碳纳米管的活化处理及对其电化学容量影响的研究

采用KOH为活性剂,对碳纳米管进行活化处理,经透射电子显微镜和高分辨透射电子显微镜从不同角度观察,发现得到了两端开口,管长较短,管壁粗糙的活性碳纳米管．用氮气自动吸附仪测试了活化前后两种碳纳米管的比表面积,发现活性碳纳米管具有比活化前碳纳米管更高的有效比表面积,将这两种碳纳米管分别作为电极材料应用于电化学超级电容器,经测试,发现活化后的碳纳米管的电化学容量大大提高,在有机电解液中达到了50F／g．     

磷钼酸作为低温碳燃料电池的碳间接电氧化介质

以磷钼酸作为低温下碳间接电氧化的介质构建新型碳燃料电池。通过线性电位扫描和计时电流法研究不同碳材料、不同反应条件、不同反应时间、不同磷钼酸浓度对碳间接电氧化性能的影响。采用循环伏安法研究碳在磷钼酸介质中的间接电氧化机理。研究结果表明,椰壳活性炭的间接电氧化活性要明显高于煤和煤质活性炭。以磷钼酸为介质时,采用光照与升温80oC避光的条件均可以提高碳间接电氧化性能,且提高程度接近。由循环伏安测试分析出磷钼酸中+6价Mo可将碳氧化,且被还原成+5价Mo,随后又在阳极上重新被电氧化回+6价Mo,通过该过程将从碳材料上获得的电子转移到阳极上,从而实现碳在低温条件下的间接电氧化过程。并且通过对光照条件的分析,证实光对磷钼酸催化碳电氧化反应有两方面的促进作用:一方面光的热效应使反应温度升高,从而提高反应速率;另一方面磷钼酸利用其特有结构吸收光能,提高磷钼酸与碳的反应速率,且后者促进作用更明显。以VO2+/VO2+为阴极构建的碳燃料电池全电池室温下功率是0.087m W?cm-2,验证了碳燃料电池在常温条件下运行的可行性。     

HCSE method for detection of small carbon–carbon couplings and their signs,comparison with SLAP pulse sequence

Performance of homonuclear coupling sign edited (HCSE) experiment applied to detection of signed carbon–carbon couplings is discussed using a set of already measured samples of nine monosubstituted benzenes. It is shown that coupling sign detection is insensitive to the settings of carbon–carbon polarization transfer delays. The HCSE spectra of ten from the total of 43 measured carbon–carbon couplings were considerably influenced by relaxations and proton–proton strong couplings. These effects are quantitatively discussed. The results of HCSE and SLAP experiments are compared. It is shown that the two methods may complement each other in detection of signed carbon–carbon couplings. Copyright © 2013 John Wiley & Sons, Ltd.     

镍铝催化剂吸附动力学参数的非线性动态分析

在推导出适应于甲烷化反应体系非线性动态分析不同吸附物种动力学参数模型的基础上，采用计算优化出工业镍铝甲烷化催化剂上可逆吸附氢和可逆吸附一氧化碳的吸附速率常数和吸附平衡常数。结果表明，镍铝催化剂上吸附可逆氢要比吸附一氧化碳快２．２倍左右。该结果为镍铝催化剂上甲烷化产物的生成主要依赖于一氧化碳的吸附这一判断提供了理论依据。由于镍铝催化剂上甲烷化是可逆吸附氢与不可逆吸附一氧化碳共同作用的结果，且不可逆吸     

The Nature of One‐Dimensional Carbon: Polyynic versus Cumulenic

A question of both fundamental as well as practical importance is the nature of one‐dimensional carbon, in particular whether a one‐dimensional carbon allotrope is polyynic or cumulenic, that is, whether bond‐length alternation occurs or not. By combining the concept of aromaticity and antiaromaticity with the rule of Peierls distortion, the occurrence and magnitude of bond‐length alternation in carbon chains with periodic boundary conditions and corresponding carbon rings as a function of the chain or ring length can be explained. The electronic properties of one‐dimensional carbon depend crucially on the bond‐length alternation. Whereas it is generally accepted that carbon chains in the limit of infinite length have a polyynic structure at the minimum of the potential energy surface with bond‐length alternation, we show here that zero‐point vibrations lead to an effective equalization of all carbon–carbon bond lengths and thus to a cumulenic structure.     

