钾掺杂多壁纳米碳管储氢性能研究

使用自制的钴催化裂解碳氢气法制备多壁纳米碳管,并对其进行退火、掺杂等一系列预处理,然后使用高压高纯氢源,在中压(12 MPa)和室温条件下,进行钾掺杂多壁纳米碳管的储氢性能实验.结果表明:预处理对纳米碳管的储氢性能有很大影响.实验条件下,经过氮气退火,并在1.0 mol/L硝酸钾溶液中掺杂的多壁纳米碳管吸氢量最大(H/C质量分数为3.2%).上述样品在室温下的放氢量一般不超过其吸氢量的50.8%.     

Fe—Co双金属催化剂对纳米碳管规模化生产的影响

在C2H2和N2的氛围下,以Fe－Co双金属氧化物为催化剂,利用催化裂解法大量制备了多壁纳米碳管,实验结果表明,以Fe－Co双金属氧化物为催化剂制备纳米碳管的产量明显高于Fe或Co单独存在时所得的纳米碳管的产量,且Fe摩尔分数为0.2时效果最佳;同时发现,在制备的产品中存在很多螺旋形的纳米碳管,此方法工艺简单,有利于纳米碳管的规模化、大批量生产,为纳米碳管的深入研究及广泛应用打下了基础。     

纳米碳管负载金属镍催化叶绿素加氢反应

用等体积浸渍法制备了纳米碳管负载金属镍催化剂，采用电镜(TEM）、红外光谱（IR）对催化剂的形貌、结构进行了表征.并考察了常温常压下不同Ni负载量的催化剂对叶绿素加氢反应的性能.结果表明，纳米碳管负载镍催化剂在催化反应过程中保持高分散态，不会发生团聚.而经过硝酸氧化后的纳米碳管负载镍催化剂在催化反应中表现出高的活性.当Ni负载量为7％时，催化活性最好，叶绿素分子开环生成各种小分子.     

高Co含量的Co-Mo系列催化剂甲烷裂解制备单壁纳米碳管

制备了高Co含量的Co-Mo／γ-A12O3系列催化剂，发现此类催化剂可以在温和的反应温度下制备高质量的单壁纳米碳管．讨论了Mo组分的作用．认为Mo分散、稳定金属颗粒，促进了SWNTs的生长．同时，Mo组分的升华决定了单壁纳米碳管的生长和管径分布．这为可控地制备单壁纳米碳管提供了依据．     

减压化学气相沉积法制备规则螺旋状纳米碳管

以硅胶负载的Co纳米颗粒为催化剂,在低流量的减压体系中通过化学气相沉积法制备了规则螺旋状的纳米碳管.通过TEM和HRTEM研究了螺旋碳管的形貌、尺度分布以及管身、曲面和节点处的晶型;讨论了催化剂制备中pH值对催化剂的尺寸、规则程度和存在形态以致对螺旋碳管产量、管径厚度以及螺旋管的相对比例的影响;此外,还分析了反应压力对碳管生长的影响.     

多壁纳米碳管约束二硫化锡作为锂离子电池负极的电化学行为

通过两步法制备多壁纳米碳管约束SnS_2纳米材料(SnS_2@MWCNT)。采用直流电弧等离子体法在甲烷气氛下制备多壁纳米碳管约束金属锡纳米结构(Sn@MWCNT)作为前驱体,再通过硫化反应获得SnS_2@MWCNT纳米结构。对材料进行Raman、X射线衍射(XRD)、透射电镜(TEM)等物理表征的结果显示多壁纳米碳管长约400nm,表面碳层晶化程度良好,碳层厚度约10 nm。以Sn S2@MWCNT纳米结构作为负极材料的锂离子电池显示出较为良好的电化学性能。其首次充放电库伦效率为71%,循环50次后,容量仍保持703 mAh?g~(-1)。SnS_2@MWCNT纳米结构电极的高容量特性源于多种活性物质共同提供容量,且各物质反应平台不同。平台呈现明显阶梯型,缓解了体积膨胀效应对电极材料的破坏。     

单壁纳米碳管的纯化及表征

利用微孔膜及空气氧化法逐步除去电弧放电法制备的单壁纳米碳管(SWCNTs)中的金属催化剂粒子、碳纳米粒子、无定形碳等杂质,并利用热重分析（TGA）、高分辨透射电子显微镜（HRTEM）及拉曼（Raman）光谱,对每一步得到的产物进行分析表征.实验证明,该方法对单壁纳米碳管的纯化是比较有效的,可以得到纯度在90％以上的单壁纳米碳管.     

