阴离子表面活性剂调控的双电层: 提高酸性CO2电解的法拉第效率

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

催化学报

阴离子表面活性剂调控的双电层: 提高酸性CO₂电解的法拉第效率

张正^a,b, 唐雷^a, 朱以华^b, 葛旺鑫^a,*, 江宏亮^a,*, 李春忠^a,b,*

^a华东理工大学化工学院, 超细材料制备与应用教育部重点实验室, 上海 200237;
^b华东理工大学材料科学与工程学院, 上海多级结构纳米材料工程技术研究中心, 上海 200237

收稿日期:2025-09-08 接受日期:2025-09-08
通讯作者: *电子信箱: gwx@ecust.edu.cn (葛旺鑫), jhlworld@ecust.edu.cn (江宏亮), czli@ecust.edu.cn (李春忠).
基金资助:
国家自然科学基金(22222804, U22B20143); 国家重点研发计划(2022YFB3808400); 上海市科学技术委员会(22dz1205900); 上海市科技重大专项.

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

Zheng Zhang^a,b, Lei Tang^a, Yihua Zhu^b, Wangxin Ge^a,*, Hongliang Jiang^a,*, Chunzhong Li^a,b,*

^aKey Laboratory for Ultrafine Materials of Ministry of Education, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
^bShanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2025-09-08 Accepted:2025-09-08
Contact: *E-mail: gwx@ecust.edu.cn (W. Ge), jhlworld@ecust.edu.cn (H. Jiang), czli@ecust.edu.cn/czlilab@sjtu.edu.cn (C. Li).
Supported by:
National Natural Science Foundation of China (22222804, U22B20143), the National Key R&D program (2022YFB3808400), the Science and Technology Commission of Shanghai Municipality (22dz1205900), and the Shanghai Municipal Science and Technology Major Project.

摘要/Abstract

摘要： 电催化二氧化碳还原反应(CO₂RR)能够将CO₂转化为高附加值化学品和燃料, 对实现碳中和目标具有重要意义. 传统中性/碱性电解液中的CO₂RR存在严重的碳酸盐生成与交叉问题, 导致碳效率与稳定性降低. 酸性介质可有效避免碳酸盐沉淀, 并实现CO₂原位再生循环, 展现出高碳效率与低能耗优势; 然而, 酸性条件下析氢反应(HER)的激烈竞争严重限制了CO₂RR的实际应用. 为此, 研究人员发展了多种策略以提升酸性CO₂电解性能, 包括催化剂设计、电解质调控和电解槽优化. 其中, 电解质调控通过改变电极/溶液界面双电层(EDL)结构, 直接影响反应中间体的吸附行为、传质过程及最终产物选择性, 是当前研究的关键方向.
本研究以银电极催化CO₂RR为模型反应, 提出通过添加微量阴离子表面活性剂十二烷基磺酸钠(SDS)调控EDL结构及氢键网络, 以提高酸性电解液体系的CO₂还原制CO的选择性并降低体系中碱金属K⁺的浓度. 首先, 通过核磁共振波谱(NMR)和密度泛函理论(DFT)计算探究了SDS与溶剂水的氢键作用及对阳离子溶剂化结构的影响. 核磁锂谱和氢谱证实了SDS通过Lewis碱位点(-SO₃^‒)与溶剂水形成氢键作用、与碱金属阳离子(K⁺, Li⁺⁾通过Lewis酸碱作用形成复合溶剂化结构. DFT计算证实了SDS对降低了水解离活性. 在流动型电解池中评估SDS及其类似分子对CO₂电解选择性, CO₂单程转化率, 低碱金属体系的性能及长时间电解稳定性. 在添加0.4 mmol L^-1 SDS条件下, 于250 mA cm^-2电流密度实现了94.1%的CO法拉第效率(无添加体系为78.1%), 单程碳效率达72.2%. 并且在0.05 mol L^-1的低浓度K⁺体系中仍具有75%以上的CO法拉第效率, 显著高于对照体系(约20%), 证明了该策略在低碱金属体系的适用性. 进一步, 采用旋转圆盘(RDE)和电化学阻抗谱(EIS)进行了电化学动力学分析. RDE表征结果表明, SDS重构的界面抑制了水合氢离子电迁移, 降低局部质子浓度. EIS结果说明, 重构界面促进CO₂电解过程的电子转移, 加速CO₂RR动力学并抑制HER. 采用电化学表面增强红外吸收光谱对界面氢键环境及EDL结构进行表征发现, SDS随外加电势呈现吸附-脱附的过程. 结合理论计算部分证实SDS与H₂O及阳离子间存在强氢键和路易斯酸碱作用, 导致EDL扩展和界面水网络重组, 促进*COOH生成, 并通过抑制配位水形成吸附氢来减弱析氢过程. 本文在分子尺度阐明了添加剂分子对EDL结构、质子传输路径的调节机制.
综上, 本研究通过引入微量阴离子添加剂调控EDL结构, 显著提升了酸性条件下CO₂制CO的性能. 该电解质微环境调控策略具有良好的普适性, 可扩展至其他催化体系与反应介质, 为实现高效、稳定、低能耗的CO₂电解技术提供了新途径.

关键词: 酸性CO₂电解, 阴离子表面活性剂, 电解液调节, 双电层微环境, 原位光谱

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

张正, 唐雷, 朱以华, 葛旺鑫, 江宏亮, 李春忠. 阴离子表面活性剂调控的双电层: 提高酸性CO₂电解的法拉第效率[J]. 催化学报, DOI: 10.1016/S1872-2067(26)64963-7.

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阴离子表面活性剂调控的双电层: 提高酸性CO₂电解的法拉第效率

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

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