Structure, Properties, Functionalization, and ... - ACS Publications

Review pubs.acs.org/CR

Structure, Properties, Functionalization, and Applications of Carbon Nanohorns Nikolaos Karousis,*,† Irene Suarez-Martinez,*,‡ Christopher P. Ewels,*,§ and Nikos Tagmatarchis*,† †

Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, Athens 11635, Greece ‡ Nanochemistry Research Institute, Department of Physics, Curtin University of Technology, P.O. Box U1987, Perth, Western Australia 6845, Australia § Institut des Materiaux Jean Rouxel, CNRS, Université de Nantes, 2 Rue de la Houssiniere, BP32229, 44322 Nantes, France ABSTRACT: Carbon nanohorns (sometimes also known as nanocones) are conical carbon nanostructures constructed from an sp2 carbon sheet. Nanohorns require no metal catalyst in their synthesis, and can be produced in industrial quantities. They provide a realistic and useful alternative to carbon nanotubes, and possibly graphene, in a wide range of applications. They also have their own unique behavior due to their specific conical morphology. However, their research and development has been slowed by several factors, notably during synthesis, they aggregate into spherical clusters ∼100 nm in diameter, blocking functionalization and treatment of individual nanocones. This limitation has recently been overcome with a new approach to separating these “dahlialike” clusters into individual nanocones. In this review, we describe the structure, synthesis, and topology of carbon nanohorns, and provide a detailed review of nanohorn chemistry.

CONTENTS 1. Introduction 2. A Side Note on Nomenclature 2.1. Nanocone Topology 2.2. Individual vs Aggregated Carbon Nanohorns Morphology 3. Theoretical Simulations on Carbon Nanohorns Chemistry 4. Carbon Nanohorns Synthesis 4.1. Synthesis via Arc Discharge 4.2. Synthesis via Laser Ablation 4.3. Synthesis via Joule Heating 4.4. Industrial Carbon Nanohorns Production 4.5. Dahlia Growth Models 5. Other Conical Nanostructures 6. Properties of Carbon Nanohorns 7. Chemical Functionalization of Carbon Nanohorns 7.1. Oxidation of Carbon Nanohorns 7.2. Functionalization of Oxidized Carbon Nanohorns 7.2.1. Functionalization with Photoactive Units 7.2.2. Immobilization of Bioactive Units 7.2.3. Decoration with Nanoparticles 7.2.4. Filling-Doping 7.3. Covalent Sidewall Functionalization of Intact Carbon Nanohorns 7.3.1. Addition of Polymers 7.3.2. 1,3-Dipolar Cycloaddition 7.3.3. Addition of Aryl Diazonium Salts © 2016 American Chemical Society

7.3.4. Microwave-Assisted Functionalization 7.3.5. Miscellaneous Reactions 7.4. Noncovalent Functionalization of Intact Carbon Nanohorns 7.4.1. Immobilization of Nanoparticles 8. Individualization of Carbon Nanohorns 9. Applications of Carbon Nanohorns 10. Conclusions Author Information Corresponding Authors Notes Biographies Acknowledgments References

4850 4851 4851 4852 4853 4854 4854 4854 4854 4855 4855 4855 4856 4857 4857

4865 4868 4869 4871 4873 4874 4875 4875 4875 4875 4875 4876 4876

1. INTRODUCTION Carbon nanohorns (CNHs)sometimes also known as nanoconesare closed cages of sp2-bonded carbon atoms, typically 2−5 nm in diameter and 40−50 nm in length. In one sense, they can be considered a high-aspect ratio subset of fullerenes due to their closed cage structure, although they may be opened via oxidation to increase their surface area and provide access to their interior cavity. However, their elongated shape means that a closer structural analogue is short single walled carbon nanotubes, with which they share much common chemistry.

4858 4858 4859 4861 4862 4863 4864 4865 4865

Received: October 14, 2015 Published: April 13, 2016 4850

DOI: 10.1021/acs.chemrev.5b00611 Chem. Rev. 2016, 116, 4850−4883

Chemical Reviews

Review

individual elongated closed-cage structures, dahlia to refer to the aggregated clusters of such nanohorns, and the term nanocone to describe more generally any conical nanostructure.

Indeed, nanohorns are under investigation as replacement candidates for nanotubes in a range of fields, notably energy conversion, drug delivery, gas storage, and supercapacitors.1,2 Carbon nanohorns have two key advantages over carbon nanotubes: (i) the absence of potentially toxic metal catalyst in their synthesis, and (ii) their mass production at room temperature. Specifically, the presence of metal particles introduced during the preparation of carbon nanotubes not only requires additional treatment with strong acids in order to eliminate this metal catalyst, with the handicap of damaging the graphitic structure by introducing defects, but also results in loss of the carbon material. In contrast, pure CNHs are easily available, better enabling the study and understanding of their properties and applications. Pristine CNHs possess semiconducting properties, field-emission characteristics, and thermal stability, while also displaying high resistance to oxidation. Nevertheless, the research and development of CNHs has been slowed by several factors. Computationally, their low symmetry makes them difficult to model, restricting the number of predictive quantum chemical simulations in the literature. Experimentally, during synthesis they aggregate into spherical clusters ∼100 nm in diameter, rendering dispersion and separation difficult, and thus blocking functionalization and treatment of individual nanocones. Recently, this limitation has been overcome with a new approach to separating these “dahlialike” clusters into individual nanocones. Thus, we anticipate great interest in the near future in applying nanocones to many applications currently being developed with carbon nanotubes, graphene, and fullerenes. Structurally, nanohorns are constructed from a mixture of pentagons, hexagons, and heptagons, and this combination of structural motifs and forms results in a rich and varied chemistry.

2.1. Nanocone Topology

Carbon nanoscience has been dominated by three archetypical structures: fullerenes, nanotubes, and graphene. However, sp2based carbon nanoforms include a plethora of structures.5,6 These are all based on topological distortions of a single layer of hexagonal sp2 carbon, a graphene sheet. In general, there are three possible ways to introduce conical curvature to a flat disc, as shown in Figure 2a−c. The first

Figure 2. Three ways to introduce curvature to a flat plane: (a) A double fold (coupled screw and edge dislocations), (b) removal of a segment and reconnection of the edges (a positive wedge disclination), and (c) removal of a segment coupled with an out of plane displacement resulting in a continuous helical surface (a positive wedge disclination coupled with a screw dislocation).

involves a pair of folds, such as are used to fit a disc of filter paper into a funnel. The second involves removal of a triangular segment from the disc and reconnection of the edges, resulting in a cone. The third also involves a cut but with an offset in the edge cuts, resulting in a helix. All three of these forms occur in carbon nanoobjects, and are discussed below. Terrones first suggested the transformation of ordinary graphene into graphitic cones during his studies of curved graphene models with positive, negative, and zero Gaussian7 (a continuum model with no atomistic details). While structures (a) and (c) can result in conical nanocarbon structures of arbitrary apex angle, the superposition of the graphene lattice on the surface imposes constraints on the possible cutting and reconnection angles for (b) (Figure 3). Due to the hexagonal network of graphene, only removal of wedges of 60° (or multiples of 60°) is possible in order to maintain a continuous bonding network (see Figure 3). Given the atomistic structure of graphene, this results in the formation of one pentagon per 60° wedge, marked in gray in Figure 3. The discrete number of pentagons (1 to 5) means only a discrete number of disclinations that can be produced, with only 5 possible apex angles for the nanocone. The disclination angle is n(π/3) with 0 ≤ n ≤ 5, where n is the number of pentagons. The disclination angle is related to the cone apex angle as θ = 2 sin−1(1 − n/6), giving 5 possible cone angles: 10.2°, 38°, 60°, 83°, and 112°. Six pentagons result in a structure with a zero angle tip, i.e. a nanotube with one open end, just as 12 pentagons form a closed cage, giving the family of fullerenes. Any closed convex polyhedron constructed from polygons with equal length sides must satisfy Euler’s polyhedron formula. This relates the number of vertices (V), edges (E), and faces (F) for a convex polyhedron with equal length sides as V − E + F = 2.

2. A SIDE NOTE ON NOMENCLATURE As for many carbon nanostructures, the nomenclature describing carbon conical structures in the literature can be ambiguous. With many exceptions there is a tendency to use the term “nanocone” for a free-standing structure, as shown in Figure 1a,

Figure 1. Transmission electron micrographs of carbon nanohorns: (a) close-up of individual nanohorns (Reprinted with permission from ref 3. Copyright 1996, AIP Publishing LLC), (b) aggregates of nanohorns clusters, and (c) zoom-in on a few aggregates of nanohorns, also known as dahlias, produced by laser ablation (Reprinted from ref 44. Copyright 1999, with permission from Elsevier).

while the term “nanohorn” is often reserved for the clustered arrangement, as shown in Figure 1b and c. Theoretical studies commonly use the term nanocone for individual cones. The term “buckycone” was proposed by Klein,4 for nanocones exclusively made of pentagons and hexagons, but it has rarely been used since. In an attempt to standardize carbon nanoform nomenclature, it was suggested that the individual cones should be referred to as carbon nanocones while the aggregated form as spherical clustered carbon nanocones.5 For the purposes of this review, we will use the term nanohorn to refer specifically to the 4851


Chemical Reviews

Review

Figure 3. Representation of the construction of carbon nanocones by cutting a wedge (disclination) from graphene and reconnecting the resultant dangling bonds (dotted arrows). Removing a wedge in this way necessarily results in a nonplanar structure in order to maintain covalent C−C bond lengths. The pentagons thus created are colored. (a) Single pentagon cone. (b) four pentagon cone. (c) Possible cones with their cone tip angle and number of pentagons. Up to 6 pentagons can be introduced; 6 pentagons results in a closed nanotube tip structure.

Burgers circuit around a dislocation).4 Each class is defined as cones that can be transformed from one to another via addition or removal of neighboring carbon pairs, with no sequence of transformations to convert one class into another. The result is two subclasses for each of 2-, 3-, and 4-pentagon cones. It is interesting to note these subclasses are separated from each other based on vector length multiples of three, strongly reminiscent of Clar-sextet positioning in graphene16 and semimetal behavior in carbon nanotubes. Another topological index sometimes used in the literature for defining nanocones is the Wiener index, defined as the sum of distances between all pairs of vertices of a (connected) graph.17 Another classification based on pentagon separation via (h,k) graphene vectors18 also shows 2- and 4-pentagon cones can be divided into two subsets19 depending on whether (h-k) is a multiple of three. Similarly to nanotubes, one of these classes has zero local density of states (LDoS) at the Fermi energy; for the other the LDoS is inversely proportional to the distance from the cone tip (see Figure 4). This strongly suggests that the nanocone tip chemistry should be distinctly different for these different subclasses. Unlike carbon nanotubes, nanocone helicity is not constant and increases monotonously along the cone axis. Additionally, both chiral and achiral nanocones are possible. However, chiral nanocones are only “locally” chiral, as only the apex identifies the enantiomers.4

For regular polygons nx, where x is the number of sides, the formula can be reexpressed as 3n3 + 2n4 + n5 + 0n6 − n7 − 2n8 − 3n9 − ... = 12

(1)

Thus, while pentagons are the most energetically favorable polygon to produce positive curvature, other combinations would also satisfy. Indeed, for layered materials such as boron nitride, where odd-number polygons are unfavored due to homopolar bonding, polyhedral closure via squares has been proposed.8 This relation also demonstrates that a given closed nanohorn can contain more than 12 pentagons (as is commonly the case) as long as the net number of pentagons is 12; that is, excess pentagons above this number are offset in the lattice by an equal number of heptagons. The various chemically relevant equivalences can be found in Klein.9 While nanocones contain an integer number of up to 5 pentagons, the precise position of the pentagons can be varied. An analysis of possible isomer tip structures was derived by Brinkmann and Van Cleemput,10 and nanocone geometry generators are available on the Web.11−13 While there is a vast number of possible nanocone tip structures for a given number of carbon atoms, modeling and chemical constraints can reduce this to a smaller subset. First neighboring pentagons are energetically unfavored due to chemical frustration (under-coordinated carbon atoms), known as the isolated pentagon rule.14 Using well-known fullerene structures, Han and Jaffe have evaluated the energetics and geometries of carbon nanocone tips using density functional theory,15 concluding a number of simple rules to estimate the relative stability of different isomers. There have been several attempts to classify carbon nanocones, with no “clear winner” at this point. Klein and Balaban proposed a coding system to unambiguously identify a given nanocone based on its distribution of pentagons.4 The system defines number pairs hk, where, starting from one pentagon, h is the number of polygons (usually hexagons) which must be crossed, passing through opposite sides of the polygon, followed by a left turn and k steps in this new direction, to reach a second pentagon. A nanocone with p pentagons can be defined unambiguously as [h12k12:t2(1)3:h13k13:...tp‑1(1)p:h1pk1p], where tj(i)k × 72° is the angle to the left between two successive paths. Klein also grouped nanocones into eight classes based on circumambulatory paths (“circumpaths”) formed by q acenic lines of x hexagons surrounding the apex (i.e., surrounding the pentagons) at 120° angles to each other (similar to drawing a

2.2. Individual vs Aggregated Carbon Nanohorns Morphology

The previous brief overview of nanocone topology focused on pentagons as the defining structural feature. We note that nanohorns tips typically contain five pentagons.20 However, unlike some other carbon nanocone materials, carbon nanohorns typically also contain heptagons in their structure, potentially reactive sites in their own right with their own distinct chemistry.21 The combination of pentagons and heptagons results in the elongated “short nanotube” form of nanohorns. Figure 5 gives a structural schematic of a typical carbon nanohorn. Nanohorns typically consist of a conical front-tip section followed by a short cylindrical nanotube section. While the tips typically have five pentagons, a sixth pentagon further from the tip is required for the nanohorn walls to continue parallel to the nanohorn “axis” in the same manner as a carbon nanotube. Each additional heptagon counteracts the curvature change of one 4852


Chemical Reviews

Review

Figure 6. Comparison of CNH aggregates produced from CO2 laser ablation of graphite using Ar (left) and He (right) as carrier gases (760 Torr), showing dahlia (left) and bud-like (right) structures (Reprinted from ref 26. Copyright 2002, with permission from ACS).

easily separated, and the majority of nanohorn studies to date have been performed on these nanohorn aggregates. Dahlias have advantages for certain applications, since their size limits reduce gas phase dispersion (aiding processability) and, for example, can enhance cell take-up.25 Dahlias are likely made exclusively of carbon nanohorns and graphene flakes bound tightly via van der Waals forces, since oxidative treatment to remove their outer layers finds no remaining material associated with the dahlia cores.26 Dahlia formation mechanisms are discussed further in Section 4.5 below. Finally we mention that as well as the “dahlia” type nanohorn aggregates it is also possible to produce “bud-like” aggregates of similar size26 (see Figure 6), or mixtures of the two.27 Bud-like aggregates also consist of (defective) carbon nanohorns, but they do not protrude from the aggregate surface. They are typically produced when the carrier gas mass and/or pressure during carbon laser vaporization is decreased as compared to conventional dahlia growth.

