铂粒子修饰单壁碳纳米管/聚苯胺复合膜对甲醛的电催化氧化

在溶有单壁碳纳米管(SWNTs)的苯胺溶液中, 通过电化学共聚合法成功制备了单壁碳纳米管(SWNT)/聚苯胺(PANI)复合膜. 用电沉积法将铂沉积到SWNT/PANI复合膜上. 样品的成分和形貌分别用XRD和SEM表征. 四探针和电化学交流阻抗的研究表明被PANI包裹的SWNTs整齐地排列在复合膜中, 从而提高了复合膜的电导率, 促进了电荷转移. 循环伏安(CV)说明Pt修饰的SWNT/PANI复合膜对于甲醛氧化具有良好的电催化活性及稳定性. 研究结果表明SWNT/PANI复合膜是一种非常好的催化剂载体, 有着广泛的应用前景.     

失效原子力显微镜硅针尖再生

原子力显微镜的传统商品硅针尖在使用过程中极易因磨损而失效，本文研究了一种在实验室条件下简易可行的回收利用失效硅针尖的方法。在原子力显微镜的敲击模式下使用曲率半径大于100 nm的失效硅针尖对生长单壁碳纳米管的样品表面进行扫描，把样品表面的单壁碳纳米管管束粘接到硅针尖上，可制得直径在5～20 nm的碳纳米管针尖。实验对碳纳米管针尖和新的商品硅针尖进行了成像对比，所制备的碳纳米管针尖不仅在成像分辨率而且在成像稳定性上都优于新的商品硅针尖。     

Electorchemical Studies of Cytochrome c on Electodes Modified by Single—Wall Carbon Naotubes

Single-wall carbon nanotubes(SWNTs) modified gold electrodes were prepared by using two different methods.The electrochemical behavior of cytochrome c on the modified gold electrodes was investigated.The first kind of SWNT-modified electrode (noted as SWNT/Au electrode)was prepared by the adsorption of carboxylterminated SWNTs from DMF dispersion on the gold electrode.The oxidatively processed SWNT tips were covalently modified by coupling with amines (AET) to form amide linkage.Via Au-S chemical bonding,the self-assembled monolayer of thiol-unctionalized nanotubes on gold surface was fabricated so as to prepare the others SWNT-modified electrode (noted as SWNT/AET/Au electrode).It was shown from cyclic voltammetry cxperiments that cytochrome c exhibited direct electrochemical responses on the both electrodes, but only the current of controlled diffusion existed on the SWNT/Au electrode while both the currents of controlled diffusion and adsorption of cytochrome c occurred on the SWNT/AET/Au electrode.Photoelastic Modulation Infared Reflection Absorpthion Spectroscopy (PEM-IRRAS) and Quartz Crystal Microbalance (QCM) were employed to verify the adsorption of SWNTs on the gold electrodes.The results proved that SWNTs could enhance the direct electron transfer proecss between the electrodes and redox proteins.     

共振增强拉曼光谱技术在单壁碳纳米管表征中的应用

共振增强拉曼光谱技术是表征和研究单壁碳纳米管(SWNTs)的有力工具, 它既能用于SWNTs的几何结构表征, 又能反映SWNTs的电子态密度信息. 特别指出的是, 由于共振拉曼效应, 它能够灵敏地检测单根SWNT的局域信息. 本文首先概述了SWNTs拉曼光谱的RBM峰、G峰、D峰和G'峰的特征和应用, 然后综述了共振增强拉曼光谱在SWNTs的结构表征、形变测量、缺陷测量和温度测量中的应用和进展, 最后讨论了共振拉曼光谱在SWNTs表征方面所面临的机会和挑战.     

Preparation of horizontally aligned single-walled carbon nanotubes with floating catalyst

A strategy to prepare horizontally aligned single-walled carbon nanotubes(SWNTs) at moderate temperatures(≤600 ℃) were developed.Using ferocene as the catalyst precursor,Fe nanoparticles are formed in the gaseous phase and catalyze the nucleation and growth of SWNTs in situ.Then the resultant SWNTs are deposited onto the substrates downstream and aligned by the surface lattice of the ST-cut single crystal quartz.The preparation of SWNT arrays at moderate temperatures is important for combining the tube growth with device fabrication.     