纳米碳管负载金属镍催化叶绿素加氯反应

用等体积浸渍法制备了纳米碳管负载金属镍催化剂，采用电镜（TEM）、红外光谱（IR）对催化剂的形貌、结构进行了表征，并考察了常温常压下不同Ni负载量的催化剂对叶绿素加氢反应的性能。结果表明，纳米碳管负载镍催化剂在催化反应过程中保持高分散态，不会发生团聚，而经过硝酸氧化后的纳米碳管负载镍催化剂在催化反应中表现出高的活性，当Ni负载量为7％时，催化活性最好，叶绿素分子开环生成各种小分子。     

固体单相催化剂CVD法制备成束或分散MWCNT

CVD法制备纳米碳管的催化剂多是以Al2O3、SiO2或MgO作载体,Fe、 Ni或Co等过渡族金属为活性组分[1-3].     

吸附聚丙烯酸对纳米碳管表面特征影响的研究

利用低温氮气吸附法系统研究了吸附聚丙烯酸 (PAA)的量对纳米碳管表面特征的影响 .分析结果表明 :当PAA吸附量增加到 2 68 98mg·g-1时 ,纳米碳管的比表面积下降了 46 97% ;虽然吸附PAA后的纳米碳管在 1 8nm以上的孔径分布特征基本上与原样一致 ,但孔容减少 ,这部分孔对比表面的贡献明显降低 ,同时出现 1 8nm以下的孔 ;通过氮气吸附等温线利用热力学方法计算的纳米碳管的表面分维值 (surfacefractaldimension)dSF由原样的 2 5 4下降至吸附后的 2 48,表明吸附PAA分子能够降低纳米碳管的粗糙度 .这些说明堵孔效应和屏蔽效应是纳米碳管表面特征改变的主要因素 ,这一研究对纳米碳管在吸附、催化等方面的应用有着非常重要的意义 .     

纳米CaCO3负载过渡金属CVD法制备多壁碳纳米管的研究

以纳米碳酸钙粉体为载体,用浸渍法制备了可用于化学气相沉积(CVD)法制备碳纳米管的高产率催化剂.应用FESEM,HRTEM,TEM,XRD和激光拉曼谱对产物进行了表征.结果表明,由于纳米碳酸钙具有较大的比表面积,可高密度地承载催化剂活性组分.在碳纳米管生长初期,处于缓慢分解状态的纳米碳酸钙才能有效地起到载体作用,且反应温度为700～750℃时,碳纳米管的产率较高.Fe-Co双金属催化剂在700℃,催化生长60min后,可增重10倍,而且产物中无定形碳含量极少.纳米碳酸钙载体易于提纯,用质量分数为30%的硝酸超声提纯粗产品1h,可使纯度提高到97%,且不破坏碳纳米管结构.     

聚氨酯接枝多壁碳纳米管的制备及表征

采用两步法成功地将聚氨酯分子链以共价键连接到碳纳米管表面. 首先将聚丙烯酰氯通过与强酸氧化后多壁碳纳米管表面产生的羟基及少量羧基之间的化学反应共价接枝到碳纳米管表面; 然后将接枝到碳纳米管表面的聚丙烯酰氯与端羟基聚氨酯发生酯化反应, 实现了聚氨酯对碳纳米管的表面共价接枝. 采用傅里叶变换红外光谱(FTIR)、透射电镜(TEM)、扫描电镜(SEM) 和热重分析(TGA)等对接枝后的产物进行了表征, 结果表明, 聚氨酯已共价接枝到碳纳米管表面, 被接枝的聚合物的含量接近90%.     

