Composite Based on Multi-Walled Carbon Nanotubes and Manganese Oxide with Rhenium Additive for Supercapacitors: Structural and Electrochemical Studies

The structure and electrochemical characteristics of composites based on multi-walled carbon nanotubes (MWCNTs) and manganese oxide with the addition of rhenium oxide has been studied. It has shown that the decorating of the MWCNT surface with layers or nanoparticles of manganese oxide (Mn(III) + Mn(IV)) provides more than a twofold increase in the value of the specific capacitance at low potential scan rates. However, composites based only on manganese oxide exhibit poor electrochemical behavior and the value of the specific capacitance decreases rapidly with increasing potential scan rate due to the limitation of diffusion processes. The addition of rhenium oxide to composites significantly increases their electrochemical properties due to changes in the chemical composition and morphology of composites. Studies of the structure and chemical state have shown that an improvement in the specific capacitance is provided by increasing in the proportion of Mn(IV) oxide in such composites, which has the ability to rapidly and completely reverse redox reactions and has lower electrical resistance values, compared to Mn(III) oxide. A detailed analysis of the voltammetric data showed that an increase in the rate capability in composites with the addition of rhenium oxide can also be provided by increasing the availability of the electrode surface for electrolyte ions and increasing the amount of charge stored due to the formation of a double electric layer

Composite Based on Multi-Walled Carbon Nanotubes and Manganese Oxide with Rhenium Additive for Supercapacitors: Structural and Electrochemical Studies

The structure and electrochemical characteristics of composites based on multi-walled carbon nanotubes (MWCNTs) and manganese oxide with the addition of rhenium oxide has been studied. It has shown that the decorating of the MWCNT surface with layers or nanoparticles of manganese oxide (Mn(III) + Mn(IV)) provides more than a twofold increase in the value of the specific capacitance at low potential scan rates. However, composites based only on manganese oxide exhibit poor electrochemical behavior and the value of the specific capacitance decreases rapidly with increasing potential scan rate due to the limitation of diffusion processes. The addition of rhenium oxide to composites significantly increases their electrochemical properties due to changes in the chemical composition and morphology of composites. Studies of the structure and chemical state have shown that an improvement in the specific capacitance is provided by increasing in the proportion of Mn(IV) oxide in such composites, which has the ability to rapidly and completely reverse redox reactions and has lower electrical resistance values, compared to Mn(III) oxide. A detailed analysis of the voltammetric data showed that an increase in the rate capability in composites with the addition of rhenium oxide can also be provided by increasing the availability of the electrode surface for electrolyte ions and increasing the amount of charge stored due to the formation of a double electric layer

Effect of Nitrogen Atoms in the CNT Structure on the Gas Sensing Properties of PANI/CNT Composite

Herein we report the gas-sensitive properties to ammonia (at 2–10 ppm) of individual nanostructures of a polyaniline/nitrogen-doped carbon nanotube composite with a nitrogen content of 0 at.% (uCNTs), 2 at.% (N-CNTs) and 4 at.% (N+-CNTs). Doping of nanotubes with nitrogen was carried out in order to both reduce the electron work function, to form a potential barrier at the “PANI-CNTs” interface, and reduce the contribution of nanotubes to the composite conductivity. An increase in the nitrogen content in CNTs leads to an increase in conductivity, a decrease in the work function, and the formation of defects in the outer walls of CNTs. It was found that the structural and chemical state of the polymer layer of all composites is the same. However, polymer morphology on nanotubes changes dramatically with increasing nitrogen content in CNTs: a thin smooth layer on uCNTs, a globular layer on N-CNTs, and a thick layer with a sheet-like structure on N+-CNTs. All composites showed the same response time (~20 s) and recovery time (~120 s). Ammonia sensitivity was 10.5 ± 0.2, 15.3 ± 0.5 and 2.2 ± 0.1 ppm−1 for PANI/uCNTs, PANI/N-CNTs and PANI/N+-CNTs, respectively. Based on the results obtained here, we came to the conclusion that the morphological features of the polymer layer on CNTs with different nitrogen content have a dominant effect on the gas reaction than the change in the electronic properties of the polymer at the interface “PANI-CNT”

