表面增强红外光谱电化学揭示电极-电解质界面处的抗衡离子效应

引用本文: 程晓伟, 李姗姗, 武烈, 姜秀娥. 表面增强红外光谱电化学揭示电极-电解质界面处的抗衡离子效应[J]. 分析化学, 2022, 50(3): 365-374. doi: 10.19756/j.issn.0253-3820.210873 shu

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

表面增强红外光谱电化学揭示电极-电解质界面处的抗衡离子效应

程晓伟 ^1,2, ,
李姗姗 ^1,2, ,
武烈 ^{1,
,} ,
姜秀娥 ^{1,2,
,}

¹中国科学院长春应用化学研究所, 电分析化学国家重点实验室, 长春 130022;
²中国科学技术大学应用化学与工程学院, 合肥 230026

通讯作者: 武烈,E-mail:lwu@ciac.ac.cn; 姜秀娥,E-mail:jiangxiue@ciac.ac.cn

基金项目:
中国科学院青年创新促进会项目（No.2020233）、国家自然科学基金项目（Nos.22025406，22074138）和吉林省科技发展计划项目（No.20200703021ZP）资助。

摘要: 选用4种中性电化学反应体系中常用的电解质，利用表面增强红外吸收光谱电化学技术结合振动斯塔克效应对电极-电解质溶液界面处特殊的抗衡离子效应进行谱学-电化学表征。应用不同分子长度的振动斯塔克探针，揭示了阴离子作为抗衡离子，因与电极表面相互作用强度的差异而在双电层中具有不同的浓度分布，进而对界面局域电场产生不同的屏蔽效应。与电极表面存在特异性相互作用的离子可大量吸附到紧密层，使界面局域有效电场强度显著降低。此外，本研究还提出了定量分析离子与电极界面相互作用程度的方法。本研究结果对进一步理解电化学双电层的结构以及电催化反应的构效关系具有重要意义。

关键词:

English

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

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: 01 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).

Abstract: 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.

Key words:

Vibration Stark effect
/ Surface-enhanced infrared absorption spectroelectrochemistry
/ Electric double layer
/ Electrode-electrolyte interface
/ Quantitative analysis

