不同结构的碳纳米管的氢吸附行为

Several kinds of multi-wall carbon nanotubes (MWNTs) with different morphology were synthesized using catalytic decomposition of hydrocarbons over different metal catalysts.The products were characterized by TEM, HREM and SEM. Hydrogen adsorption properties of the MWNTs were investigated by volumetric measurement at room temperature under a modest pressure(6—7 MPa).The results indicate that both the structure of the MWNTs and the metal catalysts will affect the hydrogen adsorption capacity of the sample...     

氢气在大量高纯度定向碳纳米管束中的吸附

Multi-walled carbon nanotubes with uniform diameters and automatically assembled into densely aligned bundles prepared by a bulky yield and high purity were applied as hydrogen absorbant at room temperature under moderate pressure to absorb H_2. Both the surface of nanotubes and the interstitial space among tubes are possible sites for hydrogen molecules to adhere. The hydrogen uptake capacity is 0.82% (mass)and the interstitial position is considered as a promising site for hydrogen absorption.     

Preparation of Isolated Single-walled Carbon Nanotubes with High Hydrogen Storage Capacity

Isolated single-walled carbon nanotubes with high proportion of opening tips were synthesized by using alcohol as carbon source. The mechanism of cutting action of oxygen was proposed to explain its growth. Compared with carbon nanotubes synthesized with benzene as carbon source, their specific surface area was heightened by approximately 2.2 times (from 200.5 to 648 m2/g) and the hydrogen storage capacity was increased by approximately 6.5 times (from 0.95 to 7.17%, w) which had exceeded DOE energy standard of vehicular hydrogen storage.     

Non-linear modeling of kinetic and equilibrium data for the adsorption of hexavalent chromium by carbon nanomaterials:Dimension and functionalization

The adsorption capacities for the removal of hexavalent chromium from aqueous solutions by six carbon nanomaterials have been evaluated. Single-walled and multi-walled carbon nanotubes as received and after oxidation treatment, graphene oxide and reduced graphene oxide are the materials with different dimension and functionalization compared in this research. Carbon nanotubes have been modified using hydrogen peroxide as oxidizing agent under microwave radiation. The oxidation treatment on carbon nanotubes has a positive effect increasing the adsorbent–adsorbate interaction. Rate-controlling mechanisms and equilibrium data are analyzed using non-linear models. Non-linear method is proposed as the most suitable method for determining the kinetic and equilibrium parameters. The values of adsorption energy(E) obtained from the Dubinin–Radushkevich isotherm,have been found around 0.371 and 0.870 k J·mol~(-1), indicating physical adsorption. Therefore, the pseudo-second order model represents better the kinetic experimental data. The results show that the Langmuir isotherm provides a slightly better fit to the experimental data compared with the Freundlich isotherm, indicating homogeneous distribution of active sites on carbon nanomaterials and monolayer adsorption. The separation factors RLare found in the range of 0–1, suggesting that the adsorption process is suitable for all adsorbents. The mechanisms for hexavalent chromium removal have been proposed as electrostatic interactions and hydrogen bonding.     

Adsorption equilibria of paeoniflorin and albiflorin on cyano-silica column from supercritical carbon dioxide/ethanol

Adsorption equilibria of paeoniflorin and albiflorin on a cyano-silica column(CN column) from the solution of supercritical carbon dioxide(scCO_2) modified with ethanol were studied. The adsorption capacity at 308.15 K,313.15 K, 318.15 K and 323.15 K under pressures corresponding to carbon dioxide/ethanol densities from0.347 g·cm~(-3) to 0.662 g·cm~(-3) were determined using the elution by characteristic point method(ECP). The effects of temperature and pressure on the solute loading were investigated. The results showed that the lower the temperature, the higher the adsorption capacity. With the decrease of density of scCO2, the adsorption capacity strengthens. The maximum adsorption capacity of paeoniflorin(albiflorin) on the CN column was15.24 mg·ml~(-1)(31.14 mg·ml~(-1)) in the range of 0–1.84 mg·ml~(-1)(0–1.67 mg·ml~(-1)) of paeoniflorin(albiflorin)standard solution. The adsorption capacity of albiflorin was twice as much as that of paeoniflorin under the same conditions. Adsorption data of paeoniflorin and albiflorin could be well described by the Langmuir model and Freundlich model. Compared with the two model fitting results, the adsorption of paeoniflorin and albiflorin belonged to the monolayer adsorption under conditions of 308.15–323.15 K and 10–17 MPa.     

