一种高效的用含水乙醇制备单壁碳纳米管的方法

本文采用流化床反应器,利用MgO作为催化剂载体,以Mo和Fe为催化剂。让Ar气流携带含水的乙醇蒸汽进入反应器,通过化学气相沉积(CCVD)法合成了单壁碳纳米管(SWCNTs)。利用拉曼光谱和透射电镜(TEM)对所合成的单壁碳纳米管质量进行检测。实验结果表明无水乙醇中加入7%的水反应温度在950℃时,制备的单壁碳纳米管的质量最好而且管径分布非常均匀。     

用微米级LaNi5为催化剂生长的碳管的ESR谱研究

用微米级LaNi₅合金粉末为催化剂, 以乙炔为原料, 采用化学气相沉积(CVD)法合成了多壁碳纳米管. 在100~290 K温度下测量了41 μm≤d≤150 μm粒径催化剂制备的不同直径分布的碳纳米管的电子自旋共振（ESR）谱,研究了测量温度、微米级催化剂粒径及制备过程的氢气氛对生成的碳纳米管的ESR谱线型、g因子、线宽的影响. 发现碳纳米管的g因子随其直径的增大而增大,分别为2.040 0（催化剂粒径41 μm≤d≤50 μm, 碳纳米管的直径分布为10 nm到20 nm）和2.089 8（催化剂粒径100 μm≤d≤150 μm,碳纳米管的直径分布为70 nm到120 nm）. 发现小管径纳米管的ESR谱图有一个峰, 而大管径纳米管的ESR谱图有两个峰A和B, 且随测量温度的升高, 峰B强度增大.     

催化剂组分对制备单壁碳纳米管的影响

利用柠檬酸法制备出了Mo-Fe-MgO，Mo-Co-MgO和W-Co-MgO催化剂，在小型流化床中，以Ar气为载气，在1123 K下催化裂解CH₄来制备单壁碳纳米管(SWCNTs).利用透射电子显微镜和拉曼光谱方法研究了催化剂组分对SWCNTs制备的影响，并对SWCNTs的生长机理进行了探索，研究结果表明，柠檬酸法是一种制备负载型SWCNTs催化剂的有效方法，三种催化剂都能够得到质量较好的SWCNTs,在1123 K左右，SWCNTs在三种催化剂上的生长过程可能类似于“微液相模型”.催化剂的组分对SWCNTs的管径分布影响较小，不同催化剂所得到的SWCNTs在内部结构上存在一定的差异.催化剂中加入第二组分Mo和W能有效提高产物的碳产率. 关键词： 单壁碳纳米管 催化化学气相沉积法 生长机理 拉曼光谱     

碳纳米管制备条件探索及对亚甲基蓝的吸附性能

探索了用气相沉积法制备碳纳米管时,不同温度、催化剂浓度、反应时间对碳纳米管定向性、径向管径、表面性能的影响,结果表明,反应温度750℃、催化剂浓度5g/100mL、反应时间30min是制备碳纳米管的最佳实验条件。在最佳条件下制备碳纳米管并进行对亚甲基蓝吸附的研究,探索了吸附时间、pH、吸附浓度、温度对吸附结果的影响。     

甲烷氧化偶联锂/氧化镁催化剂和纳米催化剂

采用初湿浸渍和溶胶凝胶法分别制备了Li/MgO催化剂和Li/MgO纳米催化剂. 比较两种Li/MgO催化剂对于甲烷氧化偶联反应的催化性能. 采用X射线衍射、BET吸附和透射电镜进行了表征.在973-1073 K和总压力为101 kPa下对催化剂进行了测试. 实验结果表明,Li/MgO纳米催化剂比普通催化剂对于甲烷氧化偶联反应表现为更高的甲烷转换率,较高选择性和较高的的主要产品(乙烷和乙烯)的产率.     

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Al2 O3、SiO2 或MgO作载体 ,Fe、Ni或Co等过渡族金属为活性组分[1- 3] .催化剂与载体之间的关系存在多种形式[1] ,其中固溶体催化剂[4 ,5] 使过渡金属离子能均匀地分布在载体的内部和表面 .在后续反应过程中 ,均匀分布在表面或体内的金属离子被还原成具有催化活性的金属微粒 .此法称为“原位催化分解法 (insituCVD法 )” ,常用于制备直径分布较为均匀的纳米碳管 ,但以往的这些固溶体催化剂在制备纳米碳管的产量上并没有明显的改善 .本工作报道用燃烧法制备的Fe Mo Mg O固溶体 ,不但在用于CVD法生长…     

