碳纳米管共价功能化

碳纳米管由于其独特的结构与优异的各项性能,在许多领域具有巨大的应用潜力,已引起了广泛的关注。由于碳纳米管不溶于水和有机溶剂,极大地制约了其性能应用,因此碳纳米管的功能化就成为目前研究的热点。本文侧重于碳纳米管的共价功能化,详细讨论了碳纳米管不同位置共价功能化的研究进展。     

DNA共价修饰单壁碳纳米管电极的制备及与VB6 相互作用的研究

利用单壁碳纳米管(SWNTs)上的羧基与DNA末端的氨基形成酰胺共价键从而共价修饰SWNTs,制备了新型DNA共价修饰SWNTs电极.傅立叶红外光谱表明DNA共价结合在SWNTs上,用扫描电镜(SEM)表征了SWNTs、DNA共价修饰的SWNTs的结构与形貌.循环伏安法(CV)研究了DNA修饰SWNTs电极的电化学特性,通过改变扫描速率,发现DNA修饰电极的过程属于扩散控制过程.维生素B6(VB6)与SWNTs上DNA的相互作用研究结果表明:DNA分子共价修饰在SWNTs上后仍具有生物活性,且能够与其他生物分子发生相互作用.     

基于有机功能化碳纳米管的自组装

利用自组装的方法,实现碳纳米管的有序排列可以充分有效的促进碳纳米管在各个领域的应用。本文从自组装所依赖的驱动力着手,介绍了国内外近几年来基于功能化碳纳米管的自组装开展的研究工作及取得的成果,重点介绍了通过配位作用、静电力及氢键、亲水/疏水相互作用等实现的自组装。     

高纯度可溶性单壁碳纳米管的吸收光谱

经过K₂S₂O₈的稀硫酸溶液氧化处理的粗制单壁碳纳米管样品, 在水、DMF 和乙醇等极性溶剂中具有非常好的溶解性. 通过在DMF介质中多次进行超声波分散和高速离心分离, 成功地获得了高纯度可溶性的单壁碳纳米管. UV-vis-NIR吸收光谱研究表明, 这种高纯度可溶性的单壁碳纳米管呈现出更多的吸收特征和更高的吸收强度. 进一步的研究表明, 单壁碳纳米管的纯度达到了“参比样品”的160%, 其单根分散度达到5%以上.     

非离子型水溶性卟啉功能化单壁碳纳米管的研究

合成了两种非离子型水溶性卟啉分子,并利用它们对单壁碳纳米管(SWNTs)进行了非共价表面修饰。功能化后SWNTs能够在水中均匀分散。紫外-可见光谱、荧光光谱、透射电镜的测试结果均证明非离子型水溶性卟啉分子与SWNTs之间存在强烈的相互作用。其中,含有柔性烷基取代链的卟啉分子因与SWNTs之间存在π-π和疏水双重相互作用,所形成的复合物在水中表现出更好的分散稳定性。这种既具有水溶性又具有生物相容性和良好稳定性的功能化SWNTs,在生物医药领域具有潜在的应用前景。     

NEXAFS光谱分析聚合物修饰的单壁碳纳米管

利用C1s、O1s、N1s近边X射线吸收精细结构(Near Edge X-Ray Absorption Fine Structure,NEXAFS)光谱对聚合物修饰的碳纳米管进行了分析,研究了氧化及偶联聚合物对碳纳米管结构的影响。氧化碳纳米管及十八胺修饰的、聚合物/十八胺双修饰的碳纳米管的NEXAFS光谱均出现了碳/氧K边π*(C=O)和σ*(C-O)共振峰;而十八胺修饰的、聚合物/十八胺双修饰的碳纳米管则出现了氮K边π*(N-C=O)和σ*(N1s)共振峰。分析表明,NEXAFS光谱可有效表征聚合物修饰的碳纳米管。     

碳纳米管的功能化研究进展

综述了碳纳米管功能化的一些最新研究进展,重点介绍了一些功能化方法、功能化碳纳米管的性能表征及应用前景。文献49篇。     

功能化离子液体修饰多壁碳纳米管固定化Candida antarctic lipase B

将带不同阴离子（Br^-、BF₄^-、PF₆^-、H₂PO₄^-）的咪唑离子液体修饰改性的多壁碳纳米管（MWNTs）作为一种全新的载体通过物理吸附法固定化褶皱假丝酵母脂肪酶B（CALB）,对其酶学性能进行测试。并通过透射电镜、拉曼光谱、热重分析、X射线光电子能谱对修饰前后的MWNTs进行表征,研究材料表面修饰对酶学性能的影响。研究结果表明,经过离子液体表面修饰后的MWNTs固定化CALB具有更高的比活力,耐受性（高温、高pH值）、热稳定性和重复使用性也得到进一步增强;离子液体中不同的阴离子对修饰MWNTs固定化酶的酶学性能有显著影响,其中以PF₆^-为阴离子的固定化酶比活力最高,比未修饰的MWNTs提高了5倍。固定化酶的动力学参数分析表明离子液体的引入增强了酶与底物之间的亲和力,从而增强了酶的活性。     

