表面修饰碳纳米管/二氧化钛复合光催化剂制备及催化活性研究

采用溶胶-凝胶法在聚乙烯吡咯烷酮(PVP)修饰的碳纳米管表面均匀沉积纳米级二氧化钛粒子制得复合光催化剂。采用透射电子显微镜(TEM)、X射线衍射仪(XRD)、紫外-可见吸收光谱仪(UV-Vis)和X射线光电子能谱仪(XPS)等手段对复合光催化剂进行表征。结果表明,二氧化钛粒子是呈球形、团聚,随机沉积在未修饰碳纳米管任意表面,甚至部分碳纳米管表面是完全裸露的。经PVP修饰后的碳纳米管,二氧化钛纳米粒子均匀沉积在碳纳米管表面,二氧化钛为纯锐钛矿晶体结构,没有金红石和板钛矿相。表面修饰碳纳米管/二氧化钛复合光催化剂在紫外光照射下降解亚甲基蓝,相比纯的二氧化钛和碳纳米管/二氧化钛复合光催化剂,具有非常高的催化活性。     

CO2连续激光蒸发制备单壁碳纳米管及其Raman光谱的研究

讨论了在室温下用波长10.6μm的CO2连续激光制备单壁碳纳米管的工艺条件和生长机理.用大功率CO2连续激光蒸发制备单壁碳纳米管,所用激光功率400—900W,高分辨透射电镜观察表明单壁碳纳米管直径1.1—16nm,随着激光功率的增加稍微增加.本文还分别用波长为514.5nm和632.8nm激发光测量了CO2红外激光制备的单壁碳纳米管的一级和二级Raman光谱,发现在Raman特征峰的位置、强度上都存在差异.还将用CO2红外激光制备的单壁碳纳米管的Raman光谱与用YAG激光制备的单壁碳纳米管的Raman光谱进行了比较. 关键词： 单壁碳纳米管 CO2连续激光 Raman光谱     

表面修饰纳米TiO2的贮氢合金电极的光充电行为

采用水解-沉淀法制备了锐钛矿结构的纳米级TiO2,研究了表面修饰TiO2的贮氢合金电极的光充电、循环伏安及交流阻抗特性.结果表明,表面未修饰TiO2的贮氢合金电极在光照下电极电位基本无变化,而表面修饰TiO2的贮氢合金电极在光照下,电极电位向负方向偏移,可达-0.835V,表明在光照射条件下电极表面有氢原子形成.电化学阻抗谱的结果也表明,表面修饰电极在光照时表面有吸附氢存在,并存在氢原子向贮氢合金内部的扩散过程.扫描电镜观察表明,表面修饰TiO2的贮氢合金电极在光充电后产生的氢原子被贮氢合金吸收引起膨胀,导致表面出现大量微裂纹.     

修饰银电极上单壁碳纳米管的表面增强拉曼散射

本文采用修饰了银纳米颗粒的银电极作为基底,获得了高质量的单壁碳纳米管(SWCNTs)的表面增强拉曼散射(SERS)光谱。在1100~1500 cm-1范围内观测到了一组表征SWCNTs结构的新峰。修饰在银电极上的银纳米颗粒不仅可以保证SWCNTs在这一体系中吸附的紧密性,而且通过变面等离子体共振起到了电磁放大的作用。通过对银纳米颗粒修饰银电极表面SWCNTs的SERS光谱及其随电位变化的SERS光谱的研究,我们可以研究这一过程中的SERS机制。理论和实验结果表明,银纳米颗粒修饰银电极上单壁碳纳米管的SERS很有潜力成为一种检测单壁碳纳米管合成质量的新方法。     

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。     

单壁和多壁碳纳米管的硝酸氧化对比研究

利用同步辐射X射线近边吸收谱（XANES）分别对硝酸氧化处理后的单壁碳纳米管和多壁碳纳米管进行了系统的对比研究。实验结果表明,单壁碳纳米管容易遭到硝酸的破坏,生成大量的碳碎片,氧化所产生的氧化基团大部分形成于碳碎片上,这些吸附在碳纳米管上的碳碎片可以通过氢氧化钠溶液的清洗、过滤去除。相比之下,结构稳定性更高的多壁碳纳米管在硝酸处理过程中则显得比较稳定,大量的氧化基团形成于碳管管壁上。这种不同结构碳纳米管的不同氧化结果可能会对碳纳米管的后续修饰和应用产生重要的影响。     

