One-pot synthesis of Pt/carbon nanotubes by self-regulated reduction for electrocatalysis

This paper describes a method for size-controlled synthesis of Pt nanoparticles and their attachment to the sidewalls of multiwall carbon nanotubes (CNTs) by self-regulated reduction of sodium n-dodecyl sulfate (SDS), without surface pretreatment. The size of the Pt nanoparticles is controlled by adjusting the concentration of SDS. When Pt/CNTs are heated to 500 degrees C in N2 atmosphere, Pt nanochains are formed on the CNTs; some of these nanochains contain small islands. Electrochemical measurements confirm that the electroactivities of the Pt/CNT nanocatalysts increase with a decrease in the size of the Pt nanoparticles. Additionally, comparing with the heated Pt/CNT nanocatalysts containing smooth Pt nanochains, the heated Pt/CNT nanocatalysts containing Pt nanochains with small Pt islands show higher electrocatalysis activities and stability.     

Fabrication of PtNi bimetallic nanoparticles supported on multi-walled carbon nanotubes

Platinum/nickel bimetallic nanoparticles supported on multi-walled carbon nanotubes (xPtNi/CNTs) were synthesised. The fabrication process includes the chemical modification on the graphene surface of CNTs by acid treatment and the subsequent deposition of Pt or PtNi bimetallic nanoparticles with different compositions of Pt (x = 100, 90, 80 and 70 wt%). The deposition was carried out using ethylene glycol as a reducing agent in the polyol method or using poly(amidoamine) dendrimer as a platform and sodium borohydride as a reducing agent to load the metal nanoparticles on the CNT surface. The structures of the produced PtNi/CNT nanoparticles were investigated by ultraviolet absorption spectra, X-ray diffraction (XRD) and the composite ratio consisting of 70 wt% of metal content and 30 wt% of CNTs was confirmed by the thermogravimetric analysis. The morphology and the phase identification of the produced PtNi/CNT nanoparticles were investigated by high-resolution scanning electron microscope, transmission electron microscope and XRD measurements. It was observed that the deposited Pt and PtNi bimetallic nanoparticles on the surface of CNTs had average particle sizes of 2–16 nm, when they were prepared from the polyol method. On the other hand, the PtNi/CNT nanoparticles prepared by using a dendrimer as an intermediate had a smaller particle size and more uniform size distribution of the quantum dot size ranged from 2 to 4 nm.     

Synthesis of multi-walled carbon nanotube/silver nanocomposite powders by chemical reduction in aqueous solution

Carbon nanotube (CNT)/silver nanocomposite powders with different volume fractions of CNTs 2.5, 5 and 10?vol.% were prepared by chemical reduction in solution. Multi-walled CNTs underwent surface modifications for functionalisations by acid treatments. The acid-treated CNTs were investigated by FT-IR and X-ray photoelectron spectroscopy. The spectroscopic investigations of the acid-functionalised CNTs detected that several kinds of functional groups attached with the graphene structure as well as produced short and de-caped CNTs. Acidic stannous chloride solution was used to sensitise the surface of the functionalised CNTs. Silver was deposited on the surface of sensitised CNTs with chemical reduction reaction of alkaline silver nitrate solution by formaldehyde at room temperature and pH?～?9. The morphology of the produced CNT/silver nanocomposite powder was investigated by high-resolution SEM and TEM. It was observed that the produced CNT/silver nanocomposite powders have decorated type of spherical silver particle size 2–5?nm deposited on the surface of CNTs as well as the CNTs were implanted in large spherical silver nanoparticles of particle size ～200?nm. The chemical analysis of the produced powder indicates that some oxygen content is included in the prepared powders which can be reduced by heat treatment at temperatures between 300°C and 400°C under hydrogen atmosphere.     

