Mechanisms for the Production and Suppression of Hydrogen Peroxide at the Hydrogen Electrode in Proton Exchange Membrane Fuel Cells and Water Electrolyzers: Theoretical Considerations

Hydrogen peroxide is inevitably produced at the hydrogen electrode in both the proton exchange membrane fuel cell (PEMFC) and the proton exchange membrane water electrolyzer (PEMWE) when platinum-based catalysts are used. This peroxide attacks and degrades the membrane, seriously limiting its lifetime. Here we review some of our previous efforts to suppress peroxide production using PtFe as a hydrogen evolution reaction (HER) catalyst and PtCo as a hydrogen oxidation reaction (HOR) catalyst. The mechanisms, which involve the chemical reaction of adsorbed hydrogen with oxygen, are examined using density functional theory. The onset of excess peroxide production at 0.1 V above the reversible potential has not been adequately explained thus far, and therefore a new mechanism is proposed here. This involves a unique reaction site including hydrogen adsorbed at (110) step edges adjacent to (111) terraces on the Pt surface, as well as on Pt alloys and other metals such as Rh and Ir. This mechanism helps explain the recent finding of the Wadayama group that Ir single crystal surfaces such as Ir(111) and Ir(110) produce little peroxide during the HOR. It also points the way toward the design of new catalysts for the hydrogen electrode that suppress peroxide production while retaining high HOR and HER activity.