Promoting e-chemical production by optimising the cathode–anode pair

• Developing a selective electrochemical process for converting syngas into acetate salts offers a sustainable chemical production route. • While cathode optimisation has been extensively studied, the crucial role of anode in enhancing electrochemical performance is highlighted. • High faradaic efficiency was achieved by implementing the optimised Se loaded Ni mesh and Ag nanoparticles as the anode-cathode pair. • Multiphysics simulations revealed that high OER kinetics enhancing methanol oxidation, thus, producing acetate. • Operando DRIFT evidenced that acetate production was originated from methanol oxidation. Chemical production via electroreduction may be a relevant strategy for a future sustainable chemical industry. Many studies have investigated optimal material–reactor combinations on the cathode side of electrolysers, but the anode side has been largely overlooked. We present a case study on e–acetate production to show that optimising the cathode–anode pair leads to increased cell performance: the optimised pair of electrodes can induce high single-pass e–production of sodium acetate at a Faradaic efficiency of 66.7 %. Multiphysics simulations of the optimised electrolyser design suggest that the kinetics significantly influence acetate distribution in the diffusion medium, with higher oxidation kinetic rates favouring increased acetate presence. Operando DRIFT performed using a continuous flow cell revealed that methanol is an important intermediate for acetate production from syngas.