不同氮掺杂量碳纳米管的合成和表征

以不同氮含量的有机胺为碳和氮源，用催化方法合成出了不同氮含量的大管径碳纳米管。采用Fe/SBA-15分子筛为催化剂，有机胺经过1 073 K高温裂解得到氮掺杂碳纳米管材料(CN_x)。比较了苯、三乙胺、二乙胺、乙二胺四种原料对合成CN_x形貌、产率、掺氮量和吸水率的影响；以二乙胺为原料合成出适中的氮碳比(N/C原子比为0.15)和较高产率(2.2 g·（g·cat）^-1)的竹节状CN_x材料。     

氮掺杂碳纳米管的制备及其电化学性能

采用弱反应性含氮有机物水合肼、二乙烯三胺对碳纳米管进行氮掺杂处理. 结合X射线光电子谱(XPS)分析和扫描电镜(SEM)观察, 发现两种含氮有机物处理均可使碳纳米管表面成功连接上含氮基团, 并保持了碳纳米管的本征形貌和结构. 水合肼处理的碳纳米管的氮含量(碳/氮原子比为95/2)明显高于二乙烯三胺处理的碳纳米管(碳/氮原子比为96/0.5). 氮掺杂后碳纳米管在水溶液中分散性明显改善, 且分散性随着氮含量增加进一步增强, 因此水合肼处理的碳纳米管分散性明显优于二乙烯三胺处理的碳纳米管. 作为电化学电容器电极材料, 碳纳米管含氮官能团贡献了赝电容, 但其循环性仍需进一步改进. 氮掺杂碳纳米管较好的亲水性, 改善了电解液的浸润, 循环后氮掺杂碳纳米管电极的比容量仍略高于纯碳纳米管电极的比容量.     

含氮竹节状碳纳米管的催化合成

以二乙胺为原料，用催化方法合成出了含氮大管径竹节状碳纳米管，以含铁 SAPO-5分子筛为催化剂，二乙胺经过1073K高温裂解得到的碳纳米管材料，其内径 约60nm,壁厚为6nm，并且成竹节状。它有较高的表面和较高的氮碳比。     

氮掺杂碳材料负载Pd纳米催化剂在有机反应中的最新研究进展

氮掺杂碳材料负载Pd纳米催化剂因其具有反应活性高、反应完成后便于分离和重复使用等优点,在催化领域引起了极为广泛的关注.简要综述了基于氮掺杂多孔/介孔碳NC、氮掺杂石墨烯NG、氮掺杂碳纳米管NCNT和氮掺杂碳纳米片NCNS等不同类型碳材料载体制备的负载型Pd纳米催化剂的合成与应用的最新研究进展,同时对氮掺杂碳材料负载Pd纳米催化剂的发展方向进行了展望.     

聚苯胺改性氮掺杂碳纳米管制备及其超级电容器性能

利用苯胺原位化学聚合合成聚苯胺包覆碳纳米管(CNTs), 再炭化处理制备氮掺杂碳纳米管(NCNTs).激光拉曼(Raman)光谱和X射线光电子谱(XPS)分析及透射电镜(TEM)观察表明, 苯胺包覆碳纳米管经炭化处理后, 得到以碳纳米管为核、氮掺杂碳层为壳, 具有核-壳结构的氮掺杂碳纳米管, 而碳纳米管本征结构未遭破坏. 研究表明, 随着苯胺用量的增大, 氮掺杂碳纳米管的氮掺杂碳层变厚, 氮含量从7.06%(质量分数)增加到8.64%, 而作为超级电容器电极材料, 随着氮掺杂碳层厚度降低, 氮掺杂碳纳米管在6 mol·L^-1氢氧化钾电解液中的比容量从107 F·g^-1增大到205 F·g^-1, 远高于原始碳纳米管10 F·g^-1的比容量, 且聚苯胺改性氮掺杂碳纳米管表现出较好的充放电循环性, 经1000次充放电循环后仍保持初始容量的92.8%~97.1%, 表明氮掺杂碳纳米管不仅通过表面氮杂原子引入大的法拉第电容和改善亲水性使电容量显著增大, 其具有的核壳结构特征也使循环稳定性增强。     

以吡啶为原料制备氮掺杂碳纳米管

在700～800 ℃,以吡啶为原料用CVD方法制备出了管径在20～40 nm的竹节状碳纳米管. EDX和XPS结果都表明氮掺杂到碳纳米管中. HRTEM研究发现掺氮碳纳米管的竹节由数层石墨片弯曲而成,纳米管外层石墨层逐渐消失.从Raman谱图的对照中发现,与相似条件下制备出的纯碳纳米管相比,氮掺杂碳纳米管的D谱带对G谱带的相对强度增加, TGA研究发现掺杂纳米管在较低温度下即被氧化,这些结果都说明氮掺杂使得纳米管的缺陷增加.     

