Remarkable support effect of SWNTs in Pt catalyst for methanol electrooxidation

Carbon nanotubes have been proposed as advanced metal catalyst support for electrocatalysis. In this work, different carbon support materials including single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs) and XC-72 carbon black, were compared in terms of their electrochemical properties using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The SWNTs is found to exhibit the highest accessible surface area in electrochemical reactions and the lowest charge transfer resistance at the SWNTs/electrolytes. These carbon materials are then loaded with varying amount of Pt by the electrodeposition technique to prepare carbon supported Pt catalysts. Electrochemical measurements of methanol oxidation reveal that the SWNTs supported Pt catalyst exhibits the highest mass activity (mA/mg-Pt). In comparison with Pt-XC-72 and Pt-MWNTs, the remarkably enhanced electrocatalytic activity of the Pt-SWNTs maybe attributed to a higher dispersion and utilization of the Pt particles, which are directly related to the electrochemical characteristics of SWNTs. The high concentration of oxygen-containing functional groups, high accessible surface area, low charge transfer resistance at the carbon/electrolyte interfaces can be important for the Pt dispersing and strong metal-support interaction in the Pt-SWNTs catalyst.     

Effects of SWNT and metallic catalyst on hydrogen absorption/desorption performance of MgH2

The microstructure and absorption/desorption characteristics of composite MgH2 and 5 wt % as-prepared single-walled carbon nanotubes (MgH2-5ap) obtained by the mechanical grinding method were investigated. Experimental results show that the MgH2-5ap sample exhibits faster absorption kinetics and relatively lower desorption temperature than pure MgH2 or MgH2-purified single-walled carbon nanotube composite. Storage capacities of 6.0 and 4.2 wt % hydrogen for the MgH2-5ap composite were achieved in 60 min at 423 and 373 K, respectively. Furthermore, its desorption temperature was reduced by 70 K due to the introduction of as-prepared single-walled carbon nanotubes (SWNTs). In addition, the different effects of SWNTs and metallic catalysts contained in the as-prepared SWNTs were also investigated and a hydrogenation mechanism was proposed. It is suggested that metallic particles may be mainly responsible for the improvement of the hydrogen absorption kinetics, and SWNTs for the enhancement of hydrogen absorption capacity of MgH2.     

Pyridine-functionalized single-walled carbon nanotubes as gelators for poly(acrylic acid) hydrogels

Pyridine-functionalized single-walled carbon nanotubes (SWNTs) are prepared from the addition of a pyridine diazonium salt to nanotubes. The location and distribution of the functional groups is determined by atomic force microscopy using electrostatic interactions with gold nanoparticles. The pyridine-functionalized SWNTs are able to act as cross-linkers and hydrogen bond to poly(acrylic acid) to form SWNT hydrogels. The pyridine-functionalized SWNTs are further characterized using Raman, FTIR, UV/vis-NIR, and X-ray photoelectron spectroscopy and thermogravimetric analysis-mass spectrometry.     

Single-walled carbon nanotube-templated crystallization of H2SO4: direct evidence for protonation

Liquid anhydrous sulfuric acid forms molecular "shells" wrapped around single-walled carbon nanotubes (SWNTs). Temperature-dependent X-ray scattering from aligned acid-swollen fibers shows that crystallization of the bulklike acid surrounding the structured shells is templated by the aligned SWNTs, while the structured shells remain partly ordered, at least for temperatures from 100 to 500 K. The (2 0 0) or ( 0 2) planes of the templated H2SO4 crystallites are parallel to the nanotube axes. This provides solid evidence for the direct protonation of SWNT since the molecules are terminated by hydrogen bonds.     

Noncovalent functionalization of DNA-wrapped single-walled carbon nanotubes with platinum-based DNA cross-linkers

A method for noncovalent functionalization of DNA-wrapped single-walled carbon nanotubes (SWNTs) using platinum-based DNA cross-linkers is investigated. In particular, cisplatin and potassium tetrachloroplatinate are shown to bind to DNA that encapsulates SWNTs in aqueous solution. The bound platinum salt can then be reduced to decorate the DNA-encapsulated SWNTs with platinum nanoparticles. The resulting SWNT/DNA/Pt hybrids are investigated by optical absorption spectroscopy, circular dichroism spectroscopy, Raman spectroscopy, X-ray diffraction, transmission electron microscopy, and atomic force microscopy. The unique combination of catalytic activity of nanoscale platinum, biological functionality of DNA, and optoelectronic properties of SWNTs suggests a myriad of applications including fuel cells, catalysts, biosensors, and electrochemical devices.     

