Direct Observation of Intermediates for Carbon Dioxide Reduction Reaction in Concentrated Electrolytes
Authors: Yoshimura Hiroki , Hayase Shunsuke , Morinaga Asuka , Sai Ryansu , Kondo Yasuyuki , Katayama Yu , Yamada Yuki 
Published: December 2024

There is a growing need to utilize CO2 and realize a carbon-neutral society from the perspective of environmental problems caused by CO2 from fossil fuel-based processes. In this trend, electrochemical carbon dioxide reduction reaction (CO2RR), which converts CO2 to valuable fuels and chemicals with renewable energy, is attracting attention[1]. However, CO2RR has many challenges, including its low product selectivity. In particular, the hydrogen evolution reaction (HER), which occurs at the potential close to the standard electrode potential of CO2RR, reduces the selectivity of CO2RR, especially in aqueous electrolytes such as KHCO3
[2]
[3]. Therefore, we focus on a concentrated electrolyte, which is used as a means of HER suppression in water-based Li-ion batteries[4], to improve the selectivity of CO2RR. A concentrated electrolyte is an electrolyte with a high salt concentration, which can improve the electrochemical stability of water by creating a specific water environment[5]. Furthermore, due to its high salt concentration, the effect of anions and/or cations may become significant[6][7]. However, there has been no detailed understanding of how the electrolyte concentration affects the complex reaction pathway of CO2RR.
Here, we report the effect of concentrated electrolytes on the reaction process of CO2RR by directly observing reaction intermediates in situ while applying the potential. The product selectivity of CO2RR in 22.2, 42.0, and 61.7 mol kg–
1 of concentrated electrolyte was evaluated. Gas chromatography (GC) analysis confirms the suppression of HER in the series of concentrated electrolytes compared to 0.1 M KHCO3, a common aqueous electrolyte. In addition, an increase in the Faradaic efficiency of C2H4 was observed in ~ 42.0 mol kg–
1, implying a concentration-dependent change in the CO2RR reaction pathway (Fig.1). To elucidate the cause of the high C2H4 selectivity, in situ surface-enhanced infrared absorption spectroscopy (SEIRAS), which allows direct observation of the reaction intermediates, was performed. The results showed that as the electrolyte concentration was increased, the peaks at 1400 to 1500 cm–
1 region became more pronounced at low potential. We also observed the difference in the potential dependency for the intensity of CO adsorbates peak at 2100 cm–1 by electrolyte concentration. We will then discuss the effect of electrolyte concentration on the intermediates, unraveling the concentration-dependent change of the C2H4 selectivity. The work highlights the use of concentrated electrolytes to open up additional knobs for tuning the product selectivity of CO2RR, simply by designing an electrolyte component.
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Figure 1