Density Functional Theory Study of MoO3 Molecule Encapsulated inside Single-walled Carbon Nanotubes~

The binding energies, geometric structures and electronic properties of molybdenum trioxide (MoO3) molecule encapsulated inside (8,0), (9,0), (10,0) and (14,0) single-walled carbon nanotubes (SWNTs) have been investigated using density functional theory (DFT) method. Due to curvature effect, the calculated binding energy values are different, the variation of which indicated that the stability of MoO3 /SWNT systems increases with increasing the radius of SWNTs. At the same time, owing to the presence of MoO3 molecule, the band gap of MoO3 /SWNTs systems decreases. The analysis of density of states (DOS) reveals hybridization between C-2p and Mo-4d and between C-2p and O-2p orbitals near the Fermi level, which results in electron transfer from SWNTs to MoO3 molecule. The present computations suggest that electronic properties of SWNTs can be modified by doping MoO3 molecule.     

Breakthrough in carbon nanotube growth: unique alloy nanocatalysts lead to the chirality specified tubes

<正>Since Dr.Iijima reported his observation of tubular carbon under transmission electron microscopy(TEM)in 1991,carbon nanotubes(CNTs)have attracted intensive attention.A single-walled CNT(SWNT)is a seamless cylinder formed by rolling a piece of graphene,the honeycombstructured sp2 carbon.This unique structure endows SWNTs     

纳米化学(续)

7　针尖化学———在ＳＰＭ针尖上做文章　　针尖化学是北京大学纳米化学实验室于 1 997年提出的新概念。这里的针尖是指扫描探针显微镜的探针。ＳＴＭ和ＡＦＭ是强有力的表面成像工具 ,能够看到原子、分子水平的结构细节。但是 ,它们只能看到表面上有东西 ,并不知道是什么。换句话说 ,不具备“识别”能力。如果利用特殊的功能分子对针尖进行化学修饰 ,进行能动的分子设计 ,则有可能弥补ＳＰＭ这种“只认东西不识货”的不足。事实上 ,通过能动地设计针尖 ,能动地利用针尖 ,使其具有化学识别功能、化学响应功能、化学“透镜”功能等等 ,可以…     

主族元素取代的罗丹明近红外荧光染料探针

近红外荧光染料探针因其信噪比高、组织穿透力强、对生物样品光损伤小等优势,在生物荧光成像领域备受瞩目.主族元素取代的罗丹明染料探针,不仅具有生物样品适用的近红外光谱性质,同时还保留了传统罗丹明的诸多优点,其中以硅原子取代的罗丹明分子中的氧原子而形成的硅基罗丹明染料探针最为突出.基于其优越的近红外光化学性质,硅基罗丹明染料探针已经广泛应用于生物样品的荧光识别成像.主族元素取代的罗丹明近红外荧光染料探针的发展,丰富了荧光染料探针的种类和数量,拓展了荧光染料探针的应用.本文综述了近年来主族元素取代的罗丹明染料的发展,主要探讨了探针的设计思路、荧光信号调控机制及其近红外成像应用.     

硅基纳米探针用于眼部疾病的成像检测与治疗

快速精准的诊断和高效的治疗对于减轻眼部疾病造成的危害至关重要. 在过去的几十年里, 由于具有尺寸小、 比表面积大、 表面易修饰及独特的光/电子/机械性能等优点, 纳米材料已被用于构建不同种类的高性能纳米探针. 其中, 基于其良好的生物相容性, 科学家们已经将硅纳米材料设计为可用于不同眼部疾病诊断与治疗的功能化纳米探针. 本综述主要概述了将硅基纳米探针用于检测和治疗不同眼部疾病(如角膜疾病、 视网膜疾病、 青光眼等)的近期研究进展. 首先, 重点介绍了硅基纳米探针的设计制备及在角膜新生血管、 细菌性角膜炎等角膜疾病的成像检测与治疗中的应用; 然后, 介绍了用于成像检测和治疗视网膜疾病(如色素性视网膜炎和视网膜新生血管)的硅基持续性给药系统的研究成果; 随后, 概述了多功能硅基纳米载药系统的构建及在青光眼治疗领域的应用研究进展; 最后, 简要讨论了将硅基纳米探针用于眼部疾病诊治面临的挑战并对未来的发展前景进行了展望.     

