单壁碳纳米管的电子速度及有效质量

利用单壁碳纳米管(SWCNTs)能量色散关系, 计算了最低导带的电子速度和有效质量, 重点讨论了SWCNTs中最低导带电子速度和有效质量与波矢及管径大小的关系. 结果表明, 半导体型锯齿SWCNTs的电子速度和有效质量与其结构参量(管径)有直接的关系. 各种椅型SWCNTs(金属型)和金属型锯齿SWCNTs最低导带电子速度和有效质量随波矢的变化规律分别相同, 各种半导体型锯齿SWCNTs最低导带电子速度和有效质量随波矢的变化规律则有明显差别. 这意味着在低偏压下, 不同管径的椅型SWCNTs和金属型锯齿SWCNTs输运性能相同, 而各种不同管径半导体型锯齿SWCNTs输运性能有明显差别.     

On the applicability of cluster models to study the chemical reactivity of carbon nanotubes

We have performed a comparative study on the reactivity of metallic and semiconducting nanotubes using infinite and finite models. Infinite models were created using periodic boundary conditions while finite ones were constructed by means of hydrogen terminated nanotubes sections. Cluster models systematically underestimate the reactivity of metallic single wall carbon nanotube (SWCNT)s. We have confirmed that metallic nanotubes are more reactive than semiconducting species, in disagreement with previous works. The differences can be attributed to the presence of an instability in the singlet ground state of the wavefunction corresponding to semiconducting nanotubes clusters. When lower electronic states of the pristine cluster are considered, semiconducting nanotubes become less reactive as compared with metallic SWCNTs. Particularly, if an antiferromagnetic solution is considered for the semiconducting (10,0) SWCNT cluster, it becomes less reactive than the (5,5) SWCNT, as observed for infinite models. Because semiconducting nanotubes are less reactive than metallic counterparts, their reaction energies converge faster to the values observed for graphene. For a 1.6-nm diameter semiconducting nanotube, the addition energy is comparable with graphene. Thus, semiconducting nanotubes with diameters larger than 1.6 nm are going to be as reactive as graphene and the effects of curvature will be unimportant.     

Theoretical investigation of the stability,electronic and magnetic properties of thiolated single‐wall carbon nanotubes

The addition of SH and OH groups to single‐wall carbon nanotubes (SWCNTs) was investigated employing first principles calculations. In the case of the semiconducting (10, 0) SWCNT the SWCNT‐SH binding energy is weak, 2–4 kcal/mol. However, for the metallic (5, 5) SWCNT it is larger, 7–9 kcal/mol. Thus metallic SWCNTs seem to be more reactive to SH than the semiconducting ones. Indeed, the (6, 6) SWCNT is more reactive to SH than the (10, 0) SWCNT, by 2–3 kcal/mol, something that can be explained only considering the electronic structure of the tube, because the (6, 6) has a larger diameter. The binding energies are larger for the addition of the OH group, 25 and 30 kcal/mol for the (10, 0) and (5, 5) SWCNTs, respectively. When a single OH or SH group is attached to the metallic SWCNTs, we observe important changes in the DOS at the Fermi level. However, when multiple SH groups are attached, the changes in the electronic and magnetic properties depend on the position of the SH groups. The small binding energy found for the SH addition indicates that the successful functionalization of SWCNTs with SH, SCH₃, and S(CH₂)_nSH groups is mostly due to the presence of defects created after acid treatment and to a minor extent by the metallic tubes present in the samples. Perfect semiconducting SWCNTs showed very low reactivity against the SH group. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

