Investigation on the Kinetics of Water-Dependent Electrochemical Reduction Reaction of p-dimercaptoazobenzene and Detection on Water Content

doi:10.6023/A26030081

Abstract

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

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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.

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Fig. & Tab. 7

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

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)

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

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)

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)

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

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

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