氮掺杂长竹节状碳纳米管的制备及其生长机理

本文采用电弧放电法,通过阳极棒与不锈钢片的共蒸发,制备了氮掺杂长竹节状碳纳米管。借助扫描电子显微镜（SEM）、场发射高分辨透射电子显微镜（HRTEM）及其附带能量色散X射线（EDX）光谱仪和电子能量损失谱（EELS）、透射电子显微镜（TEM）等表征方法,对产物的形貌、结构和组成进行表征。表征结果表明,氮掺杂长竹节状碳纳米管的长度在640~835nm之间,其内径在23~35nm之间,外径在28~47nm之间;且在每一节“竹节”与另一节“竹节”的连接处形成的内腔中均有一个黑色纳米颗粒,其直径尺寸以及产物中的氮掺杂长竹节状碳纳米管的含量均与熔化、蒸发的不锈钢片的面积有关。本文还对氮掺杂长竹节状碳纳米管的生长机理进行了简单的探讨。     

通过铁掺杂和造孔提高氮掺杂石墨烯/碳纳米管复合物电催化氧还原性能的研究（英文）

氧还原反应催化剂的性能直接影响着能源转换和存储器件如燃料电池和金属-空气电池的性能. 开发低成本、高性能的非铂族金属氧还原催化剂对于这类器件的实际应用和商业化十分重要,因此备受关注. 氮掺杂的石墨烯/碳纳米管复合物同时具备碳纳米管的良好导电性能和有利于传质的三维网络结构优点,以及氮掺杂石墨烯的高活性优点,因此有望发展为这类可替代铂族催化剂的氧还原电催化剂之一,但目前其催化性能还需进一步提高. 本文研究发现通过在氮掺杂石墨烯/碳纳米管复合物的过程中引入铁元素可以有效提高催化剂的氧还原活性,并且发现通过在热处理和氮掺杂过程中加入二氧化硅纳米颗粒及随后除去二氧化硅,可以在氮掺杂的石墨烯/碳纳米管复合物材料中有效地形成多孔结构. 这种多孔结构的形成不仅可以在复合物中引入更多的高活性催化位点,而且有利于暴露更多的催化活性位并促进氧还原反应中的传质过程. 结合碳纳米管、石墨烯和多孔结构的三者优点,所制备的多孔氮掺杂碳材料表现出优异的电催化氧还原性能. 进一步的实验表明,这类材料还表现出优异的抗甲醇中毒能力和良好的稳定性,因此在性能改进后有望用于燃料电池等能量转换与存储器件.     

氮掺杂碳纳米管的合成及活化过一硫酸盐的性能与机理

以多壁碳纳米管(MWCNT)为原材料, 三聚氰胺为氮前体, 采用高温煅烧法制得了含氮量约3.33%(摩尔分数)的氮掺杂碳纳米管(N-CNT-700), 该纳米管为一维材料. N-CNT-700活化过一硫酸盐(PMS)体系60 min内对苯酚的降解效率可达100%, 总有机碳(TOC)去除率可达61.6%, 体系的活化能为35.4 kJ/mol. 通过电子顺磁共振(EPR)检测、 掩蔽实验及PMS浓度测定等方式确定了体系降解机制为自由基(·OH, SO₄^·-)与非自由基共同作用, 除去9%的吸附去除外, 91%的氧化降解中自由基作用占比约49%, 单线态氧(¹O₂)作用占比约18%, 活性中间体作用占比约24%. N-CNT-700的反应活性随着重复利用次数的增加而降低, 高温处理可以恢复其高反应活性. 煅烧温度影响材料中的氮含量及种类, N-CNT的反应活性与氮含量成正比, 且与石墨氮含量密切相关.     