Equilibrium locations for nested carbon nanocones

Potentially, carbon nanostructures are very important as ideal components to create many novel nano-devices. Such devices including nano-oscillators, ultra-fast optical filters and nano-bearings, are based on the unique mechanical and electronic properties of carbon nano-structures. Common carbon nanostructures used are usually C₆₀-fullerenes, carbon nanotubes, carbon nano-bundles and carbon nanotori. In the synthesis and production of carbon nanostructures, carbon nanocones tend to occur less frequently, and it is known that five different size cones may occur, depending on the number of pentagons in the atomic network. However, the simple geometric structure of carbon nanocones certainly facilitates calculations for their potential energy. Here, the Lennard–Jones potential energy function and the usual continuum approximation are employed to determine the energy for two such nested carbon nanocones which are located co-axially. We show graphically the energy profiles for any two carbon nanocones arising from the five possible structures. For both two distinct cones and two identical cones, we find that the equilibrium location moves further away from the vertex as the number of pentagons is increased. However, we observe that the equilibrium position occurs such that one cone is always inside the other, and therefore, we might expect that nested double-cones are formed according to these results.      

Dioxetanones’ peroxide bond as a charge-shifted bond: implications in the chemiluminescence process

Six dioxetanone molecules, ranging in complexity from simple dioxetanone to firefly dioxetanone, were studied by performing M06/6-311G(d,p) calculations. The quantum theory of atoms in molecules and the electron localization function was applied to analyze the peroxide and carbon–carbon bonds of the dioxetanone ring. Both approaches demonstrated that the peroxide bond is not covalent, but charge-shifted. This means that for this bond the covalent “electron sharing” is relatively unimportant, and it is the stabilizing resonance energy that causes the bonding. For the contrary, the carbon–carbon bond is covalent. These discoveries indicate that no biradical species should be formed in the dioxetanone decomposition, and that the most probable rate-determining step should be the carbon–carbon cleavage.     

Influence of Electric Field on Dispersion of Carbon Nanotubes in Liquids

Production processes for carbon nanotubes commonly produce mixtures of solid morphologies that are mechanically entangled or that self‐associate into aggregates. The entangled or aggregated carbon nanotubes often need to be dispersed in corresponding material matrices in order to develop materials that have unique mechanical characteristics or transport properties. The most effective method for dispersion of carbon nanotubes is to prepare fluid suspensions of them in liquid media with applications of surfactant or/and ultrasonication. The authors propose an innovative dispersion method for carbon nanotubes by which an electric field is applied to suspensions of carbon nanotubes in liquids treated by surfactant and ultrasonication. Compared to dispersion without the electric field, the dispersion status of carbon nanotubes in liquid media is evidently improved with the electric field. The results indicate that the electric field conditions are effective for dispersion of carbon nanotubes in liquids and that complex effects of electric field, surfactant, and ultrasonication are beneficial for improvement of dispersion of carbon nanotubes.     

Pt/C和Pt/CNTs电极的电化学稳定性研究

采用恒电位氧化法研究了Pt/C和Pt/CNTs电极的电化学稳定性. 相同条件下, Pt/C电极的氧化电流大约为Pt/CNTs电极的2倍; 120 h氧化后, Pt/C电极Pt的电化学表面积下降了21.3%, 而Pt/CNTs电极仅下降了7.6%, 表明Pt/CNTs电极性能衰减较慢. X射线光电子能谱(XPS)分析表明, Pt/C的载体碳黑表面氧增加量大于Pt/CNTs中碳纳米管(CNTs)表面氧的增加量, 说明碳黑的被氧化程度较高, 电化学稳定性差; Pt的表面化学状态没有发生变化; 碳纳米管本身的抗电化学氧化性也大于碳黑. 所以, 载体的被氧化程度不同是两种电极性能衰减不同的主要原因之一, 并且排除了Pt表面状态的影响.     