多壁碳纳米管/铋膜修饰电极示差脉冲溶出伏安法测定水中镉和铅

制备多壁碳纳米管/壳聚糖纳米复合物修饰玻碳电极,用于同位镀铋膜法连续测定水中镉和铅离子的含量.将多壁碳纳米管分散在壳聚糖溶液中,滴涂在玻碳电极表面制得修饰电极;在含铋的溶液中,采用示差脉冲溶出伏安法测定了镉、铅离子的浓度;考察了沉积电位、富集时间对溶出电流的影响.在优化的实验条件下,对浓度在0-0.2μmol/L范围内...     

等离子体处理碳纳米管的研究现状及展望

采用等离子体处理技术对碳纳米管进行表面处理是一项新兴的技术,本文对在碳纳米管处理过程中,等离子体处理工艺参数的选择,以及处理前后表面结构变化、形貌变化、场发射效应等进行了综述,并对等离子体处理技术在碳纳米管表面修饰中的应用前景进行了展望。     

组氨酸、谷胱甘肽混合修饰金纳米团簇的光稳定性研究

金纳米团簇(简称金簇)由几到几百个金原子及修饰试剂组成,由于其尺寸接近于电子费米波长,表现出良好的发光特性及生物相容性,是一类新型纳米标记探针。目前,金纳米团簇在生物检测、细胞成像、癌症诊断及治疗等领域受到研究者的广泛关注。然而,对于光照条件下金簇的稳定性还不清楚。在合成组氨酸、谷胱甘肽混合修饰金簇的基础上,系统研究了光照条件下金簇在不同pH(5.0,7.4和9.0)的荧光变化规律,结果表明,在氙灯强光照射下,金纳米团簇的荧光会随着照射时间的增加逐渐降低,在pH 9.0条件下比pH 5.0及7.4时降低更快,说明金簇在pH 5.0及7.4时光稳定性更好。在此基础上,采用紫外-可见吸收光谱、红外光谱等手段研究了光照前后金簇表面基团的变化规律,发现光照后金簇的紫外可见吸收光谱及红外光谱均发生了明显的变化,说明光照导致金簇表面修饰基团发生了变化。当向体系中通入氮气后,金簇最大发射波长处荧光强度随照射时间的变化明显变慢,说明金簇表面基团与溶液中溶解氧发生了反应,导致金簇表面电荷及修饰试剂状态发生变化,从而导致金簇荧光产生猝灭。相关研究结果对于金纳米团簇在生命科学及分析化学等领域的进一步应用具有一定的参考价值。     

等离子体处理碳纳米管的研究现状及展望

采用等离子体处理技术对碳纳米管进行表面处理是一项新兴的技术,本文对在碳纳米管处理过程中,等离子体处理工艺参数的选择,以及处理前后表面结构变化、形貌变化、场发射效应等进行了综述,并对等离子体处理技术在碳纳米管表面修饰中的应用前景进行了展望.     

Realization, characterization and functionalization of lipidic wrapped carbon nanotubes

Mass-produced carbon nanotubes (CNTs) are strongly aggregated and highly hydrophobic, and processes to make them water soluble are required for biological applications. Both covalent and non-covalent strategies are pursued for obtaining stable, highly concentrated CNT aqueous dispersions. Covalent functionalization has the great disadvantage of producing an irreversible chemical modification of nanotubes, thus alterating their mechanical, chemical and electric properties. On the other hand, non-covalent functionalization is often obtained by employing surfactants that sensibly affect cell viability. Moreover, derivatization with biological moieties is often impossible through non-covalent CNT dispersion. This paper proposes a non-covalent dispersion of multi-wall CNT based on a lipidic mixture that can guarantee high concentration and high stability as well as high cytocompatibility. Moreover, CNTs wrapped with a lipid membrane are realized to demonstrate that the proposed CNTs can be functionalised with a dodecapeptide that specifically recognizes activated platelets without chemical modification of the nanotube itself.     

