Spectroscopic Evidence of Size-Dependent Buffering of Interfacial pH by Cation Hydrolysis during CO2 Electroreduction

Onagie Ayemoba, Angel Cuesta* (Corresponding Author)

*Corresponding author for this work

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136 Citations (Scopus)
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The nature of the electrolyte cation is known to affect the Faradaic efficiency and selectivity of CO2 electroreduction. Singh et al. (J. Am. Chem. Soc. 2016, 138, 13006–13012) recently attributed this effect to the buffering ability of cation hydrolysis at the electrical double layer. According to them, the pKa of hydrolysis decreases close to the cathode due to the polarization of the solvation water molecules sandwiched between the cation’s positive charge and the negative charge on the electrode surface. We have tested this hypothesis experimentally, by probing the pH at the gold-electrolyte interface in situ using ATR-SEIRAS. The ratio between the integrated intensity of the CO2 and HCO3– bands, which has to be inversely proportional to the concentration of H+, provided a means to determining the pH change at the electrode–electrolyte interface in situ during the electroreduction of CO2. Our results confirm that the magnitude of the pH increase at the interface follows the trend Li+ > Na+ > K+ > Cs+, adding strong experimental support to Singh’s et al.’s hypothesis. We show, however, that the pH buffering effect was overestimated by Singh et al., their overestimation being larger the larger the cation. Moreover, our results show that the activity trend of the alkali-metal cations can be inverted in the presence of impurities that alter the buffering effect of the electrolyte, although the electrolyte with maximum activity is always that for which the increase in the interfacial pH is smaller.
Original languageEnglish
Pages (from-to)27377-27382
Number of pages6
JournalACS Applied Materials & Interfaces
Issue number33
Early online date15 Aug 2017
Publication statusPublished - 23 Aug 2017

Bibliographical note

The support of the University of Aberdeen and the Leverhulme Trust (Grant No. RPG-2015-040) is gratefully acknowledged. OA acknowledges an Elphinstone Scholarship awarded by the University of Aberdeen.


  • C02RR
  • cation effects
  • cation hydrolysis
  • interfacial pH


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