炭在熔融碳酸盐中的直接电化学氧化性能

研究了活性炭粉在熔融碳酸盐中的直接电化学氧化性能. 通过线性扫描伏安曲线的测试发现, 将炭粉用酸处理, 碳酸盐中的炭含量、炭粒径、反应温度和反应气氛均会对活性炭的电化学氧化性能产生影响. 研究结果表明, 用HCl处理活性炭, 升高反应温度, 适当增加炭含量及炭粒子粒径和通入N2气均会提高活性炭的电化学氧化活性. 经HCl处理的、炭含量为15 g和炭粒径<100 μm的活性炭在850 ℃下、在N2气保护下和电位扫描速率为20 mV/s时的开路电位(OCP)为-1.40 V, 在-0.4 V下的电流密度可达到200 mA/cm2.     

Comparative Study of the Adsorption from Aqueous Solutions and the Desorption of Phenol and Nonylphenol Substrates on Activated Carbons

Adsorption of phenol and nonylphenol from aqueous solutions on microporous activated carbons has been studied. The phenol isotherm changes from L-shaped for surface oxygen group free carbon (I sample) to a two-stepped isotherm for oxidized carbon (IN sample, HNO(3) treated) Furthermore, the adsorbed amounts diminish in about 25% on IN carbon. It is proposed that a change in the adsorption mechanism take place; i.e., weak interaction forces between the pi electrons in phenol and the pi electron in carbon are present on the original I carbon, while a donor-acceptor complex on the oxidized IN carbon is operating between basic surface oxygen groups and phenol aromatic rings. The shape of nonylphenol isotherms is two-stepped for both carbons. The introduction of acidic oxygen surface groups on the carbon enhances the specific nonylphenol adsorption by about 40%. This may be interpreted as being due to the fact that nonylphenol is hydrogen-bonded to the oxidized carbon surface by means of acidic groups. Thermal desorption experiments indicate that phenol is mainly physisorbed. Thermal desorption further confirms that nonylphenol is possibly bonded to oxygen surface groups by hydrogen bonds. Copyright 2001 Academic Press.     

Analytical pyrolysis as a characterization technique for monitoring the production of carbon nanofilaments

The main step in the production of carbon nanofilaments is the catalytic nucleation and lengthening of the filament. An undesired parallel step in the production of carbon nanofilaments is their thickening by pyrolitic carbon vapor deposition consisting in an ordered polycondensation of carbon over an existing catalytic carbon nanofilament. The regular characterization of the structure of carbon nanofilaments (coated or not) is by transmission electron microscopy. However, this technique is not affordable in many cases because is expensive and complex. In the present work, the analytical pyrolysis is proposed to obtain clues of the structure of carbon nanofilaments. Several commercial carbon nanofilaments have been analyzed. The samples with a thicker soot layer evolve a higher amount of heavy PAHs in the pyrolysis runs than the ones free of soot. It has been observed that pyrene is a key compound in the pyrolytic carbon vapor deposition process and the resulting formation of soot over the carbon nanofilaments. The aim of this work is to get useful information about the quality of the carbon filaments by a cheap technique, the analytical pyrolysis.     

碳纳米管电极超大容量离子电容器交流阻抗特性

采用碳纳米管作为超大容量离子电容器的电极材料,应用交流阻抗频谱法,研究了超大容量离子电容器的频率响应特性.结果表明,用碳纳米管块作电极,超大容量离子电容器在频率250 mHz以下出现“电荷饱和”；而用活性炭块作电极, 超大容量离子电容器在频率为100 mHz时仍未出现“电荷饱和”,这说明碳纳米管电极超大容量离子电容器的频率响应特性优于活性炭电极超大容量离子电容器的频率响应特性.上述两类超大容量离子电容器的阻抗谱中均出现倾角约为45°的直线段,其相位角均远小于理想电容器的相位角90°.     

