Carbon nanotubes are important materials for a variety of scientific and technological applications due to their unique properties (Frank et al., 1998; Ganji, 2008; Hone et al., 2000; Marulanda, 2010; Yu et al., 2000). Of course, their properties depend on their structure. For instance, nanotube conductivity depends on chirality, diameter, and length (Alam & Ray, 2007; Hamada et al., 1992; Saito et al., 1992; S.H. Yang et al, 2008). The purity of the nanotubes and the presence of defects also affect their conductivity.
Chirality or helicity refers to the way the nanostructure arises by the folding of a graphene sheet. Nanotube chirality is usually characterised by two integers,
Within the numerous potential applications imagined for carbon nanotubes, hydrogen storage represents the most promising application capable of making a safe, efficient and “green” contribution to fuel cells with hydrogen management in the solid state. The principal hydrogen-adsorption mechanisms associated with nanotube hydrogen uptake are the physisorption and chemisorption of hydrogen.
During physisorption, hydrogen interacts with selected sites of a carbon nanotube or substrate. The interaction energy increases as the substrate polarisability increases. Density-functional theory calculations indicate that nanotube-hydrogen interactions are weak and that hydrogen diffusion from the nanotube is facilitated by slightly increasing temperature (Mpourmpakis et al., 2006). The hydrogen-binding energies, calculated using density-functional theory are small and similar for metallic and semiconducting nanotubes, indicating that substantial adsorption is only possible at very low temperatures (Cabria et al., 2006). The same conclusion is reached by studying hydrogen adsorption in carbon-nanotube arrays through molecular dynamic simulation (Kovalev et al., 2011), in which a second adsorption layer is detected at 80 ºK. This second layer of hydrogen is not detected at room temperature.
Through chemisorption, hydrogen is covalently bonded to carbon atoms in such a way that a change of
Experimental work by Dillon et al. (Dillon et al., 1997), which reported 10 wt. % of hydrogen uptake by single-walled carbon nanotubes at room temperature, stimulated many theoretical and experimental studies of carbon nanotubes as an ideal hydrogen carrier (Bilic & Gale, 2008; Dinadayalane et al, 2007; Kaczmarek et al, 2007). The hydrogen binding energies in these cases are clearly dependent on chirality, tube diameter, hydrogen occupancy, and endohedral vs. exohedral binding.
For example, based on density-functional theory calculations of atomic hydrogen adsorption on carbon nanotubes at very low occupancies (i.e., 1 or 2 adsorbed hydrogen atoms), F.Y. Yang et al. reported that the binding energies for
It is clear that exohedral binding is more energetically favourable than endohedral binding because the conversion of
However, from a quantitative viewpoint, some of the experiments performed at room temperature resulted in very low hydrogen-storage capacities, generating debate and much controversy (Baughman et al., 2002; G. Zhang et al., 2006). Density-functional theory calculations of both the energy-barrier and the Gibbs-free-energy changes for hydrogen on a (10,0) single-walled carbon nanotube when changing from a physisorption to a chemisorption state (Han & Lee, 2004) suggest a major obstacle for the practical use of the carbon nanotube as a hydrogen storage medium.
Several research groups’ results have indicated that hydrogen uptake depends on factors, such as the nanotube type and purity, the gas temperature and pressure, and the equipment used for the experimental determination, all of which affect reproducibility. A recent detailed discussion by Yao (Yao, 2010) about different experimental and theoretical studies critically analyses the influencing factors that must be considered for a better evaluation of carbon nanotubes as good candidates for hydrogen storage. Two important points mentioned are the nanotube purity after synthesis and the presence of some heteroatoms that could modify the nanotube surface electronic density.
Using a volumetric measurement setup specifically designed for carbon nanotubes, Liu et al. obtained results for different types of nanotubes, showing that the reliable hydrogen storage capacity of carbon nanotubes under a pressure of approximately 12 MPa at room temperature is less than 1.7 wt. % (Liu et al., 2010). This value is far below the benchmark of 6.5 wt. % set by the US Department of Energy for the on-board application of hydrogen storage systems, suggesting that hydrogen uptake in pure carbon nanotubes is not a good alternative for on-board applications.
Doping is also an important factor to consider (Griadun, 2010). Semiconducting carbon nanotubes doped with 2–10% of nitrogen become metallic (Charlier, 2002; Czerw et al., 2001). Interestingly, nitrogen-doped carbon nanotubes constitute a good metal-free catalyst system for oxygen reduction reactions in alkaline media (Gong et al., 2009). In acidic media, these nitrogen-doped carbon nanotubes show a higher current density and a higher oxygen reduction reaction rate constant compared to conventional Pt-based catalysts (Xiong et al., 2010). Nitrogen-doped carbon nanotubes behave as convenient catalysts for these reactions and have excellent environmental and economical profiles because they are electrochemically more reactive and more durable than Pt-containing materials. Density-functional theory calculations at the B3LYP/6-31G* level indicate that the metal-free nitrogen-doped carbon nanotubes have promising catalytic ability for C-H methane activation (Hu et al., 2011) that is comparable to that of noble-metal catalysts and enzymes.
