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Purication of carbon nanotubes

Peng-Xiang Hou, Chang Liu, Hui-Ming Cheng*
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016, PR China

A R T I C L E I N F O

A B S T R A C T

Article history: Received 27 June 2008 Accepted 1 September 2008 Available online 9 September 2008

It is predicted theoretically and understood experimentally that carbon nanotubes (CNTs) possess excellent physical and chemical properties and have wide-range potential applications. However, only some of these properties and applications have been veried or realized. To a great extent, this situation can be ascribed to the difculties in getting highpurity CNTs. Because as-prepared CNTs are usually accompanied by carbonaceous or metallic impurities, purication is an essential issue to be addressed. Considerable progress in the purication of CNTs has been made and a number of purication methods including chemical oxidation, physical separation, and combinations of chemical and physical techniques have been developed for obtaining CNTs with desired purity. Here we present an up-to-date overview on the purication of CNTs with focus on the principles, the advantages and limitations of different processes. The effects of purication on the structure of CNTs are discussed, and nally the main challenges and developing trends on this subject are considered. This review aims to provide guidance and to stimulate innovative thoughts on the purication of CNTs. 2008 Elsevier Ltd. All rights reserved.

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1. CNT synthesis techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2. Impurities coexisting with CNTs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3. Assessment of CNT purity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4. Purpose of this review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Purification methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Chemical oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1. Gas phase oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.2. Liquid phase oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.3. Electrochemical oxidation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.4. Brief summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Physical-based purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1. Filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Centrifugation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3. Solubilization of CNTs with functional groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4. High temperature annealing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2004 2004 2004 2005 2006 2007 2007 2007 2009 2011 2011 2011 2012 2013 2013 2013

2.

* Corresponding author: Fax: +86 24 2390 3126. E-mail address: cheng@imr.ac.cn (H.-M. Cheng). 0008-6223/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2008.09.009

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2.2.5. Other physical techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.6. Combination of purification and separation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.7. Brief summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Multi-step purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.1. HIDE-assisted multi-step purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.2. Microfiltration in combination with oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.3. Sonication in combination with oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.4. High temperature annealing in combination with extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.5. Brief summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4. Applicability of typical purification techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Purification methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. Purity assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2014 2014 2015 2016 2016 2016 2017 2018 2018 2018 2020 2020 2021 2021 2021 2021 2021

1.

Introduction

Elemental carbon in sp2 hybridization can form a variety of amazing structures, such as graphite (3D), graphene (2D), carbon nanotubes (CNTs, 1D) and fullerene (0D). CNTs dened by Iijima in 1991 [1] have a unique tubular structure with nanometer scale diameters and large length/diameter ratios. CNTs may consist of one (single-walled CNTs, SWCNTs) or up to tens and hundreds (multi-walled CNTs, MWCNTs) seamless graphene cylinders concentrically stacked with an adjacent layer spacing of $0.34 nm. Owing to the covalent sp2 bonds formed between individual carbon atoms, CNTs are stiffer and stronger potentially than any other known materials. Thus, CNTs have ultra-high Youngs modulus and tensile strength, which makes them promising in serving as a reinforcement of composite materials with desired mechanical properties. Because of the symmetry and unique electronic structure of graphene, the structure of a SWCNT determines its electrical properties. For a SWCNT with a given (n, m) index [2], when (2n + m) = 3q (q is an integer), the nanotube is metallic, otherwise the nanotube is a semiconductor. Not only do these nanotubes show amazing mechanical and electronic properties, but also possess well-dened hollow interiors and biocompatibility with living systems. As a result, CNTs are considered to be excellent candidates for many potential applications, including but not limited to: catalyst and catalyst supports [3,4], composite materials [5,6], sensors and actuators [7,8], eld emitters [9,10], tips for scanning probe microscopy [11,12], conductive lms [13,14], bio-nanomaterials [15], energy storage media [16,17] and nanoelectronic devices [18,19].

benzene, ethanol, acetylene, propylene, methane, ethylene, CO, etc.) and growth of CNTs over the catalyst (usually transition metals such as Ni, Fe, Co, etc.) in a temperature range of 3001200 C. Good alignment [22] as well as positional control on a nanometric scale [23] can be achieved by using CVD. Control over diameter, shell number, and growth rate of CNTs are also realized with this method. The chief drawback of CVD is the high defect density of the obtained CNTs owing to low synthesis temperatures, compared with arc discharge and laser ablation. As a result, the tensile strength of the CNTs synthesized by CVD is only one-tenth of those made by arc discharge [24]. Typical SWCNT content in as-prepared samples by CVD is $3050 wt%, while the content of MWCNTs is in the range of $3099 wt% depending on their diameters. The by-products are usually aromatic carbon, amorphous carbon, polyhedral carbon, metal particles, etc. Arc discharge uses two electrodes (at least one electrode is made of graphite) through which a direct current (DC) is passed in a gaseous atmosphere. MWCNTs can be obtained by arc discharge without any metal catalyst, while mixed metal catalysts inserted into the anode are required when synthesizing SWCNTs by this method. In laser ablation for producing CNTs, an intense laser beam is used to ablate/ vaporize a target consisting of a mixture of graphite and metal catalyst in a ow of inert gas. This method favors the growth of SWCNTs with controlled diameter depending on reaction temperature [24]. When using arc discharge and laser ablation for SWCNT synthesis, side products such as fullerenes, amorphous carbon, graphite particles, and graphitic polyhedrons with enclosed metal particles are also formed. The record high-purity of the SWCNTs synthesized by arc discharge has been reported to be 80% by volume [25].

1.1.

CNT synthesis techniques 1.2. Impurities coexisting with CNTs

Nowadays, CNTs can be produced in large quantities by three dominant techniques: chemical vapor deposition (CVD, including high-pressure carbon monoxide (HiPco) process) [20], arc discharge [1], and laser ablation [21]. CVD involves catalyst-assisted decomposition of hydrocarbons (commonly

As-synthesized CNTs prepared by the above methods inevitably contain carbonaceous impurities and metal catalyst particles, and the amount of the impurities commonly increases with the decrease of CNT diameter. Carbonaceous impurities

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typically include amorphous carbon, fullerenes, and carbon nanoparticles (CNPs) (as shown in Fig. 1). Because the carbon source in arc discharge and laser ablation comes from the vaporization of graphite rods, some un-vaporized graphitic particles that have fallen from the graphite rods often exist as impurity in the nal product. In addition, graphitic polyhedrons with enclosed metal particles also coexist with CNTs synthesized by arc discharge and laser ablation as well as high temperature (>1000 C) CVD. Fullerenes can be easily removed owing to their solubility in certain organic solvents. Amorphous carbon is also relatively easy to eliminate because of its high density of defects, which allow it to be oxidized under gentle conditions. The most knotty problem is how to remove polyhedral carbons and graphitic particles that have a similar oxidation rate to CNTs, especially SWCNTs. Metal impurities are usually residues from the transition metal catalysts. These metal particles are sometimes encapsulated by carbon layers (varying from disordered carbon layers to graphitic shells, as shown in Fig. 1b and c) making them impervious and unable to dissolve in acids. Another problem that needs to be overcome is that carbonaceous and metal impurities have very wide particle size distributions and different amounts of defects or curvature depending on synthesis conditions, which makes it rather difcult to develop a unied purication method to obtain reproducibly high-purity CNT materials. To fulll the vast potential applications and to investigate the fundamental physical and chemical properties of CNTs, highly efcient purication of the as-prepared CNTs is, therefore, very important.

1.3.

Assessment of CNT purity

To evaluate the purity of CNTs, the efciency of a purication method as well as changes in the structure of CNTs during purication, characterization methods with rapid, convenient and unambiguous features are urgently required. Characterization of CNT samples falls into three groups: metal catalyst, carbonaceous impurity, and CNT structure variation (defects, functional groups, cap opening, cutting, etc.). Their characterization mainly depends on electron microscopy (EM, including scanning EM (SEM), and transmission EM (TEM)), thermogravimetric analysis (TGA), Raman spectroscopy and ultravioletvisible-near infrared (UVvis-NIR) spectroscopy. EM is a useful technique allowing for direct observations of impurities, local structures as well as CNT defects. Owing to the small volume of sample analyzed and the absence of algorithms to convert images into numerical data, EM cannot give a quantitative evaluation of the purity of CNTs [28].

TGA is effective in evaluating quantitatively the quality of CNTs, in particular, the content of metal impurity. It is easy and straightforward to obtain the metal impurity content using TGA by simply burning CNT samples in air. A higher oxidation temperature (>500 C) is always associated with purer, less defective CNT samples. The homogeneity of CNT samples can be evaluated by standard deviations of the oxidation temperature and metal content obtained in several separate TGA runs [29]. The real difculty is qualitative or quantitative assessment of carbonaceous impurity, which is inuenced by the amount of defects, forms of carbon, and so on. Raman spectroscopy is a fast, convenient and non-destructive analysis technique. To some extent, it can quantify the relative fraction of impurities in the measured CNT sample using the area ratio of D/G bands under xed laser power density. In addition, the diameters and electronic structures of CNTs can be determined by using the resonance Raman scattering [30]. However, the drawback of Raman spectroscopy is that it cannot provide direct information on the nature of metal impurities, and it is not as effective in studying CNT samples with a low content of amorphous carbon [31]. UVvis-NIR spectroscopy is a rapid and convenient technique to estimate the relative purity of bulk SWCNTs based on the integrated intensity of S22 transitions compared with that of a reference SWCNT sample [28]. It is convenient to determine the concentration of SWCNTs dispersed in solution once the extinction coefcient of SWCNTs is known [32]. On the other hand, SWCNTs give rise to a series of predictable electronic band transitions between van Hove singularities in the density states of nanotubes (S11, S22, and M11), therefore this technique is also used to analyze SWCNT types, i.e., metallic or semiconducting [31,33,34], according to their electronic structure. For small diameter SWCNTs individually dispersed in solution with the assistance of surfactants or DNA molecules, the (n, m) index assignment is also possible from UVvis-NIR spectroscopy [33,34]. The drawback of this method is the difculty in repeatedly preparing the standardized SWCNT lm or solution and controlling lm thickness or solution concentration, making it difcult for quantication analysis. Furthermore, it is not yet possible to provide an absolute value of the purity of SWCNTs because there is no 100% pure standard SWCNT sample or accurate extinction coefcient for SWCNTs. Besides the above most commonly used techniques, X-ray photoelectron spectroscopy (XPS) is often used to characterize functional groups on the walls of CNTs, and energy dispersive spectroscopy (EDS) is also used to semi-quantitatively identify the metal content in CNT samples, especially for

Fig. 1 TEM images of (a) amorphous carbon and fullerene molecules on the surface of CNTs [26]; (b) metal nanoparticles covered by amorphous carbon layer, (c) metal nanoparticles covered by graphitic carbon multi-layer (reproduced with permission from [27], Copyright 2004 Amercian Chemical Society).

