Anion surfactant-tailored electric double-layer: Toward higher faradaic efficiency in acidic CO2 electrolysis

doi:10.1016/S1872-2067(26)64963-7

Abstract

Abstract:

Electric double-layer (EDL) structure critically influences electrocatalytic kinetics and performance, yet mechanistic understanding of anion-mediated EDL modulation remains limited, particularly in acidic CO₂ electrolysis. Here, we demonstrate that the prototypical anionic surfactant sodium dodecyl sulfate (SDS) induces EDL expansion and reconstruct interfacial hydrogen-bonding (H-bond) networks, thereby suppressing the competitive hydrogen evolution reaction (HER) in acidic electrolytes, while achieving 94.1% CO Faradaic efficiency at 250 mA cm^-2. Electrochemical kinetics analysis identifies that SDS-induced disruption of interfacial H-bond networks impedes proton transport kinetics, thereby suppressing HER in acid. Integrative electrolyte characterizations combined with in situ spectroscopic analysis revealed that the widening of the EDL stems from Lewis acid-base interactions between SDS and K⁺. Further, the introduction of SDS modulates interfacial water dissociation activity, thereby facilitating the hydrogenation pathway from CO₂ to *COOH. These findings establish a rational electrolyte design strategy for manipulating EDL to enhance acidic CO₂ electrolysis performance.

Key words: Acidic CO₂ electrolysis, Anionic surfactants, Electrolyte regulation, Electric double-layer microenvironment, In-situ spectroscopy

Zheng Zhang, Lei Tang, Yihua Zhu, Wangxin Ge, Hongliang Jiang, Chunzhong Li. Anion surfactant-tailored electric double-layer: Toward higher faradaic efficiency in acidic CO₂ electrolysis[J]. Chinese Journal of Catalysis, 2026, 85: 96-105.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64963-7

https://www.cjcatal.com/EN/Y2026/V85/I6/96

Figures/Tables 5

Fig. 1. Proposed strategy for enhancing FE of acidic CO2 electrolysis. (a) Schematic diagram and research perspectives of acidic CO2 electrolysis. (b) Electrolyte regulation strategies for acidic CO2 electrolysis. (c) Our proposed strategy for inhibiting the HER by modulating the EDL with the anionic surfactant SDS.

Fig. 2. Electrolyte characterization. (a) 1H NMR spectrum of the 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 electrolytes without and with 0.4 mmol L-1 SDS. (b) 7Li NMR spectrum of the 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 electrolytes without and with 0.4 mmol L-1 SDS. (c) The binding energy of K-SDS and K-H2O from quantum chemical calculations. (d) Free energy of the H2O (H2O) and H2O (SDS) clusters.

Fig. 3. Acidic CO2 electrolysis performance. (a) FE of CO in 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 electrolyte with different anionic surfactants (0.4 m mol L-1) at 250 mA cm−2. (b) FE of CO at different current densities in 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 without and with 0.4 mmol L-1 SDS. (c) FE of CO and the SPCE at different CO2 flow rate in 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 at 250 mA cm−2. (d) FE of CO in 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 without/with 0.4 mmol L-1 SDS with different concentrations of K+ at 250 mA cm−2. (e) Long-term catalytic performance in 0.05 mol L-1 H2SO4 + 0.2 M K2SO4 electrolytes with 0.4 mol L-1 SDS at 150 mA cm−2. The error bars represent three independent tests.

Fig. 4. Electrochemical kinetic studies. (a) LSV curves of 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 electrolytes with and without 0.4 mmol L-1 SDS under CO2 saturation, acquired at 50 mV s-1 scan rate. Nyquist plots (b) and Bode plots (c) for 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 electrolytes with and without 0.4 mmol L-1 SDS at -0.72 and -0.82 V vs. RHE. LSV curves of 4 mmol L-1 H2SO4 + 0.2 mol L-1 K2SO4 electrolyte without (d) and with 0.4 mmol L-1 SDS (e) under N2 saturation, scanned at 50 mV s-1. (f) Comparison of linear fitting of jplateau versus ω1/2 for RDE with and without SDS based on Levich equation.

Fig. 5. In-situ probing the EDL structure. (a) In-situ ATR-SEIRAS spectra at varied potentials in 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 electrolyte. (b) In-situ ATR-SEIRAS spectra at varied potentials in 0.1 mol L-1 H2SO4 + 0.2 mol L-1 K2SO4 with 0.4 mmol L-1 SDS electrolyte. (c) Deconvolution of νOH bands at -0.6 V vs. RHE for two systems. (d) The νCH peaks of SDS from in situ ATR-SEIRAS under various potentials. (e) Intensity of νCH peaks of SDS-containing electrolytes under various potentials. (f) Schematic of EDL structure before and after SDS introduction.

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Anion surfactant-tailored electric double-layer: Toward higher faradaic efficiency in acidic CO₂ electrolysis

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