Peanut Shell Activated Carbon： Characterization,Surface Modification and Adsorption of Pb^2＋ from Aqueous Solution

Metal ion contamination of drinking water and waste water, especially with heavy metal ion such as lead, is a serious and ongoing problem. In this work, activated carbon prepared from peanut shell （PAC） was used for the removal of Pb^2＋ from aqueous solution. The impacts of the Pb25 adsorption capacities of the acid-modified carbons oxidized with HNO3 were also investigated. The surface functional groups of PAC were confirmed by Fourier transform infrared （FTIR） spectroscopy, X-ray photoelectron spectroscopy （XPS）, Boehm titration. The textural properties （surface area, total pore volume） were evaluated from the nitrogen adsorption isotherm at 77 K. The experimental results presented indicated that the adsorption data fitted better with the Langmuir adsorption model. A comparative study with a commercial granular activated carbon （GAC） showed that PAC was 10.3 times more efficient compared to GAC based on Langmuir maximum adsorption capacity. Further analysis results by the Langmuir equation showed that HNO3 [20% （by mass）] modified PAC has larger adsorption capacity of Pb^2＋ from aqueous solution （as much as 35.5 mg·g^-1）. The adsorption capacity enhancement ascribed to pore widening, increased cation-exchange capacity by oxygen groups, and the promoted hydrophilicity of the carbon surface.     

Removal of diclofenac from aqueous solution with multi-walled carbon nanotubes modified by nitric acid☆

Modified multi-walled carbon nanotubes (MWCNTs) were used as adsorbents for removal of diclofenac. The re-action conditions were examined. Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models were applied to determine appropriate equilibrium expression. The results show that the experimental data fit the Freundlich equation well. Thermodynamic parameters show that the adsorption process is spontaneous and exothermic. The kinetic study indicates that the adsorption of diclofenac can be well described with the pseudo-second-order kinetic model and the process is controlled by multiple steps.     

碳纳米管及C60和石墨氧化动力学机理函数的分析

The oxidation of carbon nanotubes, C60 and graphite was studied by thermogravimetric (TG) analysis and differential thermal analysis (DTA) technique, and the oxidation kinetic models of three carbon materials studied were analyzed by mechanism-function method. The results indicate that three carbon species adopt different oxidation mechanisms due to their different structures. The oxidation of carbon nanotubes with cylindrical structure follows contracting volume reaction mechanism [R3 mechanism, 1-(1-α)1/3 = kt], indicating that the oxidation of carbon nanotubes takes place from the ends to the center. For graphite with planar sandwich structure, the oxidation starts at the edges initially and gradually moves toward the center, which corresponds to contracting area phase boundary reaction mechanism [R2 mechanism, 1-(1-α)1/2 = kt]. The oxidation of C60 with spherical structure, however, is complex and apparently cannot be illustrated with a single kinetic model. The values of apparent activation energy     

ZL50活性炭吸附脱除二氧化硫的吸附动力学模型(英文)

A semi-empirical adsorption kinetic model was proposed with the time compensation method to describe the chemisorption of SO2 in flue gas by carbon adsorbents for flue gas purification. The change in adsorption capacity and adsorption rate with time at different water vapor concentrations and different SO2 concentrations was studied. The model was in good agreement with experimental data. The surface reaction was probably the rate controlling step in the early stage for SO2 adsorption by ZL50 activated carbon. The parameters m and n in the nth order adsorption kinetic model were related to the magnitude of the time compensation and adsorption driving force, respectively. The change of parameter n with water vapor concentrations and sulfur dioxide concentrations was studied and some physical implications were given. The sum of square errors was less than 1.0 and the average absolute percentage deviations ranged from 0.5 to 3.2. The kinetic model was compared with other models in the literature.     

Effect of Carbon Source on Crystal Morphology of SiC in-situ Formed in AI2O3-Si-C Matrix

Three kinds of Al2O3- Si- C matrix specimens were prepared using tabular corundum powder and Si powder as starting materials,ultrafine flake graphite,nano carbon black,and carbon nanotubes as carbon sources,respectively,to research the effect of micro or nano carbon materials on structure and morphology of formed Si C crystals. The specimens were fired at 1 000,1 200 and 1 400℃ for 3 h in carbon-embedded condition,respectively.The phase composition was studied by XRD and the crystal morphology of Si C was investigated by FESEM. The results show that:( 1) the amount of Si C increases with the firing temperature rising;( 2) the in-situ reaction mechanism and the formed Si C crystal morphology vary with carbon source: carbon nanotubes are generally converted into Si C whiskers by carbon nanotubes-confined reaction; Si and nano carbon black react to nucleate quickly,and the nucleated Si C crystals grow evenly in all directions forming Si C particles; Si C whiskers are produced from edge to internal of ultrafine flake graphite.     