CVD法制备碳纳米管的TG-DTA研究--温度对CVD法制备碳纳米管的影响

基于碳纳米管粗产品中无定形碳和不同直径碳纳米管对氧的反应活性的差异 ,通过差热 -热重 (TG DTA)方法 ,结合透射电镜 (TEM)和X射线衍射 (XRD)的测试结果 ,研究了合成温度对以乙炔气体为碳源 ,用CVD法制备碳纳米管的石墨化程度、碳纳米管直径以及直径分布的影响 .结果表明 :反应中 ,由于催化剂Co/SiO2中活性组分 (Co)微晶随合成温度的升高而增大 ,导致所制备的碳纳米管的直径增大 ,从 2 0～ 30nm (6 5 0℃ )增加到 30～ 5 0nm (75 0℃ ) .碳纳米管的石墨化程度随着反应温度的升高而增加 .XRD实验结果还表明 ,当合成温度从 6 5 0℃增加到 85 0℃时 ,2θ值从 2 5 .8°增加到 2 6 .8°,(0 0 2 )晶面的层间距从 3.45 减小到 3.32 ,即随着合成温度的升高 ,碳纳米管 (0 0 2 )晶面的层间距减小 .通过DTA放热峰的峰温和半峰宽的分析得出 ,无定形碳的放热峰峰温Tp<380℃ ,其含量随着温度的升高而减小 .碳纳米管的DTA放热峰的峰温Tp 随着碳纳米管的直径和石墨化的程度的增加而升高 ,半峰宽随着碳纳米管的直径的分布范围增大而增宽 .低温 (6 5 0℃ )有利于生成直径小且均匀的多层碳纳米管 (2 0～ 30nm) ,而高温 (大于 75 0℃ )则有利于生成直径大的多层碳纳米管 (大于 30～5 0nm) .     

微量水对碳纳米管形貌的影响及其机理研究

利用介质阻挡放电等离子体化学气相沉积技术,在蒸镀有25nm Ni催化剂层的Si基片上,以CH₄和H₂作为反应气体,在973K下制备了碳纳米管,并研究了微量水的引入对碳纳米管形貌的影响.场发射扫描电子显微镜结果表明,不加水时,制备出的碳纳米管直径不均匀,分布在40—90nm之间,呈链节状的结构;加入少量水时,制备出的碳纳米管直径比较均匀,集中在70nm左右,表面为瘤状结构;当水的流量进一步增加时,得到的碳纳米管表面光滑,出现了枝状结构.原位测量了加水前后等离子体区的发射光谱,分析了微量水的引入对于碳纳米管形貌变化的影响机理. 关键词： 碳纳米管 介质阻挡放电 水 发射光谱     

具有宽过冷液相区的Fe62 Co8-x(Cr,Mo)xNb4 Zr6 B2非晶态合金的热稳定性与磁性

根据制备块状非晶态合金的三条经验准则,选择了成分为Fe62Co8-xCrxNb4Zr6B20和Fe62Co8-xMoxNb4Zr6B20(x=0,2,4)的合金系.利用单辊急冷法制备出厚为30μm宽为5mm左右的条带,并用差热分析、X射线衍射以及Faraday磁天平、静态磁性测量仪等研究了合金的热稳定性、非晶结构和磁性能.发现含2at%Cr的Fe62Co6Co6Nb4Zr20B20非晶态合金的过冷液相区ΔTx最宽,达到85K,但是合金系的饱和比磁化强度σs随Cr或Mo含量的增加而急剧下降.合金系经973K真空退火900s后,由于晶化相α-Fe等晶相析出,使得各合金的σx和Hc都迅速升高.     

MgO/Pt界面对增强Co/Ni多层膜垂直磁各向异性及热稳定性的研究

采用直流磁控溅射法在玻璃基片上制备了Pt底层和MgO/Pt双底层的Co/Ni多层膜样品, 通过反常霍尔效应研究了不同MgO厚度和退火温度对样品垂直磁各向异性(perpendicular magnetic anisotropy, PMA)的影响. 随着底层中MgO厚度的逐渐增加, 样品的矫顽力也随之增强, 霍尔电阻变化不大; 对样品进行退火处理后发现, 单纯Pt底层的Co/Ni多层膜随着退火温度的升高, 霍尔电阻逐渐降低, 矫顽力则迅速降低, 热稳定性较差; 而当MgO/Pt双底层的样品在200 ℃退火后矫顽力大幅增加, 霍尔电阻略微有所减小, 更高的退火温度使得Co和Ni合金化, 导致多层膜的PMA特征减弱.     