Carboxyl Functionalization of N-MWCNTs with Stone–Wales Defects and Possibility of HIF-1α Wave-Diffusive Delivery

Nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs) are widely used for drug delivery. One of the main challenges is to clarify their interaction with hypoxia-inducible factor 1 alpha (HIF-1α), the lack of which leads to oncological and cardiovascular diseases. In the presented study, N-MWCNTs were synthesized by catalytic chemical vapor deposition and irradiated with argon ions. Their chemical state, local structure, interfaces, Stone–Wales defects, and doping with nitrogen were analyzed by high resolution transmission electron microscopy (HRTEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Using experimental data, supercells of functionalized N-MWCNTs with an oxygen content of 2.7, 4 and 6 at. % in carboxyl groups were built by quantum chemical methods. Our analysis by the self-consistent charge density functional tight-binding (SCC DFTB) method shows that a key role in the functionalization of CNTs with carboxyl groups belongs to Stone–Wales defects. The results of research in the decoration of CNTs with HIF-1α demonstrate the possibility of wave-diffusion drug delivery. The nature of hybridization and relaxation determines the mechanism of oxygen regulation with HIF-1α molecules, namely, by OH-(OH–C) and OH-(O=C) chemical bonds. The concentration dependence of drug release in the diffusion mode suggests that the best pattern for drug delivery is provided by the tube with a carboxylic oxygen content of 6 at. %

Oxygen Sensors Based on Thin Films of Gallium Oxide Modified with Silicon

The results of an investigation of the electrical resistivity of Ga2O3 thin films modified with silicon under the influence of oxygen in the range of O2 from 9 to 100 vol. % and changes in the heating temperature of structures from 25 to 700 °C were presented. Thin films of Ga2O3 were obtained by RF magnetron sputtering of Ga2O3 targeted with pieces of Si on the target’s surface in oxygen–argon plasma. The possibility of developing selective oxygen sensors based on thin films Ga2O3 modified with silicon with a temperature of maximum response 400 °C was shown. Oxygen influence leads to a reversible increase in the samples’ resistance, due to the chemisorption of oxygen on the surface of thin Ga2O3 films. An increase in the response of sensors based on the thin polycrystalline films of gallium oxide modified with silicon is caused an increase in the adsorption centers for O−, due to an increase in the surface inhomogeneity and the appearance of additional adsorption centers Si4+

Oxygen functionalization and electronic band gap control in the disordered multi-walled carbon nanotubes

Functionalization by oxygen-containing groups, electronic band gap, and conductivity produced by the functionalization in the disordered metallic nitrogen-containing multi-wall carbon nanotubes (N-MWCNTs), are investigated experimentally and theoretically. Oxygen in the carboxyl groups is located in top sites at the nanotube surface and produces the bang gap. The energy gap is found to have a width of approximately 1.3 eV which does not depend on diameter, oxygen concentration, and structure of the groups. Oxygen localized in the bridge position in the hydroxyl group promotes the appearance of charge carriers in a gap. The charge carrier’s concentration and conductivity produced by oxygen groups are shown to be determined by the features of electron scattering. Theory connecting the functionalization, bang gap, and electronic properties of the nanotubes, is developed

Structural, electrical and gas-sensitive properties of Cr2O3 thin films

Cr2O3 thin films were synthesized by RF magnetron sputtering of a Cr target in an oxygen-argon plasma. The effect of annealing temperature on the structural, electrical, and gas-sensitive properties of the Cr2O3 thin films was studied. According to AFM, SEM, XRD, EDX, XPS, optical spectroscopy and electrical measurements the annealed films were characterized by a polycrystalline structure, high stoichiometry, p-type conductivity and a band gap energy of 3.3 ± 0.2 eV. An increase in the annealing temperature from 350 to 450 °C leads to formation of Cr2O3 grains with a diameter from 30 to 130 nm and to a significant increase in the film electrical resistance. Cr2O3 demonstrated sensitivity to NO2, H2, NH3, vapors of acetone and toluene in the heating temperature range of 25–200 °C. Changing the annealing temperature allows to control the sensitivity of the films to certain gases. Thus, Cr2O3 thin films subjected to annealing at a temperature of 450 °C were characterized by a high response to NH3, while those annealed at a temperature of 400 °C – to toluene vapors and that annealed at 350 °C – to NO2 and acetone vapors. A qualitative model of the sensory effect was proposed