Mechanisms of single-walled carbon nanotube probe-sample multistability in tapping mode AFM imaging

When using single-walled carbon nanotube (SWNT) probes to create AFM images of SWNT samples in tapping mode, elastic deformations of the probe and sample result in a decrease in the apparent width of the sample. Here we show that there are two major mechanisms for this effect, smooth gliding and snapping, and compare their dynamics to the case when a conventional silicon tip is used to image a bare silicon surface. Using atomistic and continuum simulations, we analyze in detail the shape of the tip-sample interaction potential for three model cases and show that in the absence of adhesion and friction forces, more than two discrete, physically meaningful solutions of the oscillation amplitude are possible when snapping occurs (in contrast to the existence of one attractive and one repulsive solution for conventional silicon AFM tips). We present experimental results indicating that a continuum of amplitude solutions is possible when using SWNT tips and explain this phenomenon with dynamic simulations that explicitly include tip-sample adhesion and friction forces. We also provide simulation results of SWNT tips imaging Si(111)-CH3 surface step edges and Au nanocrystals, which indicate that SWNT probe multistability may be a general phenomenon, not limited to SWNT samples.     

Atomic force microscopy measurements of peptide-wrapped single-walled carbon nanotube diameters.

With a vertical resolution of 0.1 nm, atomic force microscopy (AFM) height measurements can be used to determine accurately the diameter of single-walled carbon nanotubes (SWNT) with the assumption that they have circular cross sections. The aim of this article is to draw attention to the need to optimize operating parameters in tapping mode for quantitative AFM height (diameter) analysis of SWNTs. Using silicon tip/cantilever assemblies with force constants ranging from 0.9 to 40 N m(-1), we examined the effect of applied force on the apparent diameter of SWNT wrapped with a 29-residue amphiphilic alpha-helical peptide. A decrease in apparent height (SWNT diameter) with increasing applied force was observed for the higher force constant cantilevers. Cantilevers having force constants of 0.9 and 3 N m(-1) demonstrated minimal vertical sample compression with increasing applied force. The effects of AFM image pixel density and scan speed on the measured height (diameter) of SWNTs were also assessed.     

Growth control of single and multi-walled carbon nanotubes by thin film catalyst

Single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) were synthesized on silicon substrate by the control of catalyst size, hydrocarbon species, and carbon flux through chemical vapor deposition (CVD). Catalysts for SWNTs and MWNTs could be obtained by an agglomeration of sputtered Co–Mo and pure Co thin films, respectively. The addition of Mo in the Co catalyst provides an effective nucleation site for SWNT and the low carbon flux by using methane gas in CVD reaction makes it possible to grow a single-walled structure.     

Catalytic polymerization and facile grafting of poly(furfuryl alcohol) to single-wall carbon nanotube: preparation of nanocomposite carbon

A nanocomposite carbon was prepared by grafting a carbonizable polymer, poly(furfuryl alcohol) (PFA), to a single-wall carbon nanotube (SWNT). The SWNT was first functionalized with arylsulfonic acid groups on the sidewall via a method using a diazonium reagent. Both Raman and FTIR spectroscopies were used to identify the functional groups on the nanotube surface. HRTEM imaging shows that the SWNT bundles are exfoliated after functionalization. Once this state of the SWNTs was accomplished, the PFA-functionalized SWNT (PFA-SWNT) was prepared by in situ polymerization of furfuryl alcohol (FA). The sulfonic acid groups on the surface of the SWNT acted as a catalyst for FA polymerization, and the resulting PFA then grafted to the SWNTs. The surfaces of the SWNTs converted from hydrophilic to hydrophobic when they were wrapped with PFA. The formation of the polymer and the attraction between it and the sulfonic acid groups were confirmed by IR spectra. A nanocomposite carbon was generated by heating the PFA-SWNT in argon at 600 degrees C, a process during which the PFA was transformed to nanoporous carbon (NPC) and the sulfonic acid groups were cleaved from the SWNT. Based upon the Raman spectra and HRTEM images of the composite, it is concluded that SWNTs survive this process and a continuous phase is formed between the NPC and the SWNT.     

Noncovalent functionalization of single-walled carbon nanotubes with water-soluble porphyrins

We have employed water-soluble porphyrin molecules [meso-(tetrakis-4-sulfonatophenyl) porphine dihydrochloride] to solubilize single-walled carbon nanotubes (SWNTs), resulting in aqueous solutions that are stable for several weeks. The porphyrin-nanotube complexes have been characterized with absorption and fluorescence spectroscopy and with AFM. We find that the porphyrin/SWNT interaction is selective for the free base form, and that this interaction stabilizes the free base against protonation to the diacid. Under mildly acidic conditions nanotube-mediated J-aggregates form, which are unstable in solution and result in precipitation of the nanotubes over the course of a few days. Porphyrin-coated SWNTs can be precisely aligned on hydrophilic poly(dimethylsiloxane) (PDMS) surfaces by combing SWNT solution along a desired direction and then transferred to silicon substrates by stamping. Parallel SWNT patterns have been fabricated in this manner.     