Figure 4. Local density of states [states/(t atom)] at EF for (1,1) and (2,0) two-pentagon graphene cones vs distance r from the apex. a is the graphene lattice constant. Data from a tight-binding model. The solid curve is the continuum model result for a (1,1) cone. Reprinted from ref 19. Copyright 2004, with permission from the American Physical Society. In Klein and Balaban’s classification these would be (2,1) and (2,2) class cones, respectively.4

3. THEORETICAL SIMULATIONS ON CARBON NANOHORNS CHEMISTRY While electronic and physical properties of carbon nanocones have been the subject of extensive theoretical modeling, we limit this section to simulations relevant to nanocone chemistry. Nanocones present large electrostatic dipole moments, which increase with the number of atoms and the sharpness of the cone tip.28 In addition to “bulk” graphene-like energy levels, “apical” energy levels have been identified, their behavior consistent with classical cyclotron orbits enclosing the apex.17 This tip-related electron density has been linked to resonant acceptor bonding states of pentagons themselves;29 that is, pentagons will be negatively charged in large enough nanocones.30 Density functional simulations highlight the spatial variations in nanocone chemistry (Figure 7), with apical cone chemistry resembling that of fullerenes and cone sidewall chemistry more reminiscent of graphene and large diameter nanotubes.31 The study showed that oxygen addition to graphenic sidewalls is endothermic and epoxide oxygen will preferentially be found at nanocone tips. There it can facilitate 2 + 2 cycloaddition (via ether bridge) to fullerenes, reminiscent of C60−O-C60 formation. The modeling was supported by experimental evidence of fullerene addition to exclusively high angle nanocone tips when in the presence of oxygen. Similar enhanced tip reactivity was shown via simulations of covalent radical addition of CH3 groups to carbon nanocones32 and physisorption of NH3.33 Besides the enhanced reactivity associated with decrease in aromaticity at pentagon and heptagon defects, local chemical reactivity is also enhanced in regions of higher curvature due to pyramidal distortion of the sp2 carbon bonding.34 For both of these reasons, nanohorn chemical reactivity is assumed to be

Figure 5. HRTEM images of (a) carbon nanohorn “dahlia” aggregate (scale bar 10 nm), and (b) an individual carbon nanohorn (scale bar 2 nm). (Reprinted from ref 144. Copyright 2005, with permission from ACS). (c) Schematic showing locations of typical pentagons (blue) and heptagons (pink).

pentagon, and it is common to observe spaced heptagon/ pentagon pairs. In combination, these do not change the net nanohorn curvature but increase the diameter of the cylindrical section, and when at neighboring sites, they form a glide basal dislocation core.22 The nanotube segments of nanohorns have typical diameters from 4 to 5 nm, significantly larger than typical diameters for conventional “infinite” cylindrical single walled nanotubes (1−2 nm). This is because conventional tubes collapse above a critical radius to give a “dogbone” cross section, once the energy gain from interlayer van der Waals interaction overcomes the energy cost from increased curvature at the edges of the collapsed nanotube. Using an elastic model, the critical radius for a single wall nanotube is estimated to be ∼2.7 nm.23 This collapse effect is hindered by the conical region in carbon nanohorns. This combination of varying local curvature, zones of pentagons, and heptagons results in rich and varied nanohorn chemistry, discussed further in the section below. During synthesis, nanohorns cluster into spherical “dahlia” aggregates, with typical diameters of around 100 nm (Figure 6). Although the inner structure of aggregated CNHs lacks detailed investigation and clarification, mainly due to the numerous densely packed nanohorns that form the aggregate, a microscopy study suggested the existence of nanosized cavities of 10−20 nm around the center of the aggregate.24 These aggregates are not 4853


Chemical Reviews

Review

gas into the arc zone. Submerged arc-discharge was first attempted using DC arc-discharge between graphite electrodes in liquid nitrogen, producing around 17 g/h of nitrogen-doped nanohorns,27 and has more recently been achieved in liquid Ar.41 An alternative synthesis route was proposed using arc-discharge in water, with the gaseous zone around the arc maintained with N2 gas (the “arc in water” method).42 This appears to be an efficient route to high purity nanohorns, and a recently refined version of this where N2 or Ar gas is injected into the arc zone through holes in the graphite electrode is claimed in a conference talk to be producing 1 kg/day of nanohorns this way.43 4.2. Synthesis via Laser Ablation

Nanohorn dahlias were first synthesized by pulsed laser ablation of graphite in an Ar atmosphere, at a rate of around 10 g/h.44 The CO2 laser, operated at room temperature (wavelength 10.6 μm, maximum power 5 kW, 10 ns pulse duration) produces a soot of aggregated dahlias at typically 85−90% purity. When sonicated in ethanol the dahlias form a dark suspension which can be filtered to give a mechanically stable thin film.45 Dahlias produced in this way are typically up to twice the size of those produced via arcdischarge (around 100 nm in diameter). Different inert gas atmospheres were tested, with dahlia yields of 95% under Ar (20 kW/cm2 surface laser power density with 500 ms on−off pulses), but “bud-like” nanohorn aggregates were produced under lighter He and N2 atmospheres.26 Smaller 50 nm diameter aggregates, comparable in size with arc-discharge, are produced when a Ne gas atmosphere is used,46 and a N2 atmosphere results in damaged, highly nitrogen-doped nanohorn dahlias.47 XPSstudies indicated that nitrogen atoms were incorporated as the pyridine-like and 3-fold coordinated sp2 bonding configuration in a graphene lattice of CNHs. In conjunction with NEC, the AIST group of Iijima and Yudasaka responsible for first developing the laser ablation method have continued to develop it toward a commercially viable route to industrial-scale production of carbon nanohorns. A key step on this route was the development of a three-chamber system separating a target reservoir, the laser ablation chamber, and a collection chamber. Nanohorns produced in the laser ablation chamber are swept into the collection chamber by the Ar carrier gas, keeping the target clear and allowing continuous laser operation. Using a rotating cylindrical graphite target and optimized laser power density (15−30 kW/cm2), this method was able to produce dahlia nanohorn samples at 92−95% purity at a practical production capacity of 1 kg/day.48 This technique now forms the basis of commercial nanohorn production at NEC.

Figure 7. DFT calculated reaction enthalpies (in eV) for oxygen bridging between C60 and X, where X is C60O, an oxidized 84° nanocone tip, or an epoxide on graphene. Energies are relative to isolated nonoxidized nanoforms and 1/2 O2. Reprinted from ref 31, Copyright 2013, with permission from Elsevier.

primarily localized around pentagons, heptagons, and other defect sites, toward the nanohorn tip and, if exposed, around the open nanohorn tubular end.

4. CARBON NANOHORNS SYNTHESIS All current nanohorn synthesis methods involve sufficient injection of energy to vaporize and restructure a carbon target (typically graphite), followed by rapid quenching, normally in an inert gas. Nanohorn synthesis is distinguished from nanotube production, notably in the absence of metal catalysts. As-grown nanohorn samples also show high purity, typically a maximum of 5−15% byproducts consisting primarily of micrometric graphite particles, fullerenes, and giant carbon onions, with some amorphous carbon,31 again depending on the synthesis route. Some impurities, such as giant graphite balls, can be largely eliminated by preheating the carbon source before synthesis.35 Thus, for many applications, no purification step is required or, at most, a simple thermal anneal. Synthesis methods can be loosely classified into three families based on the technique used to inject energy into the carbon. 4.1. Synthesis via Arc Discharge

Carbon nanohorns were first observed in soot byproducts produced during arc-discharge production of fullerenes. While the soot itself was a microporous carbon, after heating to 2500− 3500 K with a positive-hearth electron gun for ∼4 h, it transformed into a mixture of single-walled and multiwalled nanohorns.36 The first arc-discharge study to produce highpurity nanohorns directly used a pulsed arc-discharge, between pure carbon rods in atmospheric pressure of air.37 Residual amorphous carbon was then removed by heating in dry air at 500 °C. Dahlias produced in this way have mean diameters of ∼50 nm. Sample quality was further improved by preheating the carbon rods to 1000 °C just before arc ignition. The necessity for both N2 and oxygen (either as O2, CO2, etc.) in the carrier gas was later confirmed in direct current (DC) arc-discharge experiments.38 Other groups have achieved low purity yields with DC arc-discharge in air and Ar,39 improving somewhat with use of AC arc-discharge.40 Submerged arc-discharge processes have proved more promising and may provide a viable route to large-scale nanohorn production. In each case the arc zone remains gaseous, either through vaporization of the host liquid or via injection of carrier

4.3. Synthesis via Joule Heating

A third route to nanohorn production rarely mentioned in the literature is heating by induction, inducing high frequency eddy currents in graphite rods which give rise to Joule heating.49 A prototype reactor (30 kW plant) was able to heat graphite rods in this way to over 3200 °C on their surface, producing a surface carbon plasma. The resultant nanohorn soot is removed via Ar or He carrier gas, resulting in dahlias or bud-like structures respectively (just as observed for laser).26 This deceptively simple method is able to produce around 0.1 kg of dahlias per hour, with the authors discussing the possibility of scale-up to MW plans producing tens of kilograms per hour. While exact purity is not discussed, the method also produces wrapped and unwrapped graphene sheets and a little amorphous carbon, and it contains Fe ≫ Cu. Decomposition of CH4 under these conditions led to the formation of cup-stacked carbon nanotubes round CNHs where Ni particles were situated at the tip of each nanotube.

solution of sodium cholate. Subsequently, the above mixture was placed in a centrifuge tube on top of a 3-layered solution of 5, 10, and 30% sucrose concentration and centrifuged for 4 h at 4,600g. Dynamic light scattering of an aliquot from the upper zone after centrifugation revealed the presence of spherical particles with average diameter of 30 nm, which were further analyzed by TEM imaging, confirming the presence of isolated individual oxidized single-walled CNHs in 61%, while small aggregates (23%) and amorphous graphitic particles (16%) were also observed (Figure 44). The incorporation of Gd2O3 nanoparticles in the individualized CNHs proved the presence of their hollow internal space.

8. INDIVIDUALIZATION OF CARBON NANOHORNS Despite the diverse methodologies applied for the chemical modification of CNHs, with some of them following harsh reaction conditions, the characteristic superstructure of dahlialike spherical aggregates of CNHs remains unaffected, thus limiting their immediate utility in biological applications, for example as drug delivery carriers. Therefore, the isolation of individual single-walled CNHs from dahlia-aggregates becomes critical. One of the first attempts to isolate small aggregates of CNHs was based on the dispersion of as-grown CNHs in a D2O solution of sodium dodecyl benzenesulfonate (NaDDBS) through 30 min sonication, followed by ultracentrifugation at 220,000g for 1−2 h.237 By this methodology, amorphous graphitic particles, which represent the main impurity of asgrown CNHs, were removed, while smaller aggregates of CNHs, with a narrower size distribution were obtained (Figure 43). Alternatively, sucrose density gradient centrifugation of a sodium cholate solution of mildly oxidized CNHs was examined.238 In this context, CNH-aggregates were initially oxidized in air at 450 °C and then dispersed in an aqueous

Figure 44. Digital photo of a sodium cholate dispersion of oxidized CNHs before (a) and after (b) sucrose density gradient centrifugation. (c) Particle-size distributions for layers I−IV measured by DLS. Reprinted with permission from ref 238. Copyright 2009 American Chemical Society.

Very recently, the reductive dissolution of CNH-aggregates in the presence of potassium naphthalenide was achieved.239 The reaction took place under an inert atmosphere in a glovebox, where the green colored solution of reduced naphthalene decolorized rapidly upon contact with intact CNHs. The reduced CNHs were easily soluble in most organic solvents with solubility 4873


Chemical Reviews

Review

up to 20 mg mL−1 for DMSO. Interestingly, TEM imaging revealed the presence of individualized CNHs with diameter of 5 nm and length of ∼50 nm, surrounded by graphitic particles. Furthermore, the so-reduced CNHs can be further functionalized upon quenching by diverse electrophiles (Figure 45).

entering the cells through a lysosomal membrane permeabilization mechanism.242 Because CNHs can be dispersed and emulsified in water, the potential for dust and aerosol formation is reduced, as well as diminishing the need for toxic organic solvents. Additionally the spherical dahlia structures of CNHs mean that, following Stoke’s law, they build less stable aerosols than other nanocarbons. Thus, one might expect CNHs to be intrinsically safer than other contemporary nanomaterials,243,244 and indeed early cytotoxicity studies with human cervical cancer cells showed no toxic response245 although further studies are underway.246 There have already been studies on nanohorn dahlia use as drug carriers,25,144 as biofuel cells,247 and as highly sensitive, reproducible biosensors,248−250 while CNH complexes have also been applied to photothermal cancer treatment.163,251,252 However, individualized nanohorns may also be well adapted for this purpose due to their large internal cavity diameter compared to nanotubes, and their needle-like structure, which could enhance their capacity for penetrating cell membranes241 We note that oxidized CNHs have the ability to mimic horseradish peroxidase, showing catalytic activity in the oxidation of tetramethylbenzidine in the presence of H2O2, thus allowing the development of a colorimetric method for glucose detection.253 A comprehensive study on the adsorption properties and the porosity of CNHs has recently been presented.254 The unique structure of CNHs, in combination with their high specific surface area, especially in the case of oxidized CNHs possessing open nanowindows, classifies this carbon allotrope as a potentially excellent adsorbent. We have already presented the wide range of noble and supercritical gases that can be adsorbed either on the outer surface or in the internal empty space of CNHs.109−115,255 Recent studies further proved that the interstitial spaces between nanocones in a dahlia structured aggregate can hold gases of very different sizes, in contrast with the corresponding nanotube bundles, following different adsorption mechanisms depending on the nature of the gas.256,257 Specifically, although the isotherm adsorption data for Ne and CF4 clearly showed the presence of two substeps, suggesting the existence of two different groups of adsorption sites on the outer surface of CNHs, there were found no distinct substeps in the case of CO2 due to the fact that CO2 presents more attraction to other CO2 molecules than to the carbon surface. Other studies on the adsorption ability of oxidized CNHs revealed the importance of the pore sizes of open CNHs, further suggesting that there are three types of adsorption sites into CNH dahlias, assigned to CNH tips, CNH sidewalls, and the central empty cativities within the dahlias.258,259 Energy applications, ranging from dye-sensitized solar cells260 to supercapacitors261 and lithium ion batteries,262 exemplify another large area that utilizes suitably modified-CNHs.263 We have already described the applicability of metal-decorated CNHs not only as effective catalysts, but also as efficiently operational electrodes in the construction of methanol and polymer-electrolyte fuel cells.223,224 In another approach, metalfree CNHs covering a glassy carbon electrode were used for the manufacture of a highly sensitive electrochemical sensor for the detection of uric acid, dopamine, and ascorbic acid in biological samples.264 Further studies proved that CNHs reinforced glassy carbon electrodes can dramatically quench the electrochemiluminescence intensity of a system consisting of tris(2,20bipyridine)-ruthenium(II) and tri-n-propylamine, allowing the development of a label-free, sensitive, and signal-on adenosine

Figure 45. Individualization of CNHs upon reduction by potassium naphthalenide in DMSO. (a) HR-TEM image of intact CNHs. (b) LRTEM image of reduced CNHs 1. (c, d) HR-TEM images of individualized CNH salts 1. Reprinted with permission from ref 239. Copyright 2015 Royal Society of Chemistry.