STORAGE OF HYDROGEN ON CARBON MATERIALS: EXPERIMENTS AND ANALYSES

Superactivated carbon and carbon nanotubes are both considered potential hydrogen carriers. Adsorption isotherms of H₂ on activated carbon AX-21 and multi-wall carbon nanotubes were collected with a volumetric method for the temperature range of 77, 233-298 K and pressures up to 7 or 10 MPa. Based on the experimental data for 233-298 K, the limiting heats of adsorption of 7.6 and 1.8 kJ/mol were obtained for activated carbon and carbon nanotubes, respectively. The absolute adsorption was determined with a recently presented method, and the adsorption behavior of H₂ on carbon nanotubes was thus reasonably explained. A comparison was given for the storage capacities of compression alone and of filling powder or pellets of the two materials. It was concluded that adsorption of H₂ on carbon nanotubes is too weak to enhance storage, but activated carbon enhances storage capacity considerably. The weight percentage of hydrogen stored in carbon powder reaches 10.8% at 77 K and 6 MPa, including the quantity compressed in the void space, and 4.1 kg H₂ was stored in a 100-liter container filled with carbon pellets for the same condition.     

STORAGE OF HYDROGEN ON CARBON MATERIALS: EXPERIMENTS AND ANALYSES

Superactivated carbon and carbon nanotubes are both considered potential hydrogen carriers. Adsorption isotherms of H₂ on activated carbon AX-21 and multi-wall carbon nanotubes were collected with a volumetric method for the temperature range of 77, 233–298 K and pressures up to 7 or 10 MPa. Based on the experimental data for 233–298 K, the limiting heats of adsorption of 7.6 and 1.8 kJ/mol were obtained for activated carbon and carbon nanotubes, respectively. The absolute adsorption was determined with a recently presented method, and the adsorption behavior of H₂ on carbon nanotubes was thus reasonably explained. A comparison was given for the storage capacities of compression alone and of filling powder or pellets of the two materials. It was concluded that adsorption of H₂ on carbon nanotubes is too weak to enhance storage, but activated carbon enhances storage capacity considerably. The weight percentage of hydrogen stored in carbon powder reaches 10.8% at 77 K and 6 MPa, including the quantity compressed in the void space, and 4.1 kg H₂ was stored in a 100-liter container filled with carbon pellets for the same condition.     

碳基吸附剂储氢吸附热的密度泛函理论

为比较狭缝孔、纳米管两种典型碳基吸附剂的储氢性能,应用非局域密度泛函理论、微观物理学、吸附平衡原理、典型吸附剂储氢试验结果计算并分析了典型碳基吸附剂的氢等量吸附热.结果表明,两类吸附剂的氢等量吸附热相差不大,等温线变化规律相似,并且只有在低温（液氮）、适度压力时吸附储氢的质量密度才有望达到DOE标准.     

纳米碳管吸附储氢

由于纳米碳管具有独特的结构和性质，纳米碳管吸附储氢一直是纳米碳管以及氢能利用技术研究的热点问题。国内外众多的实验研究结果和理论分析也展示了纳米碳管所具有的优良吸附储氢性能和广泛的应用前景。对纳米碳管储氢过程进行更为深入的实验和理论研究将有助于推动储氢技术和氢能的开发利用。     

Doping effects of B and N on hydrogen adsorption in single-walled carbon nanotubes through density functional calculations

The doping effects of B and N on atomic and molecular adsorption of hydrogen in single-walled carbon nanotubes (SWNTs) were investigated through density functional theory (DFT) calculations. The hydrogen adsorption energies and electronic structures were calculated for the pristine and B- or N-doped SWNTs. The B-doping increases the hydrogen atomic adsorption energies both in zigzag and armchair nanotubes. The B-doping forms an electron-deficient six-membered ring structure, and when hydrogen is adsorbed on top of B atom, a coordination-like B-H bond will form. The N-doping forms an electron-rich six-membered ring structure, and decreases the hydrogen atomic adsorption energies in the N-doped SWNT. In case of hydrogen molecular adsorption, both B- and N-doping decrease the adsorption energies in SWNTs.     