Polyelectrolyte functionalized carbon nanotubes as a support for noble metal electrocatalysts and their activity for methanol oxidation

A highly effective polyelectrolyte functionalization of multi-walled carbon nanotubes (MWCNTs) by poly(diallyldimethylammonium chloride) (PDDA-MWCNTs) was employed for low temperature fuel cell applications. PDDA-MWCNTs were employed as support materials for the in?situ deposition and formation of platinum nanoparticles, via the self-assembly between the negative Pt precursor and positively charged functional groups of PDDA-functionalized MWCNTs. The effect of the functionalization on the deposition and distribution of Pt nanoparticles was investigated in detail. Compared with MWCNTs functionalized by conventional acid-oxidation treatment (AO-MWCNTs), the PDDA-functionalized MWCNTs cause no structural damage on MWCNTs and provide high density and homogeneous surface functional groups for the anchoring Pt nanoparticles. Pt nanoparticles with an average particle size of 1.8 ± 0.4?nm and loading as high as 60?wt% were realized on PDDA-MWCNTs supports. The Pt/PDDA-MWCNTs electrocatalysts show significantly higher electrochemically active surface area and higher electro-catalytic activity for methanol oxidation than that of Pt/AO-MWCNTs and E-TEK Pt/C electrocatalysts.     

Electrochemical biosensing platforms using platinum nanoparticles and carbon nanotubes

Platinum nanoparticles with a diameter of 2-3 nm were prepared and used in combination with single-wall carbon nanotubes (SWCNTs) for fabricating electrochemical sensors with remarkably improved sensitivity toward hydrogen peroxide. Nafion, a perfluorosulfonated polymer, was used to solubilize SWCNTs and also displayed strong interactions with Pt nanoparticles to form a network that connected Pt nanoparticles to the electrode surface. TEM and AFM micrographs illustrated the deposition of Pt nanoparticles on carbon nanotubes whereas cyclic voltammetry confirmed an electrical contact through SWCNTs between Pt nanoparticles and the glassy carbon (GC) or carbon fiber backing. With glucose oxidase (GOx) as an enzyme model, we constructed a GC or carbon fiber microelectrode-based biosensor that responds even more sensitively to glucose than the GC/GOx electrode modified by Pt nanoparticles or CNTs alone. The response time and detection limit (S/N = 3) of this biosensor was determined to be 3 s and 0.5 microM, respectively.     

Catalytic performance of acid-treated multi-walled carbon nanotube-supported platinum catalyst for PEM fuel cells

Effects of the surface functional groups of multi-walled carbon nanotubes (MWCNTs) as catalyst support for the durability of polymer electrolyte membrane fuel cells (PEMFCs) were examined at high Pt loading conditions. The amount of oxygen functional groups on the MWCNTs surface was increased as the acid treatment time and temperature increased. We found that more functional groups in MWCNTs improved initial Pt dispersion but deteriorated durability due to the reduced carbon corrosion resistance. The experimental results also showed that despite the surface oxidation, Pt/MWCNT catalysts showed highly improved durability than Pt/C catalysts due to the graphitic nature of MWCNTs. Membrane electrode assembly (MEA) fabricated by 4 h acid treated MWCNTs at 25 °C showed 4 times better durability than commercial Pt/C based MEA at the reverse potential operation generated by fuel starvation conditions. We believe that MWCNTs can be effectively used for PEMFCs even at high loading due to their excellent anti-corrosion properties.     

Electrochemically functionalized carbon nanotubes and their application to rechargeable lithium batteries

Electrochemical polymerization of N-vinyl carbazole (VC) on carbon nanotube (CNT) films was studied by cyclic voltammetry (CV) in LiClO4/acetonitrile solutions. Comparing the cyclic voltammograms recorded on a blank Pt electrode with those obtained when single- or multi-walled carbon nanotube (SWNT or MWNT) films were previously deposited onto the Pt electrode, a downshift of the VC reduction peak potential is observed in the latter case. The influences of monomer concentration, type of solvent, and supporting electrolyte on the polymerization conditions and electrochemical properties of these composite materials are also investigated. The morphological aspects of poly(N-vinyl carbazole) (PVC)-functionalized CNTs are revealed by transmission electron microscopy (TEM) studies. A covalent functionalization of carbon nanotubes with PVC is invoked as a result of attenuated total reflection infrared (ATR-IR) spectroscopic studies. Using PVC-functionalized CNTs as a positive electrode and an electrolytic solution containing LiPF6, the charge-discharge characteristics of the rechargeable lithium cells are determined. High specific discharge capacity (approximately 45 and 115 mA h g(-1)) is reported for PVC-functionalized single- and multi-walled carbon nanotubes, respectively.     

