Proceedings of MATSUS Fall 2023 Conference (MATSUSFall23)
DOI: https://doi.org/10.29363/nanoge.matsus.2023.277
Publication date: 18th July 2023
CO2 electrolysis using silver (Ag) and copper (Cu) based catalysts have been widely studied due to their ability to produce CO and multi-carbon products respectively. In industrially relevant membrane electrode assembly configurations, long term operational stability is hampered due to (bi) carbonate precipitation at the cathode triggered by alkali metal cation crossover from the anode. In this work, we investigate the role of cation crossover for Ag and Cu based catalysts by varying cation concentrations and the cation identity. We find that cation crossover from the anode is essential for CO2 activation and cation identity (K+, Na+) affect CO2RR selectivities significantly as shown in a number of previous studies. Further, we find that cation concentration do not alter product selectivity for a Ag catalyst producing CO, but alter product distribution significantly for a Cu catalyst, showing that C-C coupling rates are significantly affected by local cation concentration at the cathode. In contrast, cation crossover is detrimental for long term operation due to (bi) carbonate precipitation at the electrolyte free cathode, that induces flooding of the gas diffusion electrode over time. These results reveal that a proper management of local cation and water concentrations are essential in order to acheive long term operational stability in zero gap CO2 electrolyzers.
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