激光辐照对二茂铁掺杂单壁碳纳米管的影响

以单壁碳纳米管和二茂铁为原料, 采用气相扩散法合成填充率较高的二茂铁掺杂单壁碳纳米管(Fc@SWNTs)的复合材料. 考察激光辐射对样品的影响, 结果表明, 当激光功率达到20 mW时, 对样品进行10 s辐照, 样品的拉曼光谱出现了稳定的新峰. 对比分析发现, 二茂铁在激光辐照后形成了碳化铁, 同时部分碳源转化成碳管形成了双层碳管. 表明碳化铁是二茂铁裂解向内层碳管转化的中间产物.     

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.     

Microwave‐Assisted Synthesis of Crosslinked Poly(vinyl alcohol) Nanocomposites Comprising Single‐Walled Carbon Nanotubes,Multi‐Walled Carbon Nanotubes,and Buckminsterfullerene

We report a facile method to accomplish the crosslinking reaction of PVA with SWNTs, MWNTs, and C‐60 using MW irradiation. Nanocomposites of PVA crosslinked with SWNT, MWNT and C‐60 were prepared expeditiously by reacting the respective carbon nanotubes with 3 wt.‐% PVA under MW irradiation, maintaining a temperature of 100 °C, representing a radical improvement over literature methods to prepare such crosslinked PVA composites. This general preparative procedure is versatile and provides a simple route to manufacture useful SWNT, MWNT and C‐60 nanocomposites.

     

Functionalization of Single‐Walled Carbon Nanotubes

Through chemical functionalization of single‐walled carbon nanotubes, the prerequisites for possible applications of such nanostructures are established. The derivatized tubes differ from the crude materials in their good solubility, which enables both a more extensive characterization and subsequent chemical reactivity. Current derivatization methods include defect and covalent sidewall functionalization, as well as noncovalent exo‐ and endohedral functionalization. In this way, for example, a range of nanotubes can be prepared: with sidewall substituents, wrapped with polymers, or with guest molecules included. The current state of the literature is presented in this Minireview.     

DFT Studies of Ag‐Loading Intrinsic and Functionalized Single‐Walled Carbon Nanotubes

The first principles study was performed on the stability of Ag adsorbed on the internal walls of single‐walled carbon nanotube (SWCNT) and loaded on acid modified SWCNT. The calculation results show that Ag can be adsorbed stably on the internal walls of SWCNT. With the increase of SWCNT diameter, the adsorption energy increases in a certain range. Ag can also be loaded on the modified SWCNT surface in the form of COOAg and OAg groups, and COOAg group is more stable than OAg group. For either the adsorption on the inner SWCNT or the load on the modified SWCNT surface, only a small proportion of the Ag ions can be stably bonded to the walls of SWCNT.     

Sorting Semiconducting Single‐Walled Carbon Nanotubes by Water‐Soluble Polyfluorene Assisted Electrophoresis and Its Application in Field‐effect Transistors

We report a considerably promising method based on agarose gel electrophoresis (AGE) to separate single‐walled carbon nanotubes by adding a water‐soluble polyfluorene (w‐PFO) as surfactant into the agarose gel. In this effective method, the AGE/w‐PFO gel network will trap more semiconducting single‐walled carbon nanotubes (SWNTs) with the assistance of w‐PFO, for the strong interaction between w‐PFO and semiconducting species. The optical absorbance, photoluminescence emission and resonant Raman scattering characterization were used to verify the separation effect. The purity of separated semiconducting species is as high as (98±1)%. The demonstrated field effect transistors give the on/off ratio and mobility about 27000 and 10.2 cm²·V^?1·s^?1, respectively.     

Hetero Diels–Alder Chemistry for the Functionalization of Single‐Walled Carbon Nanotubes with Cyclopentadienyl End‐Capped Polymer Strands

Single‐walled carbon nanotubes (SWCNTs) are pre‐functionalized with a pyridinyl‐based dithioester to undergo a hetero Diels–Alder (HDA) reaction with cyclopentadienyl end‐capped poly(methyl)methacrylate (M _n = 2700 g mol⁻¹, PDI = 1.14). Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis (EA), and X‐ray photoelectron spectroscopy (XPS) evidence the success of the grafting process. The estimated resulting grafting density (from XPS and EA) via the HDA reaction increases by a factor of more than two (0.0774 chains·nm⁻² via XPS) compared with typical values obtained via a direct cyclopentadiene driven Diels–Alder conjugation onto non‐functional SWCNTs under similar conditions.