超声分散对单壁碳纳米管分离的影响

利用凝胶柱色谱技术, 研究者们通过两步或多步淋洗的方法实现了不同导电属性或电子结构单壁碳纳米管(SWCNTs)的分离, 并提出其分离机制主要是由不同导电属性和电子结构的SWCNTs 与凝胶填料之间作用力的差异所导致的. 基于凝胶柱色谱分离技术, 本文重点考察了超声时间对单壁碳纳米管单分散以及金属型/半导体型SWCNTs 分离的影响. 在一定的低超声功率下, 适当增加超声时间有利于SWCNTs 在十二烷基硫酸钠(SDS)溶液中的单分散. 紫外-可见-近红外(UV-Vis-NIR)吸收光谱、拉曼(Raman)光谱和荧光(PL)光谱表征结果表明, 2 h的超声条件是获得高纯度的金属型以及不同直径分布的半导体型SWCNTs 的最优条件. 我们认为不同超声时间对SWCNTs 分离的影响主要是改变了SWCNTs 的单分散性和长度, 调制了不同SWCNTs 与凝胶之间作用力的差异, 从而导致了不同SWCNTs分离结果.     

Selective oxidation on metallic carbon nanotubes by halogen oxoanions

Chlorine oxoanions with the chlorine atom at different oxidation states were introduced in an attempt to systematically tailor the electronic structures of single-walled carbon nanotubes (SWCNTs). The degree of selective oxidation was controlled systematically by the different oxidation state of the chlorine oxoanion. Selective suppression of the metallic SWCNTs with a minimal effect on the semiconducting SWCNTs was observed at a high oxidation state. The adsorption behavior and charge transfer at a low oxidation state were in contrast to that observed at a high oxidation state. Density functional calculations demonstrated the chemisorption of chloro oxoanions at the low oxidation state and their physisorption at high oxidation states. These results concurred with the experimental observations from X-ray photoelectron spectroscopy. The sheet resistance of the SWCNT film decreased significantly at high oxidation states, which was explained in terms of a p-doping phenomenon that is controlled by the oxidation state.     

Nerve agents interacting with single wall carbon nanotubes: Density functional calculations

First-principles calculations based on density functional theory (DFT) method are used to investigate the adsorption properties of nerve agent DMMP on typical zigzag (semiconducting) and armchair (metallic) single wall carbon nanotubes (SWCNTs). The adsorption energies for DMMP molecule on different adsorption sites on SWCNTs are obtained. The results indicate that DMMP is weakly bound to the outer surface of both the considered SWCNTs and the obtained adsorption energy values and binding distances are typical for the physisorption. We find that DMMP adsorptive capability of metallic CNTs is about twofold that of semiconducting one. The adsorption of DMMP on the higher chiral angle nanotubes was also investigated and the results indicate that nanotube’s chirality increases the adsorption capability of the tube but however the adsorption characteristic is typical for the physisorption. Furthermore, co-adsorption of two DMMP molecules on the SWCNTs as a single-layer/bi-layer of adsorbed molecules as well as the adsorption of one DMMP molecule on the CNT bundles consisting of three SWCNTs has also been examined. The obtained results reveal that for both the considered systems the binding energy was increased for the DMMP adsorption but it’s still typical for the physisorption, consistent with the recent experimental result. The study of the electronic structures and charge analysis indicate that no significant hybridization between the respective orbital takes place and the small interaction obtained quantitatively in terms of binding energies.     

Unraveling the 13C NMR chemical shifts in single-walled carbon nanotubes: dependence on diameter and electronic structure

The atomic specificity afforded by nuclear magnetic resonance (NMR) spectroscopy could enable detailed mechanistic information about single-walled carbon nanotube (SWCNT) functionalization as well as the noncovalent molecular interactions that dictate ground-state charge transfer and separation by electronic structure and diameter. However, to date, the polydispersity present in as-synthesized SWCNT populations has obscured the dependence of the SWCNT (13)C chemical shift on intrinsic parameters such as diameter and electronic structure, meaning that no information is gleaned for specific SWCNTs with unique chiral indices. In this article, we utilize a combination of (13)C labeling and density gradient ultracentrifugation (DGU) to produce an array of (13)C-labeled SWCNT populations with varying diameter, electronic structure, and chiral angle. We find that the SWCNT isotropic (13)C chemical shift decreases systematically with increasing diameter for semiconducting SWCNTs, in agreement with recent theoretical predictions that have heretofore gone unaddressed. Furthermore, we find that the (13)C chemical shifts for small diameter metallic and semiconducting SWCNTs differ significantly, and that the full-width of the isotropic peak for metallic SWCNTs is much larger than that of semiconducting nanotubes, irrespective of diameter.     

