Аннотация:The problem of identifying correlations between catalytic and electrocatalytic processes is
one of the fundamental problems of catalysis among “simple” organic substances, and the oxidation
of CO and rCO2 is of great interest, since CO and CO2 are considered in pairs both during catalytic
and electrocatalytic transformations. In the case of electrocatalysis, this analysis is important in the
study of fuel cells. In this paper, we studied the correlation between the oxidation of reduced forms
of CO2 (rCO2) under potentiodynamic-galvanoctatic electrochemical and open-circuit conditions of
measurements on polycrystalline (pc)Pt in H2CO3. Periodic oscillations are revealed at the oxidation
of Had and rCO2 on (pc)Pt. Quantum chemical calculations were carried out on the Pt13 cluster in
order to identify the mechanisms of the rCO2 oxidation reaction. The correspondence in the energy
parameters of the oxidation process of rCO2 under open-circuit conditions and electrochemical conditions
is shown. The preliminary analysis of the system using density functional (DFT) calculations
is carried out and the most stable systems that are based on Pt13 are found, namely rOH-Pt13-(CO)n,
rOH-Pt13-(COH) and rOH-Pt13-(rCOOH). OH species was chosen as the most likely candidate for
the role of the oxidant for rCO2. Preliminary calculations for the expected reactions were carried out,
and the optimal PES is revealed.