1. [1]
  DEVANATHAN M A, TILAK B V K. Chem. Rev., 1965, 65(6):635-684.DEVANATHAN M A, TILAK B V K. Chem. Rev., 1965, 65(6):635-684.
2. [2]
  MAGNUSSEN O M, GROß A. J. Am. Chem. Soc., 2019, 141(12):4777-4790.MAGNUSSEN O M, GROß A. J. Am. Chem. Soc., 2019, 141(12):4777-4790.
3. [3]
  STEINMANN S N, WEI Z Y, SAUTET P. Proc. Natl. Acad. Sci. U.S.A., 2019, 116(16):7611-7613.STEINMANN S N, WEI Z Y, SAUTET P. Proc. Natl. Acad. Sci. U.S.A., 2019, 116(16):7611-7613.
4. [4]
  ZAERA F. Chem. Rev., 2012, 112(5):2920-2986.ZAERA F. Chem. Rev., 2012, 112(5):2920-2986.
5. [5]
  CHOI N S, CHEN Z H, FREUNBERGER S A, JI X L, SUN Y K, AMINE K, YUSHIN G, NAZAR L F, CHO J, BRUCE P G. Angew. Chem., Int. Ed., 2012, 51(40):9994-10024.CHOI N S, CHEN Z H, FREUNBERGER S A, JI X L, SUN Y K, AMINE K, YUSHIN G, NAZAR L F, CHO J, BRUCE P G. Angew. Chem., Int. Ed., 2012, 51(40):9994-10024.
6. [6]
  TRIPKOVIC D V, STRMCNIK D, VAN DER VLIET D, STAMENKOVIC V, MARKOVIC N M. Faraday Discuss., 2008, 140:25-40.TRIPKOVIC D V, STRMCNIK D, VAN DER VLIET D, STAMENKOVIC V, MARKOVIC N M. Faraday Discuss., 2008, 140:25-40.
7. [7]
  WANG H N, PILON L. J. Phys. Chem. C, 2011, 115(33):16711-16719.WANG H N, PILON L. J. Phys. Chem. C, 2011, 115(33):16711-16719.
8. [8]
  POPE J M, ZHENG T, KIMBRELL S, BUTTRY D A. J. Am. Chem. Soc., 1992, 114(25):10085-10086.POPE J M, ZHENG T, KIMBRELL S, BUTTRY D A. J. Am. Chem. Soc., 1992, 114(25):10085-10086.
9. [9]
  EGGERS P K, DARWISH N, PADDON-ROW M N, GOODING J J. J. Am. Chem. Soc., 2012, 134(17):7539-7544.EGGERS P K, DARWISH N, PADDON-ROW M N, GOODING J J. J. Am. Chem. Soc., 2012, 134(17):7539-7544.
10. [10]
  SMITH C P, WHITE H S. Anal. Chem., 1992, 64(20):2398-2405.SMITH C P, WHITE H S. Anal. Chem., 1992, 64(20):2398-2405.
11. [11]
  WEN B Y, LIN J S, ZHANG Y J, RADJENOVIC P M, ZHANG X G, TIAN Z Q, LI J F. J. Am. Chem. Soc., 2020, 142(27):11698-11702.WEN B Y, LIN J S, ZHANG Y J, RADJENOVIC P M, ZHANG X G, TIAN Z Q, LI J F. J. Am. Chem. Soc., 2020, 142(27):11698-11702.
12. [12]
  FAVARO M, JEONG B, ROSS P N, YANO J, HUSSAIN Z, LIU Z, CRUMLIN E J. Nat. Commun., 2016, 7:12695.FAVARO M, JEONG B, ROSS P N, YANO J, HUSSAIN Z, LIU Z, CRUMLIN E J. Nat. Commun., 2016, 7:12695.
13. [13]
  BROWN M A, GOEL A, ABBAS Z. Angew. Chem., Int. Ed., 2016, 55(11):3790-3794.BROWN M A, GOEL A, ABBAS Z. Angew. Chem., Int. Ed., 2016, 55(11):3790-3794.
14. [14]
  WANG X P, LIU K, WU J Z. J. Chem. Phys., 2021, 154(12):124701.WANG X P, LIU K, WU J Z. J. Chem. Phys., 2021, 154(12):124701.
15. [15]
  WU Lie, SUN Jian-Long, JIANG Xiu-E. J. Electrochem., 2019, 25(2):202-222. 武烈, 孙建龙, 姜秀娥. 电化学, 2019, 25(2):202-222.
16. [16]
  ZHANG P, WEI Y, CAI J, CHEN Y X, TIAN Z Q. Chin. J. Catal., 2016, 37(7):1156-1165.ZHANG P, WEI Y, CAI J, CHEN Y X, TIAN Z Q. Chin. J. Catal., 2016, 37(7):1156-1165.
17. [17]
  SCHKOLNIK G, SALEWSKI J, MILLO D, ZEBGER I, FRANZEN S, HILDEBRANDT P. Int. J. Mol. Sci., 2012, 13(6):7466-7482.SCHKOLNIK G, SALEWSKI J, MILLO D, ZEBGER I, FRANZEN S, HILDEBRANDT P. Int. J. Mol. Sci., 2012, 13(6):7466-7482.
18. [18]
  ZHANG N, WANG X R, YUAN Y X, WANG H F, XU M M, REN Z G, YAO J L, GU R A. J. Electroanal. Chem., 2015, 751:137-143.ZHANG N, WANG X R, YUAN Y X, WANG H F, XU M M, REN Z G, YAO J L, GU R A. J. Electroanal. Chem., 2015, 751:137-143.
19. [19]
  DREXLER C I, CRACCHIOLO O M, MYERS R L, OKUR H I, SERRANO A L, CORCELLI S A, CREMER P. J. Phys. Chem. B, 2021, 125(30):8484-8493.DREXLER C I, CRACCHIOLO O M, MYERS R L, OKUR H I, SERRANO A L, CORCELLI S A, CREMER P. J. Phys. Chem. B, 2021, 125(30):8484-8493.
20. [20]
  SARKAR S, MAITRA A, BANERJEE S, THOI V S, DAWLATY J M. J. Phys. Chem. B, 2020, 124(7):1311-1321.SARKAR S, MAITRA A, BANERJEE S, THOI V S, DAWLATY J M. J. Phys. Chem. B, 2020, 124(7):1311-1321.
21. [21]
  WU L, ZENG L, JIANG X E. J. Am. Chem. Soc., 2015, 137(32):10052-10055.WU L, ZENG L, JIANG X E. J. Am. Chem. Soc., 2015, 137(32):10052-10055.
22. [22]
  LI X, GEWIRTH A A. J. Am. Chem. Soc., 2003, 125(38):11674-11683.LI X, GEWIRTH A A. J. Am. Chem. Soc., 2003, 125(38):11674-11683.
23. [23]
  LEVINSON N M, BOLTE E E, MILLER C S, CORCELLI S A, BOXER S G. J. Am. Chem. Soc., 2011,133(34):13236-13239.LEVINSON N M, BOLTE E E, MILLER C S, CORCELLI S A, BOXER S G. J. Am. Chem. Soc., 2011,133(34):13236-13239.
24. [24]
  MAGNUSSEN O M. Chem. Rev., 2002, 102(3):679-726.MAGNUSSEN O M. Chem. Rev., 2002, 102(3):679-726.
25. [25]
  YAGUCHI M, UCHIDA T, MOTOBAYASHI K, OSAWA M. J. Phys. Chem. Lett., 2016, 7(16):3097-3102.YAGUCHI M, UCHIDA T, MOTOBAYASHI K, OSAWA M. J. Phys. Chem. Lett., 2016, 7(16):3097-3102.
26. [26]
  ZHANG Y Y, TANG J L, NI Z G, ZHAO Y, JIA F F, LUO Q, MAO L Q, ZHU Z H, WANG F Y. J. Phys. Chem. Lett., 2021, 12(22):5279-5285.ZHANG Y Y, TANG J L, NI Z G, ZHAO Y, JIA F F, LUO Q, MAO L Q, ZHU Z H, WANG F Y. J. Phys. Chem. Lett., 2021, 12(22):5279-5285.
27. [27]
  HU Q Y, WEBER C, CHENG H W, RENNER F U, VALTINER M. J. ChemPhysChem, 2017, 18(21):3056-3065.HU Q Y, WEBER C, CHENG H W, RENNER F U, VALTINER M. J. ChemPhysChem, 2017, 18(21):3056-3065.

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沈阳化工大学材料科学与工程学院沈阳 110142

表面增强红外光谱电化学揭示电极-电解质界面处的抗衡离子效应

通讯作者: 武烈,E-mail:lwu@ciac.ac.cn; 姜秀娥,E-mail:jiangxiue@ciac.ac.cn

English

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

Corresponding author: WU Lie, ; JIANG Xiu-E,

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

表面增强红外光谱电化学揭示电极-电解质界面处的抗衡离子效应

通讯作者: 武烈,E-mail:lwu@ciac.ac.cn; 姜秀娥,E-mail:jiangxiue@ciac.ac.cn

English

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

Corresponding author: WU Lie, ; JIANG Xiu-E,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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