Effect of Covalent Modification on Proton-Coupled Electron Transfer at Quinone-Functionalized Carbon Electrodes
Effect of Covalent Modification on Proton-Coupled Electron Transfer at Quinone-Functionalized Carbon Electrodes
复制标题
共价修饰对醌官能化碳电极质子耦合电子转移的影响
DOI：
10.1021/acs.jpcc.2c06356
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Kwabi, David G.
中科院分区：
文献类型：
--
作者：
Owhoso, Fiki V.;Modak, Sanat V.;Saha, Partha;Kwabi, David G.
将分子物种附着到导电碳电极上是开发高性能功能材料的一种策略，可用于各种电化学储能和转换应用。对这些功能化分子物种如何与电极/电解液界面上的双电层相互作用有一个基本的了解，这对这些材料的优化设计至关重要。在这项工作中，我们研究了由1-氨基-2-磺酸(AAQS)功能化的玻碳电极的水中电化学行为，通过两种共轭技术：酰胺偶联和自由基介导的重氮还原。这两种共轭途径使电极具有不同的氧化还原电位对pH(即Pourbai x)的斜率，这表明存在不同的质子耦合电子转移(PCET)能级。我们将每种情况下测得的Pourbai x斜率与苯二酚所经历的静电电位下降联系起来。此外，使用一个简单的双层多层介电模型，我们展示了不同的PCET能量如何作为AAQS共轭模式和电解液浓度的函数来解释，这在很大程度上可以用不同的酮部分与电极之间的距离以及不同的界面电场驱动的质子化驱动力来解释。我们的结果突出了使用PCET热化学绘制电极/电解液界面上的电场/静电电位分布的潜力，这与许多新兴的电化学技术相关。
The attachment of molecular species to conductive carbon electrodes is attracting attention as a strategy for developing high-performance functional materials for a large variety of electrochemical energy storage and conversion applications. It is critical to the optimal design of these materials that there is a fundamental understanding of how these functionalized molecular species interact with the electrical double layer at the electrode|electrolyte interface. In this work, we investigate the aqueous electrochemical behavior of glassy carbon electrodes that were functionalized with 1-aminoanthraquinone-2-sulfonic acid (AAQS) via two conjugation techniques: amide coupling and radical-mediated diazonium reduction. The two conjugation routes gave rise to electrodes with distinct redox potential versus pH (i.e., Pourbaix) slopes, suggestive of distinct proton-coupled electron transfer (PCET) energetics. We relate the measured Pourbaix slope in each case to the electrostatic potential drop experienced by the quinone. Additionally, using a simple multilayer dielectric model of the double layer, we show how differing PCET energetics as a function of AAQS conjugation mode and electrolyte concentration can be explained in large part by differing distances between the ketone moiety in each quinone and the electrode, and thus differing driving forces for interfacial electric field-driven protonation of each quinone. Our results highlight the potential for the use of PCET thermochemistry to map out the electric field/electrostatic potential profile at electrode|electrolyte interfaces of relevance to many emerging electrochemical technologies.
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影响因子：
3.7
作者：
Batchelor-McAuley, Christopher;Kozub, Barbara R.;Compton, Richard G.
通讯作者：
Compton, Richard G.
1-氨基蒽醌-2,4-二磺酸在硫酸中的溴化机理
DOI：
--
发表时间：
2006
期刊：
影响因子：
--
作者：
Xichuan Yang;Zuwang Wu;Licheng Sun;Chang
通讯作者：
Chang
影响因子：
6.6
作者：
Holm, Allan Hjarbaek;Vase, Karina Hojrup;Daasbjerg, Kim
通讯作者：
Daasbjerg, Kim
影响因子：
6.6
作者：
W. Richard;David Evrard;B. Busson;C. Humbert;L. Dalstein;A. Tadjeddine;P. Gros
通讯作者：
W. Richard;David Evrard;B. Busson;C. Humbert;L. Dalstein;A. Tadjeddine;P. Gros
影响因子：
3.7
作者：
Abhayawardhana, Anusha D.;Sutherland, Todd C.
通讯作者：
Sutherland, Todd C.