Intrinsic linear scaling of hydrogen storage capacity of carbon nanotubes with the specific surface area

The linear scaling of the gravimetric hydrogen storage capacity of single- and multi-walled carbon nanotubes (SWNTs and MWNTs) with the specific surface area is investigated at ambient temperature (298 K) and technically relevant pressures (0.9–1.6 MPa). All samples are found to adsorb hydrogen reversibly and their adsorption exhibits type-II BET isotherms according to the IUPAC classification. While there is strong sample-dependency on their pressure–composition isotherms, all of them follow the Henry's Law in the pressure range under consideration. A comparison of the observed slope of specific surface area versus gravimetric storage capacity with that of a theoretically predicted one using a hypothetical condensation model and that of chemically modified carbon nanotubes revealed that the hydrogen storage capacity depends on the accessibility of internal surfaces of nanostructured carbon. The linear scaling of hydrogen storage capacity with the respective specific surface area suggests that the hydrogen adsorption in carbon nanotubes depends on the specific surface area and is irrespective of the type of the nanotubes that is used.     

KOH activated lignin based nanostructured carbon exhibiting high hydrogen electrosorption

Carbon materials capable of efficient hydrogen electrosorption at ambient conditions can be used for negative electrode material in chemical power sources, competitive for metallic hydride alloys. This paper describes physical, chemical and electrochemical properties of active carbon (LAC) produced from lignin processed by standard carbonization and KOH activation at temperature of 950 °C. Microporous carbon with BET surface of 1946 m²/g obtained in such conditions has a complex porous structure with a considerable number of supermicropores and small mesopores (ca. 50%). As a result, efficient hydrogen electrosorption of 510 mA h/g (1.89 wt% in meaning of energy storage) is obtained and favorable discharge characteristics at current densities up to 1 A/g.     

Easy synthesis of highly nitrogen-enriched graphitic carbon with a high hydrogen storage capacity at room temperature

An easy method for synthesizing highly nitrogen-enriched graphitic carbon was developed and its hydrogen storage capacity was explored. The synthesis method uses a solution-based, stepwise condensation reaction between cyanuric chloride and melamine at low temperature (e.g., 0, 25, and 120 °C) and ambient pressure using conventional glassware without the need for an autoclave vessel. The physical and chemical structure of the synthesized highly nitrogen-enriched graphitic carbon was investigated by powder X-ray diffraction, scanning and transmission electron microscopy, selected area electron diffraction, energy dispersive spectroscopy, elemental analysis, Fourier transform infrared spectroscopy, X-ray photoemission spectroscopy, and electron energy loss spectroscopy. The analyzes confirmed that the product has a highly crystalline nitrogen-enriched graphitic structure (d₀₀₂ = 0.324 nm) with a carbon-to-nitrogen ratio of 1:1.12 (>50 atomic% nitrogen content). The material was determined to have an excellent hydrogen storage capacity of 0.34 wt% at room temperature under 100 bar in spite of its low BET surface area of only ∼10 m²/g.     

Enhanced compressive strength of carbon aerogels with low density and high specific surface areas

Journal of Porous Materials - Glycidol was firstly used as catalyst to synthesize resorcinol (R) and formaldehyde (F) aerogels and carbon aerogels (CAs). The density, morphology, specific surface...     

乙醇催化裂解法制备高储氢量碳纳米管

采用乙醇催化裂解法制备碳纳米管,有效解决了以烃为碳源制备的碳纳米管的团聚、长度不可控、分离纯化复杂、得率低的难题。透射电镜和Raman光谱分析表明,使用乙醇催化裂解法可以直接制备纯度高、管长适中的离散碳纳米管。这种碳纳米管在600℃以下时不分解,吸附性能优异,在298℃、15MPa时最大吸氢量为6.90%,远高于以苯为碳源制备的碳纳米管的最大吸氢量(1.65%),已达到美国能源车用储氢系统的标准。     

大容量镁基储氢材料及其储氢性能

结合Mg-C纳米晶复合储氢材料的研究,对目前大容量镁基储氢材料研究结果进行了分析,指出用机械合金化法制备Mg纳米晶可提高其储氢密度、改善其动力学性能,但材料放氢温度一般较高。作者课题组将碳微晶与Mg复合,并引入金属催化剂,以降低MgH2分解温度。差热扫描量热分析(DSC)表明Mg-C纳米晶复合储氢材料的初始放氢温度为201~240℃,降低了60~90℃,其热力学性能得到了较大的改善。     

Molybdenum carbide-derived carbon for hydrogen storage

Physisorption of hydrogen in microporous molybdenum carbide (Mo₂C)-derived carbons has been studied as a function of synthesis conditions. Changes in local structure induced by varying the chlorination temperature afford controllable variations in average pore size and specific surface area. Optimal hydrogen storage capacity of 4.3 wt%, measured at −196 °C and 35 bar pressure, is obtained from a sample chlorinated at 660 °C for 3 h. This optimum correlates with the largest fraction of total pore volume having average pore sizes in the 0.6–0.8 nm range.     