9. APPLICATIONS OF CARBON NANOHORNS Although CNHs are currently less exploited than carbon nanotubes and graphene, there is nonetheless a great research effort underway to take advantage of their novel structure and purity, in order to utilize them in numerous nanotechnological applications. Most of the potential applications of CNHs have already been described in the previous sections during the description of modified CNHs. These mainly include their capability to adsorb gases or other molecules, to act as drug carriers, to construct effective biosensors and electrodes for electrochemical and photoelectrochemical purposes, or to act as catalyst supports and fuel cells. In this section, we will focus on other specialized applications employing CNHs that have not already been described. One of the most promising areas in which CNHs could find wide usage deals with biological applications.240 Nanohorns do not have the high aspect ratio issues related to toxicology that are now well explored with carbon nanotubes (shorter nanotubes, typically 20 μm or less, can be cleared by the lymphatic system)241 and do not require potentially toxic metal catalysts during synthesis. However, it has been demonstrated that CNHs can produce reactive oxygen species and induce toxicity after 4874


Chemical Reviews

Review

triphosphate aptasensor.265 Similarly, a CNH-based paste electrode, prepared by mixing CNHs and methyl silicone oil and firmly packing the mixture into the electrode cavity of a Teflon sleeve, was used for the amperometric determination of concentrated hydrogen peroxide.266 More recently, a stable and easily structured electrochemical sensor modified with CNHs and carboxylic acid based ionic liquids, was built to achieve a fast detection of 4-aminophenylarsonic acid.267 It is worth noting that a novel graphene/CNH hybrid material was prepared through a solvothermal treatment exhibiting an ultrafast charge− discharge and excellent rate capability, superior to the individual components alone.268 Moreover, CNHs were shown to be an excellent adsorbent in solid phase extraction. In this frame, a CNH-modified glassy carbon electrode disclosed excellent ability of solid-phase extraction for organic compounds such as 4-nitrophenol through simple and fast electrochemical measurements.269 In another recent study, a polypropylene hollow fiber served as a scaffold for the immobilization of oxidized CNHs, constructing a very efficient sorbent material, suitable for the headspace and direct immersion solid phase extraction of volatile organic compounds. This apparatus was efficiently used for the determination of volatile organic compounds such as toluene, ethylbenzene, various xylene isomers, and styrene in bottled, river, and tap waters, with excellent detection limits reaching 3.5 ng L−1.270

reduction with potassium naphthalenide, was highlighted. Since the individualization of nanohorns is still at its infancy, further optimization of the individualization process, together with the development of substantive advances and contemporary breakthroughs, for example improved control over functionalization mechanisms and/or spatially targeted functionalization routes, will boost the applicability of nanohorns, particularly in the area of biotechnology and medical disciplines, where larger amounts of individualized nanohorns with precise size are required. It is our hope and intention that this review will catalyze the realization of new applications for carbon nanohorns, especially those at the interface of chemistry and materials science with other disciplines.

AUTHOR INFORMATION Corresponding Authors

*E-mail: [email protected] (Dr. N. Karousis). *E-mail: [email protected] (Dr. I. Suarez-Martinez). *E-mail: [email protected] (Dr. C. P. Ewels). *E-mail: [email protected] (Dr. N. Tagmatarchis). Notes

The authors declare no competing financial interest. Biographies

10. CONCLUSIONS Carbon nanohorns are an interesting and somewhat neglected carbon nanomaterial with a bright future. They can be massproduced, now in industrial quantities, at room temperature without the need of any metal catalyst. They offer a genuine and advantageous alternative to carbon nanotubes, and possibly graphene, in a wide range of applications. Understanding the unique specific conical morphology of nanohorns structure as well as their synthesis and topology is of fundamental importance for advancing their research and development. Manipulation and handling of nanohorns can be enhanced in wet media, when dispersed in common organic solvents and/or water, while integration of active moieties toward nanohorn-based functional hybrid materials opens wide avenues for a plethora of practical applications. In this context, available strategies for functionalizing CNHs and generating some novel hybrid materials have been established and described in this review, with emphasis placed on selected examples from the recent literature. The decrease in aromaticity at defect sites, pentagons and heptagons, of CNHs results in enhanced reactivity, while also regions of higher curvature in CNHs are responsible for localized chemical reactivity due to the pyramidal distortion of the sp2 hybridized bonding. Hence, the chemical reactivity of CNHs is primarily localized around defect sites and near the nanohorn tips. Moreover, the absence of metal catalysts during the production of CNHs is beneficial, particularly when compared with carbon nanotubes, in which purification processes for removing nanosized metal impurities damage the graphitic structure. Specifically, this high purity of CNHs governs the chemical functionalization as compared to carbon nanotubes, in which chemical reactions occur on associated amorphous carbon and/ or π-stacked polyaromatic impurities. Considering all the above, it is understood that surface functionalization of CNHs proceeds faster and with higher yield than that of carbon nanotubes. Lastly, a novel technology for dismantling and individualizing the otherwise spherically aggregated dahlia-type CNHs, based on

Nikolaos Karousis received his B.Sc. degree in Chemistry in 1995 and his Ph.D. degree in Organic Chemistry in 2003, at the University of Ioannina, Greece. During 2004 and 2005, he was a postdoctoral fellow working on the synthesis of 1-aroyl- and 1-aroylmethylenepyrroles as potential intermediates of the pyrrolobenzodiazepine and pyrrolobenzodiazocin group of antitumor antibiotics. In 2006, he joined Dr. Tagmatarchis group at the Theoretical and Physical Chemistry Institute in the National Hellenic Research Foundation, and was introduced to the chemistry of carbon nanostructured materials. His current research interests lie in the chemical modification of carbon nanotubes, carbon nanohorns, and graphene-based materials, for nanotechnology applications. He has published 36 papers in refereed scientific journals and 2 book chapters, and made over 30 announcements at international scientific conferences. Irene Suarez-Martinez obtained her Ph.D. from University of Sussex in 2007 on density functional modelling of nuclear irradiated graphite, followed by a postdoctoral position with Dr. Ewels at the Institute of Materials, Nantes (France), investigating metal−nanotube interfaces. Since 2009 she has worked at Curtin University (Australia) studying the properties of amorphous carbons using molecular dynamics approaches. In 2010 she secured an Australian Research Council Postdoctoral Fellowship, and she currently holds a Future Fellowship from the Australian Research Council (2014−2018) at Curtin University. Her research interest is currently focused on atmospheric carbon nanostructures. Christopher P. Ewels is a CNRS Research Director at the Institute of Materials Jean Rouxel, Nantes, France, and a visiting researcher at Toyo University, Japan. He received his Ph.D. degree in 1997 from Exeter University, followed by postdoc at Sussex University, ONERA Paris, and a Marie Curie Individual Fellowship at Paris South University, before joining the CNRS in 2005. He coordinates the Marie SklodowskasCurie “Enabling Excellence” training network on nanocarbons, a project in collaboration with Dr. Tagmatarchis. He is active in science communication and has previously worked for the science communication charity “The Vega Science Trust”, producing science videos. His research focuses on atomic scale computer modelling and electron 4875


Chemical Reviews

Review

(18) Dresselhaus, M. S.; Dresselhaus, G.; Eklund, P. C. Science of Fullerenes and Carbon Nanotubes; Academic Press: San Diego, 1996; p 919. (19) Lammert, P. E.; Crespi, V. H. Graphene Cones: Classification by Fictitious Flux and Electronic Properties. Phys. Rev. B: Condens. Matter Mater. Phys. 2004, 69, 035406−035413. (20) Petsalakis, I. D.; Pagona, G.; Theodorakopoulos, G.; Tagmatarchis, N.; Yudasaka, M.; Iijima, S. Unbalanced Strain-directed Functionalization of Carbon Nanohorns: A Theoretical Investigation Based on Complementary Methods. Chem. Phys. Lett. 2006, 429, 194− 198. (21) Hashim, D. P.; Narayanan, N. T.; Romo-Herrera, J. M.; Cullen, D. A.; Hahm, M. G.; Lezzi, P.; Suttle, J. R.; Kelkhoff, D.; Munoz-Sandoval, E.; Ganguli, S.; et al. Covalently Bonded Three-Dimensional Carbon Nanotube Solids via Boron Induced Nanojunctions. Sci. Rep. 2012, 2, 363. (22) Ewels, C. P.; Heggie, M. I.; Briddon, P. R. Adatoms and Nanoengineering of Carbon. Chem. Phys. Lett. 2002, 351, 178−182. (23) Chopra, N. G.; Benedict, L. X.; Crespi, V. H.; Cohen, M. L.; Louie, S. G.; Zettl, A. Fully Collapsed Carbon Nanotubes. Nature 1995, 377, 135−138. (24) Yuge, R.; Ichihashi, T.; Miyawaki, J.; Yoshitake, T.; Iijima, S.; Yudasaka, M. Hidden Caves in an Aggregate of Single-Wall Carbon Nanohorns found by using Gd2O3 Probes. J. Phys. Chem. C 2009, 113, 2741−2744. (25) Xu, J. X.; Yudasaka, M.; Kouraba, S.; Sekido, M.; Yamamoto, Y.; Iijima, S. Single Wall Carbon Nanohorn as a Drug Carrier for Controlled Release. Chem. Phys. Lett. 2008, 461, 189−192. (26) Kasuya, D.; Yudasaka, M.; Takahashi, K.; Kokai, F.; Iijima, S. Selective Production of Single-Wall Carbon Nanohorn Aggregates and Their Formation Mechanism. J. Phys. Chem. B 2002, 106, 4947−4951. (27) Wang, H.; Chhowalla, M.; Sano, N.; Jia, S. Large-Scale Synthesis of Single-Walled Carbon Nanohorns by Submerged Arc. Nanotechnology 2004, 15, 546−550. (28) Heiberg-Andersen, H.; Skjeltorp, A. T.; Sattler, K. Carbon Nanocones: A Variety of Non-Crystalline Graphite. J. Non-Cryst. Solids 2008, 354, 5247−5249. (29) Charlier, J.-C.; Rignanese, G.-M. Electronic Structure of Carbon Nanocones. Phys. Rev. Lett. 2001, 86, 5970−5973. (30) Compernolle, S.; Kiran, B.; Chibotaru, L. F.; Nguyen, M. T.; Ceulemans, A. Ab Initio Study of Small Graphitic Cones with Triangle, Square, and Pentagon Apex. J. Chem. Phys. 2004, 121, 2326−2336. (31) Suarez-Martinez, I.; Mittal, J.; Allouche, H.; Pacheco, M.; Monthioux, M.; Razafinimanana, M.; Ewels, C. P. Fullerene Attachment to Sharp-Angle Nanocones Mediated by Covalent Oxygen Bridging. Carbon 2013, 54, 149−154. (32) Trzaskowski, B.; Jalbout, A. F.; Adamowicz, L. Functionalization of Carbon Nanocones by Free Radicals: a Theoretical Study. Chem. Phys. Lett. 2007, 444, 314−318. (33) Baei, M. T.; Peyghan, A. A.; Bagheri, Z. Carbon Nanocone as an Ammonia Sensor: DFT Studies. Struct. Chem. 2013, 24, 1099−1103. (34) Park, S.; Srivastava, D.; Cho, K. Generalized Chemical Reactivity of Curved Surfaces: Carbon Nanotubes. Nano Lett. 2003, 3, 1273−1277. (35) Yamaguchi, T.; Bandow, S.; Iijima, S. Origin of Giant Graphite Balls Produced Together with Carbon Nanohorns Prepared by Pulsed Arc-Discharge and a Method for their Removal. Carbon 2008, 46, 1110. (36) Harris, P. J. F.; Tsang, S. C.; Claridge, J. B.; Green, M. L. H. Highresolution Electron Microscopy Studies of a Microporous Carbon Produced by Arc-Evaporation. J. Chem. Soc., Faraday Trans. 1994, 90, 2799−2802. (37) Yamaguchi, T.; Bandow, S.; Iijima, S. Synthesis of Carbon Nanohorn Particles by Simple Pulsed Arc Discharge Ignited Between Pre-Heated Carbon Rods. Chem. Phys. Lett. 2004, 389, 181−185. (38) Li, N.; Wang, Z.; Zhao, K.; Shi, Z.; Gu, Z.; Xu, S. Synthesis of Single-Wall Carbon Nanohorns by Arc-Discharge in Air and Their Formation Mechanism. Carbon 2010, 48, 1580−1585. (39) Mirabile Gattia, D.; Vittori Antisari, M.; Marazzi, R.; Pilloni, L.; Contini, V.; Montone, A. Arc-Discharge Synthesis of Carbon Nano-

microscopy of nanoscale carbons, notably defect structures, chemical functionalization, and rational materials design. Nikos Tagmatarchis is Director of Research in the Theoretical and Physical Chemistry Institute at the National Hellenic Research Foundation, in Athens, Greece. His research interests focus on the chemistry of carbon-based nanostructured materials, particularly in the context of electron transfer processes for diverse nanotechnological applications. His accomplishments in the area are reflected in a plethora of publications, with multiple citations and numerous invitations at conferences. He has been recipient of the European Young Investigator Award (2004), Visiting Professor at the Chinese Academy of Sciences (2011), and Invited Fellow by the Japan Society for the Promotion of Science in Japan (2012−2013).

