Properties of composite BxCyNz nanotubes and related heterojunctions

We review the stability and electronic properties of composite B_xC_yN_z nanotubes, including BN-, BC₂N- and B-doped carbon nanotubes. We show in particular that BC₂N systems are driven towards the segregation of pure C and BN sections. The same process of segregation into BC₃ islands is evidenced in the case of B-doped carbon nanotubes. These spontaneous segregation processes lead to the formation of quantum dots or nanotube heterojunctions with potential important technological applications.     

The Role of Boron Nitride in Graphite Plasma Arcs

Novel graphitic nanostructures (e.g. nanotubes, graphitic onions, polyhedral particles, hemitoroidal nanotube caps and branched nanotubes) are produced by arcing graphite electrodes, containing hexagonal-BN, in inert atmospheres. The introduction of BN or B inside the graphite anode generates long (≤ 20μm) and well graphitised carbon nanotubes exhibiting boron at their tips. High Resolution Electron Microscopy (HRTEM), Scaning Electron Microscopy (SEM), Electron Energy Loss Spectroscopy (EELS) and X-ray powder diffraction studies reveal the production of B₄C crsytals, in addition to little amounts of BC₃ nanotubes. Mass spectrometry (MS) studies over the generated soots indicate high yields of large fullerenes (e.g. C₇₀, C₇₆, and C₈₄) and thermo-Gravimetric analysis (TGA) of the nanostructures show high oxidation resistance.     

Metallic Oxide Catalyzed Growth of Carbon Nanotubes

Carbon nanotubes were created in the cathode deposit by DC arc-discharge evaporation of the graphite rods containing Y₂O₃, La₂O₃ or SC₂O₃ These metallic oxides have the catalytic action to promote the growth o nanotubes. The most remarkable catalytic effect was observed for the case of metallic oxide annexation of 2∼8wt % and arc current of 165∼196A.     

A STUDY ON THE THERMAL STABILITY TO 1000°C OF VARIOUS CARBON ALLOTROPES AND CARBONACEOUS MATTER BOTH UNDER NITROGEN AND IN AIR

The thermal behavior of graphite, C₆₀ fullerene, fullerene black (carbon soot containing fullerenes), extracted fullerene black and diamond has been analyzed to 1000°C by TGA-DTA (thermogravimetric analysis and differential thermal analysis) under a nitrogen flow at a heating rate of 20°C/min. Very small weight losses have been recorded in the case of graphite and diamond. Furthermore no diamond graphitization has been observed. The sublimation of pure C₆₀ and the fullerene fraction of fullerene black (both pristine and extracted) has been observed and discussed.

The combustion reaction in air flow of graphite, C₆₀ and C₇₀ fullerenes, fullerene black (both unextracted and extracted), carbon nanotubes and diamond has been studied by TGA-DTA at a heating rate of 20°C/min. C₇₀ fullerene and fullerene black have been found to be the most reactive carbon materials with O₂. The role played by C₇₀ in the degradation of fullerites has been discussed. Among the carbon materials examined, the best resistance to O₂ attack has been shown by diamond and carbon nanotubes. The behavior of graphite is intermediate between diamond and fullerene blacks. The behavior of C₆₀ fullerene appears closer to that of graphite although it appears to be more reactive with O₂. Samples of graphite and carbon blacks N375 and N234 have been studied by TGA-DTA in air flow before and after a radiation treatment with neutrons or γ radiation. The effect of the radiation damage in the combustion reaction of these carbon materials has been discussed.     

Preparation and visible-light-driven photoelectrocatalytic properties of boron-doped TiO2 nanotubes

In the present study, chemical vapour deposition (CVD) was applied to dope boron into TiO₂ nanotubes anodized Ti in C₂H₂O₄·2H₂O + NH₄F electrolyte with the goal of improving the photocatalytic (PC) activity under visible light. The undoped TiO₂ nanotubes had a highly self-organized structure. However, after doping through CVD, TiO₂ nanotubes suffered from an observable disintegration of morphological integrity. X-ray diffraction (XRD) results confirmed that annealing temperature had an influence on the phase structure and boron impurities could retard anatase–rutile phase transition. Diffuse reflectance absorption spectra (DRS) analysis indicated that B-doped samples displayed stronger absorption in both UV and visible range. B-doped TiO₂ nanotubes electrode annealed at 700 °C through CVD showed higher photoelectrocatalytic (PEC) efficiency in methyl orange (MO) degradation than that annealed at 400 °C and 550 °C. MO degradation was substantially enhanced with the increasing applied bias potential. Moreover, there was a synergetic effect between the electrochemical and photocatalytic processes, and the synergetic factor R reached 1.45. B-doped TiO₂ nanotubes electrode showed good stability after 10 times by repeating photoelectrocatalysis of MO.     

