Investigation of Gas Diffusion Electrode Systems for the Electrochemical CO2 Conversion

Electrochemical CO2 reduction is a promising carbon capture and utilisation technology.
Herein, a continuous flow gas diffusion electrode (GDE)-cell configuration has been studied to
convert CO2 via electrochemical reduction under atmospheric conditions. To this purpose, Cu-based
electrocatalysts immobilised on a porous and conductive GDE have been tested. Many system
variables have been evaluated to find the most promising conditions able to lead to increased
production of CO2 reduction liquid products, specifically: applied potentials, catalyst loading,
Nafion content, KHCO3 electrolyte concentration, and the presence of metal oxides, like ZnO or/and
Al2O3. In particular, the CO productivity increased at the lowest Nafion content of 15%, leading to
syngas with an H2/CO ratio of ~1. Meanwhile, at the highest Nafion content (45%), C2+ products
formation has been increased, and the CO selectivity has been decreased by 80%. The reported results
revealed that the liquid crossover through the GDE highly impacts CO2 diffusion to the catalyst
active sites, thus reducing the CO2 conversion efficiency. Through mathematical modelling, it has
been confirmed that the increase of the local pH, coupled to the electrode-wetting, promotes the
formation of bicarbonate species that deactivate the catalysts surface, hindering the mechanisms
for the C2+ liquid products generation. These results want to shine the spotlight on kinetics and
transport limitations, shifting the focus from catalytic activity of materials to other involved factors.