer composites. However, due to strong van der Waals interactions, deleterious aggregation of CNTs is typically observed in polymer nanocomposites. Moreover, due to low stress transfer between the matrix polymer and the nanotube filler, only limited reinforcement is obtained. We report here a novel functionalization strategy to obtain CNTs with pendant self-complementary hydrogen bonding groups in order to address these limitations. Multi-walled CNTs were functionalized with ureidopyrimidinone (UPy) groups, which display multiple hydrogen bonding. The functionalized CNTs were blended with acrylic copolymers containing pendant UPy moieties and significant enhancement in tensile performance of the nanocomposites was observed.     

Surfactant-free nanofluids containing double- and single-walled carbon nanotubes functionalized by a wet-mechanochemical reaction

Single-walled carbon nanotubes (SWNTs) and double-walled carbon nanotubes (DWNTs) have been functionalized through the wet-mechanochemical reaction method. Results from the infrared spectrum and zeta potential measurements show that the hydroxyl groups have been introduced onto the treated SWNT and DWNT surfaces. Transmission electron microscope observations revealed that the SWNTs and DWNTs were cut short after being milled. SWNTs and DWNTs with optimized aspect ratio can be obtained by adjusting the ball milling parameters. Thermal conductivity enhancement of water-based nanofluids containing treated carbon nanotubes (CNTs) shows augmentation with the increase of temperature mainly due to the effects of an ordering liquid layer forming around the chemical surfaces of CNTs. Moreover, the thicker interfacial layer of water molecules on the surfaces of CNTs with smaller diameter, such as SWNTs, is in favor of greater thermal conductivity enhancement compared with the thinner one on the surfaces of DWNTs or MWNTs with larger diameter.     

π‐Plasmon absorbance films of carboxylic functionalized CNTs coupled with renewable PGP platforms

π‐Plasmon absorbance films of carboxylic functionalized multiwall carbon nanotubes (CNTs) coupled with renewable and recycled polycaprolactone grafted pectin (PGP) platforms as successful alternative for ordinary nondegradable platforms were investigated. Characterization of the synthesized carboxylic functionalized CNTs was performed using ¹H NMR and attenuated total reflectance Fourier transform infrared for structural identification, thermogravimetric analysis and derivative thermogravimetric analysis for thermal stability, and X‐ray powder diffraction for crystal structure, whereas the characterization of prepared PGP was done by means of attenuated total reflectance Fourier transform infrared for chemical structure, differential scanning calorimetry for melting endotherms of polycaprolactone and high crystalline structure of PGP, and thermogravimetric analysis and derivative thermogravimetric analysis for thermal stability of PGP. Fabrication of water‐dispersed carboxylic functionalized CNTs coupled with PGP films was performed by casting technique in the presence of Ca²⁺ as cross‐linker. The thin films were tested for π‐plasmon absorbance using UV‐Vis spectrometry. Different fractions of carboxylic functionalized CNTs and PGP films demonstrated π‐plasmon absorbance broad peaks at λ_max = 232 nm, which corresponded to 5.36 eV. The fabrication of novel films from renewable recycled PGP platform and advanced carboxylic functionalized CNTs properties will be the key features for many of next forthcoming technologies. The PGP considered as environment‐friendly and easily degradable platforms will be a successful alternative for conventional nondegradable electronic platforms, and water‐dispersed carboxylic functionalized CNTs with advanced properties will be finding accelerating executive applications.     

碳纳米管结构对碳纳米管载Pt催化剂电催化性能的影响

在制备单、双壁及不同管径的多壁碳纳米管(CNTs)的基础上, 用液相还原法把Pt沉积到单、双壁和管径不同的多壁CNTs上. 发现制得的CNTs载Pt(Pt/CNTs)催化剂对甲醇氧化的电催化活性随CNTs管径减小而增加. 这归结于管径小的CNTs的比表面积较大, 含氧基团多, 有利于提高Pt粒子分散度, 加上管径小的单壁CNTs具有更高的导电性, 这些因素都有利于提高Pt/CNTs催化剂对甲醇氧化的电催化活性.     

Multipurpose organically modified carbon nanotubes: from functionalization to nanotube composites

We show that covalent functionalization of carbon nanotubes (CNTs) via 1,3-dipolar cycloaddition is a powerful method for enhancing the ability to process CNTs and facilitating the preparation of hybrid composites, which is achieved solely by mixing. CNTs were functionalized with phenol groups, providing stable dispersions in a range of polar solvents, including water. Additionally, the functionalized CNTs could easily be combined with polymers and layered aluminosilicate clay minerals to give homogeneous, coherent, transparent CNT thin films and gels.     

A simple route for the attachment of colloidal nanocrystals to noncovalently modified multiwalled carbon nanotubes

A simple strategy for the fabrication of multiwalled carbon nanotubes (MWNTs)–nanocrystal (NC) heterostructures is shown. Different nanoparticles can be covalently coupled to functionalized carbon nanotubes (CNTs) in a uniform and controllable manner. MWNTs have been functionalized by a polymer wrapping—technique that is non-invasive, and does not introduce defects to the structure of CNTs; the polymer is noncovalently adsorbed on the MWNT's surface. Moreover, this method ensures good dispersion and high stability in any commonly used organic or inorganic solvent. In this manner, our strategy allows the attachment of various colloidal nanoparticles to CNTs, independent of their surface properties, i.e. hydrophilic or hydrophobic.