生物质基双功能氮掺杂多孔碳在对硝基苯酚还原和苯乙烯氧化中的应用（英文）

大多数催化过程需以金属甚至贵金属作为活性位点,尽管金属基催化剂在很多情况下可以展现出较好的催化性能,但其实际应用受到价格较高、储量有限、组分流失和金属位点烧结等因素的限制.在非金属催化剂中,碳材料由于具有来源丰富、稳定性好以及可调控性强等特点而得到了广泛应用.研究表明,将具有供电子或吸电子特征的异质原子如氮、硼、硫和磷等掺入碳结构中是一种可行的策略,可通过电子结构调控产生缺陷来提高催化性能.其中,氮原子与碳原子的原子半径相近,可有效改善碳的化学惰性,是一种理想的掺杂原子.基于这些认识,各类氮掺杂碳材料,如碳纳米管、碳纳米球、石墨烯、介孔碳、碳纤维等已经被开发出来且显示出令人满意的催化效果.然而,传统氮掺杂碳材料的制备还存在反应条件苛刻、需要使用各类有毒试剂以及制备过程复杂等缺点.近年来,以廉价易得的生物质为原料,通过简单绿色方法合成氮掺杂碳材料,并进一步探索其在更多催化领域如有机催化中的应用得到了广泛关注.对硝基苯酚的催化还原反应和苯乙烯的催化氧化反应一般需要金属催化剂.其中,对硝基苯酚是化学工业中常见的难降解污染物,可对环境和人类健康造成严重威胁.在所有减轻其污染和危害的方法中,从环境和工业角度出发,将其催化还原成对氨基苯酚是最经济的方法.苯乙烯的氧化反应可用于生产各类高附加值化学品,例如环氧苯乙烷是合成增塑剂、香料和药品等的重要中间体.对于这两个反应,开发高效的生物质基碳氮掺杂碳材料作为非金属催化剂仍具有挑战性.本文以价廉易得的萝卜为原料,通过耦合氮掺杂、碳化和氢氧化钾活化过程,采用简单的一步法制备得到了一系列氮掺杂多孔碳(NKC),发现其在对硝基苯酚还原反应和苯乙烯氧化反应中均表现出良好的催化性能.NKC系列催化剂的比表面积、孔体积和N掺杂含量分别为918.9–3062.7 m~2 g~(-1), 1.01–2.04 cm~3 g~(-1)和1.29–15.3 at%.综合表征结果和催化反应结果发现,催化性能与结构参数并不直接相关,而是与催化剂中石墨化氮的含量呈正相关关系.在NKC系列催化剂中, NKC-3-800对于这两个反应的催化反应效果最佳,其催化效果可达到或超过已报道的金属甚至贵金属催化剂.此外,本文还计算了两个反应的各类动力学和热力学参数,并分析了可能的催化反应机理.本文不仅为生物质的高附加值利用提供了新的思路,而且为廉价和丰富的生物质基碳催化剂在有机反应中的进一步应用开辟了更多的可能性.     

Large-scale synthesis of carbon nanotubes by an ethanol thermal reduction process

The bamboo-shaped carbon nanotubes were synthesized on a large scale through an ethanol thermal reduction process, in which ethanol was used as the carbon source and magnesium was used as the reductant. The toxic or corrosive reagents have been completely avoided. Furthermore, Y-junction carbon nanotubes obtained from our experiment can be used as the building blocks of nanoelectronics. Because of the simplicity and high yield of this route, it may potentially be applied on the scale of industrial production.     

Generation of hydrophilic, bamboo-shaped multiwalled carbon nanotubes by solid-state pyrolysis and its electrochemical studies

A simple, efficient, and novel method was developed for the direct preparation of hydrophilic, bamboo-shaped carbon nanotubes by the pyrolysis of ruthenium(III) acetylacetonate in a Swagelock cell is reported. The obtained product exhibits mostly bamboo-shaped, straight, periodic twisted, multiwalled carbon nanotubes possessing diameters of 50-80 nm and lengths of around 10 microm. The pyrolyzed product was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), micro-Raman, and cyclic voltammetric techniques. HRTEM studies showed that the walls of bamboo-shaped carbon nanotubes consisted of oblique grapheme planes with respect to the tube axis. The interlayer spacing between two graphitic layers was found to be 0.342 nm. XPS measurements have suggested that as-prepared carbon nanotubes consist the surface functional groups on the surface of carbon nanotubes. The electrochemical properties of synthesized carbon nanotubes have been evaluated. Thermogravimetric analysis (TGA), IR, and cyclic voltammetric studies showed the presence of oxygen functionalities. Raman studies revealed the presence of disorder in the graphitic carbon and the presence of exposed edge plane defects in the generated carbon nanotubes for influencing the surface behavior and electrochemical properties. The electrochemical behavior of electrodes made of bamboo-shaped carbon nanotubes served for an oxygen reduction reaction.     

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.     

CVD growth of N-doped carbon nanotubes on silicon substrates and its mechanism

In the present study, we report the chemical vapor deposition (CVD) of nitrogen-doped (N-doped) aligned carbon nanotubes on a silicon (Si) substrate using ferrocene (Fe(C5H5)2) as catalyst and acetonitrile (CH3CN) as the carbon source. The effect of experimental conditions such as temperature, gaseous environment, and substrates on the structure and morphology of N-doped carbon nanotubes arrays is reported. From XPS and EELS data, it was found that the nitrogen content of the nanotubes could be determined over a wide range, from 1.9% to 12%, by adding the addition of hydrogen (H2) to the reaction system. It was also shown by SEM that N-doped carbon nanotube arrays could be produced on Si and SiO2 substrates at suitable temperatures, although at different growth rates. Using these concentrations, it was possible to produce three-dimensional (3D) carbon nanotubes architectures on predetermined Si/SiO2 patterns. The mechanism underlying the effect of nitrogen containing carbon sources on nanotube formation was explored using X-ray photoelectron spectroscopy (XPS).     