Fullerenes and Nanotubes from Coal

Graphite has normally been used to synthesise fullerenes and nanotubes. However, coal is a cheaper and more suitable industrial material. Because coal is a molecular solid, unlike graphite, the mechanism by which fullerene and nanotubes are formed is different. Moreover, other products such as polyaromatic hydrocarbons (PAHs) and microfibres are also formed. In this review, the mechanism of formation of fullerene and nanotubes from coal is discussed. It is shown that the pathway involved is other than through the C₁ intermediate route. The influence of other elements in coal such as hydrogen, oxygen, sulfur and iron is also discussed. It appears that, hydrogen, oxygen, iron and sulfur affect the yield and type of fullerenes and nanotubes formed.     

Formation of MoTe2 Nanotubes by Electron Irradiation

In this article, we report the study and to our knowledge the first production of MoTe₂ (Molybdenum telluride) nanotubes by irradiation with high doses of electrons. a 2 MeV Van de Graaff accelerator was used to irradiate the samples at the following conditions: 1.3 MeV voltage, 5μA current, dose rate 25 kGy/min, total dosage 1000 kGy. the samples were examined in a high-resolution transmission electron microscope. the principal characteristic observed was huge nanotubes of the order of several nm long and few nm wide, which seems to be hollow. It is necessary to point out that searching carefully through out other areas of the sample, we were not able to locate either onionlike structures or nanoparticles as it is usual to find in graphite, WS₂ or MoS₂.     

Effects of Supercritical Fluids Activation on Carbon Nanotube Field Emitters

This paper proposes a novel method to enhance the emission characteristics of carbon nanotubes (CNTs). It is extremely possible for CNTs to adsorb moisture and other contaminants during the fabrication processes, leading to the degraded field emission characteristics. In this work, CNT emitters are activated with commonly used heating process and supercritical carbon dioxide (SCCO₂) fluids technology for removing adsorbed residue moisture. Experimental results have demonstrated that the electrical stability and field emission enhancement of CNT emitters are effectively achieved by the SCCO₂ fluids treatment compared to the heating process, due to the minimization of residuary moisture in CNTs     

Carbon Nanotubes Grown on the Surface of Cathode Deposit by Arc Discharge

Carbon nanotubes prepared by de arc discharge of graphite electrodes in He and CH₄ gas took markedly different morphology. Thick nanotubes embellished with many carbon nanoparticles were obtained by evaporation under high CH₄ gas pressure and high arc current. Thin and long carbon nanotubes were obtained under a CH₄ gas pressure of 50Torr and an arc current of 20A for the anode with a diameter of 6mm.     

PRODUCTION OF CARBON NANOTUBES IN AIR

Carbon nanotubes were produced by plasma discharging of graphite electrodes in air at 1 atm. The combined yield of CNTs and carbon nanoparticles is ∼20 wt % relative to the mass of cathode deposits or 14 wt% of graphite electrode consumed. The yields of CNTs and carbon nanoparticles under different inert gas atmospheres, such as He, Ar, N₂, and air were compared.     

Ti1Li3Al2-LDHs/g-C3N4复合材料的制备及其光催化CO2-甲苯反应特性

光催化CO₂还原是实现CO₂绿色转化利用的重要途径之一,但一直受其反应转化效率低的制约。开发新的CO₂还原反应体系和提高光催化剂的可见光利用率及光生电子与空穴的分离效率是解决上述问题的有效方法。本文利用甲苯作为底物,构建了光催化CO₂-甲苯耦合反应的新体系,并通过静电组装法合成了Ti₁Li₃Al₂-层状双氢氧化物(LDHs)/石墨相氮化碳(g-C₃N₄)复合光催化剂。重点研究了该复合光催化剂的光电性质及在CO₂-甲苯耦合反应体系中的光催化反应特性。结果表明,在光催化CO₂-甲苯耦合体系中,Ti₁Li₃Al₂-LDHs/g-C₃N₄作用下,CO₂被还原为CO,甲苯被氧化为苯甲醇、苯甲醛及苯甲酸苄酯,其中苯甲醛和苯甲醇的含...     

Mass-Spectrometric Investigation of Gases Evolved from Fluorinated Multi-Walled Carbon Nanotubes at Heating

The mass-spectrometric investigation of the gases evolved from fluorinated multi-walled carbon nanotubes under heating was carried out. It was shown that in temperature interval from 20°C to 120°C the gases are composed predominantly of CO₂, CO and H₂O. Molecules of COF₂ can be finding in gas phase of products of decomposition at 120-300°C. Molecules of CF₄ and C₂F₆ realized from fluorinated nanotubes at 300-450°C.     