In addition, the nitrogen doping of carbon nanotubes has a significant effect on hydrogen storage capacity. Density-functional theory calculations for atomic hydrogen adsorption indicate that nitrogen-doping forms an electron-rich six-membered ring structure and decreases the adsorption energies in single-walled carbon nanotubes (Zhou, et al., 2006). Nevertheless, doping nanotubes with nitrogen considerably enhances the hydrogen dissociative adsorption, substantially reducing the hydrogen diffusion barrier according to density-functional theory studies on nitrogen-doped (8,0) nanotubes (Z.Y. Zhang & Cho, 2007).
Hydrogen molecules can diffuse inside nitrogen-doped
Experimental measurements on hydrogen storage associated with other nitrogen-doped carbon structures indicated that nitrogen-doped microporous carbon had both an 18% higher hydrogen-storage capacity and significantly higher heats of hydrogen adsorption than a pure carbon structure with a similar surface area (L.F. Wang & R.T. Yang, 2009). In addition, nitrogen-doped carbon xerogels enhanced hydrogen adsorption at 35°C (K.Y. Kang et al., 2009).
Because the incorporation of nitrogen atoms into carbon nanotubes affords structures with the ability to participate in hydrogen bonding, these nitrogen-doped nanostructures may have additional chemical properties, such as the immobilization of transition metals (Feng et al., 2010), or the coupling of gold nanoparticles (Allen et al., 2008), which could be useful for potential biomedical applications.
Nitrogen-doped nanotubes are less toxic than undoped carbon nanotubes, but some concern about their safe use remains (Pastorin, 2009; Stern & McNeil, 2008). Experimental research involving the analysis of the toxicological effects on both mice and amoeba cell viability caused by nitrogen-doped or undoped carbon nanotubes indicates that nitrogen-doped carbon nanotubes are less harmful and more biocompatible than the undoped nanotubes (Terrones, 2007).
For undoped carbon nanotubes, a recent scientific study (Nayak et al., 2010) investigated a variety of parameters concerning the toxicity of either single- or multi-walled carbon nanotubes, with and without functionalisation, to assess their cytotoxic profile; this assessment was based on several critical parameters, such as tube length, concentration, dispersibility, and purity, using colorimetric assays to measure the activity of mitochondrial reductase. The results of these studies show that the purity and dispersibility of the nanotubes are the most critical parameters to guarantee their safe application in biology and medicine when used in a normal concentration range (10-150 µg/ml). This finding is an important contribution to the field, assuring the safe use of ultrapure nanotubes.
All of the aforementioned features make the study of the properties, stability and hydrogen chemisorption energies of carbon nanotubes with high nitrogen content quite interesting and necessary. As an extreme, nitrogen nanotubes or nitrogen nanoneedles formed by units of N2m (m = 2-6) with hydrogen as the terminal atoms (with almost 100 wt. % of nitrogen) as well as nitrogen nanobundles with a carbon backbone have been studied using the density-functional theory method (J.L. Wang et al., 2006). J.L. Wang et al. reported that the mentioned nitrogen nanostructures and the nitrogen nanobundles have low stability but are proper minima with all real frequencies at the level of B3LYP/6-31G** having electronic properties that might be modulated as a function of the local charge environment.
There are only a few studies on nitrogen-containing carbon nanotubes with high nitrogen content. However, the synthesis of nitrogen-doped carbon nanotubes (Trasobares et al., 2002) can be selectively performed with either
Fully exohydrogenated nitrogen-containing carbon nanotubes with high nitrogen content, having
Our aim in this work is to theoretically investigate the structural geometry, energetic stabilities, and electronic properties and to calculate the hydrogen-chemisorption energy for a particular family of nitrogen-containing carbon nanotubes using the density-functional theory method at the B3LYP/6-31G* level of theory. These nanotubes have very small diameters (≈0.3 nm) and a C4N2 cyclic unit with a pyrimidine-like disposition as the repetitive layer (with 36-37 wt. % nitrogen content). We also would like to clarify whether their structural and electronic properties are affected by the presence of different terminating units at the nanotube ends. The final aim of this work is the evaluation of the possibility that these nitrogen-containing carbon nanotubes behave as hydrogen-storage materials and to determine the influence of both the nanotube configuration and length on their properties.