ACKNOWLEDGMENTS The authors wish to thank all of their colleagues whose names appear in the references for fruitful collaborations and stimulating discussions in the field of carbon nanohorns. This project has received funding from the Eurpean Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 642742. REFERENCES (1) Pagona, G.; Mountrichas, G.; Rotas, G.; Karousis, N.; Pispas, S.; Tagmatarchis, N. Properties, Applications and Functionalisation of Carbon Nanohorns. Int. J. Nanotechnol. 2009, 6, 176−195. (2) Zhu, S.; Xu, G. Single-walled Carbon Nanohorns and their Applications. Nanoscale 2010, 2, 2538−2549. (3) Saito, Y.; Nishikubo, K.; Kawabata, K.; Matsumoto, T. Carbon Nanocapsules and Single-layered Nanotubes Produced with Platinumgroup Metals (Ru, Rh, Pd, Os, Ir, Pt) by Arc Discharge. J. Appl. Phys. 1996, 80, 3062−3067. (4) Klein, D. J.; Balaban, A. T. The Eight Classes of Positive-Curvature Graphitic Nanocones. J. Chem. Inf. Model. 2006, 46, 307−320. (5) Suarez-Martinez, I.; Grobert, N.; Ewels, C. P. Nomenclature of sp2 Carbon Nanoforms. Carbon 2012, 50, 741−747. (6) Suarez-Martinez, I.; Grobert, N.; Ewels, C. P. Encyclopedia of Carbon Nanoforms. In Handbook of Carbon Nanomaterials Science and Applications; Pan Stanford Publishing Pte Ltd: Singapore, 2011; p 1−52. (7) Terrones, H. Curved Graphivte and its Mathematical Transformations. J. Math. Chem. 1994, 15, 143−156. (8) Golberg, D.; Bando, Y.; Huang, Y.; Terao, T.; Mitome, M.; Tang, C.; Zhi, C. Boron Nitride Nanotubes and Nanosheets. ACS Nano 2010, 4, 2979−2993. (9) Klein, D. J. Topo-Combinatoric Categorization of Quasi-Local Graphitic Defects. Phys. Chem. Chem. Phys. 2002, 4, 2099−2110. (10) Brinkmann, G.; Van Cleemput, N. Classification and Generation of Nanocones. Discrete Appl. Math. 2011, 159, 1528−1539. (11) https://github.com/yoosofan/single_wall_carbon_nanohorn (accessed on March 29, 2016). (12) Yoosofan, A.; Ashrafi, A. R. Automatic Generation of Adjacency Matrix of Single-Wall Carbon Nanohorn. Optoelectron. Adv. Mater. 2010, 4, 900−901. (13) Brinkmann, G.; Friedrichs, O. D.; Lisken, S.; Peeters, A.; Van Cleemput, N. CaGe - a Virtual Environment for Studying Some Special Classes of Plane Graphs - an Update. Match-Commun. Math. Co. 2010, 63, 533−552. (14) Kroto, H. W. The Stability of the Fullerenes Cn, with N = 24, 28, 32, 36, 50, 60 and 70. Nature 1987, 329, 529−531. (15) Han, J.; Jaffe, R. Energetics and Geometries of Carbon Nanoconic Tips. J. Chem. Phys. 1998, 108, 2817−2823. (16) Baldoni, M.; Sgamellotti, A.; Mercuri, F. Electronic Properties and Stability of Graphene Nanoribbons: an Interpretation Based on Clar Sextet Theory. Chem. Phys. Lett. 2008, 464, 202−207. (17) Wiener, H. Structural Determination of Paraffin Boiling Points. J. Am. Chem. Soc. 1947, 69, 17−20. 4876


Chemical Reviews

Review

horns and Multiwalled Carbon Nanotubes. Mater. Sci. Forum 2006, 518, 23−28. (40) Gattia, D. M.; Antisari, M. V.; Marazzi, R. AC Arc Discharge Synthesis of Single-Walled Nanohorns and Highly Convoluted Graphene Sheets. Nanotechnology 2007, 18, 255604−255608. (41) Vasu, K.; Pramoda, K.; Moses, K.; Govindaraj, A.; Rao, C. N. R. Single-Walled Nanohorns and Other Nanocarbons Generated by Submerged Arc Discharge Between Carbon Electrodes in Liquid Argon and Other Media. Mater. Res. Express 2014, 1, 015001. (42) Sano, N. Low-Cost Synthesis of Single-Walled Carbon Nanohorns Using the Arc in Water Method with Gas Injection. J. Phys. D: Appl. Phys. 2004, 37, L17−L20. (43) Hayashi, Y.; Iijima, T.; Kitamura, T.; Uesugi, Y.; Takahashi, H.; Unten, M.; Tokunaga, T. Low-Cost and Large-Scale Production of HighPurity Carbon Nanohorns by Arc in Water towards Environmental Devices. Paper TP-3-5, IEEE Nanotechnology Materials and Devices Conference (IEEE NMDC 2013), Oct 7−9, 2013, National Cheng Kung University: Tainan, Taiwan. (44) Iijima, S.; Yudasaka, M.; Yamada, R.; Bandow, S.; Suenaga, K.; Kokai, F.; Takahashi, K. Nano-Aggregates of Single-Walled Graphitic Carbon Nano-Horns. Chem. Phys. Lett. 1999, 309, 165−170. (45) Bonard, J. M.; Gaál, R.; Garaj, S.; Thien-Nga, L.; Forró, L.; Takahashi, K.; Kokai, F.; Yudasaka, M.; Iijima, S. Field Emission Properties of Carbon Nanohorn Films. J. Appl. Phys. 2002, 91, 10107− 10114. (46) Azami, T.; Kasuya, D.; Yoshitake, T.; Kubo, Y.; Yudasaka, M.; Ichihashi, T.; Iijima, S. Production of Small Single-Wall Carbon Nanohorns by CO2 Laser Ablation of Graphite in Ne-Gas Atmosphere. Carbon 2007, 45, 1364−1367. (47) Yuge, R.; Bandow, S.; Nakahara, K.; Yudasaka, M.; Toyama, K.; Yamaguchi, T.; Iijima, S.; Manako, T. Structure and Electronic States of Single-Wall Carbon Nanohorns Prepared Under Nitrogen Atmosphere. Carbon 2014, 75, 322−326. (48) Azami, T.; Kasuya, D.; Yuge, R.; Yudasaka, S.; Iijima; Tsutomu Yoshitake, A.; Yoshimi, K. Large-Scale Production of Single-Wall Carbon Nanohorns with High Purity. J. Phys. Chem. C 2008, 112, 1330− 1334. (49) Schiavon, M. Device and Method for Production of Carbon Nanotubes, Fullerene and their Derivatives. U.S. Patent 7,125,525; EP 1428794 (Filed 2003, granted 2006). (50) Pagura, C.; Barison, S.; Battiston, S.; Schiavon, M. Synthesis and Characterization of Single Wall Carbon Nanohorns Produced by Direct Vaporization of Graphite. Conference: Nanotechnology 2010: Advanced Materials, CNTs, Particles, Films and Composites - Technical Proceedings of the 2010 NSTI Nanotechnology Conference and Expo, NSTI-Nanotech; 2010, Volume: 1. (51) Pagura, C.; Barison, S.; Mortalò, C.; Comisso, N.; Schiavon, M. Large Scale and Low Cost Production of Pristine and Oxidized Single Wall Carbon Nanohorns as Material for Hydrogen Storage. Nanosci. Nanotechnol. Lett. 2012, 4, 160−164. (52) http://web.archive.org/web/20011111231950/http://www.ee. nec.de/News/Releases/pr283-01.html (accessed on April 5, 2016). (53) NEC. http://www.nec.com/en/global/prod/cnh/ (accessed on March 29, 2016). (54) Carbonium SRL. http://www.carbonium.it (accessed on March 29, 2016). (55) TIE GmbH. http://www.t-i-e.eu (accessed on March 29, 2016). (56) Barrett, S. NEC to Mass Produce Carbon Nanohorns. Fuel Cells Bulletin 2003, 9 (5), 1. (57) Yudasaka, M.; Iijima, S.; Crespi, V. H. Single-Wall Carbon Nanohorns and Nanocones. In Carbon Nanotubes. Topics in Applied Physics; Springer Berlin Heidelberg: Berlin, Heidelberg, 2007; pp 605− 629. (58) Kasuya, D.; Yudasaka, M. Growth Mechanisms of Carbon Nanotubes and Nanohorns. New Diamond 2004, 73 (2), 1. (59) Kawai, T.; Miyamoto, Y.; Sugino, O.; Koga, Y. Nanotube and Nanohorn Nucleation from Graphitic Patches: Tight-Binding Molecular-Dynamics Simulations. Phys. Rev. B: Condens. Matter Mater. Phys. 2002, 66, 033404−033404.

(60) Kokai, F.; Koshio, A.; Kasuya, D.; Hirahara, K.; Takahashi, K.; Nakayama, A.; Ishihara, M.; Koga, Y.; Iijima, S. Three Nanostructured Graphitic Particles and their Growth Mechanisms from High-Temperature Carbon Vapor Confined by Ar Gas. Carbon 2004, 42, 2515−2520. (61) Tsuzuku, T. Proc. 3rd Conf. on Carbon. Pergamon: New York, 1957; p 433. (62) Amelinckx, S.; Luyten, W.; Krekels, T. Conical, Helically Wound, Graphite Whiskers: a Limiting Member of the “Fullerenes? J. Cryst. Growth 1992, 121, 543−558. (63) Ge, M. H.; Sattler, K. Observation of Fullerene Cones. Chem. Phys. Lett. 1994, 220, 192−196. (64) Krishnan, A.; Dujardin, E.; Treacy, M.; Hugdahl, J.; Lynum, S.; Ebbesen, T. W. Graphitic Cones and the Nucleation of Curved Carbon Surfaces. Nature 1997, 388, 451−454. (65) Tsakadze, Z. L.; Levchenko, I.; Ostrikov, K.; Xu, S. PlasmaAssisted Self-Organized Growth of Uniform Carbon Nanocone Arrays. Carbon 2007, 45, 2022−2030. (66) Zhang, G. Tubular Graphite Cones. Science 2003, 300, 472−474. (67) Mani, R. C.; Li, X.; Sunkara, M. K.; Rajan, K. Carbon Nanopipettes. Nano Lett. 2003, 3, 671−673. (68) Liu, J.; Lin, W.; Chen, X.; Zhang, S.; Li, F.; Qian, Y. Fabrication of Hollow Carbon Cones. Carbon 2004, 42, 669−671. (69) Gogotsi, Y.; Dimovski, S.; Libera, J. A. Conical Crystals of Graphite. Carbon 2002, 40, 2263−2267. (70) Dumpala, S.; Bhimarasetti, G.; Gubbala, S.; Meduri, P. Carbon Microtubes and Conical Carbon Nanotubes. In Smart Materials; CRC Press: 2008; Chapter 22. (71) Zhao, Y.; Tang, Y.; Chen, Y.; Star, A. Corking Carbon Nanotube Cups with Gold Nanoparticles. ACS Nano 2012, 6, 6912−6921. (72) Saito, K.; Ohtani, M.; Fukuzumi, S. Electron-Transfer Reduction of Cup-Stacked Carbon Nanotubes Affording Cup-Shaped Carbons with Controlled Diameter and Size. J. Am. Chem. Soc. 2006, 128, 14216− 14217. (73) Allen, B. L.; Kichambare, P. D.; Star, A. Synthesis, Characterization, and Manipulation of Nitrogen-Doped Carbon Nanotube Cups. ACS Nano 2008, 2, 1914−1920. (74) Bandow, S.; Rao, A. M.; Sumanasekera, G. U.; Eklund, P. C.; Kokai, F.; Takahashi, K.; Yudasaka, M.; Iijima, S. Evidence for Anomalously Small Charge Transfer in Doped Single-Wall Carbon Nanohorn Aggregates with Li, K and Br. Appl. Phys. A: Mater. Sci. Process. 2000, 71, 561−564. (75) Berber, S.; Kwon, Y. K.; Tomanek, D. Electronic and Structural Properties of Carbon Nanohorns. Phys. Rev. B: Condens. Matter Mater. Phys. 2000, 62, R2291−R2294. (76) Kolesnikov, D. V.; Osipov, V. A. Electronic Structure of Carbon Nanohorns near the Fermi Level. JETP Lett. 2004, 79, 532−536. (77) Jordan, S. P.; Crespi, V. H. Theory of Carbon Nanocones: Mechanical Chiral Inversion of a Micron-Scale Three-Dimensional Object. Phys. Rev. Lett. 2004, 93, 255504. (78) Shenderova, O. A.; Lawson, B. L.; Areshkin, D.; Brenner, D. W. Predicted Structure and Electronic Properties of Individual Carbon Nanocones and Nanostructures Assembled From Nanocones. Nanotechnology 2001, 12, 191−197. (79) Zhang, S.; Yao, Z.; Zhao, S.; Zhang, E. Buckling and Competition of Energy and Entropy Lead Conformation of Single-Walled Carbon Nanocones. Appl. Phys. Lett. 2006, 89, 131923. (80) Murata, K.; Kaneko, K.; Steele, W. A.; Kokai, F.; Takahashi, K.; Kasuya, D.; Hirahara, K.; Yudasaka, M.; Iijima, S. Molecular Potential Structures of Heat-Treated Single-Wall Carbon Nanohorn Assemblies. J. Phys. Chem. B 2001, 105, 10210−10216. (81) Utsumi, S.; Miyawaki, J.; Tanaka, H.; Hattori, Y.; Itoi, T.; Ichikuni, N.; Kanoh, H.; Yudasaka, M.; Iijima, S.; Kaneko, K. Opening Mechanism of Internal Nanoporosity of Single-Wall Carbon Nanohorn. J. Phys. Chem. B 2005, 109, 14319−14324. (82) Fan, J.; Yudasaka, M.; Miyawaki, J.; Ajima, K.; Murata, K.; Iijima, S. Control of Hole Opening in Single-Wall Carbon Nanotubes and Single-Wall Carbon Nanohorns Using Oxygen. J. Phys. Chem. B 2006, 110, 1587−1591. 4877


