Metal-diboride nanotubes as high-capacity hydrogen storage media

We investigate the potential for hydrogen storage of a new class of nanomaterials, metal-diboride nanotubes. These materials have the merits of a high density of binding sites on the tubular surfaces without the adverse effects of metal clustering. Using the TiB2 (8,0) and (5,5) nanotubes as prototype examples, we show through first-principles calculations that each Ti atom can host two intact H2 units, leading to a retrievable hydrogen storage capacity of 5.5 wt %. Most strikingly, the binding energies fall in the desirable range of 0.2-0.6 eV per H2 molecule, endowing these structures with the potential for room-temperature, near-ambient-pressure applications.     

Layer-by-layer assembly of imogolite nanotubes and polyelectrolytes into core-shell particles and their conversion to hierarchically porous spheres

Core-shell particles were prepared by the layer-by-layer (LbL) assembly of imogolite (IMO) nanotubes and poly(sodium 4-styrenesulfonate) (PSS) on polystyrene particles (diameter: 800 nm) coated preliminarily with poly(diallyldimethylammonium chloride) (PDDA). PSS and imogolite were alternately adsorbed on the particles to form core-shell particles with one to three bilayers of PSS/IMO. Macroporous hollow spheres were formed by removing polystyrene cores via heat treatment or extraction when the number of bilayers was 2 or 3. The sample formed by extraction (the number of bilayer was 3) showed only macroporosity and PSS remained in the shell, whereas the heat-treated sample showed hierarchical micro- and macroporosities. When the diameter of polystyrene particles decreased from 800 nm to 300 or 100 nm, hollow spheres were deformed because of the increase in the relative length of imogolite nanotubes against the size of polystyrene particles. Imogolite is a promising building block of hierarchically porous materials with core-shell morphologies using LbL assembly.     

Hydrogen storage in carbon nanotubes

The article gives a comprehensive overview of hydrogen storage in carbon nanostructures, including experimental results and theoretical calculations. Soon after the discovery of carbon nanotubes in 1991, different research groups succeeded in filling carbon nanotubes with some elements, and, therefore, the question arose of filling carbon nanotubes with hydrogen by possibly using new effects such as nano-capillarity. Subsequently, very promising experiments claiming high hydrogen storage capacities in different carbon nanostructures initiated enormous research activity. Hydrogen storage capacities have been reported that exceed the benchmark for automotive application of 6.5 wt% set by the U.S. Department of Energy. However, the experimental data obtained with different methods for various carbon nanostructures show an extreme scatter. Classical calculations based on physisorption of hydrogen molecules could not explain the high storage capacities measured at ambient temperature, and, assuming chemisorption of hydrogen atoms, hydrogen release requires temperatures too high for technical applications. Up to now, only a few calculations and experiments indicate the possibility of an intermediate binding energy. Recently, serious doubt has arisen in relation to several key experiments, causing considerable controversy. Furthermore, high hydrogen storage capacities measured for carbon nanofibers did not survive cross-checking in different laboratories. Therefore, in light of today's knowledge, it is becoming less likely that at moderate pressures around room temperature carbon nanostructures can store the amount of hydrogen required for automotive applications.     

碳纳米管及其掺杂氧化物半导体气敏传感器

碳纳米管气敏传感器以其工作温度低和最低检出限较低等优点而备受关注,而碳纳米管掺杂氧化物半导体气敏传感器兼备了氧化物半导体气敏传感器和碳纳米管气敏传感器二者的优点,具有灵敏度较高、最低检出限低和工作温度低等特性。综述了这两类传感器的研究进展,介绍了其气敏机理,并对相应存在的问题及今后的发展趋势进行了概述。     

Carbon nanotubes anchored with SnO2 nanosheets as anode for enhanced Li-ion storage

The carbon nanotubes (CNTs) anchored with SnO₂ nanosheets were prepared using a hydrothermal method. The as-prepared products were characterized by X-ray diffraction, fourier transform infrared spectroscopy, thermogravimetric analyses, field emission scanning electron microscope and transmission electron microscope. The electrochemical performances of SnO₂ nanosheets/CNTs composite were measured by galvanostatic charge/discharge cycling, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the SnO₂ nanosheets/CNTs composite maintains high lithium storage capacity and good cycling stability. The designed structure plays key role in improving electrochemical performance. The CNTs anchored with SnO₂ nanosheets will be an ideal candidate of anode material for lithium ion batteries.     

