碳纳米管/羟基磷灰石复合材料的制备及表征

以含钴介孔分子筛为催化剂、乙醇为碳源, 采用CVD法制备碳纳米管(CNTs)。通过原位合成法制备一系列不同碳纳米管含量的碳纳米管/羟基磷灰石(CNTs/HA)复合材料。分别采用XRD、FTIR、TEM、N₂吸附-脱附和Raman光谱等分析手段, 对所合成CNTs/HA复合材料的晶相、结构、形貌和比表面积等进行了表征。同时研究了碳纳米管的添加量对所合成CNTs/HA复合材料形貌的影响。XRD与Raman结果表明, 所得CNTs/HA复合粉体中仅有CNTs与HA两种物相, 纯度较高, 结晶度较好; TEM结果显示, CNTs/HA复合材料中CNTs表面均匀包裹着一层纳米级的针状HA晶粒, 两者形成了较强的界面结合, 且当CNTs与HA的质量比为3:17时, CNTs与HA形成最佳结合状态; N₂吸附-脱附表征结果表明, 与HA的比表面积相比, CNTs/HA复合材料具有较高比表面积。     

Synthesis of carbon and carbon–nitrogen nanotubes using green precursor: jatropha-derived biodiesel

The jatropha-derived biodiesel, a green precursor was found to be a new and promising precursor for the synthesis of carbon nanotubes (CNTs) and carbon–nitrogen (C–N) nanotubes. The CNTs and C–N nanotubes have been synthesised by spray pyrolysis of biodiesel with ferrocene and ferrocene–acetonitrile, respectively, at elevated temperature under an argon atmosphere. The typical length and diameter of as-grown CNTs are 20?µm and 20–50?nm, respectively. The C–N nanotubes are found in bundles with effective length of ～30?µm and diameter ranging between 30 and 60?nm with bamboo-shaped morphology. The as-grown CNTs and C–N nanotubes were characterised through scanning and transmission electron microscopes, X-ray photoelectron, Raman and Fourier transform infrared spectroscopic techniques. These investigations revealed that the nanotubes synthesised by jatropha-derived biodiesel are clean from carbonaceous impurities and the bamboo compartment formations in C–N nanotubes are due to nitrogen incorporation. The nitrogen concentration in C–N nanotubes decreases with the increase in synthesis temperature.     

Growth of carbon nanotubes on cobalt catalyst film using electron cyclotron resonance chemical vapour deposition without thermal heating

This paper demonstrates that carbon nanotubes (CNTs) can be synthesized on a cobalt coated silicon substrate using electron cyclotron chemical vapour deposition and without intentionally heating the substrate. With the mixed gases of C(3)H(8)/N(2), CNTs with a multi-walled structure and a diameter up to 70?nm have been observed. Results show that the diameter of the CNTs increases with the thickness of the cobalt catalyst film and the amount of nitrogen incorporated in the CNT films considerably influences the structures of the CNTs. Vertically aligned CNTs can be fabricated with a microwave power as low as 300?W and the flow rate ratio of C(3)H(8)/N(2) = 20/20?sccm. The CNTs exhibit a turn-on field of 0.2?V?μm(-1) determined at the emission current density of 10?μA?cm(-2).     

RuO(2) nanoparticles dispersed on carbon nanotubes with high electrochemical activity using N incorporation

The N incorporation into carbon nanotubes (CNTs) supporting ultrafine RuO(2) nanoparticles (NPs) has been studied. With increasing N dopant, the Raman spectrum shifts to higher wavenumbers and x-ray photoelectron spectroscopy results show the intensity ratio of graphene-?to pyridine-like bonding is reduced. Cross-sectional scanning electron microscope images reveal that the uniform RuO(2)?NPs are dispersed on CNTs at the N(2) flow rate of 20?sccm. Electrochemical (EC) measurements show N-doped CNTs covered with RuO(2)?NPs at an N(2) flow rate of 20 sccm provide the optimal capacitive behavior with larger energy density and can be performed at the higher scan rate of 2000?mV?s(-1). The distribution of RuO(2)?NPs on CNT surfaces deduced from N-induced defect sites is the key point in controlling the capacitive characteristics of CNT-RuO(2) nanocomposites (NCs). The high capacitance is due to the well-dispersed RuO(2) particles on CNTs incorporated with N atoms. Such NCs are promising for energy storage devices with high EC efficiency.     