Preparation of short carbon nanotubes by mechanical ball milling and their hydrogen adsorption behavior

Short multi-wall carbon nanotubes (MWNTs) with open tips were obtained by mechanical ball milling. The microstructure characteristics of MWNTs before and after ball milling were checked by transmission electron microscopy (TEM). The effect of ball milling on the hydrogen adsorption behavior of the MWNTs was studied. The hydrogen adsorption experiments were carried out at room temperature under a pressure of 8-9 MPa. The hydrogen adsorption capacity of carbon nanotubes milled for 10 h was 0.66 wt%, which was about six times that of MWNTs without milling. For the carbon nanotubes milled with MgO for 1 h, a hydrogen adsorption capacity of 0.69 wt% was obtained. The enhancement of hydrogen adsorption might result from the increase of defects and surface area of the MWNTs caused by ball milling.     

单壁纳米碳管的纯化及其储氢特性

针对半连续氢电弧法制备的单壁纳米碳管提出了一种纯化方法。采用HNO3和H2O2回流水煮的方法对单壁纳米碳管进行了纯化处理，透射电镜观察及热重分析表明样品中的无定形炭、纳米碳颗粒及金属催化剂颗粒等杂质可被有效去除，提纯后单壁纳米碳管的收率约为35％，纯度在95％以上；研究发现该纯化方法对单壁纳米碳管的孔径分布和比表面积有较大影响。采用体积法测定了纯化前后单壁纳米碳管样品的储氢容量，结果表明纯化样品的储氢量为1．65％，比未提纯样品（0．56％）有较大提高。     

过渡金属修饰的碳纳米管降低烟气中氢氰酸

分别制备了高产率的修饰铁、钴、镍的碳纳米管,将铁、钴、镍修饰的碳纳米管添加到卷烟嘴棒中可提高烟气中有害成分氢氰酸的吸附效果。实验结果表明：添加了修饰铁、钻、镍的碳纳米管的卷烟嘴棒,可明显选择性降低烟气中有害成分氢氰酸的含量,其中铁修饰碳纳米管降低氢氰酸和焦油的效果最好,随着铁修饰碳纳米管的添加量增加,烟气中氢氰酸和焦油的量减少,烟气中氢氰酸的含量减少16．8％-32％,焦油的含量降低9．8％～26％。     

Adsorption of hydrogen on single-walled carbon nanotubes with defects

We present molecular dynamics (MD) simulations and density functional theory (DFT) calculations of hydrogen adsorption on single-walled carbon nanotubes (SWCNT) with various kinds of defects. The nature of defects, which is characterized here by the number of carbon atoms present in a ring on the surface of nanotube, plays a significant role in determining the hydrogen adsorption capacity of the SWCNT. Nanotubes containing the Stone–Wales defect with 5 and 8-member rings were found to have the largest hydrogen adsorption ability that increases further with the number of rings with such defects. Whereas, the presence of defects with 5, 3-5-8-member rings and the Stone–Wales defect with 5 and 7-member rings decreases the adsorption ability of the defective SWCNT significantly with respect to defect-free nanotubes. Our results indicate that the huge discrepancies in hydrogen storage capacities of SWCNT reported in the literature could be attributed to the nature of defects present in nanotubes. DFT calculations also reveal that the adsorption energy depends not only on the nature and number of defects present on the surface of nanotube but also on the equilibrium structure of rings.     

Hydrogen adsorption in different carbon nanostructures

Hydrogen adsorption in different carbonaceous materials with optimized structure was investigated at room temperature and 77 K. Activated carbon, amorphous carbon nanotubes, SWCNTs and porous carbon samples all show the same adsorption properties. The fast kinetics and complete reversibility of the process indicate that the interaction between hydrogen molecules and the carbon nanostructure is due to physisorption. At 77 K the adsorption isotherm of all samples can be explained with the Langmuir model, while at room temperature the storage capacity is a linear function of the pressure. The surface area and pore size of the carbon materials were characterized by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. A linear relation between hydrogen uptake and specific surface area (SSA) is obtained for all samples independent of the nature of the carbon material. The best material with a SSA of 2560 m²/g shows a storage capacity of 4.5 wt% at 77 K.