Chemical Reviews

Review

(83) Yang, C. M.; Noguchi, H.; Murata, K.; Yudasaka, M.; Hashimoto, A.; Iijima, S.; Kaneko, K. Highly Ultramicroporous Single-Walled Carbon Nanohorn Assemblies. Adv. Mater. 2005, 17, 866−870. (84) Miyawaki, J.; Yuge, R.; Kawai, T.; Yudasaka, M.; Iijima, S. Evidence of Thermal Closing of Atomic-Vacancy Holes in Single-Wall Carbon Nanohorns. J. Phys. Chem. C 2007, 111, 1553−1555. (85) Fan, J.; Yuge, R.; Miyawaki, J.; Kawai, T.; Iijimia, S.; Yudasaka, M. Close-Open-Close Evolution of Holes at the Tips of Conical Graphenes of Single-Wall Carbon Nanohorns. J. Phys. Chem. C 2008, 112, 8600− 8603. (86) Bekyarova, E.; Kaneko, K.; Yudasaka, M.; Kasuya, D.; Iijima, S.; Huidobro, A.; Rodriguez-Reinoso, F. Controlled Opening of SingleWall Carbon Nanohorns by Heat Treatment in Carbon Dioxide. J. Phys. Chem. B 2003, 107, 4479−4484. (87) Urita, K.; Seki, S.; Utsumi, S.; Noguchi, D.; Kanoh, H.; Tanaka, H.; Hattori, Y.; Ochiai, Y.; Aoki, N.; Yudasaka, M.; et al. Effects of Gas Adsorption on the Electrical Conductivity of Single-Wall Carbon Nanohorns. Nano Lett. 2006, 6, 1325−1328. (88) Murata, K.; Kaneko, K.; Kokai, F.; Takahashi, K.; Yudasaka, M.; Iijima, S. Pore Structure of Single-Wall Carbon Nanohorn Aggregates. Chem. Phys. Lett. 2000, 331, 14−20. (89) Ohba, T.; Omori, T.; Kanoh, H.; Yudasaka, M.; Iijima, S.; Kaneko, K. Interstitial Nanopore Change of Single Wall Carbon Nanohorn Assemblies with High Temperature Treatment. Chem. Phys. Lett. 2004, 389, 332−336. (90) Bekyarova, E.; Hanzawa, Y.; Kaneko, K.; Silvestre-Albero, J.; Sepulveda-Escribano, A.; Rodriguez-Reinoso, F.; Kasuya, D.; Yudasaka, M.; Iijima, S. Cluster-Mediated Filling of Water Vapor in Intratube and Interstitial Nanospaces of Single-Wall Carbon Nanohorns. Chem. Phys. Lett. 2002, 366, 463−468. (91) Bekyarova, E.; Murata, K.; Yudasaka, M.; Kasuya, D.; Iijima, S.; Tanaka, H.; Kahoh, H.; Kaneko, K. Single-Wall Nanostructured Carbon for Methane Storage. J. Phys. Chem. B 2003, 107, 4681−4684. (92) Ambrosi, A.; Pumera, M. Nanographite Impurities Dominate Electrochemistry of Carbon Nanotubes. Chem. - Eur. J. 2010, 16, 10946−10949. (93) Verdejo, R.; Lamoriniere, S.; Cottam, B. Bismarck, A.; Shaffer, M. Removal of Oxidation Debris from Multi-Walled Carbon Nanotubes. Chem. Commun. (Cambridge, U. K.) 2007, 513−515. (94) Fogden, S.; Verdejo, R.; Cottam, B.; Shaffer, M. Purification of Single Walled Carbon Nanotubes: The Problem with Oxidation Debris. Chem. Phys. Lett. 2008, 460, 162−167. (95) Bellunato, A.; Arjmandi Tash, H.; Cesa, Y.; Schneider, G. F. Chemistry at the Edge of Graphene. ChemPhysChem 2016, 17, 785− 801. (96) Wong, C. H. A.; Sofer, Z.; Kubešová, M.; Kučera, J.; Matějková, S.; Pumera, M. Synthetic Routes Contaminate Graphene Materials with a Whole Spectrum of Unanticipated Metallic Elements. Proc. Natl. Acad. Sci. U. S. A. 2014, 111, 13774−13779. (97) Karousis, N.; Tagmatarchis, N.; Tasis, D. Current Progress on the Chemical Modification of Carbon Nanotubes. Chem. Rev. 2010, 110, 5366−5397. (98) Georgakilas, V.; Otyepka, M.; Bourlinos, A. B.; Chandra, V.; Kim, N.; Kemp, K. C.; Hobza, P.; Zboril, R.; Kim, K. S. Functionalization of Graphene: Covalent and Non-Covalent Approaches, Derivatives and Applications. Chem. Rev. 2012, 112, 6156−6214. (99) Georgakilas, V.; Perman, J. A.; Tucek, J.; Zboril, R. Broad Family of Carbon Nanoallotropes: Classification, Chemistry, and Applications of Fullerenes, Carbon Dots, Nanotubes, Graphene, Nanodiamonds, and Combined Superstructures. Chem. Rev. 2015, 115, 4744−4822. (100) Aryee, E.; Dalai, A.; Adjaye, J. Functionalization and Characterization of Carbon Nanohorns (CNHs) for Hydrotreating of Gas Oils. Top. Catal. 2014, 57, 796−805. (101) Bekyarova, E.; Kaneko, K.; Yudasaka, M.; Murata, K.; Kasuya, D.; Iijima, S. Micropore Development and Structure Rearrangement of Single-Wall Carbon Nanohorn Assemblies by Compression. Adv. Mater. 2002, 14, 973−975.

(102) Bekyarova, E.; Kaneko, K.; Kasuya, D.; Murata, K.; Yudasaka, M.; Iijima, S. Oxidation and Porosity Evaluation of Budlike Single-Wall Carbon Nanohorn Aggregates. Langmuir 2002, 18, 4138−4141. (103) Yudasaka, M.; Ichihashi, T.; Kasuya, D.; Kataura, H.; Iijima, S. Structure Changes of Single-Wall Carbon Nanotubes and Single-Wall Carbon Nanohorns Caused by Heat Treatment. Carbon 2003, 41, 1273−1280. (104) Zhu, J.; Yudasaka, M.; Zhang, M.; Fan, J.; Kasuya, D.; Iijima, S. Directed Assembly of Nanostructured Carbon Materials on to Patterned Polymer Surfaces. Appl. Phys. A: Mater. Sci. Process. 2005, 81, 449−452. (105) Pagona, G.; Tagmatarchis, N.; Fan, J.; Yudasaka, M.; Iijima, S. Cone-End Functionalization of Carbon Nanohorns. Chem. Mater. 2006, 18, 3918−3920. (106) Yang, C. M.; Kim, Y. J.; Endo, M.; Kanoh, H.; Yudasaka, M.; Iijima, S.; Kaneko, K. Nanowindow-Regulated Specific Capacitance of Supercapacitor Electrodes of Single-Wall Carbon Nanohorns. J. Am. Chem. Soc. 2007, 129, 20−21. (107) Yang, C.-M.; Kim, Y.-J.; Miyawaki, J.; Kim, Y. A.; Yudasaka, M.; Iijima, S.; Kaneko, K. Effect of the Size and Position of Ion-Accessible Nanoholes on the Specific Capacitance of Single-Walled Carbon Nanohorns for Supercapacitor Applications. J. Phys. Chem. C 2015, 119, 2935−2940. (108) Yuge, R.; Manako, T.; Nakahara, K.; Yasui, M.; Iwasa, S.; Yoshitake, T. The Production of an Electrochemical Capacitor Electrode Using Holey Single-Wall Carbon Nanohorns with High Specific Surface Area. Carbon 2012, 50, 5569−5573. (109) Khoerunnisa, F.; Fujimori, T.; Itoh, T.; Kanoh, H.; Ohba, T.; Yudasaka, M.; Iijima, S.; Kaneko, K. Electronically Modified Single Wall Carbon Nanohorns with Iodine Adsorption. Chem. Phys. Lett. 2011, 501, 485−490. (110) Comisso, N.; Berlouis, L. E. A.; Morrow, J.; Pagura, C. Changes in Hydrogen Storage Properties of Carbon Nano-Horns Submitted to Thermal Oxidation. Int. J. Hydrogen Energy 2010, 35, 9070−9081. (111) Murata, K.; Kaneko, K.; Steele, W. A.; Kokai, F.; Takahashi, K.; Kasuya, D.; Yudasaka, M.; Iijima, S. Porosity Evaluation of Intrinsic Intraparticle Nanopores of Single Wall Carbon Nanohorn. Nano Lett. 2001, 1, 197−199. (112) Tanaka, H.; Kanoh, H.; El-Merraoui, M.; Steele, W. A.; Yudasaka, M.; Iijima, S.; Kaneko, K. Quantum Effects on Hydrogen Adsorption in Internal Nanospaces of Single-Wall Carbon Nanohorns. J. Phys. Chem. B 2004, 108, 17457−17465. (113) Hashimoto, S.; Fujimori, T.; Tanaka, H.; Urita, K.; Ohba, T.; Kanoh, H.; Itoh, T.; Asai, M.; Sakamoto, H.; Niimura, S.; et al. Anomaly of CH4 Molecular Assembly Confined in Single-Wall Carbon Nanohorn Spaces. J. Am. Chem. Soc. 2011, 133, 2022−2024. (114) Krungleviciute, V.; Ziegler, C. A.; Banjara, S. R.; Yudasaka, M.; Iijima, S.; Migone, A. D. Neon and CO2 Adsorption on Open Carbon Nanohorns. Langmuir 2013, 29, 9388−9397. (115) Ohba, T.; Kanoh, H.; Kaneko, K. Superuniform Molecular Nanogate Fabrication on Graphene Sheets of Single Wall Carbon Nanohorns for Selective Molecular Separation of CO2 and CH4. Chem. Lett. 2011, 40, 1089−1091. (116) Ohba, T.; Kanoh, H.; Kaneko, K. Facilitation of Water Penetration through Zero-Dimensional Gates on Rolled-up Graphene by Cluster-Chain-Cluster Transformations. J. Phys. Chem. C 2012, 116, 12339−12345. (117) Pina-Salazar, E. Z.; Kaneko, K. Adsorption of Water Vapor on Mesoporosity-Controlled Singe Wall Carbon Nanohorn. Colloid Interface Sci. Commun. 2015, 5, 8−11. (118) Zhang, M. F.; Yudasaka, M.; Ajima, K.; Miyawaki, A.; Lijima, S. Light-Assisted Oxidation of Single-Wall Carbon Nanohorns for Abundant Creation of Oxygenated Groups that Enable Chemical Modifications with Proteins to Enhance Biocompatibility. ACS Nano 2007, 1, 265−272. (119) Xu, J.; Zhang, M.; Nakamura, M.; Iijima, S.; Yudasaka, M. Double Oxidation with Oxygen and Hydrogen Peroxide for HoleForming in Single Wall Carbon Nanohorns. Appl. Phys. A: Mater. Sci. Process. 2010, 100, 379−383. 4878


Chemical Reviews

Review

(120) Zhang, M.; Yang, M.; Bussy, C.; Iijima, S.; Kostarelos, K.; Yudasaka, M. Biodegradation of Carbon Nanohorns in Macrophage Cells. Nanoscale 2015, 7, 2834−2840. (121) Yoshida, S.; Sano, M. Microwave-Assisted Chemical Modification of Carbon Nanohorns: Oxidation and Pt Deposition. Chem. Phys. Lett. 2006, 433, 97−100. (122) Shu, C. Y.; Zhang, J. F.; Ge, J. C.; Sim, J. H.; Burke, B. G.; Williams, K. A.; Rylander, W. M.; Campbell, T.; Puretzky, A.; Rouleau, C.; et al. A Facile High-speed Vibration Milling Method to Waterdisperse Single-walled Carbon Nanohorns. Chem. Mater. 2010, 22, 347−351. (123) Huang, W.; Zhang, J. F.; Dorn, H. C.; Geohegan, D.; Zhang, C. M. Assembly of Single-Walled Carbon Nanohorn Supported Liposome Particles. Bioconjugate Chem. 2011, 22, 1012−1016. (124) Valentini, F.; Ciambella, E.; Conte, V.; Sabatini, L.; Ditaranto, N.; Cataldo, F.; Palleschi, G.; Bonchio, M.; Giacalone, F.; Syrgiannis, Z.; et al. Biosens. Bioelectron. 2014, 59, 94−98. (125) Sandanayaka, A. S. D.; Pagona, G.; Fan, J.; Tagmatarchis, N.; Yudasaka, M.; Iijima, S.; Araki, Y.; Ito, O. Photoinduced ElectronTransfer Processes of Carbon Nanohorns with Covalently Linked Pyrene Chromophores: Charge-Separation and Electron-Migration Systems. J. Mater. Chem. 2007, 17, 2540−2546. (126) Mountrichas, G.; Tagmatarchis, N.; Pispas, S. Functionalization of Carbon Nanohorns with Polyethylene Oxide: Synthesis and Incorporation in a Polymer Matrix. J. Nanosci. Nanotechnol. 2009, 9, 3775−3779. (127) Karousis, N.; Ichihashi, T.; Chen, S.; Shinohara, H.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Imidazolium Modified Carbon Nanohorns: Switchable Solubility and Stabilization of Metal Nanoparticles. J. Mater. Chem. 2010, 20, 2959−2964. (128) Zimmermann, K.; Inglefield, D., Jr.; Zhang, J.; Dorn, H.; Long, T.; Rylander, C.; Rylander, M. N. Single-Walled Carbon Nanohorns Decorated with Semiconductor Quantum Dots to Evaluate Intracellular Transport. J. Nanopart. Res. 2014, 16 (2078), 1−18. (129) Deng, S. Y.; Lei, J. P.; Huang, Y.; Yao, X. N.; Ding, L.; Ju, H. X. Electrocatalytic Reduction of Coreactant by Highly Loaded DendrimerEncapsulated Palladium Nanoparticles for Sensitive Electrochemiluminescent Immunoassay. Chem. Commun. 2012, 48, 9159−9161. (130) Zhao, C.; Wu, J.; Ju, H.; Yan, F. Multiplexed Electrochemical Immunoassay using Streptavidin/Nanogold/Carbon Nanohorn as a Signal Tag to Induce Silver Deposition. Anal. Chim. Acta 2014, 847, 37− 43. (131) Pagona, G.; Sandanayaka, A. S. D.; Araki, Y.; Fan, J.; Tagmatarchis, N.; Charalambidis, G.; Coutsolelos, A. G.; Boitrel, B.; Yudasaka, M.; Iijima, S.; et al. Covalent Functionalization of Carbon Nanohorns with Porphyrins: Nanohybrid Formation and Photoinduced Electron and Energy Transfer. Adv. Funct. Mater. 2007, 17, 1705−1711. (132) Pagona, G.; Sandanayaka, A. S. D.; Hasobe, T.; Charalambidis, G.; Coutsolelos, A. G.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Characterization and Photoelectrochemical Properties of Nanostructured Thin Film Composed of Carbon Nanohorns Covalently Functionalized with Porphyrins. J. Phys. Chem. C 2008, 112, 15735− 15741. (133) Cioffi, C.; Campidelli, S.; Sooambar, C.; Marcaccio, M.; Marcolongo, G.; Meneghetti, M.; Paolucci, D.; Paolucci, F.; Ehli, C.; Rahman, G. M. A.; et al. Synthesis, Characterization, and Photoinduced Electron Transfer in Functionalized Single Wall Carbon Nanohorns. J. Am. Chem. Soc. 2007, 129, 3938−3945. (134) Rotas, G.; Sandanayaka, A. S. D.; Tagmatarchis, N.; Ichihashi, T.; Yudasaka, M.; Iijima, S.; Ito, O. Terpyridine)copper(II)−Carbon Nanohorns: Metallo-nanocomplexes for Photoinduced Charge Separation. J. Am. Chem. Soc. 2008, 130, 4725−4731. (135) Zhang, M.; Murakami, T.; Ajima, K.; Tsuchida, K.; Sandanayaka, A. S. D.; Ito, O.; Iijima, S.; Yudasaka, M. Fabrication of ZnPc/Protein Nanohorns for Double Photodynamic and Hyperthermic Cancer Phototherapy. Proc. Natl. Acad. Sci. U. S. A. 2008, 105, 14773−14778. (136) Sandanayaka, A. S. D.; Ito, O.; Zhang, M.; Ajima, K.; Iijima, S.; Yudasaka, M.; Murakami, T.; Tsuchida, K. Photoinduced Electron