催化剂对碳纳米管产率及质量的影响

本文研究了添加钴/二茂铁、镍/二茂铁、钴、镍/钴不同催化剂对高温热解法制备碳纳米管质量、产率等的影响。高分辨率透射电镜图象显示在800℃左右,镍/二茂铁、钴/二茂铁和钴催化条件下,有多壁碳纳米管生成,而用镍/钴作催化剂时,只有直径在0 5μm左右,长度十几个微米的非晶态棒状物生成。通过对生成碳纳米管的质量和产量进行比较,催化剂的催化活性满足二茂铁>钴>镍。简单分析了在碳源高温热解环境下不同金属催化剂的性能差异,并对不同催化条件下生成物的拉曼光谱进行了分析。     

Effects of catalysts on the internal structures of carbon nanotubes and corresponding electron field-emission properties

Using a chemical vapor deposition (CVD) method, multi-walled carbon nanotubes with uniform diameters of approximately 10 nm were synthesized on silicon substrates by the decomposition of acetylene using Fe, Co and Ni as the catalysts. Catalyst effects on the internal structures of the carbon nanotubes were evident in the Fe, Co and Ni catalyzed nanotubes. Although these nanotubes demonstrated similar morphologies, due to the variety of internal structures, the nanotubes synthesized from different catalysts demonstrated various electron field-emission characteristics including turn-on field, threshold field and field enhancement factor. Compared with carbon nanotubes from Ni catalyst, nanotubes from Fe and Co with the same diameters have better field-emission properties. Graphite layers in nanotubes from Fe and Co are much straighter and more parallel to the tube axis with fewer defects. For instance, the turn-on field and threshold field for nanotubes from Ni are 5 V/m and 9 V/m, respectively. These electric fields are much higher than those for nanotubes from Fe, which are 0.35 V/m and 2.8 V/m, respectively. This could be due to the effect of catalysts on the work function of nanotubes, since the catalyst particle usually terminates the free end of the nanotube, and the influence of internal structure on electron transportation along the nanotube axis. Therefore, this study suggests that besides a small diameter, good graphitization (crystallization) is an important prerequisite for a good carbon nanotube emitter. PACS 79.70.+q; 68.37.Lp; 81.07.De     

Single-walled carbon nanotube formation with double laser vaporization technique

Single-walled carbon nanotubes (SWNTs) were prepared with double laser vaporization of a graphite target and a metal/alloy target inside an electric furnace at 1200 ^°C ambient temperature with 500 torr Ar gas atmosphere. Each target was vaporized simultaneously with a different Nd:YAG laser. Several kinds of metal/alloy target (Ni, Co, Fe, and permalloy) were tested in order to see the difference in the resulting SWNT yield and the diameter distribution of them. The Raman spectra of SWNT-containing soot prepared by use of this technique with permalloy/carbon system indicated that permalloy gives almost the same yield as compared with Ni/Co carbon composite rod with single laser vaporization technique, though the diameter distribution of them is slightly different. Also, time-resolved images of the plume by carbon and permalloy nanoparticles after laser vaporization were collected using a high-speed video camera. These images suggest that the hot plumes due to carbon and permalloy nanoparticles do not mix together so extensively, at least in a few hundred microseconds after laser vaporization. The effect of time delay between two laser pulses on the yield and the diameter distribution of SWNTs was also presented and discussed.     

催化剂比例对单壁碳纳米管制备的影响

采用电弧放电法以Y/Ni为催化剂制备了单壁碳纳米管 ,研究了不同催化剂比例对制备产物的影响。获得了不同激发波长下 (476 5～ 1 0 6 4nm)单壁碳纳米管的拉曼光谱 ,采用图表法对径向呼吸模的谱峰进行了认定。结果表明 :样品中碳管的直径分布在 1 2～ 1 6nm之间 ,直径在 1 43nm附近的碳管居多。催化剂的比例只是影响碳管的产额 ,对其直径分布的影响很小     

Effects of composition of catalysts on the preparation of single-walled carbon nanotubes synthesized over W–Co–MgO catalysts

A series of W–Co–MgO catalysts were prepared for the first time by decomposing a mixture of magnesium nitrate, ammonium paratungstate, citric acid, and cobalt nitrate. Single-walled carbon nanotubes (SWCNTs) were synthesized over these W–Co–MgO catalysts and the effects of the quantity of metal in the catalysts on the synthesis of SWCNTs were investigated by Raman spectroscopy and transmission electron microscopy (TEM). The results show that, among W–Co–MgO catalysts, the W1–Co5 catalyst was found to be most effective for synthesizing SWCNTs. The diameter distribution of as-grown SWCNTs prepared over the W1–Co5 catalyst was estimated to range from 0.72–1.64 nm. When the molar ratios of W:MgO and Co:MgO in the catalysts are more than 2:100 and 5:100, respectively, the amorphous carbon content or defect concentration of SWCNTs may be increased with the increase of the quantity of metal in the catalysts. The dependence of the diameter distribution of SWCNTs on the quantity of W in the catalysts is small. However, the proportion of SWCNTs with larger diameter is increased as the quantity of Co in the catalysts is increased owing to the increase in the number of larger active sites.     

