(Invited) Oxygen Reduction at Low-Pt-Content-Catalysts in Acid Media: Development of Systems and Electroanalytical Diagnostic Methodology
Authors: Kulesza Pawel J. , Zdunek Kinga , Rutkowska Iwona A. , Kostuch Aldona , Wadas Anna , Dembinska Beata , Di Noto Vito , Negro Enrico , Vezzu Keti 
Published: July 2022

The proton-exchange membrane fuel cell (PEMFC) technology is one of the most promising approaches for energy conversion in automotive applications. Despite the use of expensive noble metal electrocatalysts, the sluggish kinetics of the oxygen reduction reaction (ORR) in acid media, and formation of the undesirable hydrogen peroxide intermediate are still the main drawbacks, on top of the stability problems, when it comes to the widespread commercialization of PEMFC devices. The progress in this subject is greatly hindered by the high cost and scarcity of the state-of-the-art platinum-based materials which are regarded as the most effective cathode catalysts. Therefore, most of the current research studies have been devoted to the optimization of active centers and maximization of their utilization, which should allow the lowering of the cathode Pt loadings without loss of performance and durability. Unfortunately, the problem of electrochemical stability and the danger of generation of higher quantities of the undesirable hydrogen peroxide intermediate may become even more serious in the case of systems utilizing lower amounts of the Pt catalyst
Among important strategies is hybridization, activation, and stabilization of carbon-supported Pt catalysts by functionalization through admixing with certain nanostructured and typically substoichiometric metal oxides. Special attention is paid to application of the bi- or multi-metallic Pt-based alloys in their various forms and structures. Additionally, doping of carbon carriers with heteroatoms would produce surface functional groups and active centers capable of not only improving the catalysts’ performance, but also affecting their stability. Among other important issues are such features as porosity, hydrophilicity, and degree of graphitization of carbon components, in addition to the existence of metal–support interactions, high electrochemical active surface area, electronic structure of interfacial Pt, and the feasibility of adsorptive or activating interactions with oxygen molecules.
Voltammetric approaches, particularly the rotating ring-disk electrode (RRDE) methodology, are typically applied to diagnose mechanisms and dynamics of ORR. A tempting alternative for recording the electrochemical responses is to integrate the current and to report charge passed as a function of time. Chronocoulometry offers important advantages including good signal-to-noise ratio because the act of integration smooths random noise on the current transients. Furthermore, by integrating the responses, it is possible to separate surface phenomena (e.g. interfacial oxidation of carbon or platinum) more readily from bulk electrochemical responses (ORR). The double-potential-step chronocoulometry permits, in principle, estimation of the number of electrons (n) involved in the oxygen reduction and the percent of formation of the H2O2 intermediate. The problem lies in understanding the reaction kinetics and mechanisms in order to define properly experimental parameters (potential steps and pulse times). Comparative measurements are performed using RRDE voltammetry. Hybrid supports, which utilize metal oxides (e.g., CeO2, WO3, or ZrO2) have been demonstrated to stabilize Pt and carbon nanostructures and diminish their corrosion while exhibiting high activity toward the four-electron (most efficient) reduction of oxygen.

Acknowledgements: This work was supported by the National Science Center (Poland) under Opus Project (2018/29/B/ST5/02627) and under auspices of the European Union EIT Raw Materials ALPE 19247 Project (Specific Grant Agreement No. EIT/RAW MATERIALS/SGA2020/1).