Ni催化剂在N2O／N2／NH3中退火对碳纳米管表面结构及场发射特性的影响

研究在N2O/N2/NH3氛围中对Ni催化剂进行退火处理,旨在探讨退火处理对所生成碳纳米管的表面结构及其发射特性的影响.从表面结构及表面元素分析结果发现:Ni催化剂在N2O/N2/NH3氛围中退火处理之后,Ni催化剂的颗粒大小及催化剂的化学成分发生改变,进而影响所合成的碳纳米管的表面结构及场发射特性.扫描电镜显示:经过N2O退火前处理后,催化金属薄膜在成核时较易形成均匀性的金属颗粒,且金属颗粒较小.比较经N2O/N2/NH3氛围退火处理之后所合成的碳纳米管结果,经过N2O前处理可以有效抑制非品质碳的成长,使所成长出的碳纳米管数量最多、场发射电流最大.原因主要是因为N2O对催化剂镍膜金属前处理过程中分解出的氮原子及氧原子会活化及氧化催化剂Ni金属,并使所形成的Ni金属颗粒较小且更为均匀,造成表面型态上的显著改变,有助于使合成的碳纳米管场发射电流变大.     

碳纳米管对Fe-P非晶的力学性能和晶化行为影响的研究

采用快速凝固技术制备了碳纳米管／铁碳非晶复合材料,并对其组织、力学性能和热稳定性进行了研究检测结果表明,碳纳米管在非晶基体中的弥散存在,使得非晶抗拉强度提高,晶化激活能增加,晶化特征温度明显提高,加入２Ｗ／％碳纳米管,使铁磷非晶的室温抗拉强度提高了１２０％,晶化激活能增加了约４０％,晶化开始温度提高了约１００Ｋ,此外,在温度高于其晶化温度约２００Ｋ时,碳纳米管和非晶基体界面间发生了固相反应。     

一步法制备聚氨酯/碳纳米管复合泡沫材料及其性能

采用球磨法将碳纳米管分散到聚醚三元醇中,以水为发泡剂,采用一步法原位聚合制备了聚氨酯(PU)/碳纳米管(CNTs)复合泡沫材料,研究了发泡剂水的添加量和碳纳米管的含量对复合材料密度和性能的影响.结果表明,随水添加量的增加,泡沫材料的密度、压缩模量、拉伸模量以及断裂伸长率呈下降的趋势;碳纳米管的加入大幅度提高了材料的压缩...     

具有负温度系数效应的导电硬质聚氨酯泡沫

采用高能球磨分散方法制备了稳定的聚合物多元醇/碳纳米管分散液,并通过原位聚合制备了导电聚氨酯（PU）/碳纳米管（CNTs）硬质泡沫复合材料。采用扫描电镜（SEM）表征了泡沫复合材料的结构,研究了CNTs含量对泡沫材料导电性的影响以及泡沫材料的负温度系数（NTC）效应,通过压缩测试考察了泡沫材料的力学性能。结果表明,CN...     

A novel high yield method for dry functionalization of carbon nanotubes

A novel and high yield (> 80%) dry method to functionalize (dry functionalization) carbon nanotubes (CNTs) using hydrothermal method, is reported here. The hydrothermal solution was prepared with HNO3, H2SO4 and H2O2 (1:3:2 vol. ratios) and reaction was carried out from 120 to 200 degrees C for 24 h. CNTs (multi wall) were kept in a way to avoid the direct contact with the solution. Treatment above 180 degrees C resulted in better functionalization of nanotubes as observed from Fourier transform infrared absorption spectroscopic (FTIR) measurements. Field emission scanning electron microscopic (FESEM) images showed that after functionalization, the nanotubes are seen with open ends, granular surface, twisted and are joined together. These clearly indicate the destruction of the graphite structure on the surface. This indicates that after treatment, CNTs reactivity has increased at the ends as well as at the side walls. X-ray Photoelectron Spectroscopic (XPS) studies show a shift in the C 1s peak position, increase in O 1s peak intensity and appearance of an N 1s peak.     

Synthesis of carbon nanotubes using Ni95Ti5 nanocrystalline film as a catalyst

Carbon nanotubes (CNTs) were synthesized by low-pressure chemical vapour deposition (LPCVD) using N2:C2H2:H2 gas mixtures on nanocrystalline Ni95Ti5 film. This nanocrystalline film was deposited on silicon substrate using vapour condensation method. The growth temperature and growth time was kept at 800 degrees C and 30 mins, respectively and the pressure was maintained at 10 Torr. The growth mechanism of CNTs was investigated using FESEM, TEM, HRTEM, and Raman Spectroscopy. From FESEM image of Ni95Ti5 nanocrystalline film, it is clear that the particle size varies from 5-10 nm. EDX analysis suggests that Ni95Ti5 alloy contains Ni and Ti both. It is clear from TEM images that CNTs are multiwalled with the diameter varying from 10-30 nm and length of several micrometers. HRTEM image shows that the structure of these multi-walled nanotube (MWNTs) is bamboo-shaped and the catalyst exists at the tip of MWNTs. Fourier Transform Raman Spectroscopy confirmed that graphitic structure of as-prepared CNTs. Field emission measurements reveal that the carbon nanotubes grown for 30 mins showed a turn-on field of 7.2 V/microm, when the current density achieves 10 microA/cm2. The field enhancement factor was calculated to be 708.50 for carbon nanotubes grown for 30 mins.     