聚醚醚酮/碳纤维复合材料的界面结构以及结晶形态的研究

本文采用扫描电子显微镜观察经氩等离子刻蚀后PEEK/碳纤维复合材料的界面层结构和PEEK树脂的结晶形态。无论是从熔体还是从橡胶体结晶,PEEK树脂的结晶都是从碳纤维表面诱导开始,最后形成横穿晶体结构。在高碳纤维含量的复合材料中,PEEK的球晶尺寸主要由碳纤维之间的距离控制,受温度的影响较小。在PEEK/碳纤维复合材料的结晶过程中,第一片晶片在碳纤维表面取向生长方式为:晶体的ā轴(厚度方向)平行于维纤径 向。b轴(晶片生长方向)与纤维最小圆截面的切线重合,(?)轴(垂直晶片平面的方向)平行于纤维轴向。由于球晶成核过程是取向生长,因而生成的球晶也按一定的方式取向。     

固体核磁碳结构参数的修正及其在煤结构分析中的应用

为消除~(13)C CP/M AS/TOSS NM R测试中碳核NOE效应,获得相对准确的碳结构参数,考察了不同模型化合物的碳核NOE效应强度。结果表明,不同模型化合物碳谱分峰拟合的测试值与样品碳结构参数的理论值之间存在明显误差,其中,脂肪碳在25%-125%、芳香碳为4%-50%,NOE效应在固体核磁碳谱测试中影响显著。为此,将模型化合物脂肪碳和芳香碳的实测值和理论值进行回归分析,得到非线性回归方程。用该方程对9,10-二甲基蒽进行碳结构修正,发现修正后脂肪碳实测值与理论值之间误差由不修正时的119.60%减小至7.84%,芳香碳误差为由不修正时的-17.10%到1.11%,修正后误差均在10%以内;同时用该回归方程修正了不同煤的碳结构参数,发现不同煤未修正的H/C原子比与其元素分析H/C原子比误差在45%-53%,修正后误差只有4%-13%,与元素分析结果具有一致性,表明非线性回归方程能够方便、准确地消除固体核磁NOE效应,为煤中碳结构分析提供新的技术支撑。     

Synthesis of carbon nanotubes by catalytic pyrolysis method with Feitknecht compound as precursor of NiZnAl catalyst

Carbon nanotubes are synthesized by catalytic pyrolysis method with a kind of new type catalyst--nickel-zinc-alumina catalyst prepared from Feitknecht compound. Tubular carbon nanotubes, bamboo-shaped carbon naotubes, herringbone carbon nanotubues and branched carbon nanotubes are all found formed at moderate temperature. It is important for the formation of quasi-liquid state of the metal nanoparticles at the tip of carbon naotubes during the growth of carbon nanotubes to lead to different kinds of carbon nanotubes. It is likely that the addition of zinc make the activity of nickel catalyst after calcinations and reduction changed strangely.     

Carbon nanostructures based on IR-pyrolyzed polyacrylonitrile

For the first time, it is shown that IR pyrolysis of a composite based on polyacrylonitrile and gadolinium chloride produces a metal-carbon nanocomposite where metal particles with a size of 4–11 nm form a fine dispersion in the structure of the carbon matrix. The carbon phase of the composite is a carbon-carbon nanocomposite with a structure in which carbon nanoparticles (bamboolike carbon nanotubes, carbon nanospheres, or octahedral carbon nanoparticles) are incorporated into the matrix graphite-like material.     

Anomalous vibrational energy diffusion in carbon nanotubes

We study the vibrational energy diffusion in single-walled carbon nanotubes by using the molecular-dynamics method. It is found that energy transports ballistically at low temperature and superdiffusively at room temperature. The velocity of energy transport along the axis in carbon nanotube at room temperature is about 0.10 A/fs. It is also found that energy transport in carbon nanotube is different from that one in one-dimensional carbon lattice with the same interaction potential.     

铜锌催化剂上吸附动力学参数的非线性动态分析

本文得到了适应于一氧化碳加氢加压体系非线性动态分析不同吸附物种动力学参数的模型，并优化出工业铜锌催化剂上合成甲醇反应中可逆吸附氢和可逆吸附一氧化碳的吸附速率常数及吸附平衡常数。结果表明：铜锌催化剂上吸附可逆氢比吸附一氧化碳快７倍左右。由于铜锌催化剂上甲醇的生成是可逆吸附氢与可逆吸附一氧化碳共同作用的结果，且铜锌催化剂 可逆吸一氧化碳的表面浓度随气相一氧化碳分压的增加而增加，因而加压将有利于合成甲醇