2. Computational methodology
In this work, chemisorption refers to exhaustive chemisorption with completely saturated products. The full exohydrogenated nanostructures were built using the HyperChem v7.0 program (Hyperchem, release 7.0), starting from layers defined as cyclic units containing four
Nanostructures were built by covalently arranging one layer on top of the other in such a way that the carbon and nitrogen atoms were
All nanostructures were optimised by the density-functional theory (DFT) method at the B3LYP/6-31G* level of theory (Becke, 1993; Lee et al., 1988) using the Gaussian 03 suite of programs (Frisch et al., 2004). For the verification and characterisation of energy minima,
harmonic vibrational frequency calculations for optimised geometries at the same level of theory were performed, all of which yielded zero imaginary frequencies. Band gaps were calculated as the difference of ELUMO – EHOMO. No symmetry constraints were used. Charges were assigned using the Mulliken population analysis method, which partitions the total charge among the atoms in the molecule (in the present study, the sum of the Mulliken charges = 0.000 for each nanostructure).
All of the nanotubes studied in this work are nitrogen-containing carbon nanotubes with high nitrogen content, as was explained previously. Chemisorption is done to 100% hydrogen coverage.
2.1.2. Length of the tube
This term describes the number assigned for determining how many layers or cyclic units of pyrimidinic topology are participating, which is expressed before the configuration character under consideration. For instance, 8M is assigned to a nanotube having 8 layers with a rotation angle between contiguous layers of 120°. Different structures of 4 to 12 layers and nanotubes of up to 20 layers for some configurations have been studied.
All nanostructures studied here belong to the (3,0) type with a diameter value of ≈0.3 nm. No variations in diameter have been considered.
2.1.4. Terminal groups
Open nanotubes ended with hydrogen atoms located coaxially to the nanotube were studied. The orientation variation of these hydrogen atoms may affect the total energy of the nanotube up to ≈50 kcal/mol (Contreras, et al., 2010; J.L. Wang et al., 2006). The effect of the terminal groups created by changing the three terminal hydrogen atoms by one unit of nitrogen, phosphorus, NO3 group or a cycle of five carbon atoms (designated as 5C) at each end of the nanotube was also studied. In this way, the nanotubes remain closed at both extremes.
A capital letter H is added to the name of the terminal group for nanotubes with adsorbed hydrogen (chemisorbed). The considered nanotubes have both extremes symmetrically bonded. In this way, a nanotube of 8 layers with an M configuration with chemisorbed hydrogen and with nitrogen as the terminal group at both extremes is designated as 8M-N-H. With no hydrogen chemisorption, the notation of 8M-N is used. If there are also no terminal groups that are different from hydrogen, the nanotube is designated simply as 8M. Therefore, in general terms, the notation is
Chemisorption, when present, is exhaustively considered with the formation of completely saturated nanostructures. Therefore, a saturated nanotube in this work is a nanotube for which hydrogen chemisorption occurred exhaustively.
2.1.6. Further calculations
Calculations for nanotubes with 20 layers (206 atoms and 1972 basis functions) were conducted using the Jaguar v7.5 (Jaguar, 2008) and the DFT method at the B3LYP/6-31G* level of theory (Becke, 1993; Lee et al., 1988); with the Gaussian 03, it was not possible to optimise these structures after several days of computation.
Formation energies (or substitution energies) were calculated as
where ENCNT and ECNT are the total energies for saturated carbon nanotubes with the same number of layers with and without nitrogen, respectively; EC, EH, and EN are the total energies of an isolated carbon atom, hydrogen atom, and nitrogen atom, respectively; and n is the total number of layers in the nanotube. EC was calculated as
and EH and EN were derived from one half of the calculated total energy for a hydrogen molecule and a nitrogen molecule, respectively, at the same level of theory. For a better understanding, the process considered for a 6-layer nitrogen-containing carbon nanotube can be written as
Reaction energies for hydrogen chemisorption (Er) on the external surface of nitrogen-containing carbon nanotubes were calculated using the formula below.
where E(H chemisorbed) denotes the total energy of the hydrogen-chemisorbed nanotube;
with n representing the number of layers or the length of the nanotube. Er/H, the reaction energy per hydrogen atom, is calculated as
Some of the C4nH6N2n nanostructures (after being optimised to proper minima -with entirely real vibrational frequencies), formed small cycles at both ends of the tube in GaussView (graphical interface of Gaussian 03). To calculate Er/H using more stable structures, nanotubes with the first and the last layers completely saturated were considered for chemisorption. Expressions (6) and (7) remain, respectively, as the following (8) and (9) expressions:
3. Results and discussion
Results will be presented in sections following the indicated order. First, the results obtained for completely hydrogenated open nitrogen-containing nanotubes and ended by hydrogen atoms will be shown, which represent 100% chemisorption. Next, the effect of closing the open nanotubes with different terminal groups will be shown. The results for the nanotubes without chemisorption will follow. Finally, the calculated energies of chemisorption will be presented.
