The dioxygen molecule has two bound states, singlet and triplet, which are different in energy, lifetime, and reactivity. In the context of oxygen electrocatalysis as applied to fuel cells and water splitting the involved O₂ is typically considered to be exclusively in its triplet ground state. However, applying spin-conservation rules for the transformation between triplet O₂ and singlet OH⁻/H₂O reaction intermediates predicts an additional free energy barrier associated with the required spin flip. As a result, for conditions under which both can form, the formation of triplet dioxygen from the singlet OH⁻/H₂O might be slower than the formation of singlet O₂. Correspondingly, singlet O₂ might be more active than triplet O₂ in the oxygen reduction reaction. Here, we discuss the possible existence and influence of singlet oxygen in oxygen electrocatalysis. Some perspectives for studying singlet oxygen in oxygen electrocatalysis are also provided.

The relationship between magnetism and catalysis has been an important topic since the mid-20th century. At present time, the scientific community is well aware that a full comprehension of this relationship is required to face modern challenges, such as the need for clean energy technology. The successful use of (para-)magnetic materials has already been corroborated in catalytic processes, such as hydrogenation, Fenton reaction and ammonia synthesis. These catalysts typically contain transition metals from the first to the third row and are affected by the presence of an external magnetic field. Nowadays, it appears that the most promising approach to reach the goal of a more sustainable future is via ferromagnetic conducting catalysts containing open-shell metals (i.e., Fe, Co and Ni) with extra stabilization coming from the presence of an external magnetic field. However, understanding how intrinsic and extrinsic magnetic features are related to catalysis is still a complex task, especially when catalytic performances are improved by these magnetic phenomena. In the present review, we introduce the relationship between magnetism and catalysis and outline its importance in the production of clean energy, by describing the representative case of 3d metal Pt-based alloys, which are extensively investigated and exploited in PEM fuel cells.

To reach a long term viable green hydrogen economy, rational design of active oxygen evolution reaction (OER) catalysts is critical. An important hurdle in this reaction originates from the fact that the reactants are singlet molecules, whereas the oxygen molecule has a triplet ground state with parallel spin alignment, implying that magnetic order in the catalyst is essential. Accordingly, multiple experimentalists reported a positive effect of external magnetic fields on OER activity of ferromagnetic catalysts. However, it remains a challenge to investigate the influence of the intrinsic magnetic order on catalytic activity. Here, we tuned the intrinsic magnetic order of epitaxial La0.67Sr0.33MnO3 thin film model catalysts from ferro- to paramagnetic by changing the temperature in situ during water electrolysis. Using this strategy, we show that ferromagnetic ordering below the Curie temperature enhances OER activity. Moreover, we show a slight current density enhancement upon application of an external magnetic field and find that the dependence of magnetic field direction correlates with the magnetic anisotropy in the catalyst film. Our work, thus, suggests that both the intrinsic magnetic order in La0.67Sr0.33MnO3 films and magnetic domain alignment increase their catalytic activity. We observe no long-range magnetic order at the catalytic surface, implying that the OER enhancement is connected to the magnetic order of the bulk catalyst. Combining the effects found with existing literature, we propose a unifying picture for the spin-polarized enhancement in magnetic oxide catalysts.