Bulk polymerized polystyrene in the presence of multiwalled carbon nanotubes

The in situ bulk polymerization method was applied to synthesize composites of multiwalled carbon nanotubes (MWNTs) and polystyrene (PS) under ultrasonication to open π-bonds in the MWNTs. Morphology of the composite products was studied by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Thermal properties and molecular weight of the PS synthesized in the presence of the MWNTs were examined by thermogravimetric analysis (TGA) and gel permeation chromatography (GPC), respectively. The MWNTs were observed to play an important role as initiator consumers during the polymerization reaction. Electrical conductivity of a film-type sample of the PS/MWNT nanocomposite was found to increase with increased amount of MWNTs added, following the percolation theory.     

Characterization and electrical properties of polypyrrole/multiwalled carbon nanotube composites synthesized by in situ chemical oxidative polymerization

This study describes the preparation of polypyrrole (PPy)/multiwalled carbon nanotube (MWNT) composites by in situ chemical oxidative polymerization. Various ratios of MWNTs, which served as hard templates, were first dispersed in aqueous solutions with the surfactant cetyltrimethylammonium bromide to form micelle/MWNT templates and overcome the difficulty of MWNTs dispersing into insoluble solutions of pyrrole monomer, and PPy was then synthesized via in situ chemical oxidative polymerization on the surface of the templates. Raman spectroscopy, Fourier transform infrared (FTIR), field‐emission scanning electron microscopy (FESEM), and high‐resolution transmission electron microscopy (HRTEM) were used to characterize the structure and morphology of the fabricated composites. Structural analysis using FESEM and HRTEM showed that the PPy/MWNT composites were core (MWNT)–shell (PPy) tubular structures. Raman and FTIR spectra of the composites were almost identical to those of PPy, supporting the idea that MWNTs served as the core in the formation of a coaxial nanostructure for the composites. The conductivities of these PPy/MWNT composites were about 150% higher than those of PPy without MWNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1413–1418, 2006     

Well-dispersed multi-walled carbon nanotube/polyaniline composite films

Multi-walled carbon nanotube (MWNT)/polyaniline (PANI) composite films with good uniformity and dispersion were prepared by electrochemical polymerization of aniline containing well-dispersed MWNTs. The results of transmission electron microscopy (TEM) show that aniline can be used to solve MWNTs via formation of donor–acceptor complexes. Scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) revealed that the well arrangement of PANI-coated MWNTs in these films facilitated improved electron and ion transfer relative to pure PANI films and this may be due to the strong interaction between MWNTs and PANI.     

非离子表面活性剂对多壁碳纳米管在乙醇中高浓度分散的作用

如果能在无需聚合物或共价官能团辅助的条件下, 将多壁碳纳米管(MWNTs)高浓度地分散在乙醇中, 那么向各种复合材料引入MWNTs的过程就会更加便捷. 为此, 制备了多种含有表面活性剂的多壁碳纳米管乙醇悬浮液并对比考查了它们的稳定性. 非离子表面活性剂Triton X-100 和Tween 65显示出了在乙醇中分散悬浮高浓度MWNTs的能力, 能够使1.0 g·L-1 MWNTs乙醇悬浮液的上层清液经240 h后浓度仍分别在0.50和0.35 g·L-1以上. 这样长时间稳定的、没有聚合物或共价官能团辅助的MWNTs乙醇悬浮液, 其浓度比文献报道的值高. 进一步探讨了这些非离子表面活性剂分子结构对于分散MWNTs的优势, 并直观给出了其吸附于碳纳米管表面的可能形式. X射线光电子能谱和透射电子显微镜的表征结果都证实了表面活性剂分子吸附于碳纳米管表面.     