3.1. Geometrical structures
The considered fully hydrogenated nitrogen-containing carbon nanotubes formed by C4N2H4 units and ended by hydrogen atoms are ≈0.28 nm in diameter and 0.66—3.96 nm in length. The interlayer bond lengths calculated by density-functional theory for N—N, N—C, and C—C bonds are 1.52 Å, 1.48—1.50 Å, and 1.55—1.56 Å, respectively. A typical (sp3)C—C(sp3) bond length is 1.54 Å. The C—N bond length for amines is 1.479 Å. The N—N bond length in nitrogen nanotubes calculated at the density-functional theory level range from 1.42 to 1.52 Å (J.L. Wang et al., 2006).
To analyse the bond lengths and bond angles inside each nanotube layer, all nanotube geometries were optimised at the same level of theory, including pyrimidine and its saturated isomer as a reference. Based on the comparison of the bond angles and bond lengths of pyrimidine and its saturated isomer, the saturated structure has smaller bond angles and higher bond lengths than pyrimidine, as was expected for these structures (see Figure 3).
To analyse the same parameters for nanotubes, an 8M (8 layers, with M configuration) nanotube was selected at random and only layer 2 and layer 4 were considered for the analysis of both the nanotube without hydrogen adsorption (8M-H) and the totally saturated (8M-H-H) nanotube (see Figure 4).
For the saturated 8M-H-H nanotube, a good correlation is observed among layers 2 and 4 when the C—C and C—N bond lengths and bond angles are compared. However, for the 8M-H nanotube, there is no a good correlation for these values. These results may be explained by the fact that saturated structure environments around layers 2 and 4 are more similar, and thus the characteristics of the layers along the tube are likely to be maintained. However, for the unsaturated structure, layer 2 is nearest to layer 1, which has three covalent bonds to hydrogen atoms, compared to layer 4, which has no neighbours bonded to hydrogen. Based on the analysis of the intralayer parameters, there is only one pair of C—C bonds in layer 2 that are longer for the saturated structure than those for the unsaturated one. Instead, in layer 4, there are several bonds in the saturated structure that are longer than those in the unsaturated one (except for the N1—C2 and N3—C4 bonds).
3.2. Formation energies
The formation energies of the nitrogen-containing carbon nanotubes were calculated using the density-functional theory method at the B3LYP/6-31-G* level and equation (2). Figure 5 shows the values obtained for nitrogen-containing carbon nanotubes that were totally hydrogenated with different configurations as a function of nanotube length.
A clear difference in stability for different configurations can easily be seen, with an expected regular trend of increasing formation energy as the nanotube length increases. The
configuration was of intermediate stability. For undoped carbon nanostructures of the type H3(C6)mH3 with m=3—6, values equivalent to 8—43 eV have been reported (J.L. Wang, et al., 2006), as calculated using density-functional theory methods. For a nitrogen-doped (5,5) nanotube (C74N6) with a diameter of approximately twice the size of those used in this work, a formation energy of 10.86 eV has been reported (H.S. Kang & Jeong, 2004). A 6
The formation-energy values have a close relationship to the nanotube structures in this study (see Figure 6). It is clearly observed that the
3.3. Charge analysis
Charge analysis was conducted for carbon 2 (contiguous to the two nitrogen atoms on each layer) of the most stable configuration of the hydrogen-chemisorbed nanotubes with between 1 and 10 layers. It was found that the charge value on this atom increases from the layer at the extremes of the tube up to the central layers, increasing from -0.031 for layer 1 to 0.297–0.303 for internal layers and then decreasing to 0.259–0.261 for the final layer, while charges for the nitrogen atoms remain constant at -0.481 and -0.486 for N1 and N3, respectively (Contreras et al, 2010).
Charge analysis clearly shows that, in the four configurations studied, the charge on C2 has a maximum value at the centre of the nanotube and that the greatest charge difference between the extremes and between one extreme and the maximum value corresponds to the
3.4. Terminal group effect
Figure 8 shows the optimised structures with all real vibrational frequencies obtained for the nanotubes containing terminal groups that close the nanotubes at both extremes as observed from the top and side views for each one.
Figure 9 shows the effect of terminal groups on the band gaps. Here, the band-gap values for nitrogen-containing carbon nanotubes are presented. Those nanotubes with chemisorbed hydrogen correspond to the group of curves above 4 eV, and the group below 4 eV is the corresponding nitrogen-containing carbon nanotubes without chemisorbed hydrogen. The nanotubes of this last group, designed by a single character H, only have hydrogen atoms in the first and in the last layers, with three hydrogen atoms on both end sides, and the nanotube is open.
