The active centers of carbon nonplatinum catalysts doped with cobalt, iron, nickel, and copper have been simulated by quantum-chemical density functional theory methods. The thermodynamics of the electrochemical oxygen reduction reaction (ORR) on model catalysts has been determined. It was found that among the studied catalysts, graphene doped with cobalt and iron showed the best properties. A two-state reactivity effect has been found on a cobalt-containing catalyst, and a more detailed reaction mechanism has been proposed, including the stages of charging by an extra electron and association with water. The proposed mechanism explains several effects that have arisen during the modeling in relation to the classical mechanism.

Electronic structure/Rice−Ramsperger−Kassel−Marcus Master equation calculations were applied to unravel the oxidation mechanism and kinetics of the cyclopenta[a]naphthalenyl radical with molecular oxygen. The reaction has been shown to proceed through the addition of O 2 in the orthoposition in the five-membered ring of C 13 H 9 . At low temperatures, the reaction yields a collisionally stabilized C 13 H 9 O 2 complex, which rapidly decomposes back to the reactants. In the high-temperature regime, above 800, 900, 1125, and 1375 K at pressures of 0.03, 1, 10, and 100 atm, respectively, the reaction forms bimolecular products including 3H-/1Hcyclopenta[a]naphthalen-3-one + OH as the prevailing product together with 1-ethanol-substituted 2-naphthyl radical + CO and 3H-benzo[f ]chromen-3-one + H as minor ones, with the branching ratio of the OH elimination channel growing with temperature and the rate constants for the individual bimolecular channels being independent of pressure. The calculated rate constants and product branching for cyclopenta[a]naphthalenyl + O 2 closely agree with those reported earlier for the indenyl + O 2 reaction and are recommended for the combustion kinetic models for the oxidation reactions of five-membered rings on free edges of larger polycyclic aromatic hydrocarbon molecules. The results also confirm that the oxidation of a π radical located on a five-membered ring with molecular oxygen is very slow.

Bimetallic catalysts based on multi-walled carbon nanotubes (MWCNT), graphene oxide (GO) and ultradispersed diamonds (UDD) supports for the process of electroreduction of oxygen from alkaline electrolyte were obtained using high-temperature synthesis. The materials were characterized by low-temperature nitrogen adsorption, Raman spectroscopy, scanning electron microscopy and X-ray structure analysis. The synthesized bimetallic catalysts contain meso- and micropores. Based on the study by Raman spectroscopy, it is shown that high-temperature synthesis of MWCNT with metal phthalocyanines leads to doping of this material with nitrogen and the appearance of significant defects in the structure. Carbon nanotube-based catalysts showed enhanced activity compared to other carbon materials. Moreover, bimetallic catalysts based on cobalt phthalocyanine and palladium (MWCNT_CoPc_Pd) are characterized by higher activity on all carbon supports compared to materials contain on copper and palladium. The specific current density in the diffusion region of the MWCNT_CoPc_Pd catalyst is comparable to a commercial platinum electrode (Pt(20%)/C) and equals to 2.65 mA/cm2. The area of the electrochemically active surface of all the obtained catalysts was calculated from the CV data in a nitrogen atmosphere. The MWCNT_CoPc_Pd catalyst is characterized by high corrosivity: after 2500 revolutions, the current density in the diffusion region decreases by 7%, and, also, an increase in the values of E1/2 and Eonset is observed.

The active centers of carbon catalysts doped with cobalt, nickel, copper, manganese, zinc, and chromium were modeled by density functional theory methods. Likewise, the thermodynamics of the oxygen reduction reaction (ORR) on model catalysts were determined. The features of the chemical properties of chromium-containing material, namely its spontaneous oxidation into the hydroxo form, were revealed. In addition, it was established that among the studied catalysts, graphene doped with cobalt showed the best properties.

The main obstacle to the widespread dissemination of fuel cells is the high cost, so researchers are actively searching for ways to replace the expensive platinum catalyst with cheaper analogs. In this paper we studied the Ag- and Pd-containing carbon catalysts based on carbon nanotubes and graphene oxide. The study of the textural characteristics of the catalysts showed that the greatest specific surface area has a catalyst based on MWCNT containing 10% silver, all synthesized catalysts are mainly mesoporous, and the content of micropores is insignificant. Raman spectroscopy and SEM data indicate a significant change in the structure of the modified carriers compared to pure MWCNT and GO. An electrochemical experiment was performed and linear voltammetric diagrams were obtained and compared with the voltammetric diagrams obtained on the platinum catalyst. GO_Ag 10% and MWCNT_Ag 10% Pd 10% are closest in the values of kinetic parameters in both kinetic and diffusion regions. GO_Ag 10% has the highest initial potential Eonset = −0.145 V and MWCNT_Ag 10% Pd 10% has the highest half-wave potential E½ = −0.23 V. The studied catalysts have characteristics comparable to those presented in the literature.