High Dispersion and Electrocatalytic Properties of Platinum on Functional Multi‐Walled Carbon Nanotubes

Platinum (Pt) nanoparticles were electrochemically dispersed on 4‐aminobenzene monolayer‐grafted multi‐walled carbon nanotubes (MWNTs) by a potential‐step method. The structure and nature of the resulting Pt‐MWNT composites were characterized by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The electrocatalytic properties of Pt‐MWNT composites for methanol oxidation have been investigated by cyclic voltammetry (CV) and high electrocatalytic activity can be observed. This may be attributed to the small particle size, high dispersion of platinum particles and the particular properties of MWNT supports. The results imply that the Pt‐MWNT composites have good potential applications in direct methanol fuel cell (DMFC). Additionally, the long‐term cycling stability of platinum catalysts was also investigated.     

Cumene Liquid Oxidation to Cumene Hydroperoxide over CuO Nanoparticle with Molecular Oxygen under Mild Condition

CuO nanoparticle was synthesized via wet chemical method and was characterized by X-ray diffraction(XRD),nitrogen adsorption-desorption,and scanning electron microscopy(SEM).Catalytic oxidation of cumene with molecular oxygen was studied over CuO nanoparticle.The catalysts showed markedly higher activities as compared to CuO prepared by conventional method,CuO/Al_2O_3,or ho- mogeneous copper catalyst under comparable reaction conditions.The cumene conversion,comene hy- droperoxide(CHP)yield,and selectivity using 0.25 g CuO nanoparticle catalyst and 0.1 mol cumene at 358 K for 7 h were 44.2%,41.2% and 93.2%,respectively.The catalyst can be recycled.After 6 recycled experiments,no loss of catalytic activity was observed.     

Preparation and characterization of multi‐walled carbon nanotubes decorated with silver nanoparticles through ultraviolet irradiation reduction

A facile, green and efficient approach was applied to synthesize multi‐walled carbon nanotubes (MWNTs) decorated with silver nanoparticles (MWNT‐Ag) for further potential application. Oxidized MWNTs were decorated with silver nanoparticles (Ag NPs) via a method combining ultraviolet irradiation‐induced reduction and conventional silver mirror reaction without any reducing agent. The obtained product was characterized using various methods. X‐ray diffraction proved that the Ag NPs were synthesized successfully. Moreover, Ag NPs with a diameter of 80 nm, attached onto MWNTs, could be clearly observed in field emission scanning electron microscopy images, which also confirmed Ag NPs. Energy‐dispersive spectroscopy and transmission electron microscopy also indicated the presence of Ag NPs. Furthermore, thermogravimetric analysis was used to measure the content of Ag NPs in MWNT‐Ag, the result indicating that the weight content of Ag NPs was up to 31.88%. UV–visible absorption spectroscopy was adopted to evaluate the dispersion property of MWNT‐Ag. The result illustrated that MWNT‐Ag had a good dispersibility and stability in water. Characterization was also carried out through Fourier transform infrared spectroscopy, Raman spectroscopy and dynamic light scattering analysis.     

Modification of vertically aligned carbon nanotube arrays with palladium nanoparticles for electrocatalytic reduction of oxygen

A novel type of palladium nanoparticles-modified multiwalled carbon nanotubes composite-electrode with electrocatalytic activity for oxygen reduction is presented. The nanocomposite was prepared by magnetron sputtering deposition with Pd in Ar atmosphere on MWNTs, which were synthesized on Ta plates by chemical vapor deposition. Both scanning electron microscopy and transmission electron microscopy were employed to observe the surface morphology. The Pd nanoparticles, with diameters around 5 nm, are dispersed at the tips and on the sidewalls of the MWNTs. Voltammetry, amperometry and electrochemical impedance measurements were used to demonstrate the strong electrocatalytic activity of the nanocomposite in acid solution. Compared to the bare MWNT electrode, the PdNPs/MWNT nanocomposite shows a positive shift of the O₂ reduction current at onset potentials from +400 to +500 mV, a concurrent 1.5-fold increase in the O₂ reduction peak current with high stability. The successful preparation of PdNPs/MWNTs nanocomposite by magnetron sputtering deposition opens a new path for an efficient dispersion of promising nanoparticles for fuel cells and O₂ sensors.