The possible implications of magnetic field effect on understanding the reactant of water splitting

Electrochemical water splitting consists of two elementary reactions i.e., hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Developing robust HER and OER technologies necessitates a molecular picture of reaction mechanism, yet the reactants for water splitting reactions are unfortunately not fully understood. Here we utilize magnetic field to understand proton transport in HER, and hydroxide ion transport in OER, to discuss the possible implications on understanding the reactants for HER and OER. Magnetic field is a known tool for changing the movement of charged species like ions, e.g. the magnetic-field-improved Cu2+ transportation near the electrode in Cu electrodeposition. However, applying a magnetic field does not affect the HER or OER rate across various pH, which challenges the traditional opinion that charged species (i.e. proton and hydroxide ion) act as the reactant. This anomalous response of HER and OER to magnetic field, and the fact that the transport of proton and hydroxide ion follow Grotthuss mechanism, collectively indicate water may act as the universal reactant for HER and OER across various pH. With the aid of magnetic field, this work serves as an understanding of water might be the reactant in HER and OER, and possibly in other electrocatalysis reactions involving protonation and deprotonation step. A model that simply focuses on the charged species but overlooking the complexity of the whole electrolyte phase where water is the dominant species, may not reasonably reflect the electrochemistry of HER and OER in aqueous electrolyte.