Fabrication of nanocomposites based on carbon nanotubes containing Pt nanoparticles and TiO<Subscript>2</Subscript>

Using conical multiwalled carbon nanotubes (CNTs), we have prepared Pt/CNT and Pt/TiO₂/CNT nanocomposites with an average platinum particle size of 3–5 nm, Pt/Ti molar ratio on the surface in the range 3.5–4, and C/Pt = 21–22. Titania was deposited onto the CNTs through titanium tetrachloride (TiCl₄) hydrolysis. Platinum particles were produced by reducing chloroplatinic acid (H₂PtCl₆) with sodium borohydride (NaBH₄) in the presence of CNTs. The composition and structure of the composites have been studied using X-ray photoelectron spectroscopy, electron microscopy, X-ray diffraction, and thermogravimetry. The materials have been tested as catalysts for hydrogen oxidation and oxygen reduction. The results demonstrate that the modification of Pt/CNT with titania enhances the catalytic activity of the material.     

碳纳米管在超级电容器中的应用研究进展

超级电容器是近年来发展起来的一种新型储能装置。碳纳米管由于具有独特的中空结构，良好的导电性和高的比表面积，被认为是超级电容器理想的电极材料之一，引起了广泛的关注。通过介绍碳纳米管在超级电容器中的应用研究进展，评述了碳纳米管、活化碳纳米管、碳纳米管／金属氧化物复合物以及碳纳米管／导电聚合物复合物用做超级电容器电极材料的特点和性能。认为单纯的碳纳米管由于比表面积小，比容量偏低。化学活化可以显著提高碳纳米管的比表面积，增大其比电容。将碳纳米管与准电容材料金属氧化物或导电聚合物复合。可以发挥各自的优势，从而得到低成本、高性能的复合电极材料，将是今后发展的一个方向。     

Magnetic carbon nanotubes with particle-free surfaces and high drug loading capacity

Open-ended, multi-wall carbon nanotubes (CNTs) with magnetic nanoparticles encapsulated within their graphitic walls (magCNTs) were fabricated by a combined action of templated growth and a ferrofluid catalyst/carbon precursor, and tested as drug hosts. The hybrid nanotubes are stable under extreme pH conditions due to particle protection provided by the graphitic shell. The magCNTs are promising for high capacity drug loading given that the magnetic functionalization did not block any of the active sites available for drug attachment, either from the CNT internal void or on the internal and external surfaces. This is in contrast to typical approaches of loading CNTs with particles that proceed through surface attachment or capillary filling of the tube interior. Additionally, the CNTs exhibit enhanced hydrophilic character, as shown by water adsorption measurements, which make them suitable for biological applications. The morphological and structural characteristics of the hybrid CNTs are evaluated in conjunction to their magnetic properties and ability for drug loading (diaminophenothiazine). The fact that the magnetic functionality is provided from 'inside the walls' can allow for multimode functionalization of the graphitic surfaces and makes the magCNTs promising for targeted therapeutic applications.     