Synthesis of Nitrogen Incorporated Carbon Nanotubes with Different Diameters by Catalytic Pyrolysis of Butylamine

Bamboo-like nitrogen-doped carbon(CNx) nanotubes were synthesized by chemical vapor deposition (CVD) at a high reaction temperature of 600―900 °C. The butylamine and Fe/SBA-15 molecular sieve have been used as precursor and catalyst, respectively. Transmission electron microscopy(TEM) and high resolution transmission electron microscopy(HRTEM) observations show that the outer diameter and wall thickness as well as the inner diameter were increased with increasing reaction temperature in a temperature range of 600―800 °C. A synergism mechanism of the growth through bulk diffusion and the competitive growth through surface diffusion functions during the synthesis of CNx nanotubes was proposed.     

Temperature and flow rate of NH3 effects on nitrogen content and doping environments of carbon nanotubes grown by injection CVD method

Large-scale and vertically aligned nitrogen-doped carbon nanotubes were synthesized by pyrolysis of pyridine with ferrocene as the catalysts under either pure NH3 or a mixture of NH3 and argon atmosphere using injection chemical vapor deposition method. Nitrogen content ranges from 4.8 at. % to 8.8 at. % and changes as a function of growth temperature and the flow rate of NH3. NH3 not only increases the nitrogen content of carbon nanotubes but also increases the proportion of pyridine-like N doping in the carbon nanotubes. It suggests that nitrogen concentration and nitrogen doping environments of carbon nanotubes could be controlled by changing the growth temperature or flow rate of NH3.     

Highly graphitized carbon-wrapped PtFeCo alloy with enhanced durability and activity toward methanol electro-oxidation

Exploring efficient strategies to construct durable and active Pt-based electrocatalysts toward methanol oxidation reaction (MOR) remains great significance for the application of direct methanol fuel cells (DMFCs). Here, we report a facile pyrolysis procedure for fabricating carbon layer wrapped PtFeCo alloy nanoparticles supported on nitrogen-doped carbon nanotubes (NCNT). Physical characterizations demonstrate that the nitrogen-doped carbon support is highly graphitized and the PtFeCo particles are firmly wrapped by the graphitized carbon. Since the wrapping of highly graphitized carbon effectively prevents PtFeCo alloy from metal dissolution, the durability of the synthesized PtFeCo/Co–NCNT_a catalyst has been substantially improved, remaining about 76% of its initial mass activity after 1000 cycles of durability test in acid condition. In addition, due to the strain and ligand effects caused by alloying Pt with Fe and Co, the PtFeCo/Co–NCNT_a catalyst exhibits a greatly enhanced mass activity of 4.2-fold and a specific activity of 6.3-fold higher than those of commercial Pt/C-JM catalyst. Consequently, this work may provide an effective route for preparing durable and active Pt-based catalysts for methanol electro-oxidation.     

竹节状硅纳米管的制备及锂离子嵌入/脱出性能研究

应用改进的化学气相沉积法,成功地合成出一种新的竹节状硅纳米管材料.微电极循环伏安测试表明:锂离子在该硅纳米材料中可能存在两种嵌入位,即实心节部嵌入位和空心管壁嵌入位.作为锂离子电池负极材料,该材料也在一定程度上抑制了一般硅材料所面临的体积效应问题.     

Influence of acid treatments of carbon nanotube precursors on Ni/CNT in the synthesis of carbon nanotubes

The Ni/CNT catalyst was fabricated by directly dipping carbon nanotube precursors refluxed in 4 M of nitric acid into Ni electroless plating bath, and used to synthesize new carbon nanotubes. The experimental results indicate that the duration of acid-treatment of carbon nanotubes precursors exerts a great influence on the catalysis of Ni/CNT in the synthesis of carbon nanotubes and hence the structures of the new carbon nanotubes. When the carbon nanotubes precursors were refluxed for 0.5 h in 4 M of nitric acid, bamboo-shaped carbon nanotubes (BSCNT) or Y junction carbon nanotubes in the carbon products were obtained. As the duration of acid-treatment of carbon nanotubes precursors increased to 6 h, the as-prepared Ni/CNT displayed higher activity, and the carbon nanotube products were high pure without any Y junction structure or any separation layers in hollow.