Controllable synthesis of single- and double-walled carbon nanotubes from petroleum coke and their application to solar cells

Single- and double-walled carbon nanotubes (SWCNTs and DWCNTs) have been controllably synthesized by an arc discharge in different atmosphere using petroleum coke as carbon source. The morphology and properties of two kinds of carbon nanotubes (CNTs) synthesized with Fe as catalyst were characterized by scanning electron microscopy, high-resolution transmission electron microscopy, Raman spectroscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, UV–visible spectroscopy, inductively coupled plasma optical emission spectrometer, thermogravimetric analysis and infrared spectroscopy. In the He gas atmosphere only SWCNTs were found to be synthesized by arc discharge in contrast to the case in Ar gas atmosphere in which only DWCNTs were formed, In addition, properties of solar cells based on both kinds of CNTs and n-type Si are examined under illumination of light emission diode (LED). It is found that the performance of solar cells depends significantly on the type of CNTs, i.e., SWCNTs-based solar cells show better performance under LED illumination with wavelengths in the range of 400–940 nm than the case of DWCNTs which exhibit high performance under illumination of the 1310 nm infrared light.     

Effects of nitrogen-doped carbon nanotubes on the discharge performance of Li-air batteries

Carbon nanotubes (CNTs) and nitrogen-doped carbon nanotubes (N-CNTs) were synthesized using a floating catalyst chemical vapor deposition method and characterized by scanning electron microscopy (SEM), transmission electron microscopy, Raman and X-ray photoelectron spectroscopy. The study found that the as-prepared CNTs and N-CNTs showed different discharge capacity as cathode materials in Li-air battery. To further study the reason why N-doping improves the electrochemical performance exceptionally, the discharge products on the two kinds of nanotubes were detected by SEM, XRD and Raman. SEM study showed, for the first time, that more uniform distribution of discharge products on the surface of CNTs arising from N-doping affected the boost of discharge capacity, a result which was discussed in detail. In comparison to non-doped CNTs, nitrogen doping was considered to be a promising way to improve the performance of carbon based cathode material for Li-air batteries.     

Ethylene diamine-grafted carbon nanotubes: A promising catalyst support for methanol electro-oxidation

In this paper, carbon nanotubes (CNTs) were modified by ethylene diamine (ED) and then used as the support of the Pt-Ru catalyst. The cyclic voltammetry (CV) and Fourier transform infrared spectroscopy were employed to study the interaction between ED and CNTs. The morphology and elemental composition of the as-prepared Pt-Ru/ED/CNT electrode were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. The electrocatalytic properties of the Pt-Ru/ED/CNT electrode for methanol electro-oxidation were investigated by CV, polarization method and electrochemical impedance spectroscopy. The long-term stability of the Pt-Ru/ED/CNT electrode was also evaluated. Compared with the Pt-Ru/CNT electrode, the Pt-Ru/ED/CNT electrode exhibits excellent electrocatalytic properties and long-term stability. These results show that the ED-grafted CNTs are the promising catalyst support for methanol electro-oxidation.     

以煤炭直接液化残渣为原料制备炭纳米管

以煤炭直接液化残渣为原料,采用直流电弧放电法成功制备出炭纳米管.采用扫描电子显微镜、透射电子显微镜、高分辨透射电镜以及X射线衍射等手段对炭纳米管的形貌和结构进行了表征.结果表明,所得直而长的多壁炭纳米管具有很好的石墨化程度;其长度达几微米,内径约80 nm,外径约120 nm;残留在液化残渣中的黄铁矿及液化过程中产生的磁黄铁矿对炭纳米管的形成有催化作用.     

Performance improvement of pasted nickel electrodes with multi-wall carbon nanotubes for rechargeable nickel batteries

Carbon nanotubes (CNTs) were employed as a functional additive to improve the electrochemical performance of pasted nickel-foam electrodes for rechargeable nickel-based batteries. The nickel electrodes were prepared with spherical β-Ni(OH)₂ powder as the active material and various amounts of CNTs as additives. Galvanostatic charge/discharge cycling tests showed that in comparison with the electrode without CNTs, the pasted nickel electrode with added CNTs exhibited better electrochemical properties in the chargeability, specific discharge capacity, active material utilization, discharge voltage, high-rate capability and cycling stability. Meanwhile, the CNT addition also lowered the packing density of Ni(OH)₂ particles in the three-dimensional porous nickel-foam substrate, which could lead to the decrease in the active material loading and discharge capacity of the electrode. Hence, the amount of CNTs added to Ni(OH)₂ should be optimized to obtain a high-performance nickel electrode, and an optimum amount of CNT addition was found to be 3 wt.%. The superior electrochemical performance of the nickel electrode with CNTs could be attributed to lower electrochemical impedance and less γ-NiOOH formed during charge/discharge cycling, as indicated by electrochemical impedance spectroscopy and X-ray diffraction analyses. Thus, it was an effective method to improve the electrochemical properties of pasted nickel electrodes by adding an appropriate amount of CNTs to spherical Ni(OH)₂ as the active material.     