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trace amounts. The major purity and quality assessment techniques and their efciency are summarized in Table 1. It seems that no assessment technique mentioned above can give a precise and comprehensive quantication of CNTs (Table 1). Consequently, there is a need to develop an integrated method by which the type, amount, and morphology of CNT-containing materials can be accurately and precisely quantied [35]. Alternatively, a combination of different assessment techniques may be a good choice to give a full understanding of CNTs but this takes more time. Furthermore, a precise denition of purity should be established because purity can be different from different points of view, such as CNT content, structure integrity, and SWCNT content. From this respect, we dene the purity of CNTs as given in Table 2. Meanwhile, the major purity assessment techniques and how to evaluate them are also briey included.

1.4.

Purpose of this review

As mentioned above, a series of problems involving the presence of impurities in CNTs, the non-uniformity in morphology and structure of both CNTs and impurities, as well as the absence of precise characterization methods limit the

applications of CNTs. Thus great attention has been paid to the issue of purication. The developed purication schemes usually take advantage of differences in the aspect ratio and oxidation rate between CNTs and carbonaceous impurities. In most cases, CNT purications involve one or more of the following steps: gas phase oxidation, wet chemical oxidation/treatment, centrifugation, ltration, and chromatography, etc. However, a reproducible and reliable purication protocol with high selectivity, especially for SWCNTs, is still a great challenge, because the purity of CNTs depends on not only purication itself, but also many other factors, including CNT type (SWCNTs or MWCNTs), morphology and structure (defects, whether or not they exist in bundles, diameter), impurity type and their morphology (particle size, defect, curvature, the number and crystallinity of carbon layers wrapping metal particles), purity assessment technique, and so on. This article attempts to give a comprehensive survey and analysis of the purication of CNTs. The challenges existing in the purication methods, synthesis techniques and purity assessments, which have to be overcome in order to enable the wide applications of CNTs, will be discussed. The purity in this article generally is referred to as CNT content in the

Table 1 Summary of commonly used techniques for detecting the impurities in CNT samples Technique C-Ia M-Ib F-Gc S-Dd C-Fe
EM TGA Raman UVvis-NIR XPS EDS a b c d e f g h Df J D J   D J    J g    J  Jh  D      J J  

Advantages
Direct observation Precise content of carbon and metals Diameter, quality and conductivity of SWCNTs Conductivity feature and content of SWCNTs Accurate assessment of F-G on CNTs Elemental contents, special for trace amounts

Limitations
A small amount of sample is analyzed CNTs analyzed are completely destroyed Invalid for MWCNTs and metal impurities Need 100% pure SWCNTs as standard Invalid to purity assessment Invalid to evaluate CNT content

Carbonaceous impurity. Metal impurity. Functional groups. Structure defects. Conductivity feature. Qualitatively valid. Invalid. Valid.

Table 2 Denition of purity for CNTs from different points of view and the corresponding assessment techniques Purity denition
CNT content The content of CNTs in sample containing CNTs, carbonaceous and metallic impurities

Assessment technique and methods

TGA Metal content can be calculated from the ash weight after complete oxidation, and carbonaceous impurity content can be calculated by corresponding peak area ratio from DTG curve. CNTs without any other carbonaceous impurity are characterized by one DTG peak EM in combination with XPS EM can directly observe and qualitatively assess the amount of defects, amorphous carbons, fullerenes adhered on the wall of CNTs. XPS can give a quantitative characterization of type and content of functional groups Raman spectroscopy 100% pure SWCNTs should be characterized by one G band with RBM and without D band

Structure integrity

Pure CNTs without large defects and faults, and no functional groups, amorphous carbon or fullerene adhered on the tube wall

SWCNT content

The content of SWCNTs in CNTs

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as-prepared or puried samples, and the yield means the weight ratio of puried CNTs to that of the as-prepared CNT sample, unless specied otherwise.

2.

Purication methods

Purication methods of CNTs can be basically classied into three categories, namely chemical, physical, and a combination of both. The chemical method puries CNTs based on the idea of selective oxidation, wherein carbonaceous impurities are oxidized at a faster rate than CNTs, and the dissolution of metallic impurities by acids. This method can effectively remove amorphous carbon and metal particles except for those encaged in polyhedral graphitic particles. However, the chemical method always inuences the structure of CNTs due to the oxidation involved. The physical method separates CNTs from impurities based on the differences in their physical size, aspect ratio, gravity, and magnetic properties, etc. In general, the physical method is used to remove graphitic sheets, carbon nanospheres (CNSs), aggregates or separate CNTs with different diameter/length ratios. In principle, this method does not require oxidation, and therefore prevents CNTs from severe damage. However, the physical method is always complicated, time-consuming and less effective. The third kind of purication combines the merits of physical and chemical purication, and we denominate it as multi-step purication in this article. This method can lead to high yield and high-quality CNT products. Owing to the diversity of the as-prepared CNT samples, such as CNT type, CNT morphology and structure, as well as impurity type and morphology, it needs a skillful combination of different purication techniques to obtain CNTs with desired purity.

2.1.

Chemical oxidation

The carbonaceous impurities co-existing with as-synthesized CNTs are mainly amorphous carbon and CNPs. Compared with CNTs, these impurities usually have higher oxidation activity. The high oxidative activity demonstrated by amorphous carbon is due to the presence of more dangling bonds and structural defects which tend to be easily oxidized; meanwhile the high reactivity of the CNPs can be attributed to their large curvature and pentagonal carbon rings [36,37]. Therefore, chemical oxidation purication is based on the idea of selective oxidation etching, wherein carbonaceous impurities are oxidized at a faster rate than CNTs. In general, chemical oxidation includes gas phase oxidation (using air, O2, Cl2, H2O, etc.), liquid phase oxidation (acid treatment and reuxing, etc.), and electrochemical oxidation. The disadvantages of this method are that it often opens the end of CNTs, cuts CNTs, damages surface structure and introduces oxygenated functional groups (OH, C@O, and COOH) on CNTs. As a result, the puried CNTs in turn can serve as chemical reactors or a starting point for subsequent nanotube surface chemistry [38,39].

2.1.1.

Gas phase oxidation

In gas phase oxidative purication, CNTs are puried by oxidizing carbonaceous impurities at a temperature ranging from 225 C to 760 C under an oxidizing atmosphere. The

commonly used oxidants for gas phase oxidation include air [4046], a mixture of Cl2, H2O, and HCl [47], a mixture of Ar, O2, and H2O [4850], a mixture of O2, SF6 and C2H2F4 [51], H2S and O2 [52], and steam [53]. High temperature oxidation in air is found to be an extremely simple and successful strategy for purifying arc discharge derived MWCNTs, which are metal free and have fewer defects on tube walls. Ebbesen et al. [40,41] rst reported a gas phase purication to open and purify MWCNTs by oxidizing the as-prepared sample in air at 750 C for 30 min. However, only a limited amount of pure MWCNTs (12 wt%) remained after the above purication, which can be ascribed mainly to two reasons. One is uneven exposure of CNTs to air during oxidation, and the other is the limited oxidation selectivity between CNTs and carbonaceous impurities. Therefore, two routes may be helpful to increase the purication yield using this simple air oxidation. One is to ensure that the as-synthesized CNT samples are evenly exposed to air, and the other is to enhance the difference in oxidation resistance to air between CNTs and carbonaceous particles. The above suggestions have been veried by some researchers. As an example, Park and coworkers [42] increased the purication yield to $35 wt% by rotating the quartz tube in which the sample was placed, in order to evenly expose the CNTs and carbonaceous impurities to air at 760 C for 40 min. To increase the difference in oxidation resistance to air between MWCNTs and carbon impurities, the difference in oxidation rates of graphite and intercalated graphite [4345] was taken into account. Graphite intercalation compounds are formed by the insertion of atomic or molecular layers of other chemical species between graphite layers. This interaction causes an expansion of carbon interlayer spacing, which reduces the oxidation resistance of the intercalated graphite. Carbonaceous impurities have higher structural defect densities than CNTs, and are therefore more ready to act as reaction sites for intercalated atoms. Thus the oxidation resistance difference between CNTs and carbonaceous impurities can be increased. As an example, Chen et al. [43] reported a combined purication process consisting of bromination and subsequent selective oxidation with oxygen at 530 C for 3 days. Temperature programmed oxidation proles of the CNT samples with and without bromine treatment are shown in Fig. 2. It is obvious that oxidation of the brominated sample occurs more readily than that without bromination. TEM studies showed that CNTs with both ends open were enriched in the puried sample, and the yield obtained by the above process varied from 10 to 20 wt% with respect to the weight of the original carbon sample. Furthermore, they found that the yield depended crucially on the ow rate of oxidant, the amount of initial sample, the manner of packing of the carbon, and the quality of the cathodic soot. Although MWCNTs can be puried by a variety of gas phase oxidation [4145], attempts to use similar procedures for SWCNTs result in nanotubes etching away. For example, using the bromine and oxygen system, the yield was $3 wt% [47] for SWCNT purication, which implies that a large fraction of SWCNTs are consumed in the process. This large difference between MWCNTs and SWCNTs results from two factors. One is the larger amount of curvature experienced by the graphene sheet of SWCNTs, and the other is