Gas–solid interactions in the hydrogen/single-walled carbon nanotube system

Gas–solid interactions between hydrogen and single-walled carbon nanotubes (SWNTs) were investigated using highly purified SWNTs. The activation energy of hydrogen desorption, measured to be 0.21 eV, indicates that hydrogen is physisorbed in the pores and that inter-tube pores have an adsorption potential of about −0.21 eV, which induces hydrogen physisorption at ambient temperature. The total amount of adsorbed hydrogen, about 0.3 wt% at 9 MPa, shows that 38% of the inter-tube sites are occupied. These findings are interpreted in terms of the chemical potential of hydrogen and the adsorption potential of the inter-tube pores.     

Constrained iron catalysts for single-walled carbon nanotube growth

The diameter of single walled carbon nanotubes (SWNTs) determines the electronic properties of the nanotube. The diameter of carbon nanotubes is dictated by the diameter of the catalyst particle. Here we describe the use of iron nanoparticles synthesized within the Dps protein cage as catalysts for the growth of single-walled carbon nanotubes. The discrete iron particles synthesized within the Dps protein cages when used as catalyst particles gives rise to single-walled carbon nanotubes with a limited diameter distribution.     

Acyclic cucurbit[n]uril molecular containers selectively solubilize single-walled carbon nanotubes in water

Making single-walled carbon nanotubes (SWNTs) soluble in water is a challenging first step to use their remarkable electronic and optical properties in a variety of applications. We report that acyclic cucurbit[n]uril molecular containers 1 and 2 selectively solubilize small-diameter and low chiral angle SWNTs. The selectivity is tunable by increasing the concentration of the molecular containers or by adjusting the ionic strength of the solution. Even at a concentration 1000 times lower than typically required for surfactants, the molecular containers render SWNTs soluble in water. Molecular mechanics simulations suggest that these C-shaped acyclic molecules complex the SWNTs such that a large portion of nanotube sidewalls are exposed to the external environment. These "naked" nanotubes fluoresce upon patching the exposed surface with sodium dodecylbenzene sulfonate.     

Enhanced sensitivity for biosensors: multiple functions of DNA-wrapped single-walled carbon nanotubes in self-doped polyaniline nanocomposites

A nanocomposite of poly(anilineboronic acid), a self-doped polyaniline, with ss-DNA-wrapped single-walled carbon nanotubes (ss-DNA/SWNTs) was fabricated on a gold electrode by in situ electrochemical polymerization of 3-aminophenylboronic acid monomers in the presence of ssDNA/SWNTs. We used this nanocomposite to detect nanomolar concentrations of dopamine and found that the sensitivity increased 4 orders of magnitude compared to the detection at an electrode modified with only poly(anilineboronic acid). For the first time, this work reports the multiple functions of the ss-DNA/SWNTs in the fabrication and biosensor application of a self-doped polyaniline/ss-DNA/SWNT nanocomposite. First, the ss-DNA/SWNTs acted as effective molecular templates during polymerization of self-doped polyaniline so that not only was the polymerization speed increased but also the quality of the polymer was greatly improved. Second, they functioned as novel active stabilizers after the polymerization, significantly enhancing the stability of the film. Furthermore, the ss-DNA/SWNTs also acted as conductive polyanionic doping agents in the resulting polyaniline film, which showed enhanced conductivity and redox activity. Finally, the large surface area of carbon nanotubes greatly increased the density of the functional groups available for sensitive detection of the target analyte. We envision that polyaniline with other functional groups as well as other conducting polymers may be produced for different targeted applications by this approach.     

Preparation of horizontally aligned single-walled carbon nanotubes with floating catalyst

A strategy to prepare horizontally aligned single-walled carbon nanotubes(SWNTs) at moderate temperatures(≤600 ℃) were developed.Using ferocene as the catalyst precursor,Fe nanoparticles are formed in the gaseous phase and catalyze the nucleation and growth of SWNTs in situ.Then the resultant SWNTs are deposited onto the substrates downstream and aligned by the surface lattice of the ST-cut single crystal quartz.The preparation of SWNT arrays at moderate temperatures is important for combining the tube growth with device fabrication.     

Controlling the diameter of carbon nanotubes in chemical vapor deposition method by carbon feeding

It was found that the diameter distribution of single-walled carbon nanotubes (SWNTs) grown by the chemical vapor deposition (CVD) method could be controlled by the carbon feeding rate at the growth stage. A unified hypothesis on the relationship between nanoparticle size, growth condition, growth temperature, and diameter of the resulting nanotubes was developed and used to explain the relationship. It was shown that the diameters of SWNTs can be controlled even when highly polydisperse nanoparticles were used as catalyst. Such control enabled us to synthesize uniform small-diameter SWNTs at low carbon feeding rates. Additionally, understanding of the important role of the carbon feeding rate can be used to explain the cause of low growth efficiency in most CVD processes. It would also help us to design methods to improve the growth efficiency of CVD growth of nanotubes.     

单壁碳纳米管氧化过程的银纳米粒子跟踪

基于银与羧基之间的相互作用，利用银纳米粒子跟踪稀硝酸氧化单壁碳纳米管的过程.通过比较银纳米粒子对稀硝酸氧化不同时间所得单壁碳纳米管的跟踪情况，推测了该氧化可能是沿着碳纳米管的缺陷边缘处对其进行缓慢腐蚀的过程.     