温室气体提高采收率的资源化利用及地下埋存

全球气候变化是人类迄今面临的既重大又复杂的环境问题,由于温室气体大量排放而引起的全球气候变暖问题日趋严峻,正在严重地威胁着人类赖以生存的环境,国际社会必须采取积极有效措施.2006年中国国家科技部批准国家"九七三"项目--温室气体提高石油采收率的资源化利用及地下埋存研究.建立适合中国国情的CO2高效利用和埋存体系;实现CO2减排的社会效益和CO2高效利用的经济效益;发展适合中国国情的CO2埋存地下理论、多相多组分相态理论、多相多组分非线性渗流理论和CO2捕集与储运理论.通过上述基础研究,形成具有自主知识产权的CO2地质埋存和高效利用的综合技术,使中国CO2安全埋存一高效利用研究处于国际水平.必将为全球资源和环境的高水平、高效益开发和可持续发展提供理论及实践依据.     

Production of single and multi-walled carbon nanotubes using natural gas as a precursor compound

In this work, the Catalytic Chemical Vapor Deposition (CCVD) technique was used to synthesize carbon nanotubes (CNT). Natural gas (NG) was employed as a carbon source for the growing of CNT, while magnesium oxide was used as a catalyst support for the nanotubes synthesis. Two systems were utilized. The Fe–Mo/MgO system was obtained by the impregnation technique through the dispersion of iron oxide, which is the catalyst, over magnesia (with molybdenum additions). This system was tested intending to optimize the parameters for the production of single-walled carbon nanotubes (SWCNT). Moreover, Mg_1−x Fe _x MoO₄, which was prepared by the combustion synthesis method, was tested to produce multi-walled carbon nanotubes (MWCNT). The Fe-Mo/MgO tests were carried out under H₂/GN and Ar/GN atmospheres at 950 °C, whereas the Mg_1−x Fe _x MoO₄ was submitted to 1,000 °C under H₂/GN atmosphere. The Fe–Mo/MgO catalyst produced better results regarding number of CNT and their diameters under Ar/NG atmospheres than under H₂/NG atmospheres. The system Mg_1−x Fe _x MoO₄ produced MWCNT according to the expectations.     

Performance of carbon arc-discharge nanotubes to hydrogen energy storage

Adsorption properties of gram-scale samples of different kind of arc discharge nanotubes were studied, namely: (A) raw collaret collected on the cathode, (B) raw soots collected on the lateral reactor wall, (C) thermally treated soot, and (D) thermally then chemically treated soot. The morphology, structure, and composition of these materials were characterized by SEM, TEM, TGA, and BET. In addition, hydrogen adsorption isotherms were recorded experimentally for A, B, and D samples over the pressure range of 0 to 55 bar at ambient temperature. Our experiments indicated a maximum-yet weak-hydrogen storage at room temperature of approximately 0.13 H2 wt% for the purified product (D).     

Preparation of transparent mullite-silica film by heat-treatment of imogolite

Natural gel-like imogolite was dispersed in an acetic acid aqueous solution. An imogolite film was prepared by evaporating the solvent from the imogolite solution and then subjecting it to heat-treatment. It transformed to an amorphous film at around 500°C and then to a mullite-silica composite film at around 1000°C without giving pore and cracks. The film heat treated to 1200°C showed high transparency as well as a low thermal expansion coefficient of about 4×10^–6.     

SiC nanotubes: A novel material for hydrogen storage

A multiscale theoretical approach is used for the investigation of hydrogen storage in silicon-carbon nanotubes (SiCNTs). First, ab initio calculations at the density functional level of theory (DFT) showed an increase of 20% in the binding energy of H2 in SiCNTs compared with pure carbon nanotubes (CNTs). This is explained by the alternative charges that exist in the SiCNT walls. Second, classical Monte Carlo simulation of nanotube bundles showed an even larger increase of the storage capacity in SiCNTs, especially in low temperature and high-pressure conditions. Our results verify in both theoretical levels that SiCNTs seem to be more suitable materials for hydrogen storage than pure CNTs.     