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Fig. 2 Temperature programmed oxidation proles of the cathodic soot before (CS) and after (BS) bromination (reprinted with permission from [43], Copyright 1996 Wiley VCH Verlag GmbH & Co. KGaA). metal impurities catalyzing the low-temperature oxidation of carbon. There may therefore be two ways to increase the purication yield of SWCNTs using gas phase oxidation. One is to select oxidants that can selectively oxidize carbonaceous impurities by a unique selective carbon surface chemistry while leaving SWCNTs intact. The other is to remove metal particles before gas phase oxidation. Some positive results have been obtained following the above suggestions. Zimmerman et al. [47] rst reported suitable conditions allowing for the removal of amorphous or spherical carbon particles, with or without metal catalyst inside, while simultaneously protecting SWCNTs. The purication incorporates a chlorine, water, and hydrogen chloride gas mixture to remove the impurities. A SWCNT yield of $15 wt% and a purity of $90% indicate that the carbonaceous impurities are preferentially removed. Based on their experimental observation, hydrogen chloride was required for selective removal of the unwanted carbon. They proposed a mechanism for the purication. Chlorine gas mixture interacted with the nanotube cap and formed a hydroxy-chloride-functionalized nanotube cap. Hydrogen chloride in the gas phase purication mixture protected the caps that are more reactive, by preventing hydroxyl groups from deprotonating. The disadvantage of this method is that only small quantities ($5 mg) of SWCNTs were puried each time. Furthermore, the reagents and produced gases are toxic and explosive, which limits its practical use. At the same time, some other oxidants that can selectively oxidize carbonaceous impurities were also reported. For example, hydrogen sulde was reported to play a role in enhancing the removal of carbon particles as well as controlling the oxidation rate of carbon. A purity of $95% SWCNTs with a yield of 2050 wt% depending on the purity of raw material was reported [52]. In addition, steam at 1 atm pressure [53], local microwave heating in air [46], air oxidation and acid washing followed by hydrogen treatment [54] were also reported to work well to improve the purication yield. It was Chiang et al. [48,49] who clearly elucidate the role of metals in oxidizing carbons and the need for their prior removal. They found that metal particles catalyze the oxidation of carbons indiscriminately, destroying SWCNTs in the presence of oxygen and other oxidizing gases. Encapsulated metal particles can be exposed using wet Ar/O2 (or wet air) oxidation at 225 C for 18 h. This exposure was attributed to the expan-

sion of the particles because oxidation products have a much lower density (the densities of Fe and Fe2O3 are 7.86 and 5.18 g/cm3, respectively). Such signicant expansion broke the carbon shells, and the particles were exposed as a result. Based on the above results, they proposed a multi-stage procedure for purifying SWCNTs synthesized by the HiPco process. Their method begins with cracking of the carbonaceous shells encapsulating metal particles using wet oxygen (20% O2 in argon passed through a water-lled bubbler) at 225 C, followed by stirring in concentrated hydrochloric acid (HCl) to dissolve the iron particles. After ltering and drying, the oxidation and acid extraction cycle was repeated once more at 325 C, followed by an oxidative baking at 425 C. Finally, 99.9% pure SWCNTs (with respect to metal content) with a yield of $30 wt% were obtained. The validity of this method was veried by another group [50]. However, owing to the complicated purication steps, it is hard to purify SWCNTs in a large scale. Xu et al. [51] developed a controlled and scalable multistep method to remove metal catalyst and non-nanotube carbons from raw HiPco SWCNTs. Their scalable multi-step purication included two processes: oxidation and deactivation of metal oxides. In the oxidation, metal catalysts coated by nonnanotube carbon were oxidized into oxides by O2 and exposed by using a multi-step temperature increase program. In the deactivation step, the exposed metal oxides were deactivated by conversion to metal uorides through reacting with C2H2F4, SF6, or other uorine-containing gases to avoid the catalytic effect of iron oxide on SWCNT oxidation. The Fe content was remarkably decreased from $30 to $1 wt% and a yield of $2548 wt% was achieved. However, the shortcoming of this method is that it is limited to HiPco SWCNTs, in which the dominant impurity is metal catalyst. Furthermore, the toxicity of the reagents used in this method and the resulting gases are undesirable features. Gas phase oxidation is a simple method for removing carbonaceous impurities and opening the caps of CNTs without vigorously introducing sidewall defects, although it cannot directly get rid of metal catalyst and large graphite particles. Thus it is a good choice to purify arc discharge derived MWCNTs, which contains no metal catalyst. For purifying SWCNTs or MWCNTs (synthesized by other techniques), acid treatment to remove the metal catalyst is always necessary. Another point worth noting is that CNTs (SWCNTs in particular) in agglomerates prevent oxidant gas from homogeneously contacting the whole sample. In order to obtain high-purity CNTs, the amount of sample to be puried each time is quite limited (tens to a hundred milligrams). Therefore, methods that can cause the oxidant gas to homogeneously contact CNT samples are urgently required to obtain high-purity CNTs on a large scale. Recently, Tan et al. [55] mixed raw SWCNTs with zirconia beads to enhance air ow uniformity and increase the exposed surface of raw soot during thermal oxidation in air. The nal puried samples had a yield of $26 wt% and a metal impurity of $7%. Although the purity is not very high, the technique suggests a way to purify SWCNTs on a large scale using gas phase oxidation. This method can provide pure and opened CNTs without heavily damaging tube walls, which is a good choice for the application of open-ended CNTs as nano-size reaction tubes or chemical reactors [56,57]. For achieving puried CNTs on a large scale, gas phase oxidation

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need to be modied in the following ways: one is to look for a simple approach and non-toxic reagents to remove metal particles encapsulated by carbon layers; the other is to look for a way that can make oxidant gas homogeneously contact the as-prepared CNTs. In addition, the gas phase oxidation can be combined with other techniques, such as ltration or centrifugation, to further enhance the purication efciency.

2.1.2.

Liquid phase oxidation

Although the merits of gas phase oxidation are obvious, it has a drawback that metal particles cannot be directly removed, and further acid treatment is needed. In order to overcome this limitation, liquid phase purication that always simultaneously removes both amorphous carbon and metal catalyst was developed. Oxidative ions and acid ions dissolved in solution can evenly attack the network of raw samples, and therefore selection of oxidant type and precise control of treatment condition can produce high-purity CNTs in a high yield. The commonly used oxidants for liquid phase oxidation include HNO3 [5860], H2O2 or a mixture of H2O2 and HCl [6163], a mixture of H2SO4, HNO3, KMnO4 and NaOH [6467], and KMnO4 [6769]. The shortcomings of this method are that it causes reaction products on the surface of CNTs, adds functional groups, and destroys CNT structures (including cutting and opening CNTs). Nitric acid is the most commonly used reagent for SWCNT purication for its mild oxidation ability, which can selectively remove amorphous carbon. In addition, it is inexpensive and nontoxic, capable of removing metal catalysts and no secondary impurities are introduced. Dujardin et al. [58] reported a one-step method using concentric nitric acid to purify SWCNTs synthesized by laser ablation. Briey, as-synthesized SWCNTs were sonicated in concentrated nitric acid for a few minutes followed by reuxing under magnetic stirring at 120130 C for 4 h. The yield reached 3050 wt% of the raw sample and the metal amount was decreased to $1 wt%. One problem in the above purication is that the permeation rate during ltration was very low because SWCNTs packed together and the lter membrane was blocked. This makes it difcult to purify CNTs on a large scale, and some small carbonaceous impurity particles cannot permeate the lter. To solve this problem, Rinzler et al. [59] adopted hollow-ber cross-ow ltration (CFF) to ltrate SWCNTs that had been reuxed in 2.6 M HNO3 for 45 h. Highly pure SWCNTs with a yield of 1020 wt% were obtained with this readily scalable method, which opens up a way to purify SWCNTs on a large scale. Even though the effectiveness of nitric acid treatment on the purication of SWCNTs is conrmed, the relationship between purication yield and purity with systematic and quantitative measurements was not reported before Hu et al.s work [60]. They established a systematic and quantitative relationship between yield and purity by using solution phase NIR spectroscopy. In their experiments, 1 g of the as-prepared SWCNT sample was reuxed in 3 M nitric acid for 12, 24 and 48 h, in 7 M nitric acid for 6 and 12 h, and in concentrated nitric acid for 6 and 12 h. The weight percent of each component calculated from TGA and NIR spectra is plotted in Fig. 3. It is clear that the purity and the yield of SWCNTs with nitric acid treatment depend on the concentration of the nitric acid and the time of reux. The treatments of

Fig. 3 Mass balance of the normalized weight percentage of all components including SWCNTs, metal, carbonaceous impurities, and weight loss of the SWCNT samples (reprinted with permission from [60], Copyright 2003 Amercian Chemical Society).