Synthesis of vertically-aligned carbon nanotubes without a catalyst by hydrogen arc discharge

Vertically-aligned carbon nanotubes (CNTs) were prepared by hydrogen arc discharge, using pure graphite powder as carbon source without catalysts added. Scanning and transmission electron microscopy characterizations show that the aligned CNTs have a bamboo-like structure, and their lengths and diameters are about 30 μm and 40–60 nm, respectively. No metallic impurities can be detected in the samples by careful X-ray photoelectron spectroscopy detection. The activation of hydrogen radicals, the heating effect of the arc, and the electric field surrounding the arc column area are considered to play important roles for the non-catalyst growth of the CNTs.     

Electrochemical characteristics of boron doped polycrystalline diamond electrode sintered by high pressure and high temperature

The bulk B-doped polycrystalline diamond (PCD) electrode in this study was prepared by high-pressure, high-temperature (HPHT) technology. The PCD was sintered under HPHT conditions, using B-doped diamond powders and a metal catalyst as raw materials, then the metal solvent phase was dissolved by aqua regia. The morphology and composition of the PCD were investigated with a scanning electron microscope (SEM), X-ray diffraction (XRD), and energy dispersion spectrum (EDS). The results show that the sintered body possesses a polycrystalline structure with direct diamond–diamond bond and irregularly shaped pores of 1–10 μm distributed on the grain boundaries after the metal solvent phase was removed. The cyclic voltammogram and electrochemical impedance spectroscopy of this B-doped electrode have been investigated. The B-doped PCD electrode exhibits stable electrochemistry in a KCl support solution over a wide potential range. The quasi-reversible reaction occurs on the electrode for the [Fe(CN)₆]^3−/4− couples. The electrode process combines the diffusion-controlled mass transport plus the kinetic process. The electrochemical impedance spectroscopy (EIS) analysis shows the porous structure characteristic of the PCD electrode.     

直接和间接电合成制备出的高铁酸钾的物理和电化学性能

K2FeO4powders were synthesized by the ex-situ and in-situ electrochemical methods, respectively, and characterized by infrared spectrum (IR), scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and BET. Their electrochemical performances were investigated by means of galvanostatic discharge and electrochemical impedance spectroscopy (EIS). The results of physical characterization showed that the two samples have similar structural features, but their surface morphologies and oriented growth of the crystals are different, which results in smaller specific surface area and lower solubility of the ex-situ electrosynthesized K2FeO4 sample. The results of discharge experiments indicated that the ex-situ electrosythesized K2FeO4 electrode has much larger discharge capacity and lower electrode polarization than the in-situ electrosynthesized K2FeO4 electrode. It was found from the results of EIS that lower electrochemical polarization might be responsible for the improvement on the discharge performance of the ex-situ electrosynthesized K2FeO4 electrode.     

纳米铁/碳纳米管复合氧阴极电-Fenton降解RhB

制备了纳米铁/碳纳米管(Fe/CNTs)复合氧阴电极,通过SEM、EDS、XRD对电极进行了表征。基于该氧阴电极中性条件下电-Fenton降解Rhodamin B(RhB)溶液的试验表明,外加电压1.2 V、通入空气量0.1 m3/h、反应120 min、5mg/L的RhB溶液降解率达到92.1%,说明H2O2和离子态铁可以通过电化学还原在该氧阴极表面高效产生,RhB可通过E-Fenton反应高效去除。     

Helical nanocoiled and microcoiled carbon fibers as effective catalyst supports for electrooxidation of methanol

We have demonstrated a new synthesis of twist-shaped nanocoiled and herringbone-type double microcoiled carbon fibers via catalytic chemical vapor deposition of acetylene over NiCuMgAl-layered double hydroxides. The materials were characterized by power X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and N₂ adsorption-desorption experiments. For the first time, the use of electrodes modified with platinum particles supported on as-grown helical carbon fibers was studied for electrocatalytic oxidation of methanol. Especially, the electrode supported on herringbone-type double microcoiled carbon fiber showed much larger Pt active surface area than that supported on commercial carbon black. Furthermore, such electrocatalyst has exhibited about fourfold enhancement of activity and excellent anti-poisoning ability, which is believed to be attributed to the combined beneficial effects of novel microstructure and special composition of as-grown helical carbon fibers.     

