Citation: CHENG Xiao-Wei, LI Shan-Shan, WU Lie, JIANG Xiu-E. Study on Counter Ion Effect at Electrode/Electrolyte Interface by Surface-enhanced Infrared Absorption Spectroelectrochemistry[J]. Chinese Journal of Analytical Chemistry, ;2022, 50(3): 365-374. doi: 10.19756/j.issn.0253-3820.210873 shu

Study on Counter Ion Effect at Electrode/Electrolyte Interface by Surface-enhanced Infrared Absorption Spectroelectrochemistry

CHENG Xiao-Wei ^1,2 ,
LI Shan-Shan ^1,2 ,
WU Lie ^1,, ,
JIANG Xiu-E ^1,2,,

¹State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China;
²School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China

Corresponding author: WU Lie, JIANG Xiu-E,
Received Date: 1 December 2021
Revised Date: 23 December 2021

Fund Project: Supported by the Youth Innovation Promotion Association of Chinese Academy of Sciences (No.2020233), the National Natural Science Foundation of China (Nos.22025406, 22074138) and the Science and Technology Innovation Foundation of Jilin Province, China (No.20200703021ZP).

The electrode-electrolyte interface is very important in electrochemistry, but the quantitative analysis of the adsorption of counter ions on the electrode surface and its influence on the interfacial electric field is extremely lacking, which limits the in-depth understanding of the electrode-electrolyte interface. In this study, four commonly used electrolytes in neutral electrochemical reaction systems were selected, and surface-enhanced infrared absorption spectroelectrochemistry combined with the vibrational Stark effect was used to analyze the special counter-ion effect at the electrode-electrolyte interface. The difference in distributions of anions as counter ions in the electric double layer due to the difference in the strength of the interaction with the electrode surface and the resultant different shielding of the local electric field at the interface were revealed through vibrational Stark probe with different molecular length. Anions that specifically interacted with the electrode could be adsorbed in the Stern layer in large quantities, significantly reducing the local effective electric field. This had far-reaching significance for deep understanding of the electrochemical double layer structure and the structure-activity relationship of the electrocatalytic reaction. At the same time, an effective quantitative analysis method was proposed for analysis of electrode-electrolyte interface.
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