(65d) Modelling the Electrochemical Reduction of CO2 Under Gas-Liquid Taylor Flow

Electrochemical reduction of CO₂ using renewable energy sources is a promising avenue for sustainable production of bulk chemicals. However, CO₂ electrolysis in aqueous systems is severely limited by mass transfer leading to performance parameters insufficient for industrial application. A strategy to enhance mass transfer is to actively introduce CO₂ as a gas flow, while keeping diffusion paths between reactants and catalyst short, by separating the gas flow from the liquid electrolyte through a gas diffusion electrode. However, flooding, salt formation, or drying out of the gas diffusion electrode are common problems and present a major obstacle towards commercialization. A promising reactor concept that enhances mass transfer without the complexity of a gas diffusion electrode is a structured reactor operated under gas-liquid Taylor flow. While this is a proven concept to enhance mass transfer for heterogeneous catalysis in flow cells literature on this approach for electrochemical processes is scarce and the effect of process conditions on the reactor performance are poorly understood.

In this work, we propose a tubular cell design, inspired from the field of fuel cells, for CO₂ electrolysis with a zero-gap membrane electrode assembly. We further, develop a simple analytical model revealing how reactor performance in terms of faradaic efficiency and current density is governed by the key features of Taylor flow. These features film thickness, bubble velocity, and volume fraction of CO₂ bubbles over aqueous electrolyte, for a given cathode potential.

We find that the film thickness and the volume ratio of CO₂/electrolyte fed to the reactor significantly affect the limiting current density and the faradaic efficiency. Additionally, we find industrially relevant performance with faradaic efficiencies (> 90 %) at current densities of up to 500 mA cm^−2, when operating the reactor at elevated pressure beyond 5 bar. This demonstrates the general potential of this reactor concept to overcome mass transfer limitations in the field of electrolysis. We compare our predictions with numerical simulations, showing good agreement for a large window of operation conditions, illustrating when the simple predictive expressions for the current density and faradaic efficiency can be applied.
We expect that the simple predictive expressions are instrumental in guiding experimental studies and reactor design choices.