Unique hierarchical mesoporous LaCrO3 perovskite oxides for highly efficient electrochemical energy storage applications

Following sol-gel route, hierarchical mesoporous nanostructures of lanthanum chromates (LaCrO₃) perovskite oxides are successfully synthesized for supercapacitor applications. The structural behaviors of nano perovskite oxides are investigated using X-rays diffraction, low and high resolution scanning and transmission electron microscopes, photoelectron X-ray spectroscopy, and Brunauer-Emmett-Teller (BET). The as-prepared LaCrO₃ powders is mingled with activated carbon and subsequently glazed on a flexible carbon cloth current collector (LCO@CC). The electrochemical capabilities of LCO@CC based electrode, such as: cyclic voltammetry, galvanostatic charge:discharge and electrochemical impedance spectroscopy are investigated in neutral M LiCl aqueous solutions. Moreover, the fabricated LCO@CC electrode achieves maximum capacitance of 1268 F/g at 2 A/g and retains excellent cyclic ability of 91.5% after 5000 charge:discharge cycles. The efficient electrochemical performances of carbon cloth decorated LaCrO₃ electrode are credited to dynamic charge storage mechanism by fast redox reaction of electrolyte-electrode interactions with extremely low charge transfer resistance.     

直接和间接电合成制备出的高铁酸钾的物理和电化学性能

K2FeO4 powders were synthesized by the ex-situ and in-situ electrochemical methods, respectively, and characterized by infrared spectrum （IR）, scanning electron microscopy （SEM）, X-ray powder diffraction （XRD） and BET. Their electrochemical performances were investigated by means of galvanostatic discharge and electrochemical impedance spectroscopy （EIS）. The results of physical characterization showed that the two samples have simi- lar structural features, but their surface morphologies and oriented growth of the crystals are different, which results in smaller specific surface area and lower solubility of the ex-situ electrosynthesized K2FeO4 sample. The results of discharge experiments indicated that the ex-situ electrosythesized K2FeO4 electrode has much larger discharge capacity and lower electrode polarization than the in-situ electrosynthesized K2FeO4 electrode. It was found from the results of EIS that lower electrochemical polarization might be responsible for the improvement on the discharge performance of the ex-situ electrosynthesized K2FeO4 electrode.     

Synthesis of an improved hierarchical carbon-fiber composite as a catalyst support for platinum and its application in electrocatalysis

A hierarchical carbon-fiber composite was synthesized based on carbon cloth (CC) modified with primary carbon microfibers (CMF) and subsequently secondary carbon nanotubes (CNT), thus forming a three-dimensional hierarchical structure with high BET surface area. The primary CMFs and the secondary CNTs are grown with electrodeposited iron nanoparticles as catalysts from methane and ethylene, respectively. After deposition of Pt nanoparticles by chemical vapor deposition from (trimethyl)cyclopentadienylplatinum, the resulting hierarchical composite was used as catalyst in the electrocatalytic oxygen reduction (oxygen reduction reaction, ORR) as specific test reaction. The modification of the CC with CMFs and CNTs improved the electrochemical properties of the carbon composite as revealed by electrochemical impedance measurements evidencing a low charge transfer resistance for redox mediators at the modified CC. X-ray photoelectron spectroscopy measurements were carried out to identify the chemical state and the surface atomic concentration of the Pt catalysts deposited on the hierarchical carbon composites. The ORR activity of Pt supported on different composites was investigated using rotating disk electrode measurements and scanning electrochemical microscopy. These electrochemical studies revealed that the obtained structured catalyst support is very promising for electrochemical applications, e.g. fuel cells.     

Preparation of platinum nanoparticles on polyaniline-coat multi-walled carbon nanotubes for adsorptive stripping voltammetric determination of formaldehyde in aqueous solution

Platinum nanoparticles on polyaniline-coat multi-walled carbon nanotubes were fabricated by electrochemical method at paraffin-impregnated graphite electrode (Pt/PAN/MWCNTs). The material was characterized by various methods including field emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and electrochemical techniques. The electrode has been effectively applied toward formaldehyde (HCHO) sensing. A good linear response curves from 1 × 10⁻⁹ to 1 × 10⁻³ M can be obtained with a lower detection limit of 4.6 × 10⁻¹¹ M (S/N 3). The successful preparation of nanocomposites opens a new path to fabricate the promising sensor for HCHO.     