3 M HNO3 for 12 h and 7 M HNO3 for 6 h were the most efcient. Nitric acid treatment destroys SWCNTs, leading to the production of carbonaceous impurities. Nevertheless, with the ability to dissolve the metal catalyst, intercalate SWCNT bundles, attack amorphous carbon, and break large carbon particles, the nitric acid treatment can be a viable rst step for SWCNT purication. The key to achieving high-purity SWCNTs is a subsequent process for removing the carbonaceous impurities that remain in the sample after nitric acid treatment. In this case, a preferred step is hollow-ber CFF [59]. Hydrogen peroxide (H2O2) is also a mild, inexpensive and green oxidant, which can attack the carbon surface. The disadvantage of H2O2 is also obvious. It cannot remove metal particles. Therefore, it is usually used together with HCl. HCl is a widespread chemical that can be easily converted into a harmless salt. Therefore, purifying CNTs using H2O2 followed by HCl treatment to remove metal particles has also been intensely investigated. Macro-scale purication, including a rst reuxing treatment in H2O2 solution and then rinsing with HCl, was reported by Zhao et al. [61,62]. Their experimental results showed that the size of Fe particles has a great inuence on the oxidation of amorphous carbon. However, this was still a question about the effect of Fe before Wangs work [63]. Wang et al. [63] tried to explain the above question. They combined two known reactions (oxidation of amorphous carbon with H2O2 and removal of metal particles with HCl) into a single pot, which simplied the process. Surprisingly, the product yield and purity were improved. Typically, carboncoated iron impurities were simply dissolved by reacting with an aqueous mixture of H2O2 and HCl at 4070 C for 48 h. With this treatment, the purication yield was signicantly increased to $50 wt% and the purity was up to 96 wt%. According to Wang, the effect of this process on the purication can be summarized as following. First, Fe particles act as a catalyst by Fenton chemistry [70], producing hydroxyl radicals (OH), a more powerful oxidant than H2O2. Second, HCl dissolves the iron nanoparticles upon their exposure. The exposed iron releases ferrous ions as a result of dissolution of

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the Fe particles in the acid solution. The ferrous ions quickly diffuse into the acid solution, thereby eliminating iron and iron hydroxide precipitation and their unwanted catalytic effect (Fig. 4). Therefore, by conning the catalytic effect to the vicinity of the carbon-coated iron nanoparticles, both a high selectivity in removing iron particles and carbonaceous shells and a low consumption of SWCNTs are accomplished. At almost the same time, microwave-assisted inorganic acid treatment for the effective removal of metal particles was reported [7176]. The principle of this method is that inorganic acids such as HNO3, HCl, and H2SO4 can rapidly absorb microwave energy and dissolve metals efciently without damaging the tube wall structure in a short time. As discussed above, HNO3, H2O2, as well as microwave-assisted inorganic acid treatments can effectively remove metal particles, but they are not so effective in removing carbona-

Fig. 4 Scheme of localized catalytic reaction of H2O2 with carbon-coated iron nanoparticles (not drawn to scale, reprinted with permission from [63], Copyright 2007 Amercian Chemical Society).

ceous particles owing to the relative mildness in their oxidation. In order to get rid of carbonaceous impurities, liquid oxidants with stronger oxidation activity were also investigated. These oxidants are predominantly mixture of acids and KMnO4. Liu et al. [64] use a mixture of concentrated H2SO4/HNO3 (3:1 by volume) to cut highly tangled long ropes of SWCNTs into short, open-ended pipes, and thus produced many carboxylic acid groups at the open ends. Wiltshire et al. [65] reported that liquid phase oxidation could be a continuous diameter-selective process, eliminating SWCNTs with smaller diameter by oxidizing the sidewalls. Li and coworkers [66] investigated the purication effectiveness of concentrated H2SO4/HNO3 (3:1) treatment and compared this with 6 M HNO3 treatment. Typical TEM images of puried SWCNTs after different treatment conditions are shown in Fig. 5, from which it can be concluded that concentrated H2SO4/HNO3 (3:1) is more effective than nitric acid in removing impurities. Furthermore, it was reported that the best purication condition could reach 98% purity of SWCNTs with a yield of 40 wt% within 2 h, without decreasing the number of small diameter nanotubes for a 3 h reux process using a concentrated H2SO4/HNO3 mixture (3:1). Colomer et al. [68] reported an effective method for removing amorphous carbon by reuxing as-prepared MWCNTs in acidied KMnO4 at low-temperature (80 C). According to them, amorphous carbon was completely removed at the cost of more than 60% carbon loss. TEM observation of the puried CNTs indicated that all amorphous carbon aggregates were removed and the CNT caps were opened. Hernadi et al. [69] veried the above conclusion. They obtained MWCNTs with oxygen functional groups which were free from amorphous carbon by KMnO4 oxidation. Zhang et al. [67] investigated the effect of KMnO4 in alkali solution on the purication of SWCNTs. KMnO4 in alkali solution is a much more moderate

Fig. 5 TEM images of puried SWCNTs: (a) sonication in 6 M HNO3 for 4 h, (b) reuxing in 6 M HNO3 at 120 C for 4 h, (c) reuxing in concentrated H2SO4/HNO3 mixture (3:1) at 120 C for 2 h, (d) reuxing in concentrated H2SO4/HNO3 mixture at 120 C for 4 h (reprinted with permission from [66], Copyright 2004 Institute of Physics Publishing).

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oxidant than in acidic solution. The solution cannot effectively open the tube, while it is strong enough to attack the nanotube walls and generate abundant functional groups. The problem of this process is that additional steps are needed to remove the MnO2 generated during the oxidation. It is desirable to remove carbonaceous impurities by converting them into soluble or volatile products, and from this point of view, KMnO4 seems to be a less suitable oxidation agent. Liquid phase oxidation is a continuous process that can eliminate impurities on a large scale, and it is hoped that it can be widely used for industrial application in the future. This method often leads to surface modication that preferentially takes place on CNT sidewalls, which increases the chemical activity and the solubility of CNTs in most organic and aqueous solvents. This surface modication effect shows great potential for improving their physical and chemical properties for specic applications, e.g., in making mechanically reinforced composites, in use as scanning probe microscopy tips with tailored chemical sensitivity, and in producing nanotube derivatives with altered electronic structures and properties [7780]. Furthermore, CNTs can be cut into short fragments decorated with oxygen functional groups under suitable treatment conditions, which greatly increases their dispersibility and facilitates their practical applications. For example, the application of CNTs in the eld of emerging biotechnology is based on the premise that short CNTs are dispersible in water [81,82]. The main problem of this liquid oxidation strategy is the damage to CNTs, the inability to remove large graphite particles, and the loss of a large amount of SWCNTs with small diameter. It is very difcult to obtain puried SWCNTs with high-purity and high yield without damage by simply using liquid phase oxidation.

2.1.3.

Electrochemical oxidation

As with liquid phase oxidation and gas phase oxidation, carbon materials with fewer defects usually show a lower corrosion rate under electrochemical oxidation. Therefore, it is reasonable to deduce that CNTs with fewer defects should show higher electrochemical oxidation resistance than carbon impurities with more defects. Fang et al. [27] investigated the electrochemical cyclic voltammetric (CV) oxidation behavior of an arc discharge derived SWCNT sample in KOH solution. Amorphous carbon in the as-grown SWCNT sample was effectively removed by the CV oxidation, as conrmed by analyzing the sp3/sp2 carbon ratio from C1s XPS spectra and TEM observations. The removal of amorphous carbon led to the exposure of metal nanoparticles, hence facilitating the elimination of the metal impurities by subsequent HCl washing. The redox peaks from the electrochemical redox reactions of Fe and Ni impurities can be considered as an indication of the extent of removal of the amorphous carbon, and the optimum electrochemical oxidation time for the purication of the as-grown SWCNT sample can be determined in real time during the CV oxidation treatment. The above electrochemical oxidation was performed in KOH solution, which needs further acid treatment to remove metal particles. This makes the purication complex. If the solution is acidic, the post-treatment should be omitted, which makes the purication easier. Ye et al. [83] veried this.

They recently reported an ultra-fast and complete opening and purication of MWCNTs through electrochemical oxidation in acid solution. The vertically aligned MWCNT (with herringbone structure) arrays investigated were grown on a carbon microber network through DC plasma-enhanced CVD. Electrochemical oxidation for tip opening and purication of MWCNT arrays was performed in an aqueous solution of 57% H2SO4 at room temperature. SEM and TEM images before and after purication (Fig. 6) indicated that the CNT tips were opened, and entrapped metals were removed during the electrochemical oxidation. The results of inductively coupled plasma-mass spectrometry indicate that 98.8% of the Ni was removed after the electrochemical oxidation in acid. The authors also investigated a series of electrolyte solutions for electrochemical opening of CNT tips at room temperature. They concluded that if electrochemical oxidation was performed in neutral or basic aqueous solutions, no signicant tip opening was observed. If aqueous solutions of common strong or medium strength acids (5% H2SO4, 5% HNO3, or 25% HNO3 + 25% H2SO4, 5% H3PO4 and 5% CH3COOH) were used, not only can the amorphous carbon be readily etched but also the metal catalyst can be dissolved. Superior to the gas phase oxidation and wet oxidation, the optimum time and degree of electrochemical oxidation for CNT purication can be easily determined. This method can get rid of impurities to some extent, particularly for selectively opening and purifying vertically aligned CNT arrays. The desired vertical orientation can be maintained and facilitates the use of CNT arrays as fuel cell electrodes, sensor platforms, nanoreactors, eld emitter components, and other applications. However, little polyhedral carbon, graphite particles, and metal particles enwrapped by carbon layers with fewer defects can be removed by the CV oxidation. Moreover, the purity of the obtained sample greatly depends on the starting materials, and the amount of sample puried for each batch is too small to make the method practical.

2.1.4.

Brief summary

Chemical-based purication can effectively remove amorphous carbon, polyhedral carbon, and metal impurities at the expense of losing a considerable amount of CNTs or destroying CNT structures. Gas phase purication is characterized by opening the caps of CNTs without greatly increasing sidewall defects or functional groups. Liquid phase oxidation introduces functional groups and defects preferentially on CNT side walls, and may cut CNTs into shorter ones with different lengths. The electrochemical oxidation is suitable for purifying CNT arrays without destroying their alignment. These features allow chemical purication adopted by researchers to fulll different requirements. The most serious problem of this technique is that the structure of CNTs may be destroyed by the reactants, and hence limits the applications of CNTs in some elds, for example, electronic devices.