Enhanced hydrogen storage by spillover on metal-doped carbon foam: an experimental and computational study

A lightweight, oxygen-rich carbon foam was prepared and doped with Pd/Hg alloy nanoparticles. The composite revealed high H2 sorption capacity (5 wt%) at room temperature and moderate pressure (2 MPa). The results were explained on the basis of the H2 spillover mechanism using Density Functional Theory.     

碳纳米管储氢性能的研究进展

介绍了单壁碳纳米管和多壁碳纳米管对氢气的吸附实验和模拟计算研究进展;综述了该领域的最新研究成果;讨论了碳纳米管储氢性能的可行性和应用前景。     

Carbon aerogels from acetic acid catalysed resorcinol-furfural using supercritical drying for hydrogen storage

Organic aerogels were derived from acetic acid catalysed resorcinol and furfural and then dried directly in supercritical carbon dioxide without the use of a solvent exchange process. These aerogels were further carbonised in nitrogen and activated in CO₂ in order to obtain their corresponding carbon aerogels. The carbon aerogels prepared by this method had a greater proportion of micropores in addition to a much shorter preparation time (on the order of days) than those prepared by other studies. The effect of different drying techniques on the microstructure of the wet gels was investigated by nitrogen adsorption at cryogenic liquid nitrogen temperature. Nitrogen adsorption at 77 K allowed the determination of surface areas and pore volumes, further analysed by the Dubinin-Radushkevich model and density functional theory model. The surface area and micropore volume of carbon aerogels prepared by this method increased by 19% and 12%, and accordingly, hydrogen uptake capacity was increased by 10% from 4.9 ± 0.2 wt.% to 5.4 ± 0.3 wt.% at 4.6 MPa and 77 K.     

The effects of multi-walled carbon nanotubes graphitization treated with different atmospheres and electrolyte temperatures on electrochemical hydrogen storage

Using multi-walled carbon nanotubes (MWCNTs), the present study focuses on their electrochemical hydrogen storage capacities. The results showed that the hydrogen desorption process is composed of two steps with voltages around −0.75 and −0.15 V. Hydrogen adsorption at −0.15 V took place at temperatures above 30 °C, and the amount of energy required for adsorbing hydrogen was 1.68 eV. The hydrogen storage capacity increased with increasing electrolyte temperature from 30 to 60 °C in both steps. The hydrogen storage capacity of the MWCNTs treated at different atmospheres showed that the decrease in the graphitization of MWCNTs led to the increase in hydrogen adsorption. The results also showed that the MWCNTs treated in a CO₂ atmosphere had the highest hydrogen storage capacity at −0.15 V.     

Low-temperature thermal energy storage with polymer-derived ceramic aerogels

Thermal energy storage (TES) with phase change materials (PCMs) presents some advantages when shape-stabilization is performed with ceramic aerogels. These low-density and ultra-porous materials guarantee high energy density and can be easily regenerated through simple pyrolysis while accounting for moderate mechanical properties. However, the small pore size that typically characterizes these sorbents can hinder the crystallization of PCMs, slightly reducing the energy density of the stabilized compound. In this work, we present the use of polymer-derived mesoporous SiC and SiOC aerogels for the stabilization of polyethylene glycol and a fatty alcohol (PureTemp 23), having a melting temperature of 17 and 23°C, respectively. Their TES performances point out maximum thermal efficiency values of around 80%. These performances are discussed accounting for the results of thermogravimetric analysis, differential scanning calorimetry, and leaking tests.     

碳基吸附储氢材料

本文综述了活性炭、活性碳纤维、碳纳米纤维和碳纳米管的结构与储氢性能．活性炭只是在低温下才有好的吸附储氢性能,碳纳米材料吸附储氢对于工业应用还不成熟．活性碳纤维是一种可大规模生产且成本较低的微孔吸附材料,其作为储氢材料具有一定的工业前景．     

Preparation of controlled porosity carbon aerogels for energy storage in rechargeable lithium oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol and formaldehyde catalyzed by sodium carbonate followed by carbonization of the resultant aerogels in an inert atmosphere. Pore structure of carbon aerogels is adjusted by changing the molar ratio of resorcinol to catalyst during gel preparation and also pyrolysis under Ar and activation under CO₂ atmosphere at different temperatures. The prepared carbons are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested in a Li/O₂ cell. Through the galvanostatic charge/discharge measurements, it is found that the cell performance (i.e. discharge capacity and discharge voltage) depends on the morphology of carbon and a combined effect of pore volume, pore size and surface area of carbon affects the storage capacity. A Li/O₂ cell using the carbon with the largest pore volume (2.195 cm³/g) and a wide pore size (14.23 nm) showed a specific capacity of 1290 mA h g⁻¹.     

Activation of carbon nanofibres for hydrogen storage

The present study was aimed to investigate different methods of activation of carbon nanofibres, CNF, in order to determine the beneficial effect on the hydrogen sorption capacities of increasing the surface area. Two activation systems were used: physical activation with CO₂ and chemical activation with KOH. A range of potential adsorbents were thus prepared by varying the temperature and time of activation. The structure of the CNF proved more suitable to activation by KOH than by CO₂, with the former yielding higher surface area carbons (up to 1000 m² g⁻¹). The increased surface area, however, did not correspond directly with a proportional increase in hydrogen adsorption capacity. Although high surface areas are important for hydrogen storage by adsorption on solids, it would appear that it is essential that not only the physical, but also the chemical, properties of the adsorbents have to be considered in the quest for carbon based materials, with high hydrogen storage capacities.     