Pd/SWNTs负载型催化剂的制备及其催化性能

利用单壁碳纳米管(SWNTs)自身的还原性, 将PdCl2溶液中的Pd2+直接还原成金属Pd负载在SWNTs表面上, 制备了具有良好催化性能的Pd/SWNTs负载型催化剂. 通过透射电镜(TEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)和热重分析(TG)对Pd/SWNTs 进行了表征, 并利用Suzuki反应对Pd/SWNTs的催化性能进行了测试. 实验结果表明, 用SWNTs与12 mmol·L-1的PdCl2的水溶液直接作用, 得到Pd/SWNTs催化材料的Pd负载量达到14.13%(w, 质量分数), 颗粒分散均匀, 粒径小(2 nm左右), 与SWNTs结合紧密; 用经过H2还原的Pd/SWNTs作催化剂, 在90 ℃下进行Suzuki反应, 30 min后反应就基本完成, 其联苯的产率达到98.10%, 催化活性较高, 可望广泛用于有机合成反应.     

Selective host-guest interaction of single-walled carbon nanotubes with functionalised fullerenes

Exohedrally functionalised fullerenes have been inserted in single-walled carbon nanotubes (SWNTs) with the aid of supercritical carbon dioxide to form peapods; C(61)(COOEt)(2) are encapsulated in SWNTs in high yield, whereas C(61)(COOH)(2) aggregate via hydrogen bonding to form a supramolecular complex, which sterically hinders encapsulation and causes it to adhere to the exterior surface of the SWNTs.     

Selective visualization of point defects in carbon nanotubes at the atomic scale by an electron-donating molecular tip

Electron-donating molecular tips were used for the observation of single-walled carbon nanotubes (SWNTs). Defects in SWNTs were selectively visualized at the atomic scale on the basis of charge-transfer interaction with the molecular tip.     

Selective interactions of porphyrins with semiconducting single-walled carbon nanotubes

A derivatized porphyrin with long alkyl chains, 5,10,15,20-tetrakis(hexadecyloxyphenyl)-21H,23H-porphine, is selective toward semiconducting single-walled carbon nanotubes (SWNTs) in presumably noncovalent interactions, resulting in significantly enriched semiconducting SWNTs in the solubilized sample and predominantly metallic SWNTs in the residual solid sample according to Raman, near-IR absorption, and bulk conductivity characterizations.     

Cobalt-filled apoferritin for suspended single-walled carbon nanotube growth with narrow diameter distribution

Cobalt-filled apoferritin (Co-ferritin) was, for the first time, used as a wet catalyst for the synthesis of single-walled carbon nanotubes (SWNTs) with narrow diameter distribution. Co-ferritins were spin-coated and converted to cobalt nanoparticles by calcination. Using chemical vapor deposition, suspended networks of SWNTs were formed on pillar-structured substrates. The suspended SWNTs show narrow tube diameter distribution with a relatively good graphite structure. By virtue of the low diffusion coefficient of cobalt, Co-ferritin might be more useful for narrow diameter SWNTs growth than ferritins, which encase iron particles.     

Electrocatalytic oxidation of hydrazine at a chromium hexacyanoferrate/single-walled carbon nanotube modified glassy carbon electrode

Microchimica Acta - A novel route is presented for the fabrication of chromium (III) hexacyanoferrate(II) (Crhf) nanoparticles attached to single-walled carbon nanotubes (SWNTs) modified glassy...     

Thermally and molecularly stimulated relaxation of hot phonons in suspended carbon nanotubes

The high-bias electrical transport properties of suspended metallic single-walled carbon nanotubes (SWNTs) are investigated at various temperatures in vacuum, in various gases, and when coated with molecular solids. It is revealed that nonequilibrium optical phonon effects in suspended nanotubes decrease as the ambient temperature increases. Gas molecules surrounding suspended SWNTs assist the relaxation of hot phonons and afford enhanced current flow along nanotubes. Molecular solids of carbon dioxide frozen onto suspended SWNTs quench the nonequilibrium phonon effect. The discovery of strong environmental effects on high current transport in nanotubes is important to high performance nanoelectronics applications of 1D nanowires in general.     

Synthesis of nearly uniform single-walled carbon nanotubes using identical metal-containing molecular nanoclusters as catalysts

Uniform and small-diameter single-walled carbon nanotubes (SWNTs) have been produced using identical molecular nanoclusters containing Fe and Mo atoms with a defined molecular formula and a specific structure as catalysts in a chemical vapor deposition method. The average diameter of the SWNTs produced in these experiments is 1.0 nm with a standard deviation for the diameter distribution of 17%. The diameters of SWNTs were obtained by atomic force microscopy and Raman spectroscopy.