2.2.

Physical-based purication

A big problem in chemical purication is that it always destroys the structure of CNTs or changes their natural surface properties. To elucidate the inherent physical and chemical properties of CNTs, purications that do not involve oxidative

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Fig. 6 SEM (a, b) and TEM (c, d) images of MWCNT arrays: (a, c) as-grown, (b, d) puried (reprinted with permission from [83], Copyright 2006 Amercian Chemical Society).

treatment are highly desirable. The morphology and physical properties of CNTs, such as aspect ratio, physical size, solubility, gravity, and magnetism are different from impurities. These differences enable one to separate CNTs from impurities by adopting some physical techniques. Therefore, physical-based methods including ltration, chromatography, centrifugation, electrophoresis, and high temperature (1400 2800 C) annealing, have been extensively investigated. The most striking feature of these methods is a non-destructive and non-oxidizing treatment. Another feature is that the purications are mostly performed in solution, which requires the as-prepared samples to have a good dispersibility in the solutions. To meet this requirement, surfactants and/ or sonication are often used.

2.2.1.

Filtration

Separation by ltration is based on the differences in physical size, aspect ratio, and solubility of SWCNTs, CNSs, metal particles and polyaromatic carbons or fullerenes. Small size particles or soluble objects in solution can be ltered out, and SWCNTs with large aspect ratio will remain. Polyaromatic carbons or fullerenes are soluble in some organic solvents, such as CS2, toluene, etc. The impurities can be easily removed by immersing the as-prepared sample in these organic solutions followed by ltering. The impurity particles smaller than that of the lter holes ow out with the solution during ltration, while large impurity particles and small ones adhering to the CNT walls remain. One problem of this technique is that CNTs or large particles deposited on the lter often block the lter, making the ltering prohibitively slow and

inefcient. Therefore, a stable suspension of CNTs and a technique preventing them from deposition and aggregation are very important during ltration. Thus, surfactants are widely used to make a stable CNT suspension, and ultrasonication is usually adopted to prevent the lter from being blocked. Bonard et al. [84] rst applied ltration assisted with sonication to purify MWCNTs. The as-prepared MWCNTs were dispersed in water with sodium dodecyl sulfate (SDS), and a stabilized colloidal suspension was formed. The suspension was ltered using a ltration apparatus with a funnel large enough to allow the sonication of the colloidal suspension to extract larger particles. In order to enhance the separation yield, successive ltrations were carried out until the desired purity is reached. Shelimov et al. [85] used the above procedure to purify SWCNTs and obtained SWCNT material with a purity of more than 90% (estimated by EM) and a yield of 3070 wt%. Bandow et al. [86] developed a purication process (shown in Fig. 7) consisting of ltration and microltration under an overpressure ($2 atm) of N2 to separate CNSs, metal nanoparticles, polyaromatic carbons and fullerenes from SWCNTs. The microltration was repeated three times to minimize the amount of residual CNSs and metal particles. Using this technique, $84, 10, and 6 wt% of puried SWCNTs, CNSs, and CS2 extracts were separated from the as-prepared lasersynthesized SWCNTs. A major advantage of ltration is that it is driven by pure physicochemical interactions of carbon products with amphiphilic molecules and the lter membrane, leaving the nanotubes undamaged. However, this procedure relies on the quality of raw samples and is time-consuming. In addition,

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As-prepared carbonaceous sample in CS2 (SWCNT, CNS, C60, C70, polyaromatic carbons)

bon and CNPs is shown in Fig. 8. The drawback of this process is that CNTs need to be rst treated with nitric acid, which introduces functional groups on their surface.

Solids caught on filter Sonication in aqueous solutions (0.1% surfactant)

Filtration

2.2.3.
Extract Evaporate CS2

Solubilization of CNTs with functional groups

Microfiltration under over pressure (~ 2 atm) Liquid Evaporate and collect solids

Fullerenes (C60, C70), polyaromatic carbons Solids caught on filter

CNSs

Purified SWCNTs

Fig. 7 A diagram illustrating the technique used for separating coexisting CNSs, metal nanoparticles, and polyaromatic carbons or fullerenes from the laser-synthesized SWCNTs (modied with permission from [86], Copyright 1997 Amercian Chemical Society).

amorphous and spherical carbon particles stuck on the tube walls cannot be effectively removed.

2.2.2.

Centrifugation

Centrifugation is based on the effect of gravity on particles (including macromolecules) in suspension because two particles of different masses settle in a tube at different rates in response to gravity. On the other hand, centrifugation can also separate amorphous carbon and CNPs based on the different stabilities in dispersions consisting of amorphous carbon, SWCNTs, and CNPs in aqueous media. The different stabilities resulted from the different (negative) surface charges introduced by acid treatment [87,88]. Low-speed centrifugation (2000g) is effective in removing amorphous carbon and leaving SWCNTs and CNPs in the sediment. High-speed centrifugation (20000g) works well in settling CNPs, while leaving SWCNTs suspended in aqueous media. The effectiveness of centrifugation in separating SWCNTs from amorphous car-

The principle of this purication step is to solubilize CNTs by introducing functional groups onto their surface. These soluble nanotubes allow for the application of other techniques such as ltration or chromatography as a means of tube purication. To regain reasonable quantities of un-functionalized but puried nanotubes, the functional groups should be removed by thermal treatment or other techniques. Coleman et al. [89,90] described a one-step, high yield, nondestructive purication for MWCNTs containing soot using a conjugated organic polymer host (poly(m-phenylene-co-2,5-dioctoxy-p-phenylenevinylene (PmPV)) in toluene. PmPV is shown to be capable of suspending nanotubes indenitely whilst the accompanying graphitic particles settle out. Finally the host polymer was removed by Buchner ltration, giving CNTs with a purity of 91% (estimated from electron paramagnetic resonance). In this case, a yield of 17 wt% pristine nanotubes was reclaimed from the soot. Yudasaka et al. [91] mixed as-grown SWCNTs with a 2% monochlorobenzene (MCB) solution of polymethylmethacrylate (PMMA) with an ultrasonic cleaner. The mixture was homogenized through an ultrasonic-homogenizer and ltered. The MCB was removed by evaporation at 150 C, and PMMA was removed by burning it off in 200-Torr oxygen gas at 350 C. At the same time, azomethine ylides and solution phase ozonolysis (78 C) were also reported to solubilize CNTs via 1,3 dipolar cycloaddition [9294]. Recently, Jeynes et al. [95] and Sanchez-Pomales et al. [96] reported a method for purifying CNTs using RNA and DNA. Briey, arc discharge derived CNTs were sonicated in deionized water at 0 C (in an ice-water bath) for 30 min with 0.5 mg/mL total cellular RNA. The solution was then centrifuged to pellet the insoluble particles. RNA-wrapped CNTs were treated with enzyme ribonuclease to remove the RNA and thereby precipitate the CNTs. Jeynes et al. [95] also suggested that RNA/DNA was more efcient in solubilizing CNTs than SDS as there is a large surface area of phosphate backbone which interacts with water, while similarly there are many bases to bind the CNTs. The advantage of this process is that it can always preserve the surface electronic structure of CNTs. This property

Fig. 8 TEM images of (a) SWCNT-COOH material showing embedded catalyst particles, (b) puried SWCNT-COOH fraction, and (c) carbon particle fraction (reprinted with permission from [88], Copyright 2006 Amercian Chemical Society).

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is of fundamental importance for the use of nanotubes as biosensors [97]. On the other hand, the capability of dispersing CNTs in solution is a very important step for using CNTs as vectors to deliver therapeutics (drug, nucleic acid) [97]. However, the effectiveness of this technique is not high for CNT samples containing a large amount of impurities or bundled SWCNTs.

2.2.4.

High temperature annealing

For some applications of CNTs, such as their use as bio-materials, complete removal of metal particles is of particular importance. However, it is very difcult to achieve this by acid washing because most of the metal particles are enwrapped by carbon layers. The physical properties of carbon and metals are different at high temperature (>1400 C) under inert atmosphere or high vacuum. It is well known that, graphite is stable even at 3000 C, while metal evaporates at temperatures higher than their evaporation point. Therefore, it is expected that high temperature annealing can effectively remove metal particles. Lambert et al. [98] rst attempted to remove metal catalyst particles from SWCNTs by heating the material above the evaporation temperature of the metal. The results showed that this might be a good way to eliminate the catalyst particles. The effectiveness of removing metal particles in MWCNTs using high temperature annealing was also veried by a few reports [99101]. Their results suggest that high-purity (99.9%) CNTs with respect to metal particles can be obtained by a high temperature (P1800 C) annealing treatment. Further research indicated that high temperature annealing (>1400 C) can change the structure of CNTs, such as removing structural defects [102], enlarging diameter [103], transforming SWCNTs to MWCNTs [104] or MWCNTs to double-walled CNTs (DWCNTs) [105] at appropriate temperatures. In brief, high temperature annealing of CNTs is one of the most efcient methods for the removal of metal particles at the tips or in the hollow core of CNTs [98105] and also for structural evolvement from disordered to straight, crystalline layers [106]. High temperature annealing not only increases the mechanical strength and thermal stability of CNTs but also affects their electronic transport property. The drawback of this method is that carbonaceous impurities still exist and become more difcult to remove after graphitization. Therefore, this method can be used to remove residual metal particles of puried CNTs obtained by other techniques for achieving metal free CNTs. It can also be used to remove the metal particles in as-prepared CNT samples that contain a small amount of carbonaceous impurities or in the case where the existence of carbon impurities is not of much concern.

