Elucidating the Correlation between ORR Polarization Curves and Kinetics at Metal–Electrolyte Interfaces

The metal–vacuum models used to analyze the thermodynamics of the oxygen reduction reaction (ORR) completely overlook the role of electrolytes in the electrochemical process and thus cannot reflect the actual kinetic process occurring at the metal–electrolyte interface. Therefore, based on the real experimental process, the current work elucidates the chemical interactions between the electrolyte and the chemical species for the ORR via a novel metal–electrolyte model for the first time by effectively elucidating the correlation between ORR kinetics and polarization curves. Our simulation model analysis comprises the study of all possible ORR mechanisms on different Pt surfaces (Pt(111), Pt(110), and Pt(100)) and PtNi alloys with different compositions (Pt₃Ni(111), Pt₂Ni₂(111), and PtNi₃(111)). The obtained results demonstrate that the hydrogenation of adsorbed oxygen to form adsorbed hydroxyl (R8), whose immense control weight is reflected by a coverage of adsorbed oxygen (θO*) of about 1, is the rate-determining step (RDS) in the four-electron-dominated ORR process. A direct correlation has been established by the great fitting of polarization curves from theoretical ORR kinetics obtained via both the metal–electrolyte model and experimental measurement. This study reveals that among the different Pt surfaces and PtNi alloys, Pt₃Ni(111) exhibits the highest ORR activity with the lowest free energy barrier of Eₐ (0.74 eV), the smallest value of |ΔGO* – 2.46| (0.80 eV), the highest reaction rate r (9.98 × 10⁵ s–¹ per site), and a more positive half-wave potential U₁/₂ (0.93 V). In contrast to previous model studies, this work provides a more accurate theoretical system for catalyst screening, which will help researchers to better understand the experimental phenomena and will be a guiding piece of work for catalyst design and development.