Redox processes of 2,6-dichlorophenolindophenolate in different solvents. A combined electrochemical, spectroelectrochemical, photochemical, and theoretical study

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• 作者：Dana Dvoranová ; Zuzana Barbieriková…
• 关键词：2 ; 6 ; Dichlorophenolindophenolate ; Redox processes ; Cyclic voltammetry ; EPR spectroscopy ; UV ; vis spectroscopy ; Spectroelectrochemistry ; DFT calculations
• 刊名：Journal of Solid State Electrochemistry
• 出版年：2015
• 出版时间：September 2015
• 年：2015
• 卷：19
• 期：9
• 页码：2633-2642
• 全文大小：6,450 KB
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• 作者单位：Dana Dvoranová (1)
  Zuzana Barbieriková (1)
  Sandra Dorotíková (1)
  Michal Mal?ek (1)
  Adam Brincko (1)
  Lucia Ri?panová (1)
  Luká? Bu?insky (1)
  Andrej Sta?ko (1)
  Vlasta Brezová (1)
  Peter Rapta (1)
  
  1. Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, 812 37, Bratislava, Slovakia
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Physical Chemistry
  Analytical Chemistry
  Industrial Chemistry and Chemical Engineering
  Characterization and Evaluation Materials
  Condensed Matter
  Electronic and Computer Engineering
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1433-0768

文摘

Cyclic voltammetric and EPR/UV-vis-NIR spectroelectrochemical studies were performed to examine the cathodic reduction of 2,6-dichlorophenolindophenolate (DCIP) in proton-donating aqueous and methanol solutions, as well as in aprotic dimethylsulfoxide (DMSO), and to characterize the paramagnetic species generated upon the DCIP reduction. In situ EPR and UV-vis-NIR spectroelectrochemistry confirmed the formation of the radical anion DCIP?-/sup> in DMSO and methanol. The same radical anion was found also in the reaction system consisting of KO₂ mixed under argon with DCIP in DMSO or methanol, evidencing the electron transfer from superoxide radical anion to DCIP. The expected radical anion DCIP?-/sup> was not detected in the photoexcited suspensions DCIP/TiO₂/DMSO under argon, which indicates fast consecutive reactions of photogenerated DCIP?-/sup> in the vicinity of TiO₂ surface. The reduction of blue-color DCIP to the final colorless product DCIPH₂ can be realized in multiple reaction pathways determined mainly by the proton-donating capacity of the solvent. Following the calculated total DFT energies, the oxygen on the indophenol moiety represents the first proton acceptor site for DCIP, DCIP?-/sup>, as well as for DCIP2-/sup> species. Keywords 2,6-Dichlorophenolindophenolate Redox processes Cyclic voltammetry EPR spectroscopy UV-vis spectroscopy Spectroelectrochemistry DFT calculations