Kang and Park [107] demonstrated magnetophoretic purication of SWCNTs (produced by HiPco process) from superparamagnetic iron-catalyst impurities in a microuidic device. The ow of a uid through a microuidic channel is completely laminar and no turbulence occurs due to the small dimension of the microchannels. By employing microuidic and a magnetic eld-induced saw-tooth nickel microstructure, a highly enhanced magnetic force in adjoining microchannels was exploited. The iron impurities of SWCNTs were attracted towards areas of higher magnetic-ux density in the microchannels where magnetic eld was asymmetrically generated perpendicular to the streamline. SWCNTs with a purity of $9899% with respect to metal content were obtained. However, some SWCNTs containing iron particles were also removed, which decreased the yield of this method. Sc-CO2 has both gas-like and liquid-like properties; thus it can penetrate into small pores like a gas and dissolve organic substances like a liquid. Based on the above mechanism, Wang and coworkers [108] developed a two-step purication using Sc-CO2 as a solvent to clean metal impurities from asgrown SWCNTs produced by the HiPco process. The rst step of this method is a pretreatment procedure using bulk electrolysis with ethylenediaminetetraacetic acid. The second step is an in situ chelation/(Sc-CO2) extraction to remove metal particles. Over 98% of the iron impurity (measured by EDS) in the as-grown SWCNTs were removed using this two-step extraction. Thien-Nga et al. [109] developed a mechanical purication to remove ferromagnetic particles from their graphitic shells. The basic principle of the method is like a snooker game, where the energy of elastic impact between encapsulated catalysts and small hard inorganic particles is used to eject metal kernels and trap them by a strong magnet. Typically, SWCNTs were rst dispersed in various solvents. Insoluble nanoparticles (zirconium oxide, diamond, ammonium chloride, or calcium carbonate) in the given medium were then added to the suspension. This slurry was sonicated typically for 24 h. This process enables the production of laboratory quantities of SWCNTs containing no magnetic impurities.

2.2.6.

Combination of purication and separation

2.2.5.

Other physical techniques

Some other physical methods were also explored to remove metal particles, including a magnetophoretic technique [107], supercritical uid carbon dioxide (Sc-CO2) extraction [108], and a mechanically ejecting technique [109]. These techniques are reported to be effective in removing metal particles entrapped by carbon layers without changing the inherent properties of the CNTs.

Following the purication of CNTs to remove foreign materials such as catalyst, amorphous carbon, and carbon-coated nanoparticles, the sorting of SWCNTs according to their length becomes particularly important in light of their potential applications. Various techniques have been employed to purify CNTs and simultaneously sort them by length [110 113]. Chromatography is useful for the length fractionation of shortened CNTs less than 300 nm in length [110,111]. For longer CNTs, techniques such as capillary electrophoresis (CE) [112] and eld-ow fractionation (FFF) appear to be more applicable [113]. These techniques are simple and nondestructive for the purication and length-dependent separation of CNTs. These techniques require CNTs to be puried are individually dispersed. Therefore, complex procedures are needed to obtain this kind of highly dispersible CNT solution. Chromatography is a separation method that relies on differences in partitioning behavior between a owing mobile phase and a stationary phase to separate the components

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in a mixture. Materials that are smaller than the pore size can enter the pores and therefore have a longer path and longer transit time, while larger materials that cannot enter the pores are eluted rst. Different molecules, therefore, have different total transit times through the column depending on their size and shape. Chromatography was rst used to separate CNTs from carbonaceous impurities [114117]. After this, chromatography is usually used to separate CNTs by length. For example, purication and length separation of oxidatively shortened SWCNTs were achieved by this technique in an alkalescent water solution [110] and SWCNTs with different lengths were separated. Huang and coworkers [111] used chromatography to purify DNA-wrapped CNTs and sort them into fractions of uniform length. As observed by atomic force microscopy (AFM), the length variation was typically within 10% or less for each of the measured fractions (Fig. 9). Electrophoresis is caused by electrostatic forces, which are generated by applying an alternating current (AC) or DC electric eld between an electrode and a charged body. Electrophoresis can be achieved regardless of the electric elds uniformity. A charged particle is pulled along the eld lines toward the electrode carrying an opposite charge to that of the particle. In the same eld, a neutral body is merely polarized. The result may produce a torque, but not a net translational force, without which the body as a whole will not move towards either electrode. Electrophoresis can be appreciable even when the free charge per unit weight of the particle is quite small. Therefore, it is possible to purify CNTs in an electric eld by using the motion difference between CNTs and carbon impurities [118]. This motion depends not only on the intrinsic electric properties but also on the diameter and length of CNTs. Therefore, this technique can also be used to separate CNTs with length, diameter, and conductivity by rening experimental conditions. Yamamoto et al. [119] rst reported a purication and orientation method based on AC electrophoresis in isopropyl alcohol. To increase separation rate and effectiveness, Doorn et al. [112] adopted CE to purify and separate CNTs by size. The CE was performed in narrow tubes (in the order of lm) and resulted in rapid separation based on charge- and size-dependent mobility of solution phase species under the inuence of an applied electric eld. And AFM observations on fractions demonstrated a lengthbased separation mechanism that leads to elution of short tubes rst, followed progressively by longer tubes. Further work [120] indicated that CE has the potential to separate

CNTs, not only by differences in length [112] but also by differences in size or other geometric factors, such as diameter or cross section. At the same time, AC dielectrophoresis was reported to be capable of separating metallic SWCNTs from semiconducting SWCNTs in SDS suspension [121]. This method takes advantage of the difference in the relative dielectric constants of two species with respect to the solvent, resulting in an opposite movement of metallic and semiconducting tubes along the electric eld gradient. Metallic tubes are attracted toward a microelectrode array, leaving semiconducting tubes in the solvent. An enrichment of metallic tubes up to 80% was achieved by a comparative Raman spectroscopy study on the dielectrophoretically deposited tubes and a reference sample. In addition, FFF was also developed to separate CNTs by length [113,122]. FFF is a chromatography-like separation and sizing technique based on elution through a thin empty channel. The main difference between FFF and chromatography is that FFF separation is (ideally) induced only by physical interactions with an external eld rather than physicochemical interactions with a stationary phase. Compared with chromatography and CE, FFF can separate CNTs by length over a larger range and in larger quantities. These techniques can separate CNTs according to their size or electronic properties, which represents an important improvement in size and conductivity selectivity. This will promote the development and application of CNTs in the analytical, nanotechnology and nanoelectronics elds [123,124]. Therefore, they are not merely purication methods. A common feature of these techniques is that they require high dispersibility of isolated CNTs in solution. However, the CNT surface is hydrophobic, and the existing state of CNTs, especially for SWCNTs, is interconnected or in a thick bundle. In order to obtain high-purity CNTs, pre-treatment is required to obtain isolated CNTs having high dispersibility in solution.

2.2.7.

Brief summary

Physical-based purication can maintain the intrinsic structure of CNTs, which is desirable for elucidating their properties. Furthermore, some techniques such as chromatography, electrophoresis, and FFF can separate CNTs according to their differences in length or conductivity in addition to their purication function, which is a key step for using CNTs in devices such as nano- and micro-electronics. However,

Fig. 9 AFM images of three representative chromatography fractions of SWCNTs deposited onto alkyl silane-coated SiO2 substrates (reprinted with permission from [111], Copyright 2005 Amercian Chemical Society).

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there are still some problems in these techniques that need to be solved. One is that these methods are not very effective in removing impurities. Another is that they require CNT samples be highly dispersible. Therefore, the as-prepared sample is always rst dispersed in solution by adding surfactants or treated by a chemical process to cut and/or add functional groups before purication. The third problem is the limited amount of sample that can be puried each time. Based on the above facts, physical methods are more suitable for use as an assistant step combined with chemical purication, except for the case where a small amount of CNTs with a particular structure or property are required.

2.3.

Multi-step purication

As discussed above, gas phase oxidation is effective in removing amorphous carbon and polyhedral carbon at the cost of losing some CNTs but fails to remove a signicant fraction of graphite particles and metal impurities. Liquid phase oxidation with strong oxidants is effective in removing carbonaceous impurities and metal particles simultaneously, whereas puried CNTs are always cut, opened and damaged. Physical purications are effective in partly removing isolated carbonaceous or metallic impurities, while amorphous and spherical particles stuck to sidewalls or metal particles encapsulated in CNTs remain. In order to achieve desirable CNT purity with high yield, combinations of chemical and physical purications are being intensely investigated. According to different needs, various kinds of multi-step purication methods are reported. For example, it is difcult to remove carbonaceous impurities adhering to the sidewalls of CNTs for both chemical and physical purications. To solve this problem, hydrothermally initiated dynamic extraction (HIDE) [44,125127] or sonication [128133] was adopted in many chemical purication procedures. Graphite particles existing in CNTs synthesized by arc discharge or laser ablation are hard to remove by chemical oxidation, so ltration is adopted in some purication [134,135]. It is clear that metal particles catalyze the low-temperature oxidation of carbons indiscriminately, destroying SWCNTs in the presence of oxygen and other oxidizing gases. To overcome this problem, purication combining gas phase oxidation and acid treatment were widely investigated [136145]. In fact, several techniques such as oxidation, sonication, HIDE, or ltration are simultaneously adopted in one purication procedure to obtain high-purity CNTs with high yield.

particles and this allows them to be dissolved by hydrochloric acid in the nal step of the treatment [125]. Tohji et al. [125,126] rst reported a multi-step method to purify SWCNTs by combining HIDE with other processes as illustrated in Fig. 10. SWCNTs with a purity of 95 wt% and a yield of about 2 wt% were obtained by this process. Graphite fragments from the graphite rod cannot be removed by oxidation. To solve this problem, the as-prepared MWCNTs were treated by a multi-step process (shown in Fig. 11) combining wet grinding, HIDE, oxidation and other techniques [127]. TEM observations indicated that this process was effective in removing graphite and carbonaceous particles and opening CNT caps. However, the yield was only $2 wt% due to the high oxidation temperature (700 C). To increase the purication yield, we developed a multistep method combining sonication, HIDE, bromination, gas phase oxidation and acid treatment [44]. It was found that bromination can increase the purication yield from $25 to $50 wt%. The effect of bromination on the purication of CNTs was also veried by Fan et al. [148]. The problem with this technique is that it is not suitable for purifying SWCNTs. On the other hand, the onset burning temperature of MWCNTs was decreased after purication, suggesting that defects or functional groups were introduced.

