水依赖界面对二巯基偶氮苯电化学还原反应动力学研究及水含量测定

doi:10.6023/A26030081

摘要/Abstract

乙腈作为电化学合成与储能领域的重要非质子极性溶剂而得到广泛应用, 但微量水分的引入会显著改变电极界面微环境, 进而改变界面反应动力学过程, 因此亟待从动力学行为角度理解水的行为. 通常水分子拉曼散射截面小及在贵金属基底吸附弱的特点而导致采用表面增强拉曼光谱(SERS)研究仍存在一定的困难. 本研究以对界面水或质子性物种浓度高度敏感的对二巯基偶氮苯(DMAB)电化学还原反应为探针, 将均匀性与稳定性优异的Au纳米粒子单层膜(Au MLF)转移至玻碳电极表面获得SERS活性基底, 系统探究乙腈体系中不同水含量对DMAB还原反应动力学的影响规律. 研究表明, DMAB在乙腈体系中的还原反应强烈依赖于水或质子性物种, 且符合准一级动力学特征. 无水乙腈体系中, 在－0.4至－1.0 V电位区间内, DMAB仍无法发生还原反应, 当水质量分数达到0.3%时可观察到还原反应发生, 速率常数随水含量升高逐渐增大, 水质量分数≥10.0%时, 反应速率常数增速缓慢, 反应速率趋于饱和. 基于水含量与反应速率常数的定量关联, 发展了乙腈体系微量水含量的检测新方法, 所得结果与常规标准方法测定结果一致, 且该方法适用于水含量低于0.5%时的体系. 本研究可望为非水体系中水或质子性物种对界面过程的影响的研究提供一种新途径, 为非电化学相关器件溶剂的选择和体系优化提供实验基础.

关键词: 速率常数, 电化学表面增强拉曼散射(EC-SERS), 对二巯基偶氮苯, 还原反应, 水含量测定

Acetonitrile is widely employed as a crucial aprotic polar solvent in the fields of electrochemical synthesis and energy storage. However, the introduction of trace water can significantly alter the microenvironment at the electrode interface, thereby modifying the kinetic process of interfacial reactions. Accordingly, it is urgent to unravel the behavior of water from the perspective of kinetic characteristics. Conventional investigations using electrochemical surface-enhanced Raman spectroscopy (SERS) still face certain challenges, owing to the small Raman scattering cross-section of water molecules and their weak adsorption on noble metal substrates. In this study, the electrochemical reduction of p-dimercaptoazobenzene (DMAB), which is highly sensitive to the concentration of interfacial water or protic species, was utilized as a probe reaction. A gold nanoparticle monolayer film (Au MLF) with outstanding uniformity and stability was transferred onto the surface of a glassy carbon electrode to fabricate a SERS-active substrate. The influence of varying water contents on the reduction kinetics of DMAB in acetonitrile systems was systematically explored. The results demonstrate that the reduction of DMAB in acetonitrile media is strongly dependent on water or protic species, and the reaction follows pseudo-first-order kinetic characteristics. In anhydrous acetonitrile systems, DMAB cannot undergo reduction within the potential range of －0.4 V to －1.0 V. The reduction reaction is observed to occur when the mass fraction of water reaches 0.3%, and the rate constant increases gradually with the elevation of water content. When the water mass fraction is ≥10.0%, the growth rate of the reaction rate constant slows down, and the reaction rate tends to saturate. Based on the quantitative correlation between water content and reaction rate constant, a novel method for the detection of trace water in acetonitrile systems was developed. The results obtained by this method are consistent with those determined by conventional standard methods, and it is particularly applicable to systems with water content below 0.5%. This study is expected to provide a new approach for investigating the effects of water or protic species on interfacial processes in non-aqueous systems, and lay an experimental foundation for the solvent selection and system optimization of non-electrochemical related devices.