An efficient and non-precious anode electrocatalyst of NiO-modified carbon nanofibers towards electrochemical urea oxidation in alkaline media

Non-precious NiO nanoparticles were combined with carbon fibers (CFs) to design the novel electrode material; NiO-CFs. The as-synthesized NiO-CFs material was investigated in terms of Field emission scanning electron microscope (FE-SEM), Fourier-transform infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET) surface area, Energy-dispersive X-ray spectroscopy (EDX), UV–vis spectra, Transmission electron microscope (TEM), selected area diffraction (SAED) pattern and X-ray diffraction (XRD) techniques. These analyses indicate the successful synthesis of a nanocomposite of NiO-CFs. Cyclic voltammetry (CV) in addition to chronoamperometric (CA) and electrochemical impedance spectroscopy (EIS) methods were studied in the 3-electrodes system to examine the electrochemical performance of NiO-CFs material for urea oxidation in KOH medium. The synthesized nanocomposite showed improved electrochemical oxidation of urea at various urea concentrations up to 1.5 M. The decreasing of both charge transfer impedance and series resistance indicates the enhanced transfer of electrons in the occurrence of urea which could be related to the high electrochemical performance of NiO-CFs material as an electrocatalyst. The superior electrochemical activity can be due to the assembly of C-structure with NiO nanoparticles during the synthesis steps which enhance electrocatalysis, charge transfer, and structural defects.     

以负载Fe的介孔分子筛为模板合成碳纳米管

以负载Fe的介孔分子筛Fe/MCM-41和Fe/ABW分别为催化剂,乙炔为碳源,采用化学气相沉积法对催化合成碳纳米管(CNTs)进行研究,讨论了反应温度、催化剂种类以及催化剂预处理对CNTs纯度和形貌的影响,通过场发射扫描电子显微镜、高分辨透射电子显微镜和X-射线衍射仪对产物的结构和形貌进行了表征和分析,并对CNTs的生长机理进行了推测.结果表明,在反应温度为700℃,两种不同的催化剂经H2还原后,催化生长出直径均匀(20nm～30nm)且晶化程度较好的CNTs.     

Graphene nanoplate-MnO2 composites for supercapacitors: a controllable oxidation approach

Graphene nanoplate-MnO(2) composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO(2) nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material.     

一维多孔碳纳米纤维的可控制备及电化学性能研究

利用静电纺丝技术,将聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)与聚丙烯腈(PAN)纺丝原液混合,电纺得到高分子纤维膜,再结合高温碳化技术得到一维多孔PAN基碳纤维。通过X射线衍射(XRD)、差热热重(TG-DSC)、傅里叶变换红外光谱(FT-IR)和扫描电子显微镜(SEM)等对所制备电极材料的结构和形态进行了系统表征,同时将其组成三电极体系研究电化学性能。结果表明:当纺丝原液中nPAN∶nPS=60∶1时,其在电流密度为0.5 A/g下的比电容值为339.23 F/g;当纺丝原液中n PAN∶n PMMA=40∶1时,其在电流密度为0.5 A/g下的比电容值为314.54 F/g,比纯PAN基碳纤维的比电容值有所上升;同时,在循环充放电2000圈后,初始比电容的保持率分别达95.5%和94.6%,展示出了良好的电容性能和循环性能。     

Investigation of Co–B–S system as anode material for secondary alkaline battery

A series of novel Co–S–B systems were prepared by simple chemical reduction method as the anode material for secondary alkaline batteries. The prepared samples were investigated by inductivity coupled plasma optical emission spectrum (ICP), Brunauer–Emmetr–Teller (BET) method, scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray energy dispersive spectroscopy (EDS) and charge–discharge method. It was found that the BET surface area of Co–S–B system increases and its particle size decreases with increasing the sulfur content. Sulfur incorporation suppresses initial capacity fading of Co–B compound due to irreversible dissolution of boron, and Co–S–B electrodes show enhanced electrochemical capacity and excellent cycle performance. The discharge capacity of Co_75.4B₁₇S_7.6 reaches 513.6 mAh/g at a moderate current density of 100 mA/g and 470 mAh/g after 60 cycles, which is about 1.5 times that of conventional AB₅-type alloy. A proper mechanism was proposed to explain the electrochemical reaction process of Co–S–B electrode.     

Oxidative functionalization of carbon nanotubes in atmospheric pressure filamentary dielectric barrier discharge (APDBD)

The surface compositional and any structural changes that occur on carbon nanotubes using air-atmospheric pressure dielectric barrier discharge (APDBD) for functionalization are investigated employing Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), and neutron diffraction techniques. Atmospheric pressure plasmas (APP) are suggested to be particularly suitable for functionalization of aligned nanotubes, where wet chemical manipulation could damage or even destroy the highly desirable vertical alignment. In this work a detailed experimental study elucidating the effects of APDBD plasma treatment parameters (e.g. power density, discharge composition, inter-electrode gap and treatment time) on the electronic structure, physical, and chemical behaviour of carbon nanotubes has been conducted. In an atmospheric air we find an optimal oxidative functionalization of CNTs in our DBD system within few seconds (<5 s) at a discharge power of ∼0.5 kW. This investigation may find useful application as functionalization technique for CNT engineered devices and sensors.