Enhanced electrochemical carbon dioxide reduction in membrane electrode assemblies with acidic electrolytes through a silicate buffer layer

doi:10.1016/S1872-2067(24)60129-4

Abstract

Abstract:

The electrochemical reduction of CO₂ holds considerable promise in combating global climate change while yielding valuable chemical commodities. Membrane electrode assemblies operating within acidic electrolyte have exhibited noteworthy advancements in CO₂ utilization efficiency, albeit encountering formidable competition from the hydrogen evolution reaction. In our investigation, we introduced a silicate buffer layer, which yielded exceptional outcomes even using strong acid electrolyte. Notably, our approach yielded a CO Faradic efficiency of 90% and reached a substantial current density of 400 mA cm^-2. Furthermore, our system displayed remarkable stability over a 12-hour duration, and achieved a high single-pass-conversion efficiency of 67%. Leveraging in-situ Raman analysis, we attributed these performance enhancements to the augmented CO₂ adsorption and localized alkaline environment facilitated by the incorporation of the silicate buffer layer. We think the addition of buffer layer to adjust the microenvironment is essential to achieve high performance and keep stable in acid condition.

Key words: Electrocatalysis, Reduction of CO₂, Microenvironment, Acidic system, Membrane electrode

Shilei Wei, Hang Hua, Qingxuan Ren, Jingshan Luo. Enhanced electrochemical carbon dioxide reduction in membrane electrode assemblies with acidic electrolytes through a silicate buffer layer[J]. Chinese Journal of Catalysis, 2024, 66: 139-145.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60129-4

https://www.cjcatal.com/EN/Y2024/V66/I11/139

Figures/Tables 3

Fig. 1. Cation-induced CO2 reduction in acidic MEA systems. (A) FECO and FEH2 of Ag GDE during CO2RR within MEA using H2SO4 anolyte at varying pH levels, measured at a current density of 100 mA cm-2. (B) FECO and FEH2 of Ag GDE during CO2RR after introduced 1 mol L-1 Na+, K+, or Cs+ into H2SO4 anolyte, with pH adjustment to 2 using H2SO4. (C) FECO and FEH2 of Ag GDE during CO2RR employing different concentrations of Cs+ anolyte, with pH adjustment to 2 using H2SO4. (D) FECO and FEH2 of Ag GDE during CO2RR utilizing anolytes with varying pH levels, maintaining a constant Cs+ concentration of 1 mol L-1. (E) Duration performance analysis of CO2RR at 100 mA cm-2 employing the Ag GDE with anolyte containing 1 mol L-1 Cs+, pH adjusted to 2 using H2SO4. (F) XRD pattern depicting salt precipitation and the gas flow channel configuration post-experimentation (insert image). The error bars are determined from at least 3 separate experiments.

Fig. 2. Na2SiO3 modified Ag GDE for CO2 reduction. (A) FECO and FEH2 of Ag GDE and NM-Ag during CO2RR in H2SO4 anolyte containing 0.5 mol L-1 Cs+ at a current density of 100 mA cm-2. (B) FECO and FEH2 of NM-Ag during CO2RR employing varying concentrations of Cs+ anolytes, with pH adjustment to 2 using H2SO4. (C) FECO and FEH2 during CO2RR utilizing anolyte containing 1 mol L-1 Cs+ at different current densities. pH was adjusted to 2 using H2SO4. (D) FECO during CO2RR and the SPCE under varying gas flow rates at 100 mA cm-2. The anolyte contained 1 mol L-1 Cs+ and pH was adjusted to 2 using H2SO4. (E) Comparative analysis of cell voltage and FECO among Ag, SiO2-Ag, and NM-Ag for long time stability test. The error bars are determined from at least 3 separate experiments.

Fig. 3. In situ Raman spectra of (A) Ag and (B) NM-Ag samples in the range of 300-1200 cm-1 under varying applied potentials. The peak attributed to ν (Ag-O) corresponds to the vibration of metal Ag interacting with adjacent subsurface hydroxyl groups. (C) The working principal scheme and schematic illustrating of Ag GDE (left) and NM-Ag (right) for CO2RR in acidic MEA system.

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