Transfer in Zinc Phthalocyanine Loaded on Single-Walled Carbon Nanohorns in Aqueous Solution. Adv. Mater. 2009, 21, 4366−4371. (137) Vizuete, M.; Gómez-Escalonilla, M. J.; Fierro, J. L. G.; Sandanayaka, A. S. D.; Hasobe, T.; Yudasaka, M.; Iijima, S.; Ito, O.; Langa, F. A Carbon Nanohorn-Porphyrin Supramolecular Assembly for Photoinduced Electron-Transfer Processes. Chem. - Eur. J. 2010, 16, 10752−10763. (138) Vizuete, M.; Gomez-Escalonilla, M. J.; Fierro, J. L. G.; Ohkubo, K.; Fukuzumi, S.; Yudasaka, M.; Iijima, S.; Nierengarten, J.-F.; Langa, F. Photoinduced Electron Transfer in a Carbon Nanohorn-C60 Conjugate. Chem. Sci. 2014, 5, 2072−2080. (139) Tahara, Y.; Miyawaki, J.; Zhang, M. F.; Yang, M.; Waga, I.; Iijima, S.; Irie, H.; Yudasaka, M. Histological Assessments for Toxicity and Functionalization-Dependent Biodistribution of Carbon Nanohorns. Nanotechnology 2011, 22, 265106 (8 pages). (140) Miyako, E.; Deguchi, T.; Nakajima, Y.; Yudasaka, M.; Hagihara, Y.; Horie, M.; Shichiri, M.; Higuchi, Y.; Yamashita, F.; Hashida, M.; et al. Photothermic Regulation of Gene Expression Triggered by LaserInduced Carbon Nanohorns. Proc. Natl. Acad. Sci. U. S. A. 2012, 109, 7523−7528. (141) Depan, D.; Misra, R. D. K. Processing-Structure-Functional Property Relationship in Organic-Inorganic Nanostructured Scaffolds for Bone-Tissue Engineering: The Response of Preosteoblasts. J. Biomed. Mater. Res., Part A 2012, 100A, 3080−3091. (142) Li, J.; He, Y.; He, Z.; Zeng, P.; Xu, S. Synthesis of NaYF4:Yb,Er/ Single-Walled Carbon Nanohorns Nanocomposite and its Application as Cells Label. Anal. Biochem. 2012, 428, 4−6. (143) Murakami, T.; Ajima, K.; Miyawaki, J.; Yudasaka, M.; Iijima, S.; Shiba, K. Drug-Loaded Carbon Nanohorns: Adsorption and Release of Dexamethasone in Vitro. Mol. Pharmaceutics 2004, 1, 399−405. (144) Ajima, K.; Yudasaka, M.; Murakami, T.; Maigne, A.; Shiba, K.; Ijima, S. Carbon Nanohorns as Anticancer Drug Carriers. Mol. Pharmaceutics 2005, 2, 475−480. (145) Ajima, K.; Murakami, T.; Mizoguchi, Y.; Tsuchida, K.; Ichihashi, T.; Iijima, S.; Yudasaka, M. Enhancement of In Vivo Anticancer Effects of Cisplatin by Incorporation Inside Single-Wall Carbon Nanohorns. ACS Nano 2008, 2, 2057−2064. (146) Yamazaki, K.; Shinke, K.; Ogino, T. Selective Adsorption of Bilirubin Against Albumin to Oxidized Single-Wall Carbon Nanohorns. Colloids Surf., B 2013, 112, 103−107. (147) Murakami, T.; Fan, J.; Yudasaka, M.; Iijima, S.; Shiba, K. Solubilization of Single-Wall Carbon Nanohorns Using a PEG− Doxorubicin Conjugate. Mol. Pharmaceutics 2006, 3, 407−414. (148) Ma, X.; Shu, C.; Guo, J.; Pang, L.; Su, L.; Fu, D.; Zhong, W. Targeted Cancer Therapy Based on Single-Wall Carbon Nanohorns with Doxorubicin in Vitro And in Vivo. J. Nanopart. Res. 2014, 16, 1−14. (149) Murakami, T.; Sawada, H.; Tamura, G.; Yudasaka, M.; Iijima, S.; Tsucbida, K. Water-Dispersed Single-Wall Carbon Nanohorns as Drug Carriers for Local Cancer Chemotherapy. Nanomedicine 2008, 3, 453− 463. (150) Matsumura, S.; Ajima, K.; Yudasaka, M.; Iijima, S.; Shiba, K. Dispersion of Cisplatin-Loaded Carbon Nanohorns with A Conjugate Comprised Of An Artificial Peptide Aptamer And Polyethylene Glycol. Mol. Pharmaceutics 2007, 4, 723−729. (151) Li, N.; Zhao, Q.; Shu, C.; Ma, X.; Li, R.; Shen, H.; Zhong, W. Targeted Killing of Cancer Cells in Vivo And in Vitro with IGF-IR Antibody-Directed Carbon Nanohorns Based Drug Delivery. Int. J. Pharm. 2015, 478, 644−654. (152) Zhao, Q.; Li, N.; Shu, C.; Li, R.; Ma, X.; Li, X. Docetaxel-Loaded Single-Wall Carbon Nanohorns Using Anti-VEGF Antibody as a Targeting Agent: Characterization, in Vitro and in Vivo Antitumor Activity. Wang, R.; Zhong, W. J. Nanopart. Res. 2015, 17 (207), 1−14. (153) Qian, R. C.; Ding, L.; Bao, L.; He, S. J.; Ju, H. X. In Situ Electrochemical Assay of Cell Surface Sialic Acids Featuring Highly Efficient Chemoselective Recognition And A Dual-Functionalized Nanohorn Probe. Chem. Commun. 2012, 48, 3848−3850. (154) Zhu, S. Y.; Han, S.; Zhang, L.; Parveen, S.; Xu, G. B. A Novel Fluorescent Aptasensor Based on Single-Walled Carbon Nanohorns. Nanoscale 2011, 3, 4589−4592. 4879


Chemical Reviews

Review

(155) Zhu, S.; Liu, Z.; Hu, L.; Yuan, Y.; Xu, G. Turn-On Fluorescence Sensor Based on Single-Walled-Carbon-Nanohorn−Peptide Complex for the Detection of Thrombin. Chem. - Eur. J. 2012, 18, 16556−16561. (156) Ojeda, I.; Garcinuño, B.; Moreno-Guzmán, M.; GonzálezCortés, A.; Yudasaka, M.; Iijima, S.; Langa, F.; Yáñez-Sedeño, P.; Pingarrón, J. M. Carbon Nanohorns as a Scaffold for the Construction of Disposable Electrochemical Immunosensing Platforms. Application to the Determination of Fibrinogen in Human Plasma and Urine. Anal. Chem. 2014, 86, 7749−7756. (157) Bekyarova, E.; Hashimoto, A.; Yudasaka, M.; Hattori, Y.; Murata, K.; Kanoh, H.; Kasuya, D.; Iijima, S.; Kaneko, K. Palladium Nanoclusters Deposited on Single-Walled Carbon Nanohorns. J. Phys. Chem. B 2005, 109, 3711−3714. (158) Itoh, T.; Danjo, H.; Sasaki, W.; Urita, K.; Bekyarova, E.; Arai, M.; Imamoto, T.; Yudasaka, M.; Iijima, S.; Kanoh, H.; et al. Catalytic Activities of Pd-Tailored Single Wall Carbon Nanohorns. Carbon 2008, 46, 172−175. (159) Giasafaki, D.; Charalambopoulou, G.; Tampaxis, C.; Mirabile Gattia, D.; Montone, A.; Barucca, G.; Steriotis, T. Hydrogen Storage Properties of Pd-Doped Thermally Oxidized Single Wall Carbon Nanohorns. J. Alloys Compd. 2015, 645 (Supplement 1), S485−S489. (160) Liu, Y.; Brown, C. M.; Neumann, D. A.; Geohegan, D. B.; Puretzky, A. A.; Rouleau, C. M.; Hu, H.; Styers-Barnett, D.; Krasnov, P. O.; Yakobson, B. I. Metal-Assisted Hydrogen Storage on Pt-Decorated Single-Walled Carbon Nanohorns. Carbon 2012, 50, 4953−4964. (161) Utsumi, S.; Urita, K.; Kanoh, H.; Yudasaka, M.; Suenaga, K.; Iijima, S.; Kaneko, K. Preparing a Magnetically Responsive Single-Wall Carbon Nanohorn Colloid by Anchoring Magnetite Nanoparticles. J. Phys. Chem. B 2006, 110, 7165−7170. (162) Miyawaki, J.; Yudasaka, M.; Imai, H.; Yorimitsu, H.; Isobe, H.; Nakamura, E.; Iijima, S. In Vivo Magnetic Resonance Imaging of SingleWalled Carbon Nanohorns by Labeling with Magnetite Nanoparticles. Adv. Mater. 2006, 18, 1010−1014. (163) Chechetka, S. A.; Pichon, B.; Zhang, M.; Yudasaka, M.; BéginColin, S.; Bianco, A.; Miyako, E. Multifunctional Carbon Nanohorn Complexes for Cancer Treatment. Chem. - Asian J. 2015, 10, 160−165. (164) Deshmukh, A. B.; Shelke, M. V. Synthesis and Electrochemical Performance of a Single Walled Carbon Nanohorn-Fe3O4 Nanocomposite Supercapacitor Electrode. RSC Adv. 2013, 3, 21390−21393. (165) Tu, W. W.; Lei, J. P.; Ding, L.; Ju, H. X. Sandwich Nanohybrid of Single-Walled Carbon Nanohorns-TiO2-Porphyrin fFor Electrocatalysis and Amperometric Biosensing towards Chloramphenicol. Chem. Commun. 2009, 4227−4229. (166) Ajima, K.; Yudasaka, M.; Suenaga, K.; Kasuya, D.; Azami, T.; Iijima, S. Material Storage Mechanism in Porous Nanocarbon. Adv. Mater. 2004, 16, 397−401. (167) Yuge, R.; Yudasaka, M.; Miyawaki, J.; Kubo, Y.; Ichihashi, T.; Imai, H.; Nakamura, E.; Isobe, H.; Yorimitsu, H.; Iijima, S. Controlling the Incorporation and Release of C60 in Nanometer-Scale Hollow Spaces inside Single-Wall Carbon Nanohorns. J. Phys. Chem. B 2005, 109, 17861−17867. (168) Miyawaki, J.; Yudasaka, M.; Yuge, R.; Iijima, S. Organic-VaporInduced Repeatable Entrance and Exit of C60 Into/From Single-Wall Carbon Nanohorns at Room Temperature. J. Phys. Chem. C 2007, 111, 9719−9722. (169) Zhang, J. F.; Ge, J. C.; Shultz, M. D.; Chung, E. N.; Singh, G.; Shu, C. Y.; Fatouros, P. P.; Henderson, S. C.; Corwin, F. D.; Geohegan, D. B.; et al. In Vitro and in Vivo Studies of Single-Walled Carbon Nanohorns with Encapsulated Metallofullerenes and Exohedrally Functionalized Quantum Dots. Nano Lett. 2010, 10, 2843−2848. (170) Yuge, R.; Ichihashi, T.; Shimakawa, Y.; Kubo, Y.; Yudasaka, M.; Iijima, S. Preferential Deposition of Pt Nanoparticles inside SingleWalled Carbon Nanohorns. Adv. Mater. 2004, 16, 1420−1423. (171) Hashimoto, A.; Yorimitsu, H.; Ajima, K.; Suenaga, K.; Isobe, H.; Miyawaki, A.; Yudasaka, M.; Iijima, S.; Nakamura, E. Selective Deposition of a Gadolinium(III) Cluster in a Hole Opening of SingleWall Carbon Nanohorn. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 8527− 8530.