It can clearly be observed from Figure 9 that band-gap values increase for hydrogen-adsorbed nitrogen-containing carbon nanotubes having the
Thus, when the unsaturated nanotube is closed by terminal groups, its semiconducting property is not strongly affected. However, results suggest that, due to hydrogen chemisorption, the conducting property of nitrogen-containing carbon nanotubes is lost; nanotubes ending with phosphorus atoms are the least affected. This pattern was presented for the
The terminal group effect on the dipole moment is shown for saturated nitrogen-containing carbon nanotubes with
Regarding the amount of hydrogen uptake by chemisorption, each terminal group replaces three hydrogen atoms at each terminus of the nanotube, and hydrogen is adsorbed at a rate of 4 atoms per layer. In this condition, nanotubes with end-groups will have a lower hydrogen uptake capacity than nanotubes without terminal groups, with values of 4.8, 4.4, and 3.7 wt. % hydrogen uptake for nanotubes ending in N, P, and NO3, respectively, in comparison with a 7.2 wt. % hydrogen uptake capacity for a nanotube without end-groups, with all the values being for a 4-layer nitrogen-containing carbon nanotube. Therefore, the influence of the end groups is best considered as an anchorage centre for other groups, likely being useful for further functionalisation of the nanotube with specific applications (de Jonge et al., 2005) and also facilitating physisorption because interaction with hydrogen
is favoured by the donor hydrogen bond capacity of N, P, and NO3 groups and by the increase of nanotubes polarisability in the presence of these groups. A single nitrogen atom can bind up to 6 H2 molecules (Rangel et al., 2009).
3.5. Configuration effect
Previous analyses indicate that configuration strongly affects nanotube stability, with the
The effect of nanotube configuration on the band gap for 8-layered nitrogen-containing carbon nanotubes with different terminal groups coming from hydrogen chemisorption is shown in Figure 12. The same behaviour is observed for nanotubes with and without terminal groups: the band gap depends very little on the configuration, except for
The dipole moments of 8-layered nitrogen-containing carbon nanotubes for different configuration and terminal groups arising from hydrogen chemisorption are presented in Figure 13.
Calculations using density-functional theory methods afford values indicating a configuration effect on the dipole moment for the studied nanotubes, indicating a structural relationship. For
3.6. Hydrogen chemisorption energies
Values of hydrogen chemisorption energies for 100% saturation, calculated according to equations (6) and (7) above, for nitrogen-containing carbon nanotubes of different configurations and for carbon nanotubes of different lengths, with no terminal group, are shown in Table 1.
The energies were calculated considering the optimised geometries of the exhaustively chemisorbed nitrogen-containing nanostructures, meaning complete saturation (C4nH4n+6N2n). Regular tubular structures with all real vibrational frequencies for all studied nanotube configurations and lengths were obtained. However, the optimised structures of unsaturated molecules (C4nH6N2n), over which hydrogen adsorption takes place, showed three-membered cycles at both extremes of the nanotube with a C—C bond length of 1.51-1.53 Å and C—N bond lengths of 1.45-1.46 Å and 1.47-1.48 Å (Figure 14). These structures were optimised at the same level of theory as the previous structures, up to proper minima characterised by positive vibrational frequencies.
The values shown in Table 1 indicate that the configuration has a distinctive effect, especially on the 4-layered nanotubes. For nanotubes longer than 8 layers, there is no significant variation of the hydrogen chemisorption energies per hydrogen atom, with configuration or length.
Values of the hydrogen chemisorption energy for nitrogen-containing carbon nanotube structures with totally saturated first and the last layers and having the general formula C4nH14N2n are given in Table 2. In this case, the optimised regular geometries were obtained without small cycles in their structures (Figure 14).
The Er/H values for partially saturated C4nH14N2n nanotubes are less exothermic than those obtained from less stable geometries, which was expected because less energy per hydrogen atom is to be eliminated by the exhaustive hydrogen adsorption to more thermodynamically stable molecules.
The data in Table 2 indicate that, as the nanotube length increases, the hydrogen chemisorption energy increases, favouring chemisorption. The obtained values are comparable with the atomic adsorption energy of hydrogen for nitrogen-doped (8,0) carbon nanotubes with a value of -28.4 kcal/mol (Zhou et al., 2006). A strong effect of the nanotube configuration on the energy values is not observed.
Values of Er/H for hydrogen adsorption over the
The chemisorption process is somewhat more exothermic in the presence of terminal groups than for open nanotubes without terminal groups. The calculated molecular hydrogen absorption energy for a single-walled (8,0) carbon nanotube decorated with atomic nitrogen is also exothermic, with a value of -80 meV/(H2), equivalent to -1.84 kcal/mol/(H2) (Rangel et al., 2009), as determined by density-functional theory and molecular dynamics. We have not found both experimental neither theoretical studies for a more direct comparison with our results.