2.3.2.

Microltration in combination with oxidation

Bandow et al. [134] puried SWCNTs synthesized by laser ablation by combining microltration [86] with oxidation in air. In a typical procedure, as-prepared soot containing SWCNTs was rst puried using microltration to remove large CNSs. The obtained SWCNTs were then oxidized in air at 450 C for 20 min to remove CNSs adhering to the SWCNT walls, followed by soaking in concentrated HCl (36%) for 12 days at room temperature to remove metal particles. The purity of the SWCNTs after purication was greater than 90%. To remove metal particles before oxidation, Kim and Luzzi [135] developed magnetic ltration carried out in a magnetic eld. They investigated the efciency of using magnetic ltration alone, or combining it with chemical-based or annealingassisted oxidation treatments. Using magnetic ltration alone, the catalyst content was reduced from 11.7 to 3.7 wt%, much better than obtained in oxidation or chemical

As-produced SWCNTs

Purified SWCNT Removing exposed metal 6 M HCl treatment

2.3.1.

HIDE-assisted multi-step purication

HIDE treatment for 12 h

HIDE provides comminution on a microscopic scale as a result of collision between soot particles and water molecules during thermal treatment [146]. Thus during HIDE, water molecules break the network between SWCNTs, amorphous carbons and metal particles, and also attack the graphitic layers encapsulating metal particles. As a result, almost all graphitic nanoparticles and CNSs are washed out from the soot. The graphitic sheets of the CNSs, for the most part, have defects and dislocations, in contrast to SWCNTs [147]. It is believed that the reaction of H2O with carbon breaks the graphitic layers that wrap the metal particles. Consequently, incorporating HIDE in the purication procedure exposes the metal

Filtration and dry Removing Soxhlet extraction fullerenes in CS2

Removing amorphous carbon Oxidation at 470C

for 20 min

Fig. 10 A diagram showing the purication of SWCNTs with a multi-step process incorporating HIDE treatment.

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Cathode deposit (850 mg)

Sediment (320 mg) Remove small graphite

Grinding in water

Ultrasonic irradiation

Centrifugation

Ultrasonic irradiation

Add surfactant

Dispersed material, 68 mg

37 m filtration Remove large graphite Cake (460 mg)

HIDE treatment

Oxidation, 700 C for 15 min

Filtration (390 mg)

Purified MWCNTs, 16 mg

Fig. 11 A diagram showing the purication of MWCNTs with a multi-step process incorporating HIDE and wet grinding treatment (modied with permission from [127], Copyright 2001 Amercian Chemical Society).

treated samples. By combining chemical and magnetic purication, the metal catalyst content was reduced to 0.3 wt%. These results allowed the authors to conclude that magnetic ltration is effective in removing metal catalysts, producing CNTs with high-quality and yield. It is well known that metal particles can catalyze carbon oxidation in the presence of oxidants. Therefore, effective removal of metal particles is desirable for the following purication of CNTs using chemical oxidation. Thus magnetic ltration combined with chemical purication opens a new way to obtain puried CNTs with high yield.

2.3.3.

Sonication in combination with oxidation

Fig. 12 TEM images of (a) the as-prepared SWCNTs, and (b) the puried SWCNTs [128].

Sonication is identied as one of the effective processes to get rid of the amorphous impurities adhering to the walls of CNTs using suitable solvents [149]. During sonication, the solvent molecules are able to interact with CNTs and hence lead to solubilization, which can improve purication effectiveness when some other steps are followed. We [128] developed an effective multi-step purication approach to purify SWCNTs by combining sonication with oxidation in air. The biggest problem in purifying SWCNTs synthesized by arc discharge is how to remove graphite particles produced from the graphite rod. Ultrasonication in ethanol was adopted to rst remove the graphite particles. Because the SWCNTs used were rope-like, we decanted the alcohol solution containing graphite particles and other organic impurities after sonication for about 5 min. This procedure was repeated ve times. The graphite-free material was oxidized and then soaked in HCl to remove amorphous carbon and metal particles. TEM observations (Fig. 12) and Raman spectra veried the effectiveness of the above purication procedure. With this procedure, a 41 wt% yield of SWCNTs with a purity of about 96% was achieved. However, the above procedure is only applicable to SWCNTs synthesized by hydrogen arc discharge, in which SWCNTs exist as ropes with fewer defects.

We [129] also developed a multi-step method to purify SWCNTs synthesized by CVD, which includes acid washing, ultrasonication and freezing treatments in liquid nitrogen. After purication, SWCNTs with a purity of 95% (estimated from EDS and SEM) and a yield of 40 wt% were obtained and the procedure did not destroy the SWCNT bundles. Montoro and Rosolen [130] reported a four-step method to purify SWCNTs synthesized by arc discharge as shown in Fig. 13. This new procedure is efcient and appropriate for obtaining highly pure SWCNTs with minimum damage to the CNT walls and minimum modication in the CNT length. Wang et al. [132] developed a three-step method to purify and cut SWCNTs synthesized by CVD. This method included reuxing in 2.6 M HNO3 to remove metal particles, ultrasonication in acid solution (H2SO4/HNO3, H2SO4/H2O2) to cut and polish the SWCNTs, and heat treatment in an NH3 atmosphere to remove carbon impurities and heal structural defects. Recently, they [133] further improved their method mainly by replacing the above acid solution with an (NH4)2S2O8/H2SO4 solution. In addition, ultrasonication time

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As-prepared SWCNTs Fullerenes and soluble impurities Amorphous carbons

Sohxlet extraction with toluene

Extracted material

Sonication in H2O2 solution

Metallic particles Graphite and protected metallic impurities

Sonication in HNO3 /HF/ SDS

Separation in SDS solution

Fig. 14 Potential energy (per atom) of MWCNTs and CNPs (reproduced with permission from [150], Copyright 2006 Amercian Chemical Society). prediction, CNPs and MWCNTs were effectively separated from each other by choosing an appropriate polymer and suitable concentration (for instance, 0.040.1 wt% for the dispersing agent 710). Thus an effective and nondestructive method for the purication of MWCNTs with high yield ($90 wt%) was developed. Furthermore, the high temperature annealing step in this purication can improve the structures of CNTs, which will be of great importance for the exploitation of their excellent mechanical and electrical properties in various applications.

High purity SWCNTs

Fig. 13 A owchart illustrating the multi-step purication of SWCNTs. The removed species are listed to the left of the chart (modied after [130]).

was extended to 430 h to control the length of the SWCNTs. The nal SWCNT product had a metal content lower than 1 wt%, a length distribution between 1 and 2 lm, and very few defects.

2.3.5.

Brief summary

2.3.4. High temperature annealing in combination with extraction

As discussed above, high temperature annealing is an effective method to remove metal particles, while it makes the removal of carbonaceous impurities much more difcult in the following chemical treatments. To solve this problem, Zhang et al. [150] proposed a method involving high temperature annealing followed by a dispersant extraction treatment using a polymer. Briey, the MWCNT samples with micrometer lengths and diameters of 2050 nm were annealed at 2600 C for 60 min to remove metal catalyst. The graphitized MWCNT product was sonicated in a solution of dispersing agent 710 (basic urethane copolymer) to remove CNPs. Dispersing agents for carbon black have a two-component structure: one is specic anchoring groups which can be strongly adsorbed on the particle surface; the other is polymeric chains which dangle into the solvent and repel other polymers. Considering that CNPs and MWCNTs present different dimensionalities, the interaction potential between two parallel, innitely long, and perfect MWCNTs as well as two CNPs was calculated and compared on the basis of the continuum Lennard-Jones model (Fig. 14). It was found that the attractive potential between two CNPs was relatively low and of short range. Therefore, the polymer chain length and surface coverage for the dispersion of CNPs was lower than that needed for the dispersion of MWCNTs. On the basis of this theoretical

Based on the above description of multi-step purication, it can be concluded that the processes can be effective in removing both carbonaceous and metal impurities. These methods have been rapidly developed and widely used in recent years. Most importantly, one can selectively open tips, cut CNTs, add functional groups on sidewalls, separate CNTs according to length or conductivity, or maintain an undamaged CNT structure by skillfully combining different techniques. The key point of this general method is how to combine different methods according to ones requirement and the quality of the raw CNTs. Although considerable progress has been made, some merits of physico-chemical techniques have not been fully used and combined. For example, some physical methods capable of removing metal particles (magnetophoretic, Sc-CO2 extraction, etc.) are rarely reported to be combined with gas oxidation. This combination may greatly improve gas phase purication yield owing to the early elimination of metal particles, which can catalyze the CNT oxidation [48,49].

2.4.

Applicability of typical purication techniques

A high yield of high-purity CNTs can hardly be obtained using a physical or chemical method alone because of specic limitations, while high-purity and high yield CNTs can be obtained using multi-step purication by using the advantages of the both processes. Furthermore, it is possible to control the morphology and structure of CNTs by selecting suitable methods. To enable one to fully understand the characteristics of each method and make a wise combination based on

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Table 3 Applicability of some typical purication technologies Technologies Characteristics Yield (wt%) Cama/Cnpb
Chemical method Gas phase Air Cl2, H2O, HCl H2O, Ar, O2 O2, C2H2F4, SF6 HNO3 H2O2, HCl Mixture of acid or KMnO4 Microwave in inorganic acid Alkali or acid solution Opening CNT caps, low yield, less damage to tube wall $235 $15 $30 2548 $3050 1075 3075 1060 $80 $3084 $1040 $1750 $7090 $10/n / Ji J J J J J J J* J* J* J* J*   J

Applicability Carbonaceous impurity Cgc

j      J*   J* J* J*   J

Ref.