Key words: rate constant, electrochemical surface-enhanced Raman scattering (EC-SERS), p-dimercaptoazobenzene, reduction reaction, detection of water content

引用此文

余溪, 张晨杰, 徐敏敏, 袁亚仙, 姚建林. 水依赖界面对二巯基偶氮苯电化学还原反应动力学研究及水含量测定[J]. 化学学报, 2026, 84(7): 1114-1120.

Xi Yu, Chenjie Zhang, Minmin Xu, Yaxian Yuan, Jianlin Yao. Investigation on the Kinetics of Water-Dependent Electrochemical Reduction Reaction of p-dimercaptoazobenzene and Detection on Water Content[J]. Acta Chimica Sinica, 2026, 84(7): 1114-1120.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

图1. SERS谱峰相对强度比值分别依据准一级反应(a)以及二级反应(b)进行拟合分析的结果

Figure 1. Results of fitting analysis of the relative intensity ratios of SERS peaks based on pseudo-first-order reactions (a) and second-order reactions (b), respectively

图2. －0.2 V下CH3CN中DMAB还原反应过程中随时间变化的SERS光谱(a), 及1142和1073 cm−1谱峰相对强度的自然对数值随时间变化曲线(b)

Figure 2. Time dependent SERS spectra of DMAB reduction process in CH3CN (a) and the natural logarithm curves of relative intensities of the SERS peaks of 1142 and 1073 cm−1 at different time at －0.2 V (b)

图3. 不同电位下DMAB还原反应中位于1142与1073 cm−1谱峰相对强度比值的自然对数值随时间变化曲线, －0.4 V (a)、－0.6 V (b)、－0.8 V (c)和－1.0 V (d)

Figure 3. The natural logarithm curves of relative intensities of the SERS peaks of 1142 and 1073 cm−1 at different time for the DMAB reduction reaction under different potentials －0.4 V (a), －0.6 V (b), －0.8 V (c) and －1.0 V (d), respectively

图4. 电位阶跃至－1.0 V后水含量0.1% (a)和0.2% (b)的CH3CN体系中, DMAB还原反应中位于1142与1073 cm−1谱峰相对强度比值的自然对数值随时间变化曲线

Figure 4. The natural logarithm curves of relative intensities of the SERS peaks of 1142 and 1073 cm−1 at different time after potential step to －1.0 V in the CH3CN system with different content of water of 0.1% (a) and 0.2% (b)

图5. 电位阶跃至－1.0 V后水含量0.3% (a)、0.4% (b)、0.5% (c)、1.0% (d)、10.0% (e)和30.0% (f)的CH3CN体系中, DMAB还原反应中位于1142与1073 cm−1谱峰相对强度比值的自然对数值随时间变化曲线

Figure 5. The natural logarithm curves of relative intensities of the SERS peaks of 1142 and 1073 cm−1 at different time after potential step to －1.0 V in the CH3CN system with different content of water of 0.3% (a), 0.4% (b), 0.5% (c), 1.0% (d), 10.0% (e) and 30.0% (f)

图6. 反应起始和时间t后SERS谱峰相对强度比值的自然对数值随时间的变化曲线及依据准一级反应进行拟合分析的结果

Figure 6. The natural logarithm curves of relative intensities of the SERS peaks of 1142 and 1073 cm-1 at different time and the fitting results based on the pseudo-first-order reaction

图7. 不同含水量(质量分数分别为0.3%、0.4%和0.5%)的CH3CN体系中DMAB电化学还原反应速率常数测定拟合曲线图

Figure 7. The fitting curves of rate constants of DMAB reduction reaction in CH3CN systems with different H2O content (mass fractions) of 0.3%, 0.4%, and 0.5% respectively

