(Invited) Enhancement of Activity of Low-Pt-Content-Catalysts Toward Oxygen Reduction through Admixing with Metal Oxide Cocatalysts
Authors: Kulesza Pawel J. , Rutkowska Iwona A. , Kostuch Aldona , Lukowska Marta , Zoladek Sylwia , Di Noto Vito , Negro Enrico , Vezzù Keti 
Published: February 2024

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.
Platinum is a main catalyst for the electroreduction of oxygen, the reaction of primary importance to the technology of low-temperature fuel cells. Because of high cost of platinum. there is a need to significantly lower its loadings at interfaces. But then O2-reduction proceeds often at less positive potentials and produces higher amounts of undesirable H2O2-intermediate. Hybrid supports, which utilize metal oxides (e.g., CeO2, WO3, Ta2O5, Nb2O5, ZrO2), stabilize Pt and carbon nanostructures, diminish their corrosion while exhibiting high activity toward the four-electron (most efficient) reduction of oxygen. Porosity of carbon supports facilitates dispersion and stability of Pt nanoparticles. The catalytic efficiency depends on geometric (decrease of Pt–Pt bond distances) and electronic (increase of d-electron vacancy in Pt) factors, in addition to possible metal-support interactions and interfacial structural changes affecting adsorption and activation of O2-molecule.