The structural and energy aspects of hydrogen atom chemisorption on small-diameter nitrogen-containing carbon nanotubes having high nitrogen content have been investigated. The adsorption of hydrogen was examined at full coverage. Stable nanotube structures were fully optimised to proper minima before and after hydrogen chemisorption using density-functional theory methods at the level of B3LYP/6-31G* with all real vibrational frequencies.
The stability was strongly dependant on the configuration of the saturated nitrogen-containing carbon nanotubes, the
Hydrogen chemisorption energies for open nitrogen-containing carbon nanotubes ended by hydrogen atoms and similar nanotubes closed at both ends with different units were found to be exothermic and independent of both configuration and length, except for shorter nanotubes.
Chemisorption increases the band gaps (ELUMO – HOMO) of the studied nanostructures (from 1–1.6 eV to 4.5–6.5 eV). These band-gap values decrease by approximately 0.4 eV and 1.6 eV, respectively, for nitrogen and phosphorus terminal groups when compared with open saturated nanotubes without terminal groups. Unsaturated nanotube band gaps are insensitive to terminal groups and length.
The dipole moments of saturated nitrogen-containing carbon nanotubes depend more on the tube length than on the type of terminal group, with a variation within 2—3 D for the different end-groups at the considered lengths. In general, the dipole moment increases as the number of layers increases. This finding is also true for open saturated nitrogen-containing carbon nanotubes of different configurations ended by hydrogen atoms.
Nitrogen-containing carbon nanotubes with small diameters have the capacity to store a full monolayer of hydrogen via chemisorption. Shorter nanotubes and nanotubes without end-groups have higher capacities for hydrogen storage. Hydrogen physisorption studies on these nitrogen-containing carbon nanotubes and the effect of increasing the nanotube diameter constitute an important next step.
Important remaining goals are related to the molecular modelling methods and tools necessary for predicting the properties a particular nanostructure will have —as a hydrogen-storage material, a conductive material, a catalyst, or a further functionalisation centre— which continues to be a scientifically interesting and challenging task.
This work was partially supported by the Direction of Scientific and Technological Research DICYT-USACH project Nr 061042CF and by the SDT-USACH project Nr CIA 2981. Additionally, the central cluster of the Faculty of Chemistry and Biology and the VRID of the University of Santiago de Chile, Usach, are acknowledged for allocating computational resources.
Alam K. M. Ray A. K. 2007 A hybrid density functional study of zigzag SiC nanotubes., 18 49November 2007) 495706 EOF1
Allen B. L. Kichambare P. D. Star A. 2008Synthesis, characterization, and manipulation of nitrogen-doped carbon nanotube cups. , 2 9(September 2008), 1914 1920, 1936-0851
Baughman R. H. Zakhidov A. A. de Heer W. A. 2002Carbon nanotubes- the route toward applications. , 297 5582(August 2002), 787 792, 0036-8075
Becke A. D. J. 1993 Density-functional thermochemistry. 3. The role of exact exchange., 98 7 5648 5652, 0021-9606
Bilic A. Gale J. D. 2008Chemisorption of molecular hydrogen on carbon nanotubes: a route to effective hydrogen storage? , 112 32(July 2008), 12568 12575, 1932-7447
Cabria I. Lopez M. J. Alonso J. A. 2006 Density functional study of molecular hydrogen coverage on carbon nanotubes. , 35 3(March 2006), 238 242, 0927-0256
Charlier J. C. 2002 Defects in carbon nanotubes., 35 12(December 2002), 1063 1069, 0001-4842
Contreras M. L. Avila D. Alvarez J. Rozas R. 2010 Exploring the structural and electronic properties of nitrogen-containing exohydrogenated carbon nanotubes: a quantum chemistry study. , 21 3(June 2010), 573 581, 1040-0400
Contreras M. L. Benítez E. Alvarez J. Rozas R. 2009 Algorithm for nanotubes computer generation with different configurations. , 2 1(February 2009), 108 120, E 1999-4893