Molybdenum doped carbon aerogels with catalytic potential

Mo-doped carbon aerogels were obtained in the polycondensation reaction of aqueous resorcinol and formaldehyde by adding Mo-salt at two different stages of the synthesis: (i) to the initial sol; (ii) by incipient wetting impregnation of the supercritically dried polymer gel. Molybdenum added during the polymerization yielded a more compact gel structure with practically no mesoporosity. With post-impregnation, by contrast, mesopores of diameter 3–15 nm were generated. Carbonization appreciably enhanced the microporous character of both samples, but in the mesopore range their pore size distribution was conserved. The Mo-content of the samples was also different: Mo was lost during the solvent exchange before the supercritical drying (i.e., the Mo failed to bind chemically to the polymer matrix). The residual Mo congregated into 25–60 nm bulk clusters of α-Mo₂C. In the other carbon aerogel, finely dispersed α-Mo₂C and η-Mo₃C₂ crystals formed, of size 8–20 nm. On the surface of both carbons the Mo formed oxides. In the model test reaction (acetic acid hydroconversion) the catalytic activity of both carbon aerogels was enhanced by molybdenum. The more open pore structure, higher concentration and finer Mo distribution, as well as its chemical form, may all be responsible for the greater conversion and higher value products obtained with the post-impregnated sample.     

Structural changes in carbon aerogels with high temperature treatment

The structural change of carbon aerogels at high temperatures up to 2800°C has been investigated. Change in microtexture of fine particles, which constitute carbon aerogels derived from phenolic resin, was of a typical non-graphitized carbon. The microporosity decreased with an increase of heat-treatment temperature, and disappeared at 2000°C. The mesoporosity still remained even after heat-treatment up to 2800°C, though 50% of mesopore volume was lost because of the fusion of the particles with the change of carbon microtexture.     

Metal-assisted hydrogen storage on Pt-decorated single-walled carbon nanohorns

The catalytic dissociation of hydrogen molecules by metal nanoparticles and spillover of atomic hydrogen onto various supports is a well-established phenomenon in catalysis. However, the mechanisms by which metal catalyst nanoparticles can assist in enhanced hydrogen storage on high-surface area supports are still under debate. Experimental measurements of metal-assisted hydrogen storage have been hampered by inaccurate estimation of atomically stored hydrogen deduced from comparative measurements between metal-decorated and undecorated samples. Here we report a temperature cycling technique combined with inelastic neutron scattering (INS) measurements of quantum rotational transitions of molecular H₂ to more accurately quantify adsorbed hydrogen aided by catalytic particles using single samples. Temperature cycling measurements on single-wall carbon nanohorns (SWCNHs) decorated with 2–3 nm Pt nanoparticles showed 0.17% mass fraction of metal-assisted hydrogen storage (at ≈0.5 MPa) at room temperature. Temperature cycling of Pt-decorated SWCNHs using a Sievert’s apparatus also indicated metal-assisted hydrogen adsorption of ≈0.08% mass fraction at 5 MPa at room temperature. No additional metal-assisted hydrogen storage was observed in SWCNH samples without Pt nanoparticles cycled to room temperature. The possible formation of C–H bonds due to spilled-over atomic hydrogen was also investigated using both INS and density functional theory calculations.     

等离子体法制备掺杂Ni碳材料的储氢性能

引言氢能是可再生的理想洁净能源,人类出于对环境的保护和化石燃料趋于短缺的考虑,太阳能和氢能的利用已是本世纪能源领域发展的必然趋势。特别是在燃料电池迅速发展并获得突破的今天,更安全、灵活和有效的氢能储藏技术的研究受到全球的广泛关注[1]。在吸附储氢材料中,碳质材料由于其质量轻、比表面积高和合适的结构引起了广泛的重视[2-10]。Yang等[11-12]发现在碳上掺杂过渡金属(Rh、Pt、     

Hydrogen storage in trimethylamine hydrate: Thermodynamic stability and hydrogen storage capacity of hydrogen+trimethylamine mixed semi-clathrate hydrate

The thermodynamic stability and hydrogen occupancy for the hydrogen+trimethylamine mixed semi-clathrate hydrate system were investigated by means of phase equilibrium (pressure–temperature) measurements and Raman spectroscopic analyses. The hydrogen molecule gradually advanced to occupy the empty small cage of trimethylamine hydrate in proportion to pressure increase. Almost all small cages were filled up with the hydrogen molecules at about 80 MPa. Isothermal Raman spectroscopic analysis showed that the absorption-rate of hydrogen to the pre-treated trimethylamine hydrate was comparable to those of tetrahydrofuran hydrate. Only one hydrogen molecule was enclosed with one small cage at the equilibrium state in pre-treated trimethylamine hydrate.