参考文献 36

[1]	Kwak, W.-J.; Rosy, S. D.; Xia, C.; Kim, H.; Johnson, L. R.; Bruce, P. G.; Nazar, L. F.; Sun, Y.-K.; Frimer, A. A.; Noked, M.; Freunberger, S. A.; Aurbach, D. Chem. Rev. 2020, 120, 6626. doi: 10.1021/acs.chemrev.9b00609
[2]	Yoshida, J.-i.; Kataoka, K.; Horcajada, R.; Nagaki, A. Chem. Rev. 2008, 108, 2265. doi: 10.1021/cr0680843
[3]	Yan, M.; Kawamata, Y.; Baran, P. S. Chem. Rev. 2017, 117, 13230. doi: 10.1021/acs.chemrev.7b00397
[4]	He, Q. J.; Zhang, C. J.; Xu, M. M.; Yuan, Y. X.; Yao, J. L. Acta Chim. Sinica 2024, 82, 1202 (in Chinese). doi: 10.6023/A24090260
	(贺乾军, 张晨杰, 徐敏敏, 袁亚仙, 姚建林, 化学学报, 2024, 82, 1202.) doi: 10.6023/A24090260
[5]	Gunasekaran, P.; Cuesta, A. J. Solid State Electrochem. 2025, 29, 2213. doi: 10.1007/s10008-025-06305-1
[6]	Mei, Y.; Liao, P.; Zhang, Y. Org. Biomol. Chem. 2025, 23, 9752. doi: 10.1039/D5OB00647C
[7]	Nakamura, H.; Komatsu, H.; Yoshio, M. J. Power Sources 1996, 62, 219. doi: 10.1016/S0378-7753(96)02417-2
[8]	Ledezma-Yanez, I.; Díaz-Morales, O.; Figueiredo, M. C.; Koper, M. T. M. ChemElectroChem 2015, 2, 1612. doi: 10.1002/celc.v2.10
[9]	Rudnev, A. V.; Molodkina, E. B.; Danilov, A. I.; Polukarov, Y. M.; Berna, A.; Feliu, J. M. Electrochim. Acta 2009, 54, 3692. doi: 10.1016/j.electacta.2009.01.047
[10]	Angerstein-Kozlowska, H.; Macdougall, B.; Conway, B. E. J. Electroanal. Chem. Interfacial Electrochem. 1972, 39, 287. doi: 10.1016/S0022-0728(72)80153-0
[11]	Barrett, P.; Pruszkowska, E. Anal. Chem. 1984, 56, 1927. doi: 10.1021/ac00275a038
[12]	Morin, S.; Conway, B. E.; Edens, G. J.; Weaver, M. J. J. Electroanal. Chem. 1997, 421, 213. doi: 10.1016/S0022-0728(96)04839-5
[13]	Harlow, G. S.; Aldous, I. M.; Thompson, P.; Gründer, Y.; Hardwick, L. J.; Lucas, C. A. Phys. Chem. Chem. Phys. 2019, 21, 8654. doi: 10.1039/c9cp00499h pmid: 30816395
[14]	Kundu, A.; Dahms, F.; Fingerhut, B. P.; Nibbering, E. T. J.; Pines, E.; Elsaesser, T. J. Phys. Chem. Lett. 2019, 10, 2287. doi: 10.1021/acs.jpclett.9b00756
[15]	Gu, R. A.; Sun, Y. H.; Cao, P. G.; Yao, J. L.; Ren, B.; Tian, Z. Q. Chem. J. Chinese Universities 2002, 23, 1960 (in Chinese).
	(顾仁敖, 孙玉华, 曹佩根, 姚建林, 任斌, 田中群, 高等学校化学学报, 2002, 23, 1960.)
[16]	Niu, T.; Yuan, Y.; Yao, J.; Lu, F.; Gu, R. Sci. China Chem. 2011, 54, 200. doi: 10.1007/s11426-010-4184-8
[17]	Wu, D.-Y.; Li, J.-F.; Ren, B.; Tian, Z.-Q. Chem. Soc. Rev. 2008, 37, 1025. doi: 10.1039/b707872m
