Hybrids of carbon nanotubes and graphene/graphene oxide

This paper reviews recent progress in hybrids based on carbon nanotubes (CNTs) and graphene (G) or graphene oxide (GO). The combination of CNTs, including single-walled (SW), double-walled (DW) and multi-walled (MW), and G or GO resulted in various hybrids. CNTs–G/GO hybrid thin films are usually prepared by using solution/suspension casting and layer-by-layer (LbL) deposition, free-standing sheets are fabricated by using vacuum filtration and 3D hierarchical structures are produced by using chemical vapor deposition (CVD). CNTs–G/GO hybrids have also been used as fillers to fabricate polymer composites with synergistic effects. The composites have significantly improved electrical, mechanical and thermal properties, which make them very useful for various potential applications, such as transparent electrodes replacing ITO, electrodes for supercapacitors, lithium-ion batteries and dye-sensitized solar cells.     

Effect of Co and Ni nanoparticles formation on carbon nanotubes growth via PECVD

The effect of cobalt (Co) and nickel (Ni) nanoparticle catalysts on the growth of carbon nanotubes (CNTs) were studied, where the CNTs were vertically grown by plasma enhanced chemical vapour deposition (PECVD) method. The growth conditions were fixed at a temperature of 700 °C with a pressure of 1000 mTorr for 40 minutes with various thicknesses of sputtered metal catalysts. Only multi-walled carbon nanotubes are present from the growth as large average diameter of outer tube (～10–30 nm) were measured for both of the catalysts used. Experimental results show that high density of CNTs was observed especially towards thicker catalysts layers where larger and thicker nanotubes were formed. The nucleation of the catalyst with various thicknesses was also studied as the absorption of the carbon feedstock is dependent on the initial size of the catalyst island. The average diameter of particle size increases from 4 to 10 nm for Co and Ni catalysts. A linear relationship is shown between the nanoparticle size and the diameter of tubes with catalyst thicknesses for both catalysts. The average growth rate of Co catalyst is about 1.5 times higher than Ni catalyst, which indicates that Co catalyst has a better role in growing CNTs with thinner catalyst layer. It is found that Co yields higher growth rate, bigger diameter of nanotube and thicker wall as compared to Ni catalyst. However, variation in Co and Ni catalysts thicknesses did not influence the quality of CNTs grown, as only minor variation in I_G/I_D ratio from Raman spectra analysis. The study reveals that the catalysts thickness strongly affects not only nanotube diameter and growth rate but also morphology of the nanoparticles formed during the process without influencing the quality of CNTs.     

Deposition of metal nanoparticles on carbon nanotubes via hexane modified water-in-CO2 microemulsion at room temperature

Carbon nanotube-supported metallic nanoparticles (Pd, Rh, and bimetallic Pd-Rh) with diameters in the range 2-10 nm can be synthesized by hydrogen reduction of metal ions dissolved in the water core of a CO2 microemulsion in liquid CO2 at room temperature. The microemulsion is stabilized by sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and dissolved in liquid CO2 with the aid of hexane as a modifier. The metal nanoparticles synthesized in the microemulsion can be deposited on surfaces of multi-walled carbon nanotubes (MWCNTs) by stirring in the liquid CO2 phase. This simple method produces uniformly distributed metal nanoparticles on surfaces of the MWCNTs with high yields. The carbon nanotube-supported Pd/Rh bimetallic nanoparticles exhibit high catalytic activities for hydrogenation of aromatic compounds and can be reused without losing catalytic activity.     

Functionalization of carbon nanotubes via dissolving metal reductions

In this study we present direct sidewall functionalization of single-walled nanotubes, carried out via two different dissolving metal reduction methods. A modified Birch reduction scheme and a novel synthetic route were applied to form carbanion complexes on the surface of the nanotubes in liquid NH3 and tetrahydrofuran, respectively. The carbanion complex was reacted with a series of alkyl and aryl halogenides resulting in the corresponding SWNT derivatives. We determined the chemical composition and the thermal stability of the functionalized nanotubes by thermogravimetry/mass spectrometry and pyrolysis-gas chromatography. Characteristic decomposition peaks, observed in the temperature range of 350-600 degrees C, suggest the formation of covalent derivatives upon functionalization that is also supported by Raman spectroscopic studies. The influence of the functional groups and the type of nanotubes on the thermal stability, as well as the relationship between the functional group content and the intensity of the Raman D peak are discussed.     