A novel continuous process for synthesis of carbon nanotubes using iron floating catalyst and MgO particles for CVD of methane in a fluidized bed reactor

A novel continuous process is used for production of carbon nanotubes (CNTs) by catalytic chemical vapor deposition (CVD) of methane on iron floating catalyst in situ deposited on MgO in a fluidized bed reactor. In the hot zone of the reactor, sublimed ferrocene vapors were contacted with MgO powder fluidized by methane feed to produce Fe/MgO catalyst in situ. An annular tube was used to enhance the ferrocene and MgO contacting efficiency. Multi-wall as well as single-wall CNTs was grown on the Fe/MgO catalyst while falling down the reactor. The CNTs were continuously collected at the bottom of the reactor, only when MgO powder was used. The annular tube enhanced the contacting efficiency and improved both the quality and quantity of CNTs.The SEM and TEM micrographs of the products reveal that the CNTs are mostly entangled bundles with diameters of about 10-20 nm. Raman spectra show that the CNTs have low amount of amorphous/defected carbon with I_G/I_D ratios as high as 10.2 for synthesis at 900 °C. The RBM Raman peaks indicate formation of single-walled carbon nanotubes (SWNTs) of 1.0-1.2 nm diameter.     

硼碳氮纳米管的拉曼光谱研究

对不同温度和不同催化条件下用高温热解法制备的硼碳氮(BCN)纳米管的拉曼光谱进行了分析。随着制备温度的升高,拉曼光谱中D带和G带的强度比I_D/I_G由小变大,而后又变小,说明存在一个最佳温度,在该温度下生成的BCN纳米管中B、N元素掺杂浓度最大。不同催化剂对BCN纳米管的拉曼光谱也有影响,当以钴/二茂铁和镍/二茂铁为催化剂时的I_D/I_G值比以钴、镍和钴/镍为催化剂时大,说明这时的B、N的掺杂浓度较高,纳米管的质量较好,这与透射电子显微镜观察结果一致。     

Impact of Mo and Ce on growth of single-walled carbon nanotubes by chemical vapour deposition using MgO-supported Fe catalysts

A series of nine catalysts containing Ce/Fe and Mo/Fe at various loadings on MgO supports have been studied as catalysts for chemical vapour deposition (CVD) of single-walled carbon nanotubes (SWCNTs) using a methane carbon source. Our results show that the Ce/Fe system is very suitable as a catalyst that favours SWCNT growth, and we question the special importance that has been attributed to Mo as an additive to Fe-based catalysts for SWCNT growth, as it appears that Ce is equally effective. Our results indicate that dehydroaromatization (DHA) is not a defining step for the growth mechanism, as has been suggested for Mo/Fe systems previously, and show that Ce and Mo do not seriously perturb the well-known Fe/MgO system for growth of high quality SWCNT. Using Raman spectroscopy, we have shown that the Ce/Fe/MgO catalyst system favours growth of SWCNTs with a different distribution of chiralities compared to the analogous Mo/Fe/MgO system.     

Raman light scattering and electron microscopy of nanocomposites with the metal core-carbon shell structure

The structural state of carbon in nanocomposites that are based on metals (Fe, Ni, Co, and Ag) encapsulated in carbon and produced by the gas-phase synthesis has been investigated using Raman spectroscopy and high-resolution transmission electron microscopy. The average diameter of particles of the initial nanocomposites after the gas-phase synthesis, including the carbon shell, is less than 15 nm and can vary as a function of the conditions and regimes used for their preparation. The shell of the initial nanocomposites, irrespectively of the metal core type, consists of carbon fragments in the form of curved layers with sizes of less than 10 nm in the lateral direction. In the initial nanocomposites, there is no periodicity in the packing of carbon layers in the radial and lateral directions. The structure of the coating is assumed to be similar to the glassy carbon structure characterized by a curvature of carbon layers in different directions, which requires that, in addition to conventional hexagonal cells, the layers should contain pentagonal and heptagonal cells. Heat treatment of the initial nanocomposites Fe@C and Ni@C in butane (700°C, 60 min) not only significantly increases the thickness of the carbon coating but also increases the degree of ordering of curved carbon fragments in the lateral and radial directions. In the composites with Fe, Ni, and Co, along with this form of carbon, semiconducting nanotubes with a diameter of 1.3–1.5 nm are also formed. The composites with silver nanoparticles exhibit the effect of time-fluctuating giant enhancement of the Raman scattering intensity.