酚醛树脂原位催化裂解制备低维碳纳米结构

以Ni（NO₃）₂·6H₂O为催化剂前躯体,原位催化裂解酚醛树脂制备了碳洋葱、竹节碳和碳纳米管等低维碳纳米结构;用粉体X-射线衍射（XRD）、扫描电镜（SEM）和透射电镜（TEM）等手段对低维碳纳米结构进行了表征。结果表明;当Ni（NO₃）₂·6H₂O与苯酚物质量比小于0.01时,Ni催化剂易分散,碳纳米管易生成,管径均一、分布稠密;当Ni（NO₃）₂·6H₂O与苯酚物质量比大于0.04时,Ni催化剂易团聚,碳纳米管管径分布较宽,分布稀疏;当Ni（NO₃）₂·6H₂O与苯酚物质量比为0.10时,Ni催化剂团聚现象严重,难以生成碳纳米管;提出了碳洋葱、竹节碳和碳纳米管不同碳纳米结构可能的形成机理。     

改性碳纳米管/环氧树脂复合材料的介电性能

实验采用混酸法对碳纳米管(CNTs)表面进行改性,制得羧基化碳纳米管(C-CNTs)。采用溶胶-凝胶法制得SiO₂包覆的C-CNTs (C-CNTs@SiO₂)、TiO₂包覆的C-CNTs (C-CNTs@TiO₂),采用原位聚合法制得聚苯胺包覆的C-CNTs (C-CNTs@ PANI)。以环氧树脂(EP)为基体材料,通过溶液共混法制备出C-CNTs/EP、C-CNTs@SiO₂/EP、C-CNTs@TiO₂/EP和C-CNTs@PANI/EP四种复合材料。研究结果表明:当掺杂相的质量分数均为1 wt%时,四种EP基复合材料的冲击强度相对于未改性的环氧树脂均有不同程度的提高。当掺杂相质量分数为7 wt%时,C-CNTs/EP、C-CNTs@SiO₂/EP、C-CNTs@TiO₂/EP和C-CNTs@PANI/EP四种复合材料的介电常数分别是EP的14.1、7.2、2.5、18.8倍。在实验掺杂量下,C-CNTs@SiO₂/EP和C-CNTs@TiO₂/EP的介电损耗几乎没有变化,C-CNTs@PANI/EP的介电损耗略有增加。当掺杂相质量分数为1 wt%时,C-CNTs@SiO₂/EP和C-CNTs@TiO₂/EP的击穿强度相对于EP明显提高。      

碳纳米管-Ti3AlC2/AZ91D复合材料的微观组织及力学性能

采用化学镀铜的方法对增强相碳纳米管(CNTs)和Ti₃AlC₂进行表面改性,热压烧结制备了CNTs-Ti₃AlC₂/AZ91D复合材料,研究了其微观组织和力学性能的变化及增强机制。结果表明:CNTs-Ti₃AlC₂/AZ91D复合材料内部主要物相为CNTs、Ti₃AlC₂、Mg和Al₁₂Mg₁₇,增强相均匀分布在基体内,在增强相与基体的界面处存在U相(MgAlCu),使二者界面结合良好。当增强相CNTs 和Ti₃AlC₂含量分别为1wt%和25wt%时,较镁合金AZ91D,CNTs-Ti₃AlC₂/AZ91D复合材料的弹性模量、拉伸强度、屈服强度和延伸率分别提高了120.30%、25.72%、126.50%和36.84%,弯曲强度和压缩强度分别为337.92 MPa和436.27 MPa。CNTs-Ti₃AlC₂/AZ91D复合材料的断裂方式表现为脆性断裂,其强化机制主要为热配错强化、Orowan强化和细晶强化机制。      

石墨/TiO2复合光催化剂的制备和性能

以石墨和纯的TiO₂为原料,采用球磨工艺制备了石墨/TiO₂复合光催化剂。使用XRD、SEM、TEM、XPS和DRS等手段对其性能进行了表征。以甲基橙为模拟污染物,研究了石墨掺入量、球磨时间对复合光催化剂光催化活性的影响。结果表明,石墨/TiO₂复合光催化剂具有锐钛矿结构,球磨后TiO₂(101)面的衍射峰宽化并右移,TiO₂成为200 nm左右的不规则球状颗粒,在其表面均匀分布着石墨。TiO₂晶粒的Ti-O键的结合能变高,且表面有缺陷产生,使其在可见光区具有显著的吸收。石墨掺入量为5%、球磨时间为12 h的石墨/TiO₂样品对甲基橙具有优异的光催化降解效果,在70 min的降解时间内甲基橙的降解去除率可达95.08%。石墨/TiO₂复合光催化剂的光催化反应速率常数k为0.043035 min^-1,是纯TiO₂的2.64倍。     