Loading behavior of Pt nanoparticles on the surface of multiwalled carbon nanotubes having defects formed via microwave treatment

We developed a simple and efficient method to load Pt nanoparticles (NPs) uniformly on defects generated in multiwalled CNTs (MWCNTs) without using reduction agents or organic reagents. Defects on the surfaces of MWCNTs were artificially generated by microwave treatment at various exposure times. Nucleation of Pt NPs occurs on the defect sites spontaneously due to an innate electropotential difference. Because of the correlation between defects and Pt NPs, we were able to control the size of Pt NPs by changing defect size, quantity and distribution, which was confirmed by Raman spectroscopy and TEM. After microwave treatment for 3 min, more uniform and smaller Pt NPs were observed. Also, the defects via microwave treatment make adhesion of Pt NPs stronger, which can be helpful to improve the reliability for applications. Finally, the methanol oxidation behavior of MWCNTs with Pt NPs was examined by cyclic voltammetry (CV).     

Interfacial resistive heating and mechanical properties of graphene oxide assisted CuO nanoparticles in woven carbon fiber/polyester composite

Woven carbon fiber (WCF)-based polyester composites were developed via a vacuum-assisted resin transfer molding (VARTM) process in combination with CuO and graphene oxide (GO). The interlaminar resistive heating behavior and allied mechanical properties of the composites were investigated. The CuO nanoparticles were synthesized from copper nitrate and hexamethylenetetramine precursors using traditional microwave green synthesis, while the GO was synthesized by slight modification of Hummer’s method. The nanoparticle shapes and sizes were assessed via scanning electron microscopy, and the nanoparticle distributions in the composites and their chemical interactions were examined using X-ray diffraction and Fourier transform infrared spectroscopy. It was found that the composite strengths and moduli were enhanced by up to 61.2% and 57.5%, whereas the interfacial shear strength was enhanced by 89.9%. A composite filled with 120-mM CuO and 1.2-phr GO exhibited maximum performance as regards mechanical and resistive heating. Impact resistance measurements were conducted at 3-J penetration energy, and a 154.2% increase in nanofiller content was achieved. The addition of CuO nanoparticles increased the interlaminar resistive heating of the composite and, at 120-mM concentration, a 78.9% increment in the average temperature was attained. The presence of nanoparticles in the interlaminar region also decelerated the cooling process.     

TEM characterization of metal and metal oxide particles supported by multi-wall carbon nanotubes

Composites of Sn–Pd particles and multi-walled carbon nanotubes (MWNTs), and of Ni–Co particles and MWNTs were investigated by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The Sn–Pd particle composites were prepared by impregnation deposition, and the Ni–Co particle composites were prepared by electroless deposition on MWNTs synthesized by a chemical vapor deposition method using thermal catalytic decomposition of hydrocarbon. The morphologies and the microstructure of the deposited particles were investigated upon annealing the composites with and without hydrogen. Both the crystalline particle structure and the particle morphology are observed to be different for the samples annealed with and without hydrogen.     

Observation and formation mechanism of individual graphene foils inside multi-walled carbon nanotubes

The formation of individual graphene foils (GF) has been evidenced in the present study inside multi-walled carbon nanotubes. The graphene foils are attached on one side to a catalyst nanoparticle and on the other side to the internal walls of the nanotube. Moreover, results suggest that a necking process occurs in which internal carbon walls are deformed until formation of the graphene foil. A possible mechanism for the GF formation is then proposed.     

