N 1s core-level binding energies in nitrogen-doped carbon nanotubes: a combined experimental and theoretical study.

We report a combined experimental and theoretical study dedicated to analyze the N 1s core-level binding energies (CLBE) in N-doped carbon nanotubes (N-CNTs). X-ray photoelectron spectroscopy (XPS) data are obtained from N-CNT samples synthesized using the chemical vapor deposition technique. Extensive density functional theory (DFT) calculations are performed on various model single- and double-walled N-CNTs where N 1s CLBEs are determined using Koopman's theorem. However, we also present additional calculations within the (Z + 1) approximation to analyze the role of final-state effects. From XPS data up to 2 at% of N content was found in our samples and the high resolution analysis of the N 1s line shows, according to previous experimental results, that N species exist in CNTs as graphitic, pyrrolic, pyridinic, and molecular configurations. However, peak decomposition is characterized by five broad Gaussian curves that overlap considerably among them, having different widths and heights, implying a more complex distribution of N atoms within the structures. DFT calculations performed on model N-CNTs reveal a strong dependence of N 1s CLBE values and their shifts on the local atomic environment. Different types of graphitic N cover an energy range of 3 eV, while various configurations for pyridinic, pyrrolic, and molecular species reveal a dispersion in their energy values of 5.7, 2.7, and 5.2 eV, respectively. The previous distributions of theoretical CLBEs also strongly overlap, implying that some peaks in the XPS spectra must be understood as composite signals where the signals of different N defects coexist. We find, in agreement with the experimental data, that freestanding molecular nitrogen and (weakly interacting) encapsulated N2 within the hollow core of model CNTs have very similar CLBEs. Furthermore, we predict that chemisorbed N2 on defective regions of the nanotube walls has N 1s binding energy values that are considerably larger when compared to encapsulated N2, thus making possible their identification. In contrast to previous reports, we find a nontrivial dependence between CLBEs and the local electronic occupation at N sites. The assignment of spectral details in the XPS data to well-defined N-defects on CNTs is not straightforward and needs to be more deeply analyzed.

Magnetic properties of encapsulated nanoparticles in nitrogen-doped multiwalled cabon nanotubes embedded in SiOx matrices.

We report the production, characterization, thermal transformations (400-1000 degrees C), and magnetic properties of nanoparticles encapsulated in nitrogen-doped multiwall carbon nanotubes (CNx-MWNT), which were embedded in silicon oxide (SiOx) matrices via sol-gel techniques. The vapor chemical deposition (CVD) method with ferrocene-benzelamine mixtures was used to synthesize Fe and Fe3C nanoparticles inside CNx-MWNTs. Composites consisting of CNx-MWNTs (filler) and SiOx (matrix) were fabricated and thermally treated to different temperatures and exposure times (t). All samples were characterized using scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), thermogravimetic analysis (TGA), and magnetometry (vibrating sample). We found that upon thermal treatment, the ferromagnetic nanoparticles modify their morphology, composition and aspect ratio, thus resulting in drastic changes in the magnetic and structural properties. In particular, as produced encapsulated nanoparticles mainly consisting of Fe and Fe3C phases were thermally modified into magnetite (Fe3O4). We have also observed that the hysteresis loops are very sensitive to the thermal treatment of the sample. Thus we can control the magnetic properties of the samples using thermal treatments.

Synthesis, electronic structure, and Raman scattering of phosphorus-doped single-wall carbon nanotubes.

Substitutional phosphorus doping in single-wall carbon nanotubes (SWNTs) is investigated by density functional theory and resonance Raman spectroscopy. Electronic structure calculations predict charge localization on the phosphorus atom, generating nondispersive valence and conduction bands close to the Fermi level. Besides confirming sustitutional doping, accurate analysis of electron and phonon renormalization effects in the double-resonance Raman process elucidates the different nature of the phosphorus donor doping (localized) when compared to nitrogen substitutional doping (nonlocalized) in SWNTs.

Covalently bonded three-dimensional carbon nanotube solids via boron induced nanojunctions.

The establishment of covalent junctions between carbon nanotubes (CNTs) and the modification of their straight tubular morphology are two strategies needed to successfully synthesize nanotube-based three-dimensional (3D) frameworks exhibiting superior material properties. Engineering such 3D structures in scalable synthetic processes still remains a challenge. This work pioneers the bulk synthesis of 3D macroscale nanotube elastic solids directly via a boron-doping strategy during chemical vapour deposition, which influences the formation of atomic-scale "elbow" junctions and nanotube covalent interconnections. Detailed elemental analysis revealed that the "elbow" junctions are preferred sites for excess boron atoms, indicating the role of boron and curvature in the junction formation mechanism, in agreement with our first principle theoretical calculations. Exploiting this material's ultra-light weight, super-hydrophobicity, high porosity, thermal stability, and mechanical flexibility, the strongly oleophilic sponge-like solids are demonstrated as unique reusable sorbent scaffolds able to efficiently remove oil from contaminated seawater even after repeated use.

Creation of helical vortices during magnetization of aligned carbon nanotubes filled with Fe: theory and experiment.

We report a novel magnetic phenomenon consisting of the formation of helical spin configurations during the magnetization of densely packed ferromagnetic nanowires encapsulated inside carbon nanotubes. We studied the hysteresis loops when the magnetic fields are applied parallel and perpendicular to the nanotubes axes. We also performed theoretical calculations on aligned nanowire arrays that clearly indicate the creation of helical spin vortices in the hysteresis loops. The latter are caused by the presence of strong dipolar interactions among neighboring wires.

Production and characterization of single-crystal FeCo nanowires inside carbon nanotubes.

We describe the synthesis of novel monocrystalline FeCo nanowires encapsulated inside multiwalled carbon nanotubes (MWNTs). These FeCo nanowires exhibit homogeneous Fe and Co concentrations and do not contain an external oxide layer due to the presence of insulating nanotube layers. The method involves the aerosol thermolysis of toluene-ferrocene-cobaltocene solutions in inert atmospheres. The materials have been carefully characterized using state-of-the-art high-resolution transmission electron microscopy (HRTEM), electron-energy-loss spectroscopy (EELS), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), electron diffraction, HREELS-STM elemental mapping, X-ray powder diffraction, and SQUID magnetometry. We noted that the formation of FeCo alloys occurs at relatively low pyrolytic temperatures (e.g., 650-750 degrees C). These single-crystal nanowires, which have not been reported hitherto, always exhibit the FeCo (110) plane parallel to the carbon nanotube axis. The FeCo nanomaterials have shown large coercive fields at room temperature (e.g., 900 Oe). We envisage that these aligned ferromagnetic nanowires could be used in the fabrication of high-density magnetic storage devices and magnetic composites.