Czerw R. Terrones M. Charlier J. C. Blase X. Foley B. Kamalakaran R. Grobert N. Terrones H. Ajayan P. M. Blau W. Tekleab D. Rühle M. Carroll D. L. 2001 Identification of electron donor states in N-doped carbon nanotubes. , 1 9(September 2001), 457 460, 1530-6984
De Jonge N. Doytcheva M. Allioux M. Kaiser M. Mentink S. A. M. Teo K. B. K. Lacerda R. G. Milne W. I. 2005 Cap closing of thin carbon nanotubes. , 17 4(February 2005), 451 455, 0935-9648
Dillon A. C. Jones K. M. Bekkedahl T. A. Kiang C. H. Bethune D. S. Heben M. J. 1997 Storage of hydrogen in single-walled carbon nanotubes. , 386 6623(March 1997), 377 379, 0028-0836
Dinadayalane T. C. Kaczmarek A. Łukaszewicz J. Leszczynski J. 2007Chemisorption of hydrogen atoms on the sidewalls of armchair single-walled carbon nanotubes., 111 20(May 2007), 7376 7383, 1932-7447
Feng H. Ma J. Hu Z. 2010 Nitrogen-doped carbon nanotubes functionalized by transition metal atoms: a density functional study. , 20 9(January 2010), 1702 1708, 0959-9428
Frank S. Poncharal P. Wang Z. L. de Heer W. A. 1998 Carbon nanotube quantum resistors. , 280 5370(June 1998), 1744 1746, 0036-8075
Frisch M.J 2004Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Montgomery, J.A. Jr.; Vreven, T.; Kudin, K.N.; Burant, J.C.; Millam, J.M.; Iyengar, S.S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G.A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J.E.; Hratchian, H.P.; Cross, J.B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R.E.; Yazyev, O.; Austin, A.J.; Cammi, R.; Pomelli, C.; Ochterski, J.W.; Ayala, P.Y.; Morokuma, K.; Voth, G.A.; Salvador, P.; Dannenberg, J.J.; Zakrzewski, V.G.; Dapprich, S.; Daniels, A.D.; Strain, M.C.; Farkas, O.; Malick, D.K.; Rabuck, A.D.; Raghavachari, K.; Foresman, J.B.; Ortiz, J.V.; Cui, Q.; Baboul, A.G.; Clifford, S.; Cioslowski, J.; Stefanov, B.B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R.L.; Fox, D.J.; Keith, T.; Al-Laham, M.A.; Peng, C.Y.; Nanayakkara, A.; Challacombe, M.; Gill, P.M.W.; Johnson, B.; Chen, W.; Wong, M.W.; Gonzalez, C. & Pople, J.A. Gaussian 03, Gaussian Inc, Wallingford CT, Revision D01
Ganji M. D. 2008 Behavior of a single nitrogen molecule on the pentagon at a carbon nanotube tip: a first-principles study. , 19 2(December 2007), 025709
Gong K. P. Du Z. H. Xia Z. H. Durstock M. Dai L. M. 2009 Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. , 323 5915(February 2009), 760 764, 0036-8075
Griadun V. 2010Doped Carbon Nanotubes Properties, In, Marulanda, J.M. (Ed), 147 168, In-Teh, 978-9-53307-054-4India
Hamada N. Sawada S. Oshiyama A. 1992 New one-dimensional conductors-graphitic microtubules,, 68 10(March 1992), 1579 1581, 0031-9007
Han S. S. Lee H. M. 2004Adsorption properties of hydrogen on (10,0) single-walled carbon nanotube through density functional theory. , 42 11(May 2004) 2169 2177, 0008-6223
Hone J. Batlogg B. Benes Z. Johnson A. T. Fisher J. E. 2000 Quantized phonon spectrum of single-wall carbon nanotubes. , 289 5485(September 2000), 1730 1733, 0036-8075
Hu X. Zhou Z. Lin Q. Wu Y. Zhang Z. 2011 High reactivity of metal-free nitrogen-doped carbon nanotube for the C-H activation. , 503 4-6, (February 2011), 287 291, 0009-2614Hyperchem release 7.0, Hypercube Inc, 1115 NW 4th Street, Gainesville, Florida 32601, USA
Jaguar version 7.5 2008Schrödinger, LLC, New York, NY
Kang H. S. Jeong S. 2004 Nitrogen doping and chirality of carbon nanotubes, , 70 23December 2004), 233411 233411-233411-4. 1098-0121
Kang K. Y. Lee B. I. Lee J. S. 2009 Hydrogen adsorption on nitrogen-doped carbon xerogels. , 47 4(April 2009), 1171 1180, 0008-6223
Kaczmarek A. Dinadayalane T. C. Łukaszewicz J. Leszczynski J. 2007Effect of tube length on the chemisorptions of one and two hydrogen atoms on the sidewalls of (3,3) and (4,4) single-walled carbon nanotubes: a theoretical study. , 107 12(October 2007), 2211 2219, 0020-7608
Kovalev V. Yakunchikov A. Li F. 2011 Simulation of hydrogen adsorption in carbon nanotube arrays. , 68 7-8, (April-May 2011), 681 685