The Use of Carbon-Containing Compounds to Prepare Functional and Structural Composite Materials: A Review

The review presents data on the synthesis, properties of carbon-containing compounds, and their application in the technology of obtaining functional and structural composites. Such materials are widely used in recent years due to their good physical and mechanical properties. The review discusses in detail the influence of the chemical composition of various carbon-containing substances and the size of the dispersed phase on the mechanical and physical properties of produced metal matrix composite. The review also concerns methods for the modern synthesis of graphene, carbon nanotubes, and metallic functional and structural composites with reinforcing carbon-containing compounds. Additionally, the results of metal matrix composite modeling are presented. They show that the improved mechanical properties of CNT–Al composites can be attributed to three factors: CNT hardening, matrix grain refinement, and layered architecture

The Valence Band Structure of the [Ni(Salen)] Complex: An Ultraviolet, Soft X-ray and Resonant Photoemission Spectroscopy Study

The valence band photoemission (VB PE) spectra of the [Ni(Salen)] molecular complex were measured by ultraviolet, soft X-ray and resonant photoemission (ResPE) using photons with energies ranging from 21.2 eV to 860 eV. It was found that the Ni 3d atomic orbitals’ (AOs) contributions are most significant for molecular orbitals (MOs), which are responsible for the low-energy PE band at a binding energy of 3.8 eV in the VB PE spectra. In turn, the PE bands in the binding energies range of 8–16 eV are due to the photoionization of the MOs of the [Ni(Salen)] complex with dominant contributions from C 2p AOs. A detailed consideration was made for the ResPE spectra obtained using photons with absorption resonance energies in the Ni 2p3/2, N 1s, and O 1s Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra. A strong increase in the intensity of the PE band ab was found when using photons with an energy 854.4 eV in the Ni 2p3/2 NEXAFS spectrum. This finding is due to the high probability of the participator-Auger decay of the Ni 2p3/2−13d9 excitation and confirms the relationship between the PE band ab with the Ni 3d-derived MOs

Comparative Study of the Structural Features and Electrochemical Properties of Nitrogen-Containing Multi-Walled Carbon Nanotubes after Ion-Beam Irradiation and Hydrochloric Acid Treatment

Using a set of microscopic, spectroscopic, and electrochemical methods, a detailed study of the interrelation between the structural and electrochemical properties of the as-prepared nitrogen-containing multi-walled carbon nanotubes (N-MWCNTs) and their modified derivatives is carried out. It was found that after treatment of nanotubes with hydrochloric acid, their structure is improved by removing amorphous carbon from the outer layers of N-MWCNTs. On the contrary, ion bombardment leads to the formation of vacancy-type structural defects both on the surface and in the bulk of N-MWCNTs. It is shown that the treated nanotubes have an increased specific capacitance (up to 27 F·g-1) compared to the as-prepared nanotubes (13 F·g-1). This is due to an increase in the redox capacitance. It is associated with the reversible Faraday reactions with the participation of electrochemically active pyridinic and pyrrolic nitrogen inclusions and oxygen-containing functional groups (OCFG). Based on the comparison between cyclic voltammograms of N-MWCNTs treated in HCl and with an ion beam, the peaks on these curves were separated and assigned to specific nitrogen inclusions and OCFGs. It is shown that the rate of redox reactions with the participation of OCFGs is significantly higher than that of reactions with nitrogen inclusions in the pyridinic and pyrrolic forms. Moreover, it was established that treatment of N-MWCNTs in HCl is accompanied by a significant increase in the activity of nitrogen centers, which, in turn, leads to an increase in the rate of redox reactions involving OCFGs. Due to the significant contribution of redox capacitance, the obtained results can be used to develop supercapacitors with increased total specific capacitance.Peer reviewe