The oxygen evolution reaction (OER) is the bottleneck that limits the energy efficiency of water-splitting. The process involves four electrons’ transfer and the generation of triplet state O₂ from singlet state species (OH^- or H₂O). Recently, explicit spin selection was described as a possible way to promote OER in alkaline conditions, but the specific spin-polarized kinetics remains unclear. Here, we report that by using ferromagnetic ordered catalysts as the spin polarizer for spin selection under a constant magnetic field, the OER can be enhanced. However, it does not applicable to non-ferromagnetic catalysts. We found that the spin polarization occurs at the first electron transfer step in OER, where coherent spin exchange happens between the ferromagnetic catalyst and the adsorbed oxygen species with fast kinetics, under the principle of spin angular momentum conservation. In the next three electron transfer steps, as the adsorbed O species adopt fixed spin direction, the OER electrons need to follow the Hund rule and Pauling exclusion principle, thus to carry out spin polarization spontaneously and finally lead to the generation of triplet state O₂. Here, we showcase spin-polarized kinetics of oxygen evolution reaction, which gives references in the understanding and design of spin-dependent catalysts.

Water electrolysis is the most promising method for efficient production of high purity hydrogen (and oxygen), while the required power input for the electrolysis process can be provided by renewable sources (e.g. solar or wind). The thus produced hydrogen can be used either directly as a fuel or as a reducing agent in chemical processes, such as in Fischer–Tropsch synthesis. Water splitting can be realized both at low temperatures (typically below 100 °C) and at high temperatures (steam water electrolysis at 500–1000 °C), while different ionic agents can be electrochemically transferred during the electrolysis process (OH−, H+, O2−). Singular requirements apply in each of the electrolysis technologies (alkaline, polymer electrolyte membrane and solid oxide electrolysis) for ensuring high electrocatalytic activity and long-term stability. The aim of the present article is to provide a brief overview on the effect of the nature and structure of the catalyst–electrode materials on the electrolyzer's performance. Past findings and recent progress in the development of efficient anode and cathode materials appropriate for large-scale water electrolysis are presented. The current trends, limitations and perspectives for future developments are summarized for the diverse electrolysis technologies of water splitting, while the case of CO2/H2O co-electrolysis (for synthesis gas production) is also discussed

Producing hydrogen by water electrolysis suffers from the kinetic barriers in the oxygen evolution reaction (OER) that limits the overall efficiency. With spin-dependent kinetics in OER, to manipulate the spin ordering of ferromagnetic OER catalysts (e.g., by magnetization) can reduce the kinetic barrier. However, most active OER catalysts are not ferromagnetic, which makes the spin manipulation challenging. In this work, we report a strategy with spin pinning effect to make the spins in paramagnetic oxyhydroxides more aligned for higher intrinsic OER activity. The spin pinning effect is established in oxide_FM/oxyhydroxide interface which is realized by a controlled surface reconstruction of ferromagnetic oxides. Under spin pinning, simple magnetization further increases the spin alignment and thus the OER activity, which validates the spin effect in rate-limiting OER step. The spin polarization in OER highly relies on oxyl radicals (O∙) created by 1^st dehydrogenation to reduce the barrier for subsequent O-O coupling.

The technological interest of oxygen reduction and evolution reactions, ORR and OER, for the clean use and storage of energy has resulted in the discovery of multiple catalysts; and the physical and catalytic properties of the most active compositions are only comprehensible with the consideration of magnetic interactions. Spin dependent potentials via exchange interactions, spin–orbit coupling or through magneto-electric effects catalyse the oxygen electrochemistry. The best catalysts show metal sites with localized spins and electron delocalization; a correlation exists between the rate constant for charge transfer reactions and spin-dependent electron mobility. Since during the OER and ORR the number of unpaired electrons is not conserved, magnetic potentials in optimum catalysts act as selective gates to enhance the transport of local spin currents. Overall magnetic potentials can reduce the bonding properties of the, donor or acceptor, orbitals in the catalyst, and electrons more easily transfer over the conduction band. The influence of spin dependent forces is generally applicable to oxygen catalysis, and supplements the physical interactions relevant for inorganic or organic, electro or photo, artificial or natural processes.