Functionalization of carbon nanotubes with magnetic nanoparticles: general nonaqueous synthesis and magnetic properties

A novel approach has been developed to synthesize magnetic nanoparticle and carbon nanotube (CNT) core-shell nanostructures, such as CoO/CNTs and Mn(3)O(4)/CNTs, by the nonaqueous solvothermal treatment of metal carbonyl on CNT templates using hexane as the solvent. The morphological and structural characterizations indicate that numerous cubic CoO or tetragonal Mn(3)O(4) nanoparticles are deposited on the surfaces of the CNTs to form CNT-based core-shell nanostructures. It is revealed that the hydrophobic interaction between nanoparticles and CNTs in hexane plays the critical role for the formation of CNT-based core-shell nanostructures. A physical property measurement system (PPMS-9, Quantum Design) analysis indicates that the CoO/CNT core-shell nanostructures show weak ferromagnetic performance at 300?K due to the ferromagnetic Co clusters and the uncompensated surface spin states, while the Mn(3)O(4)/CNT core-shell nanostructures display ferromagnetic behavior at low temperature (34.5?K), which transforms into paramagnetic behavior with increasing temperature.     

Single-step high-speed nanogranulation of metal alloy around carbon nanotubes by flash light irradiation

We demonstrate to decorate carbon nanotubes (CNTs) with metal alloy nanoparticles by flash light from a xenon lamp highlighting dramatically simplified process and ultrafast speed of millisecond. By managing the pulse energy of the irradiation, we customize the nucleation and growth rates of homogeneous binary and ternary nanoparticles with Pt–Ru and Pt–Ru–Mo thin layers that are e-beam deposited onto CNTs. No damage of CNTs during the light-induced nanogranulation is guaranteed by the rapid and surface-localized heating mechanism. The fabricated nanoparticle/CNT nanostructures are characterized using variety of microscopic and spectroscopic techniques such as SEM, TEM and Raman spectroscopy.     

Neural stimulation with a carbon nanotube microelectrode array

We present a novel prototype neural interface using vertically aligned multiwalled carbon nanotube (CNT) pillars as microelectrodes. Functionalized hydrophilic CNT microelectrodes offer a high charge injection limit (1-1.6 mC/cm2) without faradic reactions. The first repeated in vitro stimulation of hippocampal neurons with CNT electrodes is demonstrated. These results suggest that CNTs are capable of providing far safer and more efficacious solutions for neural prostheses than previous metal electrode approaches.     

Multi-branching carbon nanotubes via self-seeded catalysts

A novel multi-branching carbon nanotube (CNT) structure is synthesized by direct current plasma enhanced chemical vapor deposition. The structure consists of aligned CNTs which have branches of smaller diameters growing aligned along a direction perpendicular to the original CNT. The mechanism of branching is explained in terms of a self-seeding of Ni catalyst which is transferred by sputtering from the original catalyst particles in the backbone CNTs to the walls of those CNTs. It is also shown that the branching induced a large increase in surface area and total nanotube length and can be beneficial in supporting very fine Pt nanoparticles for fuel cell and other catalytic applications. Such an array of Y-junction nanostructures could be useful for the fabrication of a high-density array of nanoelectronics switches and transistors.     

Dispersion of metal nanoparticles on carbon nanotubes with few surface oxygen functional groups

Homogeneous dispersion of metal oxide nanoparticles was achieved on carbon nanotubes (CNTs) even with a very small amount of surface oxygen functional groups (SOFGs) aided by using ethylene glycol (EG) and sodium hydroxide during the process. Similar particle size distributions were obtained for iron deposited on CNTs containing various amounts of SOFGs. We proposed that formation of hydrogen bonds between EG on the CNT surface and sodium hydroxide is likely responsible, which creates precipitating sites for iron ions on the CNT surface. This facile method is expected to find applications not only for catalysis but also in the fields such as sensors and magnetic materials in particular where a perfect sp² hybridized carbon structure is preferred.     

SnO2 nanoparticles distributed on multi-walled carbon nanotubes and ball-milled graphite as anode materials of lithium ion batteries

SnO2 nanoparticles were supported on ball-milled graphite (BMG) or carbon nanotubes (CNTs) using a chemical reduction method with ethylene glycol, and the electrochemical properties of the nanocomposites were evaluated as anode active materials of lithium-ion batteries. The BMG and CNTs contributed to an increase in both the capacity enhancement and cyclic stability compared to that of commercial graphite. In particular, the mixture electrode of SnO2/BMG:SnO2/CNT = 3:1 (in weight ratio) showed higher performance in the reversible capacity and cyclic stability than did the SnO2/BMG and SnO2/CNT electrodes. This might be resulted from the network formation for excellent electronic path by CNT distributed on SnO2/BMG composites.     