水热法合成蓝宝石的化学成分及光谱学表征

蓝宝石作为五大名贵宝石之一,经济价值极高,其中“皇家蓝”、“矢车菊蓝”最为昂贵。而水热法可合成出颜色与“皇家蓝”色极为相似的蓝宝石,且合成出的晶体较大,可通过切磨加工获得内部纯净的样品,仅凭外观及常规方法难以鉴别。选取了7颗水热法合成蓝色蓝宝石为实验对象,采用LA-ICP-MS、拉曼光谱仪、红外光谱仪、紫外-可见分光光度计和三维荧光光谱仪,对其化学成分、谱学特征进行研究,并与外观极为相似的天然蓝宝石、焰熔法合成蓝宝石进行对比分析。分析表明,水热法合成蓝宝石总体成分较为单一,而天然蓝宝石则含有丰富的微量元素。三种样品拉曼光谱均呈现典型的刚玉振动模式,显示A_1g和E_g振动模的拉曼峰。在红外光谱的指纹区,三种样品的吸收峰均无明显差别,与拉曼光谱的结果耦合。但在官能团区3 000～4 000 cm^-1波数范围,水热法合成蓝宝石存在由含水矿物包裹体产生的羟基振动峰,而天然蓝宝石和焰熔法合成蓝宝石未显示此特征。紫外-可见光谱表明三种样品均为Fe²⁺-Ti⁴⁺对致色,但水热法与焰熔法合成蓝宝...     

Systematic investigation on the properties of carbon nanotube electrodes with different chemical treatments

The functionalization of carbon nanotubes (CNTs) was carried out by using different chemical treatment methods. These functionalized CNTs were characterized by TEM image and FT-IR spectra. The CNT electrodes are measured by thermal resistivity and cyclic voltammetry experiments. The results showed that two important factors controlled the electrochemical properties of the CNT film electrode: one is the active functional group; another is activation energy of the CNT film. From our experiments, we have found the electrode of 10 min nitric acid treated CNTs have the optimal peaks in relation to carboxylic acids, the highest redox peak currents, the biggest value of k⁰ and well-defined quasi-reversible voltammograms for redox of iron couples, in which the two factors best match.     

Surface‐enhanced Raman scattering of pyridine‐functionalized multi‐walled carbon nanotubes

Carbon nanotubes (CNTs) have attracted great attention for their potential use in many applications because of their intrinsic properties. The importance other than the impact of the application of CNT‐embedded membranes in the area of water technology development is immense. In this context, the identification and quantification of CNTs in aqueous resources during relevant water purification processes can be proven of high significance. Surface‐enhanced Raman scattering (SERS) potentially has the sensitivity required for trace analysis and has been previously used for CNT identification on solid substrates. A thorough study for the identification and quantification of small concentrations of multi‐walled CNTs (MWCNTs) in water suspensions via SERS has been performed. The functionalization of MWCNTs with pyridine groups seems to favor the surface enhancement of relevant Raman signal. This study constitutes the first step of a work in progress for the characterization of CNTs at quite low concentration range by SERS in any water suspension. It is based on an ex ante functionalization of the CNTs by pyridine, demonstrating the potential of the method. Our long‐term aim is its general application built, however, in an ex post relevant functionalization of the CNTs in any aqueous solution. Copyright © 2014 John Wiley & Sons, Ltd.     

Hydrothermal conversion of graphite to carbon nanotubes (CNTs) induced by bubble collapse

Cu–Fe–CNTs and Ni–Fe–CNTs coatings were deposited on gray cast iron by a hydrothermal approach. It was demonstrated that, the flaky graphite of gray cast iron was exfoliated to graphene nanosheets under hydrothermal reactions, and graphene nanosheets were scrolled to CNTs. After high temperature treatments, the volume losses of Cu–Fe–CNTs and Ni–Fe–CNTs coatings were 52.6 % and 40.0 % of gray cast iron substrate at 60 min wear tests, respectively, obviously increasing the wear properties of gray cast iron. During hydrothermal reactions, water jets and shock waves were produced by bubble collapse. Induced by the water jets and shock waves, exfoliation of flaky graphite was performed, producing exfoliated graphene nanosheets. Attacked by the radially distributed water jets and shock waves, graphene nanosheets were curved, shaped to semicircle morphology and eventually scrolled to tubular CNTs.     