N2对碳纳米管生长和结构的影响

用热丝化学气相沉积制备了碳纳米管,并用扫描电子显微镜和透射电子显微镜研究了它们的结构.结果表明,用CH4和H2为反应气体制备的碳纳米管是弯曲和中空的,它们的直径较大,生长速率较低;在反应气体中加入N2气后,碳纳米管的平均直径减小,生长速率增大,它们是准直的和竹节型的.分析和讨论了N2对碳纳米管生长和结构的影响.     

Synthesis of nano-carbon (nanotubes,nanofibres, graphene) materials

In the present study, we report the synthesis of carbon nanotubes (CNTs) using a new natural precursor: castor oil. The CNTs were synthesized by spray pyrolysis of castor oil-ferrocene solution at 850°C under an Ar atmosphere. We also report the synthesis of carbon nitrogen (C-N) nanotubes using castor oil-ferrocene-ammonia precursor. The as-grown CNTs and C-N nanotubes were characterized through scanning and transmission electron microscopic techniques. Graphitic nanofibres (GNFs) were synthesized by thermal decomposition of acetylene (C₂H₂) gas using Ni catalyst at 600°C. As-grown GNFs reveal both planar and helical morphology. We have investigated the structural and electrical properties of multi-walled CNTs (MWNTs)-polymer (polyacrylamide (PAM)) composites. The MWNTs-PAM composites were prepared using as purified, with ball milling and functionalized MWNTs by solution cast technique and characterized through SEM. A comparative study has been made on the electrical property of these MWNTs-PAM composites with different MWNTs loadings. It is shown that the ball milling and functionalization of MWNTs improves the dispersion of MWNTs into the polymer matrix. Enhanced electrical conductivity was observed for the MWNTs-PAM composites. Graphene samples were prepared by thermal exfoliation of graphite oxide. XRD analysis confirms the formation of graphene.     

Designing Nanogadgetry for Nanoelectronic Devices with Nitrogen‐Doped Capped Carbon Nanotubes

A systematic analysis of electron transport characteristics for 1D heterojunctions with two nitrogen‐doped (N‐doped) capped carbon nanotubes (CNTs) facing one another at different conformations is presented considering the chirality of CNTs (armchair(5,5) and zigzag(9,0)) and spatial arrangement of N‐dopants. The results show that the modification of the molecular orbitals by the N‐dopants generates a conducting channel in the designed CNT junctions, inducing a negative differential resistance (NDR) behavior, which is a characteristic feature of the Esaki‐like diode, that is, tunneling diode. The NDR behavior significantly depends on the N‐doping site and the facing conformations of the N‐doped capped CNT junctions. Furthermore, a clear interpretation is presented for the NDR behavior by a rigid shift model of the HOMO‐ and LUMO‐filtered energy levels in the left and right electrodes under the applied biases. These results give an insight into the design and implementation of various electronic logic functions based on CNTs for applications in the field of nanoelectronics.     

Atomically Dispersed Transition Metals on Carbon Nanotubes with Ultrahigh Loading for Selective Electrochemical Carbon Dioxide Reduction

Single‐atom catalysts (SACs) are the smallest entities for catalytic reactions with projected high atomic efficiency, superior activity, and selectivity; however, practical applications of SACs suffer from a very low metal loading of 1–2 wt%. Here, a class of SACs based on atomically dispersed transition metals on nitrogen‐doped carbon nanotubes (MSA‐N‐CNTs, where M = Ni, Co, NiCo, CoFe, and NiPt) is synthesized with an extraordinarily high metal loading, e.g., 20 wt% in the case of NiSA‐N‐CNTs, using a new multistep pyrolysis process. Among these materials, NiSA‐N‐CNTs show an excellent selectivity and activity for the electrochemical reduction of CO₂ to CO, achieving a turnover frequency (TOF) of 11.7 s^?1 at ?0.55 V (vs reversible hydrogen electrode (RHE)), two orders of magnitude higher than Ni nanoparticles supported on CNTs.     

