Influence of Water Molecules on CO2 Reduction at the Pt Electrocatalyst in the Membrane Electrode Assembly System

CO2 electroreduction using a Pt catalyst in an aqueous solution system is known to produce only H-2. Recently, a remarkable result has been reported that CH4 can be obtained by reducing CO2 using a membrane electrode assembly (MEA) containing a Pt catalyst. A big difference that exists between the two systems is the number of water molecules. Therefore, this study investigated the influence of water molecules on the CO2-reduction process at the Pt electrocatalyst in the MEA system. As a result, cyclic voltammetry indicated that adsorbed CO (COads) was formed by CO2 reduction in the MEA system more preferably than the aqueous solution system. In detail, the ratio of COads at the atop sites (linear CO, COL) on Pt, which participates in the CH4 generation reaction, to the total COads formed by the CO2 reduction became higher as the lower relative humidity (RH) at 50 degrees C in the MEA system. Cyclic voltammetry combined with in-line mass spectrometry revealed that the amount of COL and CH4 generated by the CO2 reduction reached their maximums at 63.1% RH. CH4 production by the extremely low-overpotential CO2 reduction was significantly achieved under all the RH conditions. Consequently, the Faradaic efficiency of the CH4 production at 63.1% RH was improved by 1.35 times compared to that at 100% RH. These results would be mainly obtained based on the H2O-involved chemical equilibrium of the reactions for the COads and CH4 formation. Overall, the present study experimentally clarified that the formation of COads (particularly COL) and the following CH4 from the CO2 reduction at the Pt electrocatalyst in the MEA system was facilitated by appropriately controlling the water-molecule content.