Finite-length models of carbon nanotubes based on Clar sextet theory

Finite-length models of metallic and semiconducting carbon nanotubes (CNTs) based on Clar sextet theory of aromatic systems are proposed. For metallic CNTs, the electronic properties of finite-length models converge monotonically to the values expected for quasi-monodimensional metallic systems. For semiconducting CNTs, the use of finite-length models as proposed in this work leads to a fast convergence of the electronic properties to the values expected for the corresponding infinite-length nanotube.     

Selective oxidation of semiconducting single-wall carbon nanotubes by hydrogen peroxide

Selective oxidation of single-wall carbon nanotubes (SWCNTs) by H2O2 was conducted at varying heating times and monitored by UV-vis-NIR spectroscopy. A major increase in the relative absorption intensity indicated a higher than 80% concentration of metallic SWCNTs in the final product. Here, it is suggested that semiconducting SWCNTs are more reactive than metallic SWCNTs because of hole-doping by H2O2, resulting in faster oxidation.     

Selective removal of metallic single-walled carbon nanotubes with small diameters by using nitric and sulfuric acids

Coexistence of metallic and semiconducting carbon nanotubes has often been a bottleneck in many applications and much fundamental research. Single-walled carbon nanotubes (SWCNTs) were dissolved in HNO3/H2SO4 mixture to confirm differing reactivity between metallic (m) and semiconducting (s) SWCNTs. With HNO3/H2SO4 treatment, s-SWCNTs remained intact, while m-SWCNTs were completely removed for SWCNTs with small diameters less than 1.1 nm, which was confirmed by resonant Raman and optical absorption spectra. We also showed that nitronium ions (NO2+) dissolved in the HNO3/H2SO4 solution could preferably attack the m-SWCNTs, which was supported by our theoretical calculation. This clear selectivity can be explained by the preferential adsorption of positively charged NO2+ on m-SWCNTs due to more available electron densities at the Fermi level in the m-SWCNTs. We report for the first time a selective removal of small-diameter m-SWCNTs by using HNO3/H2SO4 solution, which presented a striking contrast to the diameter-selective removal of SWCNTs by oxidative etching reported previously.     

Extraction of (9,8) Single‐Walled Carbon Nanotubes by Fluorene‐Based Polymers

Selective polymer wrapping is a promising approach to obtain high‐chiral‐purity single‐walled carbon nanotubes (SWCNTs) needed in technical applications and scientific studies. We showed that among three fluorene‐based polymers with different side‐chain lengths and backbones, poly[(9,9‐dihexylfluorenyl‐2,7‐diyl)‐co‐(9,10‐anthracene)] (PFH‐A) can selectively extract SWCNTs synthesized from the CoSO₄/SiO₂ catalyst, which results in enrichment of 78.3 % (9,8) and 12.2 % (9,7) nanotubes among all semiconducting species. These high‐chiral‐purity SWCNTs may find potential applications in electronics, optoelectronics, and photovoltaics. Furthermore, molecular dynamics simulations suggest that the extraction selectivity of PFH‐A relates to the bending and alignment of its alkyl chains and the twisting of its two aromatic backbone units (biphenyl and anthracene) relative to SWCNTs. The strong π–π interaction between polymers and SWCNTs would increase the extraction yield, but it is not beneficial for chiral selectivity. Our findings suggest that the matching between the curvature of SWCNTs and the flexibility of the polymer side chains and the aromatic backbone units is essential in designing novel polymers for selective extraction of (n,m) species.     