Hydrothermal Coating of Patterned Carbon Nanotube Forest for Structured Lithium‐Ion Battery Electrodes

Controlling the arrangement and interface of nanoparticles is essential to achieve good transfer of charge, heat, or mechanical load. This is particularly challenging in systems requiring hybrid nanoparticle mixtures such as combinations of organic and inorganic materials. This work presents a process to coat vertically aligned carbon nanotube (CNT) forests with metal oxide nanoparticles using microwave‐assisted hydrothermal synthesis. Hydrothermal processes normally damage delicate CNT forests, which is addressed here by a combination of lithographic patterning, transfer printing, and reduction of the synthesis time. This process is applied for the fabrication of structured Li‐ion battery (LIB) electrodes where the aligned CNTs provide a straight electron transport path through the electrode and the hydrothermal coating process is used to coat the CNTs with conversion anode materials for LIBs. These nanoparticles are anchored on the surface of the CNTs and batteries fabricated following this process show a fourfold longer cyclability. Finally, this process is used to create thick electrodes (350 µm) with a gravimetric capacity of over 900 mAh g^?1.     

Electrochemical detection of nitrite based on the polythionine/carbon nanotube modified electrode

In this paper, thionine was electro-polymerized onto the surface of carbon nanotube (CNT)-modified glassy carbon (GC) to fabricate the polythionine (PTH)/CNT/GC electrode. It was found that the electro-reduction current of nitrite was enhanced greatly at the PTH/CNT/GC electrode. It may be demonstrated that PTH was used as a mediator for electrocatalytic reduction of nitrite, and CNTs as an excellent nanomaterial can improve the electron transfer between the electrode and nitrite. Therefore, based on the synergic effect of PTH and CNTs, the PTH/CNT/GC electrode was employed to detect nitrite, and the high sensitivity of 5.81 μA mM^− 1, and the detection limit of 1.4 × 10^− 6 M were obtained. Besides, the modified electrode showed an inherent stability, fast response time, and good anti-interference ability. These suggested that the PTH/CNT/GC electrode was favorable and reliable for the detection of nitrite.     

Effect of carbon nanotubes support on band gap energy of MgO nanoparticles

In this study, the effect of carbon nanotube supports (CNT) on the morphology and band gap of MgO nanoparticles was studied. The synthesis of MgO nanoparticles on the surface of CNT supports was carried out by direct precipitation method and using magnesium nitrate in aqueous solutions containing CNT. The prepared samples were characterized using X-ray diffraction. The optical properties of the nanoparticles were studied using UV–Vis spectrometer. The results indicated that the presence of CNTs decrease the average size of the MgO nanoparticles. Also the use of CNTs as support has reduced the band gap energy of MgO nanoparticles, considerably.     

Drying induced upright sliding and reorganization of carbon nanotube arrays

Driven by capillary force, wet carbon nanotube (CNT) arrays have been found to reorganize into cellular structures upon drying. During the reorganization process, individual CNTs are firmly attached to the substrate and have to lie down on the substrate at cell bottoms, forming closed cells. Here we demonstrate that by modifying catalyst structures, the adhesion of CNTs to the substrate can be weakened. Upon drying such CNT arrays, CNTs may slide away from their original sites on the surface and self-assemble into cellular patterns with bottoms open. It is also found that the sliding distance of CNTs increases with array height, and drying millimetre tall arrays leads to the sliding of CNTs over a few hundred micrometres and the eventual self-assembly into discrete islands. By introducing regular vacancies in CNT arrays, CNTs may be manipulated into different patterns.