Variation in chemical,colloidal and electrochemical properties of carbon nanotubes with the degree of carboxylation

Multiwalled carbon nanotubes (CNTs) were carboxylated via microwave irradiation where the treatment time was varied to alter the degree of functionalization, and as many as one in 15 carbons in the CNT could be oxidized. Chemical, physical, electrochemical, and colloidal behavior of the carboxylated CNTs was studied. All properties changed with the degree of functionalization to a point beyond which they appeared to remain constant. The surface area increased from 173.9 to 270.9 m²/g while the critical coagulation concentration (CCC) values increased from 142.14 to 168.69 mM in the presence of NaCl, and the corresponding increase was from 0.97 to 5.32 mM in the presence of MgCl₂. As seen from cyclic voltammetry curves, the functionalized CNTs showed mainly non-Faradic interactions with Na₂SO_4, but showed Faradic behaviors in alkaline KOH.     

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     

Photo-directed organization of silver nanoparticles in mesostructured silica and titania films

Carbon nanotubes (CNTs) have the potential to enhance the strength, toughness, and multifunctional ability of composite materials. However, suitable dispersion and interfacial bonding remain as key challenges. Composites that are formed by reactions with water, like Portland cement concrete and mortar, pose a special challenge for dispersing the inherently hydrophobic nanotubes. The hydration of Portland cement also offers a specific chemical framework for interfacial bonding. In this study, nanoscale silica functional groups are covalently bonded to CNTs to improve their dispersion in water while providing interfacial bond sites for the proposed matrix material. The bond signatures of treated nanotubes are characterized using Fourier transform infrared spectroscopy. In situ dispersion is characterized using cryogenic transmission electron microscopy and point of zero charge (PZC) measurements. At the nanoscale, interparticle spacing was greatly increased. A slight increase in the PZC after treatment indicates the importance of steric effects in the dispersion mechanism. Overall, results indicate successful functionalization and dramatically improved dispersion stability in water.

     

Polyoxometalates nanoparticles: synthesis, characterization and carbon nanotube modification

In this paper, we described a large-scale synthesis method of the polyoxometalates (POMs) nanoparticles and the modification of carbon nanotube (CNTs) through a chemical modified approach. Four types of POMs nanoparticles were prepared by a one-step solid-state reaction at room temperature and characterized by IR, elemental analyses, XRD and TEM. These uniform nanoparticles have an average size of 8-10 nm. Furthermore, based on chemical adsorption between POMs and carboxylic acid groups, which were introduced to the CNTs by adding dilute nitric acid, POMs nanoparticles were successfully located on the CNTs as the modifier.     

A cytosine-assisted carbon nanotubes junction: DFT studies

Since nucleobase-functionalized carbon nanotubes (CNTs) are important in the biological applications; the junction of a pair of CNTs through a bridging cytosine linkage is investigated based on density functional theory (DFT) calculations. In the exact model of study, the CNTs are bound to N₁ and C₅ atomic sites of cytosine to make possible the CNT–cytosine–CNT model. To systematically investigate the purpose, the models of original CNT, original cytosine, and primary models of cytosine–CNT in which one CNT is only bound to N₁ or C₅ atomic site of cytosine are also considered. The results of dipole moments and binding energies indicated that the CNT–cytosine–CNT model is the most stable one among all three possible models cytosine-functionalized CNT. The values of energy gaps indicated that the conducting properties of primary cytosine–CNT models are not changed referring to the original CNT but better conductivity could be observed for the CNT–cytosine–CNT model. The values of evaluated quadrupole coupling constants indicated that the electronic densities of nitrogen and oxygen atoms of cytosine detect notable affects during the functionalization processes by the zigzag CNTs and the oxygen atom of CNT–cytosine–CNT model could be proposed as the most proper interacting site of cytosine among other functionalized zigzag models and also the original cytosine. However, the changes of quadrupole coupling constants for the atoms of cytosine are almost negligible during the functionalization processes by the armchair CNTs.