Selective photochemical functionalization of surfactant-dispersed single wall carbon nanotubes in water

Ultraviolet (UV) irradiation of single wall carbon nanotubes (SWCNTs) individually dispersed in surfactants leads to diameter and type-selective photohydroxylation of the nanotubes. Photohydroxylation of first semiconductor and then small diameter metallic SWCNTs was confirmed after 254 nm UV irradiation in acidic, neutral, and basic aqueous solutions at ambient and elevated temperatures. The increased oxygen content of the SWCNTs after UV irradiation, as detected by X-ray photoelectron spectroscopy, suggests that SWCNTs were hydroxylated by reaction with water. Attenuated total reflectance Fourier transform infrared analysis provides evidence of hydroxyl functional groups on their surface. This photochemical reaction is impeded by molecular oxygen and appears to involve a reactive intermediate generated in the vicinity of semiconducting SWCNTs. This represents a noncontaminating selective reaction in the liquid phase that uses an intrinsic property of the tubes.     

Improvement of SWCNT transparent conductive films via transition metal doping

To realize transparent conductive films based on single-walled carbon nanotubes (SWCNTs), we applied a spray coating process with transition metal doping to SWCNT networks. Schottky contacts between metallic and semiconducting SWCNTs changed to Ohmic contacts due to the reduction of metals on the SWCNT surfaces via direct conversion from solution.     

Structure-dependent reactivity of semiconducting single-walled carbon nanotubes with benzenediazonium salts

The addition of diazonium salts to single-walled carbon nanotubes (SWCNTs) in aqueous surfactant suspensions quenches the intrinsic near-infrared fluorescence of semiconducting SWCNTs through sidewall chemical reactions. Spectrally resolved fluorescence spectroscopy of mixed SWCNT samples has been used to measure structure-dependent relative reactivities in the initial stages of these reactions. For several 4-substituted benzenediazonium salts, Ar-R (Ar = N 2 (+)-C 6H 4 and R = Cl, NO 2, OMe), reactivities at pH 10 were found to be greatest for SWCNTs having the largest band gaps. The magnitude of this band gap dependence varies according to the R-group of the salt, with R = OMe showing the strongest variation. For R = OH, acidification of the sample to pH 5.5 results in reversal of the structural trend, as smaller band gap SWCNTs show slightly greater reactivities. The derivatization reactions observed here proceed concurrently, although at different rates, for semiconducting and metallic SWCNT species. These results therefore provide insight into the difficulties of separating metallic and semiconducting SWCNTs through selective reaction schemes and underscore the need for fluorescence spectroscopy to be used in assessing semiconducting SWCNT reactions.     

Chirality- and diameter-dependent reactivity of NO2 on carbon nanotube walls

We report the density-functional calculations of NO2 adsorption on single-walled carbon nanotube walls. A single molecular adsorption was endothermic with an activation barrier, but a collective adsorption with several molecules became exothermic without an activation barrier. We find that NO2 adsorption is strongly electronic structure- and strain-dependent. The NO2 adsorption on metallic nanotubes was energetically more favorable than that on semiconducting nanotubes and furthermore the adsorption became less stable with increasing diameters of nanotubes. The adsorption barrier height shows similar dependence on the electronic structure and diameter to the adsorption energy. Our theoretical model can be a good guideline for the separation of nanotubes by electronic structures using various adsorbates.     

Light-induced dielectric transparency in single-walled carbon nanotube films

Light-induced difference THz spectroscopy was used to investigate the dielectric response of free-stand single-walled carbon nanotubes (SWCNTs) films in THz region. We observed an enhanced transmission of the peak-signal of THz wave through SWCNTs films under 800 nm pump. In frequency domain, the transparency came from 0.5 to 2.1 THz and the absorption was in 2.1–3.0 THz region. The pump power dependency of the transmission showed this was a nonlinear effect. The dielectric constant response of the SWCNTs films was analyzed theoretically. The analysis suggests that the nonlinear optical properties stem from two factors, which are Drude and Lorentz term for metallic and semiconducting SWCNTs, respectively.     

