Photoelectrocatalytic response of tris(2,2′-bipyridyl)ruthenium(II)-modified mesoporous silica film on ITO electrode with methyl viologen quencher and EDTA donor

IF 2.6 4区化学 Q3 ELECTROCHEMISTRY

Journal of Solid State Electrochemistry Pub Date : 2025-03-18 DOI:10.1007/s10008-025-06254-9

Mahmoud Rahal, Neus Vilà, Christelle Despas, Malik Sebbat, Akshay Silswal, Gediminas Jonusauskas, Nathan McClenaghan, Emmanuel Oheix, Bénédicte Lebeau, Morgan Cormier, Jean-Philippe Goddard, Alain Walcarius

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Abstract

In the present paper, we investigate the photoelectrochemical behavior of a tris(bipyridine) derivative (denoted [Ru(bpy)₂(bpy′)]²⁺) covalently immobilized in the nanochannels of a vertically aligned mesoporous silica film (VMSF) generated by electrochemically assisted self-assembly (EASA) onto a transparent indium-tin oxide (ITO) electrode, in solutions containing a quencher (methyl viologen, MV²⁺) and a model substrate partner (ethylenediaminetetraacetate, EDTA). The optimal film loading was first determined according to its solid-state photophysical properties. Then, the electrochemically accessible [Ru(bpy)₂(bpy′)]²⁺ moieties were exploited in the presence of the MV²⁺ quencher alone in solution (aerated medium) to demonstrate the possible electrochemical regeneration of the photocatalyst immobilized in VMSF on ITO. This was achieved on the basis of experiments carried out by hydrodynamic amperometry at constant potential under successive sequential illumination (at 400 nm) and dark periods. Finally, the functionalized film was applied to the photoelectrocatalytic oxidation of EDTA in an oxygen-free solution containing also MV²⁺ species, thanks to the effective electrochemical regeneration of the quencher, as also evidenced by photocurrent measurements as a function of time with successive switching of light from “off” to “on” and vice versa. Such photoelectrocatalytic transformation of EDTA is possible at a much lower potential (− 0.1 V) than that observed for its direct electrocatalytic oxidation by the same [Ru(bpy)₂(bpy′)]²⁺-functionalized film operating without light (+ 1.2 V).

Graphical Abstract

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三（2,2’-联吡啶）钌（II）修饰介孔二氧化硅膜在ITO电极上的光电催化反应

在本文中，我们研究了三（联吡啶）衍生物(标记为[Ru（bpy)2(bpy ')]2+）在含有猝灭剂（甲基紫素，MV2+）和模型底物伙伴（乙二胺四乙酸酯，EDTA）的溶液中共价固定在由电化学辅助自组装（EASA）在透明氧化铟锡（ITO）电极上生成的垂直排列介孔硅膜（VMSF）的纳米通道中的光电化学行为。首先根据其固态光物理性质确定了最佳膜负载。然后，在溶液（曝气介质）中单独存在MV2+猝灭剂的情况下，利用电化学上可接近的[Ru(bpy)2(bpy ')]2+基团，证明了在ITO上固定在VMSF中的光催化剂可能的电化学再生。这是在连续连续照明（400 nm）和黑暗周期下恒定电位的流体动力安培法实验的基础上实现的。最后，由于猝灭剂的有效电化学再生，将功能化膜应用于EDTA在含有MV2+物质的无氧溶液中的光电催化氧化，光电流测量也证明了这一点，随着光从“关”到“开”的连续切换，光电流随时间的变化。EDTA的这种光电催化转化可以在−0.1 V的电位下进行，远低于在没有光（+ 1.2 V）的情况下由相同的[Ru(bpy)2(bpy ')]2+功能化膜直接电催化氧化所观察到的电位。图形抽象

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Solid State Electrochemistry 工程技术-电化学

CiteScore

4.80

自引率

4.00%

发文量

227

审稿时长

4.1 months

期刊介绍： The Journal of Solid State Electrochemistry is devoted to all aspects of solid-state chemistry and solid-state physics in electrochemistry. The Journal of Solid State Electrochemistry publishes papers on all aspects of electrochemistry of solid compounds, including experimental and theoretical, basic and applied work. It equally publishes papers on the thermodynamics and kinetics of electrochemical reactions if at least one actively participating phase is solid. Also of interest are articles on the transport of ions and electrons in solids whenever these processes are relevant to electrochemical reactions and on the use of solid-state electrochemical reactions in the analysis of solids and their surfaces. The journal covers solid-state electrochemistry and focusses on the following fields: mechanisms of solid-state electrochemical reactions, semiconductor electrochemistry, electrochemical batteries, accumulators and fuel cells, electrochemical mineral leaching, galvanic metal plating, electrochemical potential memory devices, solid-state electrochemical sensors, ion and electron transport in solid materials and polymers, electrocatalysis, photoelectrochemistry, corrosion of solid materials, solid-state electroanalysis, electrochemical machining of materials, electrochromism and electrochromic devices, new electrochemical solid-state synthesis. The Journal of Solid State Electrochemistry makes the professional in research and industry aware of this swift progress and its importance for future developments and success in the above-mentioned fields.