针尖化学方法研究单壁碳纳米管末端羧基的解离性质

针尖化学利用化学手段对扫描探针显微镜 ( SPM)的针尖进行功能化修饰 ,将其作为化学反应的“探针”用于研究表面的局域化学反应性质、跟踪表面发生的化学反应过程等 [1] .用针尖化学技术来研究自组装膜 ( SAMs)表面酸碱基团的局域解离性质 ,称之为化学力滴定 [2～ 8] .利用表面缩合方法将单壁碳纳米管短管组装到 AFM针尖上 ,通过测定针尖上碳纳米管的末端基团与羟基自组装膜表面之间的粘滞力 ,研究碳纳米管末端羧基的解离性质 ,可得到碳纳米管结构与化学性质的信息 .1　实验部分1 .1　碳纳米管针尖和羟基末端自组装膜的制备　基底 [Si( …     

SWNTs as catalyst and/or support in the catalytic decomposition of hydrocarbons

Various SWNT samples as either catalyst or catalytic support were used in the chemical vapor deposition (CVD) method for the growth of MWNTs. Catalysts were prepared by the impregnation of SWNT soot with different transition metals. Decomposition of acetylene was investigated at different temperatures (650–720 °C). The quality of both original SWNTs and the newly formed carbon nanostructures was assessed by TEM. A significant difference was found between selectivities of original (known as metallic impurities in SWNT soot) and the posteriorly deposited metallic particles. In the presence of active catalyst SWNT ropes tend to disappear, absorbed into carbon fibers or MWNTs.     

Molecular dynamics study of the catalyst particle size dependence on carbon nanotube growth

The molecular dynamics method, based on an empirical potential energy surface, was used to study the effect of catalyst particle size on the growth mechanism and structure of single-walled carbon nanotubes (SWNTs). The temperature for nanotube nucleation (800-1100 K), which occurs on the surface of the cluster, is similar to that used in catalyst chemical vapor deposition experiments, and the growth mechanism, which is described within the vapor-liquid-solid model, is the same for all cluster sizes studied here (iron clusters containing between 10 and 200 atoms were simulated). Large catalyst particles, which contain at least 20 iron atoms, nucleate SWNTs that have a far better tubular structure than SWNTs nucleated from smaller clusters. In addition, the SWNTs that grow from the larger clusters have diameters that are similar to the cluster diameter, whereas the smaller clusters, which have diameters less than 0.5 nm, nucleate nanotubes that are approximately 0.6-0.7 nm in diameter. This is in agreement with the experimental observations that SWNT diameters are similar to the catalyst particle diameter, and that the narrowest free-standing SWNT is 0.6-0.7 nm.     

Dendrimer-templated Fe nanoparticles for the growth of single-wall carbon nanotubes by plasma-enhanced CVD

A fourth-generation (G4) poly(amidoamine) (PAMAM) dendrimer (G4-NH2) has been used as a template to deliver nearly monodispersed catalyst nanoparticles to SiO2/Si, Ti/Si, sapphire, and porous anodic alumina (PAA) substrates. Fe2O3 nanoparticles obtained after calcination of the immobilized Fe3+/G4-NH2 composite served as catalytic "seeds" for the growth of single-wall carbon nanotubes (SWNTs) by microwave plasma-enhanced CVD (PECVD). To surmount the difficulty associated with SWNT growth via PECVD, reaction conditions that promote the stabilization of Fe nanoparticles, resulting in enhanced SWNT selectivity and quality, have been identified. In particular, in situ annealing of Fe catalyst in an N2 atmosphere was found to improve SWNT selectivity and quality. H2 prereduction at 900 degrees C for 5 min was also found to enhance SWNT selectivity and quality for SiO2/Si supported catalyst, albeit of lower quality for sapphire supported catalyst. The application of positive dc bias voltage (+200 V) during SWNT growth was shown to be very effective in removing amorphous carbon impurities while enhancing graphitization, SWNT selectivity, and vertical alignment. The results of this study should promote the use of exposed Fe nanoparticles supported on different substrates for the growth of high-quality SWNTs by PECVD.