UV-light mediated decomposition of a polyester for enrichment and release of semiconducting carbon nanotubes

Purification of single-walled carbon nanotubes using conjugated polymers to selectively disperse either semiconducting or metallic nanotubes is effective and has received significant attention. However, the interaction between the conjugated polymer and the nanotube surface is very strong, making it difficult to remove the adsorbed polymer. Here, we report a poly(carbazole-co-terephthalate) polymer that is not only selective for semiconducting carbon nanotubes but can also be largely removed from the nanotube surface via irradiation with UV light. Irradiation of the polymer-nanotube dispersion causes degradation of ester linkages in the polymer backbone, effectively cutting the polymer into fragments that no longer bind strongly to the nanotube surface. Characterization of the electronic nature of the samples was carried out via the combination of absorption, Raman, and fluorescence spectroscopy. In addition, thermogravimetric analysis allowed determination of the amount of polymer left on the nanotube surface after irradiation and indicated that a large proportion of the polymer is removed. The reported methodology opens new possibilities for purification of semiconducting single-walled carbon nanotubes and their isolation from the polymeric dispersant.     

Bulk electrical properties of single-walled carbon nanotubes immobilized by dielectrophoresis: evidence of metallic or semiconductor behavior

We report the electrical characterization of single-walled carbon nanotubes (SWCNTs) trapped between two electrodes by dielectrophoresis (DEP). At high frequency, SWCNTs collected by DEP are expected to be of metallic type. Indeed current-voltage (I-V) measurements for devices made at 10 MHz show high values of conductivity and exhibit metallic behavior with linear and symmetric electrical features attributed to ohmic conduction. At low frequency, SWCNTs attracted by DEP are expected to be of semiconducting nature. Devices made at 10 kHz behave as semiconductors and demonstrate nonlinear and rectifying electrical characteristics with conductivities many orders of magnitude below the sample resulting from high-frequency immobilization of SWCNTs. Conducting atomic force microscopy (C-AFM) and current density calculation results are presented to reinforce results obtained by I-V measurements which clearly show type separation of SWCNTs after DEP experiments.     

单壁碳纳米管的手性测量

单壁碳纳米管的制备方法主要包括物理法和化学法两种,不同制备方法的产物中包含很多种不同手性指数的单壁碳纳米管及杂质,而不同手性的单壁碳纳米管其作用完全不同,从而有不同的应用。采用化学方法——钴钼催化剂气相沉积法和物理方法——激光烧蚀气相沉积法制备单壁碳纳米管,用紫外–可见–近红外吸收光谱、荧光光谱及拉曼光谱法分别对其进行手性测量。结果表明,钴钼催化剂气相沉积法制得样品富含半导体型单壁碳纳米管,而激光烧蚀气相沉积法制得样品中主要为金属型单壁碳纳米管。分别得到了两种制备方法样品的手性分布。     

Selective polycarboxylation of semiconducting single-walled carbon nanotubes by reductive sidewall functionalization

The efficient and controllable synthesis, the detailed characterization, and the chemical postfunctionalization of polycarboxylated single-walled carbon nanotubes SWCNT(COOH)(n) are reported. This innovative covalent sidewall functionalization method is characterized by (a) the preservation of the integrity of the entire σ-framework of SWCNTs; (b) the possibility of achieving very high degrees of addition; (c) control of the functionalization degrees by the variation of the reaction conditions (reaction time, ultrasonic treatment, pressure); (d) the identification of conditions for the selective functionalization of semiconducting carbon nanotubes, leaving unfunctionalized metallic tubes behind; (e) the proof that the introduced carboxylic acid functionalities can serve as versatile anchor points for the coupling to functional molecules; and (f) the application of a subsequent thermal degradation step of the functionalized semiconducting tubes leaving behind intact metallic SWCNTs. Functional derivatives have been characterized in detail by means of Raman, UV-vis/nIR, IR, and fluorescence spectroscopy as well as by thermogravimetric analysis combined with mass spectrometry, atomic force microscopy, and zeta-potential measurements.