Sulfur nanoparticles encapsulated in reduced graphene oxide nanotubes for flexible lithium-sulfur batteries

Rapid development of flexible electronic devices is promoting the design of flexible energy-storage devices. Lithium-sulfur (Li-S) batteries are considered as promising candidates for high energy density energy-storage devices. Therefore, flexible Li-S batteries are desired. In this study, we fabricated composite films of freestanding reduced graphene oxide nanotubes wrapped sulfur nanoparticles (RGONTs@S) by pressing RGONTs@S composite foams, which were synthesized by combining cold quenching with freeze-drying and a subsequent reduction process. These RGONTs@S composite films can serve as self-supporting cathodes for Li-S batteries without additional binders and conductive agents. Their interconnected tubular structure allows easy electron transport throughout the network and helps to confine the polysulfides produced during the charge/discharge process. As a result, the RGONTs@S composite films exhibited a high initial specific capacity, remarkable cycling stability, and excellent rate capability. More importantly, the RGONTs@S composite films can serve as electrodes in flexible Li-S batteries. As a proof of concept, soft-packaged Li-S batteries were assembled using these electrodes and they displayed stable electrochemical performance at different bending states.

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Facile synthesis of porous hollow iron oxide nanoparticles supported on carbon nanotubes

Porous hollow iron oxide nanoparticles (PHNPs) supported on carbon nanotubes (CNTs) were facilely synthesized by etching Fe@Fe_xO_y/CNT with dilute nitric acid aqueous solution at ambient temperature without the assistance of any surfactants and ligands. The mean diameter of hollow iron oxide nanoparticles was about 17 nm, with a wall thickness of about 4 nm. The formation mechanism of PHNPs is discussed based on the characterization results from TEM, XRD and H₂-TPR. The combination of nanoscale Kirkendall effect and selective acid etching is proposed to be responsible for the formation of CNT supported PHNPs, through a transformation from core/void/shell structures to hollow nanoparticles.     

Self-assembly-induced formation of high-density silicon oxide memristor nanostructures on graphene and metal electrodes

We report the direct formation of ordered memristor nanostructures on metal and graphene electrodes by a block copolymer self-assembly process. Optimized surface functionalization provides stacking structures of Si-containing block copolymer thin films to generate uniform memristor device structures. Both the silicon oxide film and nanodot memristors, which were formed by the plasma oxidation of the self-assembled block copolymer thin films, presented unipolar switching behaviors with appropriate set and reset voltages for resistive memory applications. This approach offers a very convenient pathway to fabricate ultrahigh-density resistive memory devices without relying on high-cost lithography and pattern-transfer processes.     

用于制备优质单壁碳纳米管管束的MgO负载Fe3O4纳米粒子的合成

采用沉淀方法制备了直径分布狭窄的均匀Fe3O4纳米颗粒.Fe3O4纳粒形体几近一致,平均粒径为10.33 nm±2.99 nm(平均粒径±标准偏差).在超声作用下将MgO纳米颗粒分散在一定量Fe3O4纳米颗粒的水溶液中获得MgO负载Fe3O4的纳米颗粒.以甲烷为碳源,Fe3O4/MgO为催化剂,经化学气相沉积,在Fe3O4纳粒上制得了大量直径近乎均匀的单壁碳纳米管(SWCNTs)束.TEM显示:SWCNTs的平均直径1.22rm.热重分析显示:样品在400℃～600℃温度区间失重量约19％.拉曼光谱显示:SWCNTs的ID/IG的强度比为0.03,表明采用Fe3O4/MgO催化剂可制得高石墨化程度的单壁碳纳米管.     

The formation of magnetite nanoparticles on the sidewalls of multi-walled carbon nanotubes

Linear polyethyleneimine (PEI) was used as a non-covalent functionalizing agent to modify multi-walled carbon nanotubes (MWCNTs). Fe₃O₄ nanoparticles were then formed along the sidewalls of the as-modified MWCNTs through a simple solvothermal method. X-ray diffraction, Fourier transform infrared spectrometry, transmission electron microscopy, and vibrating sample magnetometry were used to characterize the MWCNT/Fe₃O₄ nanocomposites. Results indicated that Fe₃O₄ nanoparticles with diameters ranging from 50 to 200 nm were attached to the surface of the MWCNTs by electrostatic interaction. PEI was found to improve the electrical conductivity of the MWCNT/Fe₃O₄ nanocomposites. The magnetic saturation value of these magnetic nanocomposites was 61.8 emu g⁻¹. These magnetic MWCNT/Fe₃O₄ nanocomposites are expected to have wide applications in bionanoscience and technology.     

