Correlating substrates reactivity at electrified interfaces with electrolyte structure in synthetically relevant organic solvent/water mixtures

Abstract

Optimizing electrosynthetic reactions requires fine tuning of a vast chemical space, including charge transfer at electrocatalyst/electrode surfaces, engineering of mass transport limitations and complex interactions of reactants and products with their environment. Hybrid electrolytes, in which supporting salt ions and subtrates are dissolved in a binary mixture of organic solvent and water, represent a new piece to this complex puzzle, as they offer a unique opportunity to harvest water as the oxygen or proton source in electrosynthesis. In this work, we demonstrate that modulating water-organic solvent interactions drastically impacts the solvation properties of hybrid electrolytes. Combining various spectroscopies with synchrotron small-angle X-ray scattering (SAXS) and classical molecular dynamics (MD) simulations, we show that the size and composition of aqueous domains forming in hybrid electrolytes can be controlled. We demonstrate that water is more reactive for the hydrogen evolution reaction (HER) in aqueous domains than when strongly interacting with solvent molecules, which originates from a change in reaction kinetics rather than from a thermodynamic effect. We examplify novel opportunities arising from this new knowledge for optimizing electrosynthetic reactions in hybrid electrolytes. For reactions proceeding first via the activation of water, fine tuning of aqueous domains impact the kinetics and potentially the selectivity of the reaction. Instead, for organic substrates reacting prior to water, aqueous domains have no impact on reaction kinetics, while selectivity may be affected. We believe that such fine comprehension of solvation properties of hybrid electrolytes can be transposed to numerous electrosynthetic reactions.