     

Carbon Nanotubes Fed on “Carbs”: Coating of Single‐Walled Carbon Nanotubes by Dextran Sulfate

A facile and easily reproducible technique for assembling biohybrid nanoparticles is a core feature that is highly desired for biomedical applications, considering the nature and limited lifespan of the biopolymers used. Here we show a simple and effective method to enfold single‐walled carbon nanotubes (SWNTs) using an anionic polysaccharide, dextran sulfate. After their interactions, SWNTs were rendered dispersible in aqueous solution and were shortened and unbundled to their basic dimension. Atomic force microscopy analysis was extensively employed to elucidate the mechanism of their interfacing. This biohybrid nanoparticle holds promise for biological and biomedical applications due to the synergistic unique properties of SWNTs and dextran sulfate.

     

聚碳酸酯修饰多壁碳纳米管的制备和表征

为了制备聚合物/碳纳米管复合物,采用聚碳酸酯修饰了多壁碳纳米管。选择聚碳酸环氧丙烷己内酯,聚碳酸亚丁酯己内酯和聚碳酸亚丙酯马来酸酐酯三种聚碳酸酯修饰多壁碳纳米管,仅仅碳酸环氧丙烷己内酯修饰的碳纳米管复合物可分离得到可溶解性产物。分别采用红外光谱、扫描电镜和透射电镜表征了碳纳米管的表面修饰基团及形貌。热重分析表明,可溶解聚碳酸环氧丙烷己内酯修饰多壁碳纳米管相对接枝了较多的聚合物,因此促进了碳纳米管的溶解性,可能是因为聚碳酸环氧丙烷己内酯具有较多的端羟基提高了修饰接枝效果。可溶解聚碳酸环氧丙烷己内酯修饰多壁碳纳米管接枝了生物活性的部分,并具有一定溶解性,在药物载体领域将具有潜在用途。     

Electrochemically Functionalized Single‐Walled Carbon Nanotube Gas Sensor

We demonstrate a facile fabrication method to make chemical gas sensors using single‐walled carbon nanotubes (SWNT) electrochemically functionalized with polyaniline (PANI). The potential advantage of this method is to enable targeted functionalization with different materials to allow for creation of high‐density individually addressable nanosensor arrays. PANI‐SWNT network based sensors were tested for on‐line monitoring of ammonia gas. The results show a superior sensitivity of 2.44% ΔR/R per ppm_v NH₃ (which is more than 60 times higher than intrinsic SWNT based sensors), a detection limit as low as 50 ppb_v, and good reproducibility upon repeated exposure to 10 ppm_v NH₃. The typical response time of the sensors at room temperature is on the order of minutes and the recovery time is a few hours. Higher sensitivities were observed at lower temperatures. These results indicate that electrochemical functionalization of SWNTs provides a promising new method of creating highly advanced nanosensors with improved sensitivity, detection limit, and reproducibility.     

Probing the Chemical Functionalization of Single‐Walled Carbon Nanotubes with Multiple Carbon Ad‐Dimer Defects

Drying‐tube‐shaped single‐walled carbon nanotubes (SWCNTs) with multiple carbon ad‐dimer (CD) defects are obtained from armchair (n,n,m) SWCNTs (n=4, 5, 6, 7, 8; m=7, 13). According to the isolated‐pentagon rule (IPR) the drying‐tube‐shaped SWCNTs are unstable non‐IPR species, and their hydrogenated, fluorinated, and chlorinated derivatives are investigated. Interestingly, chemisorptions of hydrogen, fluorine, and chlorine atoms on the drying tube‐shaped SWCNTs are exothermic processes. Compared to the reaction energies for binding of H, F, and Cl atoms to perfect and Stone–Wales‐defective armchair (5,5) nanotubes, binding of F with the multiply CD defective SWCNTs is stronger than with perfect and Stone–Wales‐defective nanotubes. The reaction energy for per F₂ addition is between 85 and 88 kcal mol^?1 more negative than that per H₂ addition. Electronic structure analysis of their energy gaps shows that the CD defects have a tendency to decrease the energy gap from 1.98–2.52 to 0.80–1.17 eV. After hydrogenation, fluorination, and chlorination, the energy gaps of the drying‐tube‐shaped SWCNTs with multiple CD defects are substantially increased to 1.65–3.85 eV. Furthermore, analyses of thermodynamic stability and nucleus‐independent chemical shifts (NICS) are performed to analyze the stability of these molecules.     

Transparent and Conductive Polyethylene Oxide Film by the Introduction of Individualized Single‐Walled Carbon Nanotubes

It is demonstrated that an optically transparent and electrically conductive polyethylene oxide (PEO) film is fabricated by the introduction of individualized single‐walled carbon nanotubes (SWNTs). The incorporated SWNTs in the PEO film sustain their intrinsic electronic and optical properties and, in addition, the intrinsic properties of the polymer matrix are retained. The individualized SWNTs with smaller diameter provide high transmittance as well as good electrical conductivity in PEO films.