Clustering of aromatic rings in near-frictionless hydrogenated amorphous carbon films probed using multi-wavelength Raman spectroscopy

Multiwavelength Raman spectroscopy has been used to study the structure of hydrogenated amorphous carbon films synthesized by plasma-enhanced chemical vapor deposition. The analysis of different parameters from the Raman spectra demonstrates that the diameter, structural, and topological orders of the sp2-bonded ring clusters increase with increasing fractions of hydrogen in the source gas. We report the existence of an unusual peak at 867 cm-1 that in such extended clusters of aromatic rings, could correspond to a graphitic mode activated by a relaxation of the phonon selection-rule resulting from defects

Sulfur-doped carbon nanohorn bifunctional electrocatalyst for water splitting

Sulfur-doped carbon nanohorns (S-CNHs) were prepared by an easy one-pot solvothermal process and were employed as efficient electrocatalysts towards water splitting. Initially, oxidation of CNHs followed by thermal treatment with the Lawesson’s reagent resulted in the formation of S-CNHs with the sulfur content determined as high as 3%. The S-CNHs were thoroughly characterized by spectroscopic, thermal and electron microscopy imaging means and then electrocatalytically screened. Specifically, S-CNHs showed excellent activity and durability for both O2 and H2 evolution reactions, by showing low overpotential at 1.63 and -0.2 V vs. RHE for oxygen and hydrogen evolution reaction, respectively. Additionally, S-CNHs showed significantly lower Tafel slope value and lower current resistance compared to oxidized and pristine CNHs for both electrocatalytic reactions. The outstanding electrocatalytic properties and high conductivity, along with the high S-doping level, render S-CNHs a promising bifunctional electrocatalyst for water splitting

Clustering in a highly-hydrogenated diamond-like carbon determined using fluctuation electron microscopy and phenomenological atomistic simulations

We compare fluctuation electron microscopy data to simulations from phenomenological atomic models and demonstrate a strong correspondence between some features in the experimental data and certain atomic configurations. This allows the nature of atomic clustering in a highly hydrogenated diamondlike carbon to be determined more closely. We compare the structural information garnered from fluctuation electron microscopy and Raman spectroscopy for a particular diamondlike carbon and find consistency between the two techniques in the region where their information overlaps

High-angular-resolution electron energy loss spectroscopy of hexagonal boron nitride

High-angular-resolution electron energy loss spectroscopy (EELS) is used to study the anisotropic behavior of the boron and nitrogen K ionization edges in h-BN. This work makes significant progress toward improving the anisotropy measurements. The authors show experimentally by EELS the vanishment of the p* peak existing in these K edges in agreement with electronic structure calculations and previous soft x-ray absorption spectroscopy measurements

Atomic Configuration of Nitrogen Doped Single-Walled Carbon Nanotubes

Having access to the chemical environment at the atomic level of a dopant in a nanostructure is crucial for the understanding of its properties. We have performed atomically-resolved electron energy-loss spectroscopy to detect individual nitrogen dopants in single-walled carbon nanotubes and compared with first principles calculations. We demonstrate that nitrogen doping occurs as single atoms in different bonding configurations: graphitic-like and pyrrolic-like substitutional nitrogen neighbouring local lattice distortion such as Stone-Thrower-Wales defects. The stability under the electron beam of these nanotubes has been studied in two extreme cases of nitrogen incorporation content and configuration. These findings provide key information for the applications of these nanostructures.Comment: 25 pages, 13 figure

In vitro and in vivo biocompatibility of boron/nitrogen co-doped carbon nano-onions

Boron/nitrogen, co-doped, carbon nano-onions (BN-CNOs) have recently shown great promise as catalysts for the oxygen reduction reaction, due to the improved electronic properties imparted by the dopant atoms; however, the interactions of BN-CNOs with biological systems have not yet been explored. In this study, we examined the toxicological profiles of BN-CNOs and oxidized BN-CNOs (oxi-BN-CNOs) in vitro in both healthy and cancer cell lines, as well as on the embryonic stages of zebrafish (Danio rerio) in vivo. The cell viabilities of both cell lines cells were not affected after treatment with different concentrations of both doped CNO derivatives. On the other hand, the analysis of BN-CNOs and oxidized BN-CNO interactions with zebrafish embryos did not report any kind of perturbations, in agreement with the in vitro results. Our results show that both doped CNO derivatives possess a high biocompatibility and biosafety in cells and more complex systems. © 2021 by the authors. Licensee MDPI, Basel, Switzerland

Optoelectronic properties of calcium cobalt oxide misfit nanotubes

We report on the optoelectronic properties of a recently discovered nanotubular phase of misfit-layered calcium cobalt oxide, CaCoO2-CoO2. Individual nanotubes are investigated by spatially resolved electron energy-loss spectroscopy experiments performed in a transmission electron microscope, and complementary first-principles, time-dependent hybrid density-functional theory calculations are performed to elucidate the electronic structure and optical spectra. We find that the band gap is independent of the geometry of the nanotubes, and experimental and calculated results independently confirm an optical gap of 1.9-2.1 eV for the CaCoO2-CoO2 nanotubes. The time-dependent hybrid density-functional theory calculations also suggest the existence of strongly bound intralayer excitons (up to 0.5 eV binding energy), which could allow for optoelectronic applications of these nanotubes at near-infrared to visible (~1.5-2 eV) wavelengths

Multiwavelength Raman spectroscopy of diamond nanowires present in n-type ultrananocrystalline films

Multiwavelength Raman spectroscopy is employed to investigate ultrananocrystalline diamond films deposited by the plasma enhanced chemical vapor deposition technique. Recently, we have shown that the addition of nitrogen in the gas source during synthesis induce the formation of diamond n-type films, exhibiting the highest electrical conductivity at ambient temperature. This point is related with the formation of elongated diamond nanostructures and the presence of sp2-bonded carbon in these films. The Raman results presented here confirm these aspects and provide a better and deeper understanding of the nature of these films and their related optical and electronic properties

Spatially resolved electron energy loss spectroscopy on n-type ultrananocrystalline diamond films

The addition of nitrogen to the synthesis gas during synthesis of ultrananocrystalline-diamond (UNCD) films results in films uniquely exhibiting very high n-type electrical conductivity even at ambient temperatures. This result is due to the formation of nanowires having elongated diamond core nanostructures and a sp2-bonded C sheath surrounding the core. The work presented here provides detailed confirmation of this important result through spatially resolved-electron energy loss spectroscopy. The direct observation of nitrogen incorporated in the sheath has been enabled. The incorporation of this nitrogen provides strong support to a plausible mechanism for the n-type conduction characteristic of the UNCD films