Lee C. Yang W. Parr R. G. 1988 Development of the colle-salvetti correlation-energy formula into a functional of the electron-density. , 37 2January 1988), 785 789, 0163-1829
Liu C. Chen Y. Wu C. Z. Xu S. T. Cheng H. M. 2010Hydrogen storage in carbon nanostructures revisited. , 48 2(February 2010), 452 455, 0008-6223
Marulanda J. M. . Ed 2010, In-Teh, 978-9-53307-054-4India
Mpourmpakis G. Tylianakis E. Froudakis G. 2006 Hydrogen storage in carbon nanotubes. A multi-scale theoretical study., 6 1(January 2006), 87 90, 1533-4880
Nayak T. R. Leow P. C. Ee P. L. R. Arockiadoss T. Ramaprabhu S. Pastorin G. 2010 Crucial parameters responsible for carbon nanotubes toxicity. , 6 2(April 2010), 141 154 1573-4137
Ni M. Y. Zeng Z. 2010 Chemisorption and diffusion of hydrogen atoms on single-walled carbon nanotubes. , 10 8(August 2010), 5408 5412, 1533-4880
Oh K. S. Kim D. H. Park S. Lee J. S. Kwon O. Choi Y. K. 2008 Movement of hydrogen molecules in pristine, hydrogenated and nitrogen-doped single-walled carbon nanotubes. , 34 10-15, (September-December 2008), 1245 1252, 0892-7022
Pastorin G. 2009Crucial Functionalizations of Carbon Nanotubes for Improved Drug Delivery: A Valuable Option? , 26 4(April 2009), 746 769, 0724-8741
Rangel E. Ruiz-Chavarria G. Magana L. F. Arellano J. S. 2009 Hydrogen adsorption on N-decorated single wall carbon nanotubes. , 373 30(July 2009), 2588 2591, 0375-9601
Saito R. Fujita M. Dresselhaus G. Dresselhaus M. S. 1992Electronic-structure of chiral graphene tubules. 60 18May 1992), 2204 2206, 0003-6951
Terrones M. 2007 Synthesis, toxicity, and applications of doped carbon nanotubes. 16 1-2(Suppl. 2), 33 34
Stern S. T. Mc Neil S. E. 2008 Nanotechnology safety concerns revisited. , 101 1(June 2007), 4 21
Trasobares S. Stephan O. Colliex C. Hsu W. K. Kroto H. W. Walton D. R. M. 2002 Compartmentalized CNx nanotubes: chemistry, morphology, and growth. , 116 20May 2002) 8966 8972, 0021-9606
Wang J. L. Lushington G. H. Mezey P. G. 2006 Stability and electronic properties of nitrogen nanoneedles and nanotubes., 46 5September-October 2006), 1965 1971 1549-9596
Wang L. F. Yang R. T. 2009 Hydrogen storage properties of N-doped microporous carbon. , 113 52(December 2009), 21883 21888, 1932-7447
Xiong W. Du F. Liu Y. Perez A. Jr Supp M. Ramakrishnan T. S. Dai L. Jiang L. 2010 3-D carbon nanotube structures used as high performance catalyst for oxygen reduction reaction. , 132 45(October 2010), 15839 15841, 0002-7863
Yang F. H. Lachawiec J. Jr Yang R. T. 2006 Adsorption of spillover hydrogen atoms on single-wall carbon nanotubes., 110 12(March 2006), 6236 6244, 1520-6106
Yang S. H. Shin W. H. Kang J. K. 2008 The nature of graphite- and pyridinelike nitrogen configurations in carbon nitride nanotubes: dependence on diameter and helicity. , 4 4(April 2008), 437 441, 1613-6810
Yao Y. 2010 Hydrogen storage using carbon nanotubes, In: , Marulanda, J.M. (Ed), 543 562, In-Teh, 978-9-53307-054-4India
Yu M. F. Files B. S. Arepalli S. Ruoff R. S. 2000 Tensile loading of ropes of single wall carbon nanotubes and their mechanical properties. , 84 24(June 2000), 5552 5555, 0031-9007
Zhang G. Qi P. Wang X. Lu Y. Mann D. Li X. Dai H. 2006 Hydrogenation and hydrocarbonation and etching of single-walled carbon nanotubes., 128 18(May 2006), 6026 6027, 0002-7863
Zhang Y. Wen B. Song X. Y. Li T. J. 2010 Synthesis and bonding properties of carbon nanotubes with different nitrogen contents. , 59 5(May 2010), 3583 3588, 1000-3290
Zhang Z. Y. Cho K. 2007 Ab initio study of hydrogen interaction with pure and nitrogen-doped carbon nanotubes. , 75 7(February 2007), Art. No. 075420, 6 pp., 1098-0121
Zhong Z. Lee G. I. Mo C. B. Hong S. H. Kang J. K. 2007Tailored field-emission property of patterned carbon nitride nanotubes by a selective doping of substitutional N(sN) and pyridine-like N(pN) atoms., 19 12June 2007), 2918 2920, 0897-4756
Zhou Z. Gao X. P. Yan J. Song D. Y. 2006 Doping effects of B and N on hydrogen adsorption in single-walled carbon nanotubes through density functional calculations. , 44 5(April 2006), 939 947, 0008-6223