(172) Miyawaki, J.; Yudasaka, M.; Imai, H.; Yorimitsu, H.; Isobe, H.; Nakamura, E.; Iijima, S. Synthesis of Ultrafine Gd2O3 Nanoparticles Inside Single-Wall Carbon Nanohorns. J. Phys. Chem. B 2006, 110, 5179−5181. (173) Miyawaki, J.; Matsumura, S.; Yuge, R.; Murakami, T.; Sato, S.; Tomida, A.; Tsuruo, T.; Ichihashi, T.; Fujinami, T.; Irie, H.; et al. Biodistribution and Ultrastructural Localization of Single-Walled Carbon Nanohorns Determined In Vivo with Embedded Gd2O3 Labels. ACS Nano 2009, 3, 1399−1406. (174) Yuge, R.; Yudasaka, M.; Miyawaki, J.; Kubo, Y.; Isobe, H.; Yorimitsu, H.; Nakamura, E.; Iijima, S. Plugging and Unplugging Holes of Single-Wall Carbon Nanohorns. J. Phys. Chem. C 2007, 111, 7348− 7351. (175) Yang, M.; Zhang, M.; Kunioka, M.; Yuge, R.; Ichihashi, T.; Iijima, S.; Yudasaka, M. Photothermal Conversion of Carbon Nanohorns Enhancing Caprolactone Polymerization. Carbon 2015, 83, 15−20. (176) Kosaka, M.; Kuroshima, S.; Kobayashi, K.; Sekino, S.; Ichihashi, T.; Nakamura, S.; Yoshitake, T.; Kubo, Y. Single-Wall Carbon Nanohorns Supporting Pt Catalyst in Direct Methanol Fuel Cells. J. Phys. Chem. C 2009, 113, 8660−8667. (177) Unni, S. M.; Ramadas, S.; Illathvalappil, R.; Bhange, S. N.; Kurungot, S. Surface-Modified Single Wall Carbon Nanohorn as an Effective Electrocatalyst for Platinum-Free Fuel Cell Cathodes. J. Mater. Chem. A 2015, 3, 4361−4367. (178) Unni, S. M.; Bhange, S. N.; Illathvalappil, R.; Mutneja, N.; Patil, K. R.; Kurungot, S. Nitrogen-Induced Surface Area and Conductivity Modulation of Carbon Nanohorn and Its Function as an Efficient MetalFree Oxygen Reduction Electrocatalyst for Anion-Exchange Membrane Fuel Cells. Small 2015, 11, 352−360. (179) Sano, N. Separated Syntheses of Gd-Hybridized Single-Wall Carbon Nanohorns, Single-Wall Nanotubes and Multi-Wall Nanostructures by Arc Discharge in Water With Support of Gas Injection. Carbon 2005, 43, 450−453. (180) Sano, N.; Ukita, S. One-Step Synthesis of Pt-Supported Carbon Nanohorns for Fuel Cell Electrode by Arc Plasma in Liquid Nitrogen. Mater. Chem. Phys. 2006, 99, 447−450. (181) Poonjarernsilp, C.; Sano, N.; Charinpanitkul, T.; Mori, H.; Kikuchi, T.; Tamon, H. Single-Step Synthesis and Characterization of Single-Walled Carbon Nanohorns Hybridized with Pd Nanoparticles using N2 Gas-Injected Arc-In-Water Method. Carbon 2011, 49, 4920− 4927. (182) Sano, N.; Taniguchi, K.; Tamon, H. Hydrogen Storage in Porous Single-Walled Carbon Nanohorns Dispersed with Pd−Ni Alloy Nanoparticles. J. Phys. Chem. C 2014, 118, 3402−3408. (183) Sano, N.; Taniguchi, K.; Tamon, H. Gas Flow Rate in the GasInjected Arc-in-Water Method as a Critical Factor to Synthesize HighDispersion Pd-Ni Alloy Nanoparticles in Single-Walled Carbon Nanohorns. J. Chem. Eng. Jpn. 2014, 47, 821−826. (184) Sano, N.; Suntornlohanakul, T.; Poonjarernsilp, C.; Tamon, H.; Charinpanitkul, T. Controlled Syntheses of Various Palladium Alloy Nanoparticles Dispersed in Single-Walled Carbon Nanohorns by OneStep Formation Using an Arc Discharge Method. Ind. Eng. Chem. Res. 2014, 53, 4732−4738. (185) Sano, N.; Himara, D.; Tamon, H. Simultaneous Enhancement in Porosity and Magnetic Property of Fe-Dispersing Single-Walled Carbon Nanohorns by Oxidation using CO2. Chem. Eng. J. (Amsterdam, Neth.) 2015, 271, 43−49. (186) Hattori, Y.; Kanoh, H.; Okino, F.; Touhara, H.; Kasuya, D.; Yudasaka, M.; Iijima, S.; Kaneko, K. Direct Thermal Fluorination of Single Wall Carbon Nanohorns. J. Phys. Chem. B 2004, 108, 9614−9618. (187) Isobe, H.; Tanaka, T.; Maeda, R.; Noiri, E.; Solin, N.; Yudasaka, M.; Iijima, S.; Nakamura, E. Preparation, Purification, Characterization, and Cytotoxicity Assessment of Water-Soluble, Transition-Metal-Free Carbon Nanotube Aggregates. Angew. Chem., Int. Ed. 2006, 45, 6676− 6680. (188) Nakamura, E.; Koshino, M.; Tanaka, T.; Niimi, Y.; Harano, K.; Nakamura, Y.; Isobe, H. Imaging of Conformational Changes of Biotinylated Triamide Molecules Covalently Bonded to a Carbon Nanotube Surface. J. Am. Chem. Soc. 2008, 130, 7808−7809. 4880


Chemical Reviews

Review

Nanohorns Via [2 + 1] Nitrenes Cycloaddition. Chem. Commun. (Cambridge, U. K.) 2011, 47, 1604−1606. (208) Chronopoulos, D.; Karousis, N.; Ichihashi, T.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Benzyne Cycloaddition onto Carbon Nanohorns. Nanoscale 2013, 5, 6388−6394. (209) Zhu, J.; Kase, D.; Shiba, K.; Kasuya, D.; Yudasaka, M.; Iijima, S. Binary Nanomaterials Based on Nanocarbons: A Case for Probing Carbon Nanohorns’ Biorecognition Properties. Nano Lett. 2003, 3, 1033−1036. (210) Zhu, J.; Yudasaka, M.; Zhang, M. F.; Kasuya, D.; Iijima, S. Surface Modification Approach to the Patterned Assembly of Single-Walled Carbon Nanomaterials. Nano Lett. 2003, 3, 1239−1243. (211) Pagona, G.; Fan, J.; Maigne, A.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Aqueous Carbon Nanohorn-Pyrene-Porphyrin Nanoensembles: Controlling Charge-Transfer Interactions. Diamond Relat. Mater. 2007, 16, 1150−1153. (212) Pagona, G.; Sandanayaka, A. S. D.; Maigné, A.; Fan, J.; Papavassiliou, G. C.; Petsalakis, I. D.; Steele, B. R.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N.; et al. Photoinduced Electron Transfer on Aqueous Carbon Nanohorn−Pyrene−Tetrathiafulvalene Architectures. Chem. Eur. J. 2007, 13, 7600−7607. (213) Pagona, G.; Sandanayaka, A. S. D.; Araki, Y.; Fan, J.; Tagmatarchis, N.; Yudasaka, M.; Iijima, S.; Ito, O. Electronic Interplay on Illuminated Aqueous Carbon Nanohorn-Porphyrin Ensembles. J. Phys. Chem. B 2006, 110, 20729−20732. (214) Jiang, B.-P.; Hu, L.-F.; Shen, X.-C.; Ji, S.-C.; Shi, Z.; Liu, C.-J.; Zhang, L.; Liang, H. One-Step Preparation of a Water-Soluble Carbon Nanohorn/Phthalocyanine Hybrid for Dual-Modality Photothermal and Photodynamic Therapy. ACS Appl. Mater. Interfaces 2014, 6, 18008−18017. (215) Dai, H.; Yang, C. P.; Ma, X. L.; Lin, Y. Y.; Chen, G. N. A Highly Sensitive and Selective Sensing ECL Platform for Naringin Based On Beta-Cyclodextrin Functionalized Carbon Nanohorns. Chem. Commun. 2011, 47, 11915−11917. (216) Li, J.; He, Z.; Guo, C.; Wang, L.; Xu, S. Synthesis of Carbon Nanohorns/Chitosan/Quantum Dots Nanocomposite and its Applications in Cells Labeling and in Vivo Imaging. J. Lumin. 2014, 145, 74−80. (217) Mountrichas, G.; Ichihashi, T.; Pispas, S.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Solubilization of Carbon Nanohorns by Block Polyelectrolyte Wrapping and Templated Formation of Gold Nanoparticles. J. Phys. Chem. C 2009, 113, 5444−5449. (218) Yang, M.; Wada, M.; Zhang, M.; Kostarelos, K.; Yuge, R.; Iijima, S.; Masuda, M.; Yudasaka, M. A High Poly(Ethylene Glycol) Density on Graphene Nanomaterials Reduces the Detachmentof Lipid−Poly(Ethylene Glycol) and Macrophage Uptake. Acta Biomater. 2013, 9, 4744−4753. (219) Chen, D.; Wang, C.; Nie, X.; Li, S.; Li, R.; Guan, M.; Liu, Z.; Chen, C.; Wang, C.; Shu, C.; Wan, L. Photoacoustic Imaging Guided Near-Infrared Photothermal Therapy Using Highly Water-Dispersible Single-Walled Carbon Nanohorns as Theranostic Agents. Adv. Funct. Mater. 2014, 24, 6621−6628. (220) Liu, X. Q.; Li, H. J.; Wang, F. A.; Zhu, S. Y.; Wang, Y. L.; Xu, G. B. Functionalized Single-Walled Carbon Nanohorns for Electrochemical Biosensing. Biosens. Bioelectron. 2010, 25, 2194−2199. (221) Dai, H.; Gong, L.; Xu, G.; Li, Y.; Li, X.; Zhang, Q.; Lin, Y. Double-Amplified Photoelectrochemical Response of Hematin on Carbon Nanohorns Superstructure Support for Ultrasensitive Detection of Roxarsone. Sens. Actuators, B 2015, 215, 45−51. (222) Bhattacharjee, S.; Samanta, S. K.; Moitra, P.; Pramoda, K.; Kumar, R.; Bhattacharya, S.; Rao, C. N. R. Nanocomposite Made of an Oligo(p-phenylenevinylene)-Based Trihybrid Thixotropic Metallo(organo)gel Comprising Nanoscale Metal−Organic Particles, Carbon Nanohorns, and Silver Nanoparticles. Chem. - Eur. J. 2015, 21, 5467− 5476. (223) Yoshitake, T.; Shimakawa, Y.; Kuroshima, S.; Kimura, H.; Ichihashi, T.; Kubo, Y.; Kasuya, D.; Takahashi, K.; Kokai, F.; Yudasaka, M.; et al. Preparation of Fine Platinum Catalyst Supported on SingleWall Carbon Nanohorns for Fuel Cell Application. Phys. B 2002, 323, 124−126.

(189) Harano, K.; Homma, T.; Niimi, Y.; Koshino, M.; Suenaga, K.; Leibler, L.; Nakamura, E. Heterogeneous Nucleation of Organic Crystals Mediated by Single-Molecule Templates. Nat. Mater. 2012, 11, 877−881. (190) Sandanayaka, A. S. D.; Ito, O.; Tanaka, T.; Isobe, H.; Nakamura, E.; Yudasaka, M.; Iijima, S. Photoinduced Electron Transfer of Nanohybrids of Carbon Nanohorns with Amino Groups and Tetrabenzoic Acid Porphyrin in Aqueous Media. New J. Chem. 2009, 33, 2261−2266. (191) Lacotte, S.; Garcia, A.; Decossas, M.; Al-Jamal, W. T.; Li, S.; Kostarelos, K.; Muller, S.; Prato, M.; Dumortier, H.; Bianco, A. Interfacing Functionalized Carbon Nanohorns with Primary Phagocytic Cells. Adv. Mater. 2008, 20, 2421−2426. (192) Miyako, E.; Russier, J.; Mauro, M.; Cebrian, C.; Yawo, H.; Ménard-Moyon, C.; Hutchison, J. A.; Yudasaka, M.; Iijima, S.; De Cola, L.; Bianco, A. Photofunctional Nanomodulators for Bioexcitation. Angew. Chem., Int. Ed. 2014, 53, 13121−13125. (193) Mountrichas, G.; Pispas, S.; Tagmatarchis, N. Grafting Living Polymers onto Carbon Nanohorns. Chem. - Eur. J. 2007, 13, 7595− 7599. (194) Mountrichas, G.; Pispas, S.; Ichihasi, T.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Polymer Covalent Functionalization of Carbon Nanohorns uing Bulk Free Radical Polymerization. Chem. - Eur. J. 2010, 16, 5927−5933. (195) Tagmatarchis, N.; Maigne, A.; Yudasaka, M.; Iijima, S. Functionalization of Carbon Nanohorns with Azomethine Ylides: towards Solubility Enhancement and Electron-Transfer Processes. Small 2006, 2, 490−494. (196) Cioffi, C.; Campidelli, S.; Brunetti, F. G.; Meneghetti, M.; Prato, M. Functionalisation of Carbon Nanohorns. Chem. Commun. 2006, 2129−2131. (197) Pagona, G.; Rotas, G.; Petsalakis, I. D.; Theodorakopoulos, G.; Fan, J.; Maigne, A.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Soluble Functionalized Carbon Nanohorns. J. Nanosci. Nanotechnol. 2007, 7, 3468−3472. (198) Pagona, G.; Karousis, N.; Tagmatarchis, N. Aryl Diazonium Functionalization of Carbon Nanohorns. Carbon 2008, 46, 604−610. (199) Pagona, G.; Katerinopoulos, H. E.; Tagmatarchis, N. Synthesis, Characterization, and Photophysical Properties of a Carbon NanohornCoumarin Hybrid Material. Chem. Phys. Lett. 2011, 516, 76−81. (200) Karousis, N.; Sato, Y.; Suenaga, K.; Tagmatarchis, N. Direct Evidence for Covalent Functionalization of Carbon Nanohorns by High-Resolution Electron Microscopy Imaging of C60 Conjugated onto their Skeleton. Carbon 2012, 50, 3909−3914. (201) Vizuete, M.; Gomez-Escalonilla, M. J.; Fierro, J. L. G.; Yudasaka, M.; Iijima, S.; Vartanian, M.; Iehl, J.; Nierengarten, J. F.; Langa, F. A Soluble Hybrid Material Combining Carbon Nanohorns and C60. Chem. Commun. 2011, 47, 12771−12773. (202) Economopoulos, S. P.; Karousis, N.; Rotas, G.; Pagona, G.; Tagmatarchis, N. Microwave-assisted Functionalization of Carbon Nanostructured Materials. Curr. Org. Chem. 2011, 15, 1121−1132. (203) Rubio, N.; Herrero, M. A.; Meneghetti, M.; Diaz-Ortiz, A.; Schiavon, M.; Prato, M.; Vazquez, E. Efficient Functionalization of Carbon Nanohorns via Microwave Irradiation. J. Mater. Chem. 2009, 19, 4407−4413. (204) Guerra, J.; Herrero, M. A.; Carrion, B.; Perez-Martinez, F. C.; Lucio, M.; Rubio, N.; Meneghetti, M.; Prato, M.; Cena, V.; Vazquez, E. Carbon Nanohorns Functionalized with Polyamidoamine Dendrimers as Efficient Biocarrier Materials for Gene Therapy. Carbon 2012, 50, 2832−2844. (205) Pagona, G.; Zervaki, G. E.; Sandanayaka, A. S. D.; Ito, O.; Charalambidis, G.; Hasobe, T.; Coutsolelos, A. G.; Tagmatarchis, N. Carbon Nanohorn−Porphyrin Dimer Hybrid Material for Enhancing Light-Energy Conversion. J. Phys. Chem. C 2012, 116, 9439−9449. (206) Economopoulos, S. P.; Pagona, G.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Solvent-free microwave-assisted Bingel reaction in carbon nanohorns. J. Mater. Chem. 2009, 19, 7326−7331. (207) Karousis, N.; Ichihashi, T.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Microwave-Assisted Functionalization of Carbon 4881