Fullerenes with Non-Positive Gaussian Curvature: Holey-Balls and Holey-Tubes

Classical fullerenes such as C₆₀ and C₇₀ need 12 pentagonal rings of carbon for the closure of the cage. These pentagons produce the positive Gaussian curvature which gives the characteristic spherical shape. In this paper we propose a new family of fullerene-like structures which do not have pentagonal rings (no positive Gaussian curvature), no dangling bonds, possesing hexagons and heptagons only. The topology of this new family of perforated fullerenes (holey-balls) and nanotubes (holey-tubes) is higher than classical fullerenes presenting genus 5, 11 up to 21. Holey balls can be icosahedral (I_h) and cubic (O_h). The geometry, elastic stabilities and possible applications of holey-balls and holey-tubes are studied.     

烧绿石型富氧相Ce2Zr2O8的Rietveld结构精修及其Raman光谱研究

采用石墨还原法成功制备了烧绿石型富氧相Ce₂Zr₂O₈, 选用缺氧型烧绿石Nd₂Zr₂O₇作为Ce₂Zr₂O₈相前驱体CeZrO_3.5的替代物与之进行结构对比分析。实验结果表明: Ce₂Zr₂O₈相中富余氧主要占据前驱体中的氧空位, 且氧离子扩散不会破坏原本有序排列的阳离子(Ce/Zr)亚点阵; 同时, Ce₂Zr₂O₈相中Zr-O 配位体由前驱体中共顶联接的八面体转变为共棱联接的立方体, 其反相畴界密度和振动光谱谱带亦较前驱体明显提高。以上结果说明Ce₂Zr₂O₈相结构处于亚稳态, 该结构特征有利于氧离子的快速吸附或释放, 这为其成为汽车尾气净化剂提供了结构上的可行性, 但也说明当An₂Zr₂O₇烧绿石在自辐照条件下向富氧相An₂Zr₂O₈发生转变时, 其抗辐照和化学稳定等性能有下降趋势。     

基于二氧化钛纳米管的染料敏化电池光阳极研究

本文报道了一种基于二氧化钛(TiO₂)纳米管的染料敏化太阳能电池。用二次阳极氧化法在钛箔上生长出高度有序的TiO₂纳米管薄膜, 然后将完整剥落的纳米管薄膜结合TiO₂纳米颗粒的浆料转移到掺杂氟的SnO₂透明导电玻璃(FTO)基底上, 从而获得一种特殊的染料敏化光阳极。对比了不同长度的TiO₂纳米管的电池性能, 发现经TiCl₄处理长度为32.8 μm的TiO₂纳米管对应的电池表现较好的光电转换效率, 达到4.15%。通过X射线衍射分析了高温退火对纳米管晶化结构的影响。电化学阻抗谱分析表明: 光电子传输对光阳极纳米管层厚依赖性强, 随着纳米管长度的增长, 界面电阻呈明显的减小, 这一结果对于理解和进一步改善染料敏化电池光阳极内部电子输运过程具有重要意义。     

(K0.44,Na0.52,Li0.04) (Nb0.84,Ta0.10,Sb0.06)O3 Ferroelectric Ceramics

Recent progress in (K_0.44,Na_0.52,Li_0.043-based ceramics (KNN) with special emphasis on (K_0.44,Na_0.52,Li_0.040.84,Ta_0.10,Sb_0.06))O₃ (KNN-LT-LS) is reviewed concisely. The base KNN and its compositional derivatives are analyzed in terms of dopant-property relationships, which are then extended to the ternary derivatives. The effects of processing conditions such as humidity, precursor purity, and oxygen partial pressure during sintering are elaborated on from a phenomenological perspective. It is also shown that the spontaneous polarization is sensitive to the processing route chosen for synthesis (mixed oxide versus perovskite routes). Special attention is devoted to the discussion of the morphotropic phase boundary (MPB) dilemma in the KNN-LT-LS system, where it is shown that the origin of high piezoelectric activity is actually due to a polymorphic transition at room temperature. It is shown that prototype transducers based on pure and 1 mol% Ba²⁺ doped KNN-LT-LS exhibit performance metrics comparable to those fabricated using PZT-5H. Overall, KNNLT- LS ceramics show great promise for lead-free applications, although issues such as temperature dependence of properties and strong sensitivity to processing conditions remain as the 2 major challenges.