[18]	Zhao, L. B.; Huang, Y. F.; Wu, D. Y.; Ren, B. Acta Chim. Sinica 2014, 72, 1125 (in Chinese). doi: 10.6023/A14080602
	(赵刘斌, 黄逸凡, 吴德印, 任斌, 化学学报, 2014, 72, 1125.) doi: 10.6023/A14080602
[19]	Thiel, P. A.; Madey, T. E. Surf. Sci. Rep. 1987, 7, 211. doi: 10.1016/0167-5729(87)90001-X
[20]	Zhang, C. J.; Zhang, J.; Lin, J. R.; Jin, Q.; Xu, M. M.; Yao, J. L. Acta Chim. Sinica 2017, 75, 860 (in Chinese). doi: 10.6023/A17050198
	(张晨杰, 张婧, 林洁茹, 金琦, 徐敏敏, 姚建林, 化学学报, 2017, 75, 860.) doi: 10.6023/A17050198
[21]	Xie, W.; Schlücker, S. Chem. Commun. 2018, 54, 2326. doi: 10.1039/C7CC07951F
[22]	Lopes, D. S.; Vono, L. L. R.; Miranda, E. V.; Ando, R. A.; Corio, P. ChemCatChem 2022, 14, e202101943. doi: 10.1002/cctc.v14.5
[23]	He, L.; Liu, C.; Tang, J.; Zhou, Y.; Yang, H.; Liu, R.; Hu, J. Appl. Surf. Sci. 2018, 434, 265. doi: 10.1016/j.apsusc.2017.10.155
[24]	Zhang, K.; Li, G.; Hu, Y. Nanoscale 2015, 7, 16952. doi: 10.1039/C5NR05718C
[25]	Tang, X.; Cai, W.; Yang, L.; Liu, J. Nanoscale 2014, 6, 8612. doi: 10.1039/C4NR01939C
[26]	Zhang, Z.; Gernert, U.; Gerhardt, R. F.; Höhn, E.-M.; Belder, D.; Kneipp, J. ACS Catal. 2018, 8, 2443. doi: 10.1021/acscatal.8b00101
[27]	Sun, M. T.; Huang, Y. Z.; Xia, L. X.; Chen, X. W.; Xu, H. X. J. Phys. Chem. C 2011, 115, 9629. doi: 10.1021/jp201002v
[28]	Zhang, Z. Y.; Kneipp, J. J. Phys. Chem. Lett. 2021, 12, 1542. doi: 10.1021/acs.jpclett.0c03732
[29]	Liu, G. K.; Hu, J.; Zheng, P. C.; Shen, G. L.; Jiang, J. H.; Yu, R. Q.; Cui, Y.; Ren, B. J. Phys. Chem. C 2008, 112, 6499. doi: 10.1021/jp709869f
[30]	Irish, D. E.; Hill, I. R.; Archambault, P.; Atkinson, G. F. J. Solution Chem. 1985, 14, 221. doi: 10.1007/BF00647064
[31]	Cao, P. G.; Gu, R. A.; Qiu, L. Q.; Sun, R.; Ren, B.; Tian, Z. Q. Surf. Sci. 2003, 531, 217. doi: 10.1016/S0039-6028(03)00543-0
[32]	Gu, R. A.; Cao, P. G.; Sun, Y. H.; Tian, Z. Q. J. Electroanal. Chem. 2002, 528, 121. doi: 10.1016/S0022-0728(02)00898-7
[33]	Frens, G. Nat. Phys. Sci. 1973, 241, 20. doi: 10.1038/physci241020a0
[34]	Fang, P.-P.; Li, J.-F.; Yang, Z.-L.; Li, L.-M.; Ren, B.; Tian, Z.-Q. J. Raman Spectrosc. 2008, 39, 1679. doi: 10.1002/jrs.v39:11
[35]	Guo, Q. H.; Xu, M. M.; Yuan, Y. X.; Gu, R. A.; Yao, J. L. Langmuir 2016, 32, 4530. doi: 10.1021/acs.langmuir.5b04393
[36]	Huang, Y. F.; Zhu, H. P.; Liu, G. K.; Wu, D. Y.; Ren, B.; Tian, Z. Q. J. Am. Chem. Soc. 2010, 132, 9244. doi: 10.1021/ja101107z