Deposition of metallic nanoparticles on carbon nanotubes via a fast evaporation process

A new technique was developed for the deposition of colloidal metal nanoparticles on carbon nanotubes. It involves fast evaporation of a suspension containing sonochemically functionalized carbon nanotubes and colloidal nanoparticles. It was demonstrated that metallic nanoparticles with different sizes and concentrations can be deposited on the carbon nanotubes with only a few agglomerates. The technique does not seem to be limited by what the nanoparticles are, and therefore would be applicable to the deposition of other nanoparticles on carbon nanotubes. PtPd and CoPt(3) alloy nanoparticles were used to demonstrate the deposition process. It was found that the surfactants used to disperse the nanoparticles can hinder the nanoparticle deposition. When the nanoparticles were washed with ethanol, they could be well deposited on the carbon nanotubes. The obtained carbon nanotube supported metal nanoparticles were characterized by transmission electron microscopy, energy dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, and cyclic voltammetry.     

还原氧化石墨烯/碳纳米管透明导电薄膜的制备及性能研究

使用天然植物多酚——单宁酸(TA)作为氧化石墨烯(GO)的还原剂,通过"一步法"实现了对GO的绿色还原和功能化.随后,将TA还原氧化石墨烯(RGO)和碳纳米管(SWCNT)结合起来,共同构筑具有三维结构的石墨烯/单壁碳纳米管(RGO/SWCNT)透明导电薄膜(TCFs).该薄膜有着良好的导电性(透光率为75.1％时,面...     

Divacancies in graphene and carbon nanotubes

Divacancies are among the most important defects that alter the charge transport properties of single-walled carbon nanotubes (SWNT), and we here study, using ab initio calculations, their properties. Two structures were investigated, one that has two pentagons side by side with an octagon (585) and another composed of three pentagons and three heptagons (555777). We investigate their stability as a function of tube diameter, and calculate their charge transport properties. The 585 defect is less stable in graphene due to two broken bonds in the pentagons. We estimate that the 555777 becomes more stable than the 585 for a diameter of about 40 A (53 A) for an armchair (zigzag) SWNTs, indicating that they will prevail in large diameter multiwalled carbon nanotubes and graphene ribbons.     

Factors controlling the electrodeposition of metal nanoparticles on pristine single walled carbon nanotubes

The electrodeposition of metal (Pd and Pt) nanoparticles on networks of pristine single walled carbon nanotubes (SWNTs) has been investigated using a microelectrochemical cell. A microcapillary containing electrolyte solution and a reference electrode is contacted with a silicon oxide substrate bearing a SWNT network, connected as the working electrode. Electrodeposition is promoted by applying a potential between the SWNT network and the reference electrode. By combination of analysis of the resulting current-time curves with atomic force microscopy and field emission scanning electron microscopy imaging of the network surfaces after electrodeposition, the nature of metal nanoparticle formation on SWNTs has been elucidated. In particular, the parameters controlling nanoparticle number density, distribution, and size have been identified, with short deposition times and high driving forces favoring the formation of ultrasmall particles at high density. Capacitance and network resistance effects are minimized in the microcapillary configuration, making it possible to accurately analyze short time-scale deposition processes (millisecond time scale). Furthermore, it is also possible to make many measurements on a pristine sample, simply by moving the position of the microcapillary to a new location on the substrate.     

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.     

Reduced graphene oxide/metal oxide nanoparticles composite membranes for highly efficient molecular separation

Graphene oxide(GO) membranes play an important role in various nanofiltration applications including desalination, water purification, gas separation, and pervaporation. However, it is still very challenging to achieve both high separation efficiency and good water permeance at the same time. Here, we synthesized two kinds of GO-based composite membranes i.e. reduced GO(rGO)@MoO_2 and rGO@WO_3 by in-situ growth of metal nanoparticles on the surface of GO sheets. They show a high separation efficiency of ～100% for various organic dyes such as rhodamine B, methylene blue and evans blue, along with a water permeance over 125 Lm~(-2) h~(-1) bar~(-1). The high water permeance and rejection efficiency open up the possibility for the real applications of our GO composite membranes in water purification and wastewater treatment. Furthermore, this composite strategy can be readily extended to the fabrication of other ultrathin molecular sieving membranes for a wide range of molecular separation applications.