Hydrogen storage in polymer-functionalized Pd-decorated single wall carbon nanotubes

Palladium is usually supported on porous materials in the form of nanoparticles. The hydrogen storage capacity of such a system is usually much higher than the separated capacity of the metal (approximately 0.7 H/Pd) and the support. Pd nanoparticles provide a source of hydrogen atoms by dissociation. The atomic hydrogen spills over from the Pd structure to the support via surface diffusion and this phenomenon is known as hydrogen spillover. In this study commercial SWNTs were dispersed in PEG 200 solution. Then the precursor PdCl2 in PEG 200 was added and the whole left to react under stirring with reflux at 200 degrees C for 1 h. Succeeding washings with ethanol and centrifugation followed for several times and finally the sample was dried at 60 degrees C. Through this procedure a 3 wt% Pd loading was achieved whereas the TEM derived nanoparticle size distribution indicated a 50% percentage of Pd nanoparticles with diameter less than 8 nm. Hydrogen isotherms up to 2 MPa were carried out with the gravimetric method. The defined storage capacity of 1.2 wt% at 0.2 MPa was quite satisfactory. However, a 0.2 wt% portion of this storage capacity was attributed to the formation of water molecules through reaction of H atoms with the dissociatively adsorbed oxygen atoms on the Pd nanoparticles. This conclusion was educed from a series of thermal desorption experiments following the H2 adsorption/desorption cycles and regeneration. Through this set of experiments several other important parameters were defined as the temperature for complete hydrogen desorption and the optimum conditions for PEG removal.     

Large-scale synthesis of BN nanotubes using carbon nanotubes as template

Boron nitride nanotubes (BN-NTs) were synthesized in large scale by the reaction of NaBH₄ and NH₄Cl in the temperature range of 500-600 °C for 10-18 h, where carbon nanotubes (CNTs) were mixed together with the reactants to serve as template. Pure BN-NTs were obtained by oxidizing the product at about 800 °C in air atmosphere. The structure and morphology of the product with a surface area of 106.635 m²/g were characterized by X-ray diffraction, transmission electron microscopy, Fourier transformation infrared spectroscopy, and thermogravimetric analysis. Large scale preparation of BN-NTs could be realized by this simple and effective route.     

水热合成碳纳米管的电化学储氢性能研究

采用水热法制备了多壁碳纳米管(MCNTs)。以X射线衍射、透射电子显微镜等手段对所制碳纳米管进行了表征:管直径在50 nm左右,长度多为5~20μm,管壁厚度一般不超过10nm。电化学测试表明碳纳米管的放电容量约为398mAh.g-1,相当于1.5%的储氢量。     

化学修饰对碳纳米管的气体吸附性质的影响

利用研究碳纳米管膜在几种气体氛围中电阻相对于在大气环境中的电阻的变化,来分析研究碳纳米管膜表面的气体吸附----脱附特性.研究所用的碳纳米管是用热灯丝化学气相沉积法合成的.实验表明化学修饰后的碳纳米管具有较强的气体吸附性质,并进行了分析和讨论.     

Novel fabrication of silica nanotubes using multi-walled carbon nanotubes as template

Silica nanotubes were synthesized using multi-walled carbon nanotubes (MWCNTs) as template. The as-obtained samples were characterized by infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscope (FE-SEM) and photoluminescent (PL) spectroscopy. The results indicate that the thickness of the outer walls is about 10 nm and the inner diameter is completely dependent on the size of MWCNTs. The as-fabricated silica nanotubes emit a strong violet light under excitation of 250 nm.     

Carbon nanotubes as liquid crystals

Carbon nanotubes are the best of known materials with a combination of excellent mechanical, electronic, and thermal properties. To fully exploit individual nanotube properties for various applications, the grand challenge is to fabricate macroscopic ordered nanotube assemblies. Liquid-crystalline behavior of the nanotubes provides a unique opportunity toward reaching this challenge. In this Review, the recent developments in this area are critically reviewed by discussing the strategies for fabricating liquid-crystalline phases, addressing the solution properties of liquid-crystalline suspensions, and exploiting the practical techniques of liquid-crystal routes to prepare macroscopic nanotube fibers and films.