Metal impurity Mexpf Mpolg Mcnth

Jml Jm Jm J J J J J Jm J* J*  J J J* J*mm J*m J*m J J* J* J J*  J* J* J* J J J* J*m J*m J*m J* J* J* J* J* J/J*    J J  [4145] [47] [48,49] [51] [58,59] [6163] [6469] [7176] [27,83] [8486] [87,88] [8992] [98102] [107109] [110113]
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Cadd
J*k J* J* J* J* J* J* J*       

Csole
         J J J   

Liquid phase

Adding functional groups, cutting or opening CNTs

Electrochemical Physical method

Suitable for aligned CNTs Non-destructive Non-destructive, small amount Improve crystallinity High selectivity to metal Separate CNTs by length or conductivity High-purity, low yield High-purity respect to metal High-purity, little damage Metal free, improving crystallinity

Filtration Centrifugation Solubilization with functional groups High temperature annealing Other techniques to remove metal particles Chromatography, electrophoresis, FFF

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HIDE, wet grinding, ltration, oxidation, sonication, centrifugation Filtration/magnetic ltration, oxidation, annealing Sonication in H2O2, HNO3 /HF/ SDS, ltration High temperature annealing, extraction

$2% $920% $25 $90%

J J J J*

J  J* J*

J* J J* J

J J J J

J J J J

J* J J* J

J* J* J* J

[127] [135] [130] [150]

a b c d e f g h i j k l m n

Amorphous carbon. CNP. Graphite particles. Carbon impurity adhering to CNT walls. Soluble carbon in some organic solutions (CS2, toluene). Exposed metal. Metal wrapped by polyhedral carbon. Metal encapsulated in CNTs. Effective. Not effective. Partly removed. Further HCl treatment. Further HCl treatment and partly removed. No report.

2019

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ones need and the quality of the as-prepared CNTs, it is essential to give a clear image of the basic characteristics of different techniques. Based on up-to-date knowledge, we summarize the applicability of representative methods in Table 3. In general, chemical oxidation is effective in eliminating amorphous carbon, adding functional structures, and cutting and/or opening CNTs; inorganic acid treatment can effectively remove exposed metal particles. Physical treatment is capable of removing metal particles, sorting CNTs by length or conductivity, and, to some extent, separating isolated carbonaceous particles by size. It is well known that the content, morphology and structure of impurities in as-prepared CNT samples strongly depend on their synthesis methods and conditions. Therefore, there is no normalized method for routinely creating highquality CNTs. Here we summarize a ow chart showing representative procedures based on the function and characteristics of the purications (Fig. 15). It should be a reference for obtaining puried CNTs according to different requirements.

of high cost and long time involved. However, there are still many technical barriers to be overcome when cost, reproducibility, environment compatibility, and scaling-up are taken into account. Considering that the purication of CNTs is a complex issue involving the quality of the raw CNT sample, purication and purity assessment, we point out the following three main challenges: synthesis methods, purication and purity assessment.

3.1.

Synthesis methods

3.

Challenges

Obviously, notable progress has been made on the purication of CNTs in recent years, and small amounts of high-purity CNTs can be readily obtained in spite of the disadvantages

Carbonaceous and metallic impurities are produced as byproducts during the synthesis of CNTs. If pure CNTs without any impurity were directly synthesized, the purication would be obviated. A decade ago, Kyotani et al. [151] synthesized MWCNTs by a template CVD using an anodic aluminum oxide lm as template. The resulting MWCNTs are free of carbonaceous and metal impurities. Furthermore, the length, diameter and wall thickness of the CNTs can be uniformly controlled by easily controlling the structure of the template. Recently, Li et al. [152] reported that pure SWCNTs with a purity of $96% were produced by CVD using ethanol as carbon source. The only impurity was iron nanoparticles that were exposed on the surface and could be easily removed by acid. Batch-scale preparation of ultralong SWCNT arrays with high-

As-prepared CNT sample CS2 extraction to remove fullerene or aromatic carbon Purity evaluation Low purity High purity Physical separation method

Removing metal impurity Wrapped by carbon layers Improve crystallinity High temperature annealing Exposed metal Maintain CNT structure Other physical techniques HCl treatment

Removing carbonaceous impurity Removing carbonaceous impurity Polymer extraction Adding functional groups or cut CNTs Liquid phase oxidation Separation Conductivity Dielectrophoresis Length < 300 nm Chromatography Length > 300 nm Electrophoresis or FFF Maintain structure Opening caps

Physical method

Gas phase oxidation

Fig. 15 A ow chart showing the representative procedures based on the function and characteristics of the purications.

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quality was achieved by ultralow ow rate CVD [153]. At the same time, cloning growth from an existing nanotube segment was also reported [154,155], which ties synthesis and selectivity in chirality into one single step. Despite the progress achieved in directly synthesizing high-purity CNTs, the following challenging issues in synthesis still remain: (a) Large-scale synthesis of high-purity CNTs with controllability in diameter, length, wall thickness, chirality and conductivity. (b) Synthesis of isolated CNTs with desired structures. (c) Growth of CNTs at preset positions for device applications.

3.2.

Purication methods

As pointed out above, most of the as-prepared CNTs contain a certain amount of impurity. To obtain high-quality CNTs, purication is inevitable. The demand for obtaining uniform, high-purity CNTs with low cost and high efciency on a large scale requires the following major challenges to be overcome. (a) How to efciently combine different purication techniques according to the requirements of various applications and the characteristics of the raw CNT samples. (b) How to solve the problems brought about by the scaling-up of CNT purication, such as the uniformity of the CNTs and the homogeneous contact between impurities and oxidants. (c) How to develop novel techniques that can effectively achieve purication, structure tailoring, and structure/ property sorting of CNTs.

the purication strategy must vary according to the features of the raw CNTs, and the specic requirement and target applications of the puried CNTs. Although considerable progress has been achieved, it is still difcult to nd a simple method that can purify CNTs effectively. Multi-step methods that combine the advantages of different purications provide a solution for getting CNTs with higher purity. With regard to the different types of CNTs, the purication of MWCNTs is relatively easy and effective, whereas the purication of SWCNTs and DWCNTs always results in low yield and defect formation. Because of this, more efforts aimed at selectively sorting SWCNTs by length, diameter, transport properties, and even chirality, are required. Therefore, challenges still remain in the purication of CNTs. High-purity, high yield, low cost, and environmental friendliness are essential. Establishing a CNT purity assessment standard is necessary for evaluating and improving the validity of purication. Without question, the exploitation of efcient CNT purication techniques that can produce high-quality and homogeneous CNTs will greatly facilitate fundamental research and practical applications of CNTs.

Acknowledgements
We acknowledge nancial support from MOST (2006 CB932703), NSFC (90606008, 50672103), and Chinese Academy of Sciences. The authors appreciate very much Prof. Peter Throwers advice and comments. We thank Dr. Ren WC and Liu BL for useful discussion on Raman and UVvis-NIR characterization methods.

R E F E R E N C E S

3.3.

Purity assessment
[1] Iijima S. Helical microtubules of graphitic carbon. Nature 1991;354(6348):568. [2] Saito R, Fujita M, Dresselhaus G, Dresselhaus MS. Electronicstructure of chiral graphene tubules. Appl Phys Lett 1992;60(18):22046. [3] Planeix JM, Coustel N, Coq B, Brotons V, Kumbhar PS, Dutartre R, et al. Application of carbon nanotubes as supports in heterogeneous catalysis. J Am Chem Soc 1994;116(17):79356. [4] Pan XL, Fan ZL, Chen W, Ding YJ, Luo HY, Bao XH. Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles. Nat Mater 2007;6(7):50711. [5] Calvert P. Nanotube composites-A recipe for strength. Nature 1999;399(6733):2101. [6] He XJ, Du JH, Ying Z, Cheng HM. Positive temperature coefcient effect in multiwalled carbon nanotube/highdensity polyethylene composites. Appl Phys Lett 2005;86(6):062112. [7] Kong J, Franklin NR, Zhou CW, Chapline MG, Peng S, Cho KJ, et al. Nanotube molecular wires as chemical sensors. Science 2000;287(5453):6225. [8] Baughman RH, Cui CX, Zakhidov AA, Iqbal Z, Barisci JN, Spinks GM. Carbon nanotube actuators. Science 1999;284(5418):13404. [9] Liu C, Tong Y, Cheng HM, Golberg D, Bando Y. Field emission properties of macroscopic single-walled carbon nanotube strands. Appl Phys Lett 2005;86(22):223114. [10] Deheer WA, Chatelain A, Ugarte D. A carbon nanotube eldemission electron source. Science 1995;270(5239): 117980.

An important issue on the purication of CNTs is purity evaluation. Although several techniques have been used for evaluating the purity of CNTs, a standard and well-recognized purity assessment protocol has not been established. This leads to uncertainty in the purity of the products obtained as well as the efciency of purication processes. Therefore, the following challenges also remain for purity assessment: (a) To establish a standard characterization protocol to evaluate and compare different CNT samples. (b) To establish a standard that can fully describe the characteristics of the puried CNTs, such as CNT content, amounts of different impurities, defects, etc. (c) To establish a standard that can give an overall evaluation of the efciency purication, according to the CNT quality, yield, cost, environment compatibility, etc.

4.

Concluding remarks

Techniques for the purication of CNTs have been reviewed, with an emphasis on their purication principles. Since the quality and accompanying impurities of as-prepared CNTs strongly depend on the synthesis method and experimental conditions, it is hard to propose a universal method. In fact,

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