DNA damage induced by multiwalled carbon nanotubes in mouse embryonic stem cells

Carbon nanotubes (CNTs) have shown promise as an important new class of multifunctional building blocks and innovative tools in a large variety of applications, ranging from nanocomposite materials through nanoelectronics to biomedical devices. Because of their unusual one-dimensional hollow nanostructure and unique physicochemical properties, CNTs are particularly useful as novel drug delivery tools and imaging agents. However, such biomedical applications will not be realized if there is no proper assessment of the potential hazards of CNTs to humans and other biological systems. Although a few reports on the cytotoxicity of CNTs have been published, very little is known about the toxicity at the molecular level, or genotoxicity, of CNTs in mammalian cells. We have for the first time assessed the DNA damage response to multiwalled carbon nanotubes (MWNTs) in mouse embryonic stem (ES) cells. We found that MWNTs can accumulate and induce apoptosis in mouse ES cells and activate the tumor suppressor protein p53 within 2 h of exposure. Furthermore, we also observed increased expression of two isoforms of base excision repair protein 8-oxoguanine-DNA glycosylase 1 (OGG1), double strand break repair protein Rad 51, phosphorylation of H2AX histone at serine 139, and SUMO modification of XRCC4 following the treatment with MWNTs. A mutagenesis study using an endogenous molecular marker, adenine phosphoribosyltransferase (Aprt), showed that MWNTs increased the mutation frequency by 2-fold compared with the spontaneous mutation frequency in mouse ES cells. These results suggest that careful scrutiny of the genotoxicity of nanomaterials is needed even for those materials, like multiwalled carbon nanotubes, that have been previously demonstrated to have limited or no toxicity at the cellular level.     

SEM and raman spectroscopy of multiwalled carbon nanotubes grown by novel technique of ash supported catalysts

Multiwalled carbon nanotubes (MWCNTs) were grown on a novel ASC catalyst and on catalyst deposited by SCC method on silicon wafer, by thermal CVD of acetylene. Fe and Ni were used as catalyst for ASC. Samples were analyzed by SEM and Raman spectroscopy. SEM analysis shows that CNTs grown on ASC have narrower diameter distribution (64+/-6 nm) compared to CNTs grown on SCC (67+/-10.5 nm). However, SEM and Raman spectroscopy studies show CNTs grown on SCC are of better quality. The same samples were studied after standard purification procedure of oxidation after annealing at high temperatures. SEM and Raman spectroscopy show that overall quality of ensemble of CNTs has improved. After annealing, diameter decreases for larger diameter approximately 200 nm nanotubes while it increases for CNTs of smaller diameter approximately 70 nm. To explain the increase in diameter of approximately 70 nm CNT's, a phenomenological model has been proposed. The results of Raman spectroscopy and SEM corroborate the proposed model.     

化学气相沉积法快速生长定向纳米碳管

利用化学气相沉积法，采用二甲苯为碳源，二茂铁为催化剂，氮气作保护气，在石英基底上催化裂解生长定向纳米碳管，试验结果表明：在775℃，120min的条件下，可生长出长达200μm厚的定向纳米碳管薄膜；在775℃，反应时间为60min～120min时，纳米碳管的长度为100μm～200μm，而纳米碳管的直径变化不明显。而无氢气，较高的反应温度和连续的催化剂供给对快速生长定向纳米碳管有重要的影响。     

超声喷雾化学镀法制备镀Ni碳纳米管及其微波吸收性能

将碳纳米管（CNTs）经过酸化、敏化和活化处理后,采用超声喷雾化学镀的方法来制备镀Ni碳纳米管（Ni-CNTs）。采用TEM、EDS和拉曼光谱进行表征。结果表明,采用超声喷雾化学镀可实现Ni层在CNTs表面均匀连续的镀覆,并且改善了CNTs的分散性,有利于其在复合材料领域的应用。不同形貌的Ni-CNTs的吸波性能有明显差异。对于镀层相对较薄的Ni-CNTs试样,其反射损耗峰值为-17.12 dB,出现在9.36 GHz处;吸波频带宽度为5.28 GHz（R<-5 dB）和2 GHz（R<-10 dB）,这样的趋势有利于制造宽频复合吸波材料。     

Effect of hydrogen plasma pretreatment on growth of carbon nanotubes by MPECVD

We have grown carbon nanotubes (CNTs) with a microwave (μW) plasma enhanced chemical vapor deposition (MPECVD) method, which has been regarded as one of the most promising candidates for the synthesis of CNTs due to the vertical alignment, the low temperature and the large area growth. We use methane (CH₄) and hydrogen (H₂) gas for the growth of CNTs. Ni catalytic layer (10 nm thick) were deposited on the Ti-coated Si substrate by RF magnetron sputtering method. In this work, we report the effects of pretreatment μW power on the growth of CNTs. We have pretreated the Ni catalytic layer in different μW power (600, 700, and 800 W) and grown same μW power (800 W). Scanning electron microscopy (SEM) images show Ni catalytic layer diameter and density are varied dependent with their pretreatment conditions. Raman spectroscopy of CNTs shows that I_D/I_G ratios and G-peak positions vary with pretreatment conditions.