Chemical Reviews

Review

Toxicity by this Neglected Mechanism. Toxicol. Appl. Pharmacol. 2014, 280, 117−126. (243) Miyawaki, J.; Yudasaka, M.; Azami, T.; Kubo, Y.; Iijima, S. Toxicity of Single-Walled Carbon Nanohorns. ACS Nano 2008, 2, 213− 226. (244) Lynch, R. M.; Voy, B. H.; Glass, D. F.; Mahurin, S. M.; Zhao, B.; Hu, H.; Saxton, A. M.; Donnell, R. L.; Cheng, M.-D. Assessing the Pulmonary Toxicity of Single-Walled Carbon Nanohorns. Nanotoxicology 2007, 1, 157−166. (245) Fan, X. B.; Tan, J.; Zhang, G. L.; Zhang, F. B. Isolation of Carbon Nanohorn Assemblies and Their Potential for Intracellular Delivery. Nanotechnology 2007, 18, 195103−9. (246) Moschino, V.; Nesto, N.; Barison, S.; Agresti, F.; Colla, L.; Fedele, L.; Da Ros, L. A Preliminary Investigation on Nanohorn Toxicity in Marine Mussels and Polychaetes. Sci. Total Environ. 2014, 468−469, 111−119. (247) Wen, D.; Deng, L.; Zhou, M.; Guo, S. J.; Shang, L.; Xu, G. B.; Dong, S. J. A Biofuel Cell with a Single-Walled Carbon Nanohorn-Based Bioanode Operating at Physiological Condition. Biosens. Bioelectron. 2010, 25, 1544−1547. (248) Liu, X. Q.; Shi, L. H.; Niu, W. X.; Li, H. J.; Xu, G. B. Amperometric Glucose Biosensor Based on Single-Walled Carbon Nanohorns. Biosens. Bioelectron. 2008, 23, 1887−1890. (249) Shi, L. H.; Liu, X. Q.; Niu, W. X.; Li, H. J.; Han, S.; Chen, J.; Xu, G. B. Hydrogen peroxide biosensor based on direct electrochemistry of soybean Peroxidase immobilized on single-walled carbon nanohorn modified electrode. Biosens. Bioelectron. 2009, 24, 1159−1163. (250) Yang, F.; Han, J.; Zhuo, Y.; Yang, Z.; Chai, Y.; Yuan, R. Highly Sensitive Impedimetric Immunosensor Based on Single-Walled Carbon Nanohorns as Labels and Bienzyme Biocatalyzed Precipitation as Enhancer for Cancer Biomarker Detection. Biosens. Bioelectron. 2014, 55, 360−365. (251) Whitney, J. R.; Sarkar, S.; Zhang, J. F.; Thao, D.; Young, T.; Manson, M. K.; Campbell, T. A.; Puretzky, A. A.; Rouleau, C. M.; More, K. L.; Geohegan, D. B.; Rylander, C. G.; Dorn, H. C.; Rylander, M. N. Single Walled Carbon Nanohorns as Photothermal Cancer Agents. Lasers Surg. Med. 2011, 43, 43−51. (252) Whitney, J.; Dewitt, M.; Whited, B. M.; Carswell, W.; Simon, A.; Rylander, C. G.; Rylander, M. N. 3D Viability Imaging of Tumor Phantoms Treated With Single-Walled Carbon Nanohorns and Photothermal Therapy. Nanotechnology 2013, 24, 275102. (253) Zhu, S.; Zhao, X.-E.; You, J.; Xu, G.; Wang, H. CarboxylicGroup-Functionalized Single-Walled Carbon Nanohorns as Peroxidase Mimetics And Their Application To Glucose Detection. Analyst 2015, 140, 6398−6403. (254) Utsumi, S.; Ohba, T.; Tanaka, H.; Urita, K.; Kaneko, K. Porosity and Adsorption Properties of Single-Wall Carbon Nanohorn. In Novel Carbon Adsorbents; Elsevier: Oxford, 2012; p 401−433. (255) Adelene Nisha, J.; Yudasaka, M.; Bandow, S.; Kokai, F.; Takahashi, K.; Iijima, S. Adsorption and Catalytic Properties of SingleWall Carbon Nanohorns. Chem. Phys. Lett. 2000, 328, 381−386. (256) Krungleviciute, V.; Calbi, M. M.; Wagner, J. A.; Migone, A. D.; Yudasaka, M.; Iijima, S. Probing the Structure of Carbon Nanohorn Aggregates by Adsorbing Gases of Different Sizes. J. Phys. Chem. C 2008, 112, 5742−5746. (257) Krungleviciute, V.; Migone, A. D.; Yudasaka, M.; Iijima, S. CO2 Adsorption on Dahlia-Like Carbon Nanohorns: Isosteric Heat and Surface Area Measurements. J. Phys. Chem. C 2012, 116, 306−310. (258) Yudasaka, M.; Fan, J.; Miyawaki, J.; Iijima, S. Studies on the Adsorption of Organic Materials inside Thick Carbon Nanotubes. J. Phys. Chem. B 2005, 109, 8909−8913. (259) Okazaki, T.; Iijima, S.; Yudasaka, M. Molecular Encapsulations into Interior Spaces of Carbon Nanotubes and Nanohorns. In Chemistry of Nanocarbons; John Wiley & Sons, Ltd: Chichester, 2010; p 385−403. (260) Lodermeyer, F.; Costa, R. D.; Casillas, R.; Kohler, F. T. U.; Wasserscheid, P.; Prato, M.; Guldi, D. M. Carbon Nanohorn-Based Electrolyte for Dye-Sensitized Solar Cells. Energy Environ. Sci. 2015, 8, 241−246.

(224) Brandao, L.; Passeira, C.; Gattia, D. M.; Mendes, A. Use of Single Wall Carbon Nanohorns in Ppolymeric Electrolyte Fuel Cells. J. Mater. Sci. 2011, 46, 7198−7205. (225) Hamoudi, Z.; Brahim, A.; El Khakani, M. A.; Mohamedi, M. Electroanalytical Study of Methanol Oxidation and Oxygen Reduction at Carbon Nanohorns-Pt Nanostructured Electrodes. Electroanalysis 2013, 25, 538−545. (226) Zhang, L.; Lei, J. P.; Zhang, J.; Ding, L.; Ju, H. X. Amperometric Detection of Hypoxanthine and Xanthine by Enzymatic Amplification using a Gold Nanoparticles-Carbon Nanohorn Hybrid as The Carrier. Analyst 2012, 137, 3126−3131. (227) Liu, F.; Xiang, G.; Yuan, R.; Chen, X.; Luo, F.; Jiang, D.; Huang, S.; Li, Y.; Pu, X. Procalcitonin sensitive detection based on graphene− gold nanocomposite film sensor platform and single-walled carbon nanohorns/hollow Pt chains complex as signal tags. Biosens. Bioelectron. 2014, 60, 210−217. (228) Karousis, N.; Ichihashi, T.; Yudasaka, M.; Iijima, S.; Tagmatarchis, N. Decoration of Carbon Nanohorns with Palladium and Platinum Nanoparticles. J. Nanosci. Nanotechnol. 2009, 9, 6047− 6054. (229) Battiston, S.; Bolzan, M.; Fiameni, S.; Gerbasi, R.; Meneghetti, M.; Miorin, E.; Mortalò, C.; Pagura, C. Single Wall Carbon Nanohorns Coated with Anatase Titanium Oxide. Carbon 2009, 47, 1321−1326. (230) Xu, W.; Wang, Z.; Guo, Z.; Liu, Y.; Zhou, N.; Niu, B.; Shi, Z.; Zhang, H.; Nanoporous Anatase. TiO2/Single-Wall Carbon Nanohorns Composite as Superior Anode for Lithium Ion Batteries. J. Power Sources 2013, 232, 193−198. (231) Costa, R. D.; Feihl, S.; Kahnt, A.; Gambhir, S.; Officer, D. L.; Wallace, G. G.; Lucio, M. I.; Herrero, M. A.; Vázquez, E.; Syrgiannis, Z.; Prato, M.; Guldi, D. M. Carbon Nanohorns as Integrative Materials for Efficient Dye-Sensitized Solar Cells. Adv. Mater. 2013, 25, 6513−6518. (232) Casillas, R.; Lodermeyer, F.; Costa, R. D.; Prato, M.; Guldi, D. M. Substituting TiCl4−Carbon Nanohorn Interfaces for Dye-Sensitized Solar Cells. Adv. Energy Mater. 2014, 4, 1301577. (233) Zhao, Y.; Li, J. X.; Ding, Y. H.; Guan, L. H. Single-Walled Carbon Nanohorns Coated With Fe2O3asa Superior Anode Material for Lithium Ion Batteries. Chem. Commun. 2011, 47, 7416−7418. (234) Zhao, Y.; Li, J. X.; Ding, Y. H.; Guan, L. H. A Nanocomposite of SnO2 And Single-Walled Carbon Nanohorns asa Long Life And High Capacity Anode Material For Lithium Ion Batteries. RSC Adv. 2011, 1, 852−856. (235) Murata, K.; Hashimoto, A.; Yudasaka, M.; Kasuya, D.; Kaneko, K.; Iijima, S. The Use of Charge Transfer to Enhance the MethaneStorage Capacity of Single-Walled, Nanostructured Carbon. Adv. Mater. 2004, 16, 1520−1522. (236) Wang, S. W.; Itoh, T.; Fujimori, T.; de Castro, M. M.; SilvestreAlbero, A.; Rodriguez-Reinoso, F.; Ohba, T.; Kanoh, H.; Endo, M.; et al. Formation of COx-Free H2 and Cup-Stacked Carbon Nanotubes over Nano-Ni Dispersed Single Wall Carbon Nanohorns. Langmuir 2012, 28, 7564−7571. (237) Zhang, M.; Yudasaka, M.; Miyawaki, J.; Fan, J.; Iijima, S. Isolating Single-Wall Carbon Nanohorns as Small Aggregates through a Dispersion Method. J. Phys. Chem. B 2005, 109, 22201−22204. (238) Zhang, M. F.; Yamaguchi, T.; Iijima, S.; Yudasaka, M. Individual Single-Wall Carbon Nanohorns Separated from Aggregates. J. Phys. Chem. C 2009, 113, 11184−11186. (239) Voiry, D.; Pagona, G.; Canto, E. D.; Ortolani, L.; Morandi, V.; Noe, L.; Monthioux, M.; Tagmatarchis, N.; Penicaud, A. Reductive Dismantling and Functionalization of Carbon Nanohorns. Chem. Commun. 2015, 51, 5017−5019. (240) Zhu, S.; Xu, G. Carbon Nanohorns and Their Biomedical Applications. In Nanomaterials for the Life Sciences; Vol. 9: Carbon Nanomaterials; Wiley-VCH Verlag GmbH & Co. KGaA: 2011; pp 87− 109. (241) Kostarelos, K. The Long and Short of Carbon Nanotube Toxicity. Nat. Biotechnol. 2008, 26, 774−776. (242) Yang, M.; Zhang, M.; Tahara, Y.; Chechetka, S.; Miyako, E.; Iijima, S.; Yudasaka, M. Lysosomal Membrane Permeabilization: Carbon Nanohorn-Induced Reactive Oxygen Species Generation and 4882


Chemical Reviews

Review

(261) Hiralal, P.; Wang, H. L.; Unalan, H. E.; Liu, Y. L.; Rouvala, M.; Wei, D.; Andrew, P.; Amaratunga, G. A. J. Enhanced Supercapacitors From Hierarchical Carbon Nanotube And Nanohorn Architectures. J. Mater. Chem. 2011, 21, 17810−17815. (262) Yuge, R.; Tamura, N.; Manako, T.; Nakano, K.; Nakahara, K. High-Rate Charge/Discharge Properties of Li-Ion Battery using Carbon-Coated Composites of Graphites, Vapor Grown Carbon Fibers, and Carbon Nanohorns. J. Power Sources 2014, 266, 471−474. (263) Zhang, Z.; Han, S.; Wang, C.; Li, J.; Xu, G. Single-Walled Carbon Nanohorns for Energy Applications. Nanomaterials 2015, 5, 1732− 1755. (264) Zhu, S. Y.; Li, H. J.; Niu, W. X.; Xu, G. B. Simultaneous Electrochemical Determination of Uric Acid, Dopamine, and Ascorbic Acid at Single-Walled Carbon Nanohorn Modified Glassy Carbon Electrode. Biosens. Bioelectron. 2009, 25, 940−943. (265) Liu, Z.; Zhang, W.; Qi, W.; Gao, W.; Hanif, S.; Saqib, M.; Xu, G. Label-Free Signal-on ATP Aptasensor Based on the Remarkable Quenching of Tris(2,2’-Bipyridine)Ruthenium(II) Electrochemiluminescence by Single-Walled Carbon Nanohorn. Chem. Commun. (Cambridge, U. K.) 2015, 51, 4256−4258. (266) Zhu, S.; Fan, L.; Liu, X.; Shi, L.; Li, H.; Han, S.; Xu, G. Determination of Concentrated Hydrogen Peroxide at Single-Walled Carbon Nanohorn Paste Electrode. Electrochem. Commun. 2008, 10, 695−698. (267) Dai, H.; Gong, L.; Lu, S.; Zhang, Q.; Li, Y.; Zhang, S.; Xu, G.; Li, X.; Lin, Y.; Chen, G. Determination of 4-Aminophenylarsonic Acid Using a Glassy Carbon Electrode Modified With an Ionic Liquid and Carbon Nanohorns. Microchim. Acta 2015, 182, 1247−1254. (268) Annamalai, K. P.; Gao, J.; Liu, L.; Mei, J.; Lau, W.; Tao, Y. Nanoporous Graphene/Single Wall Carbon Nanohorn Heterostructures with Enhanced Capacitance. J. Mater. Chem. A 2015, 3, 11740− 11744. (269) Zhu, S.; Niu, W.; Li, H.; Han, S.; Xu, G. Single-Walled Carbon Nanohorn as New Solid-Phase Extraction Adsorbent for Determination of 4-Nitrophenol in Water Sample. Talanta 2009, 79, 1441−1445. (270) Fresco-Cala, B.; Jimenez-Soto, J. M.; Cardenas, S.; Valcarcel, M. Single-Walled Carbon Nanohorns Immobilized on a Microporous Hollow Polypropylene Fiber as a Sorbent for the Extraction of Volatile Organic Compounds from Water Samples. Microchim. Acta 2014, 181, 1117−1124.

4883


Structure, Properties, Functionalization, and ... - ACS Publications

Recommend Documents