Using the methods of X-ray photoelectron (XPS) and X-ray absorption near edge structure (XANES) spectroscopies with synchrotron radiation, data on changes in the electronic structure and chemical composition of nitrogen-containing multiwalled carbon nanotubes (N-MWCNTs) upon their exposure to the radiation of argon ions with an energy of 5 keV are obtained. It is found that the exposure leads to an increase in the degree of defectiveness of the N-MWCNTs structure and to the carbon oxidation with formation of various oxygen-containing groups (C–OH, C=O/COOH, C–O–C/O–C–O, and CO3). The presence of carbon–oxygen bonds on the surface of carbon nanotubes is associated with the formation of radiation defects. It is shown that an increase in the fraction of nitrogen atoms present in the substituting configuration in the N-MWCNTs wall structure due to the irradiation does not give rise to an increase in the density of the occupied states near the Fermi level against the background of an increase in the degree of structure defectiveness, carbon oxidation, and a decrease in the total nitrogen concentration. The obtained results show that the irradiation of N-MWCNTs with argon ions allows one to successfully functionalize their surface.
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.
The paper presents the results of an investigation of the nanostructure, elements, and phase composition of thin (100–140 nm) tin dioxide films obtained via magnetron sputtering and containing Ag, Y, Sc, Ag + Y, and Ag + Sc additives in the volume. Electrical and gas‐sensitive characteristics of hydrogen sensors based on these films with dispersed Pt/Pd layers deposited on the surface were studied. The additives had a significant effect on the nanostructure of the films, the density of oxygen adsorption sites on the surface of tin dioxide, the band bending at the grain boundaries of tin dioxide, the resistance values in pure air, and the responses to hydrogen in the concentration range of 50–2000 ppm. During the long‐term tests of most of the samples studied, there was an increase in the resistance of the sensors in clean air and in the response to hydrogen. It has been established that the joint introduction of Ag + Y into the volume of films prevents the increase in the resistance and response. For these sensors based on thin films of Pt/Pd/SnO2:Sb, Ag, Y the responses to 100 and 1000 ppm of H2 are 25 and 575, correspondingly, the response time at exposure to 100 and 1000 ppm of H2 are 10 and 90 s, the recovery time at exposure to 100 and 1000 ppm of H2 17 and 125 s. Possible mechanisms of the effect of additives on the properties of sensors and the stability of their parameters during long‐term operation were considered.
Nanocomposite layers based on multiwalled carbon nanotubes (MWCNTs) and non-stoichiometric tin oxide (SnO x) have been grown by magnetron deposition and CVD methods. In the case of the CVD method,...
The effect of pulsed ion irradiation and vacuum annealing on the ratio of sp2- and sp3-hybridized orbitals of carbon atoms in the layers of oriented multi-walled carbon nanotubes has been studied by...