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Electrochemical oxidation of resorcinol: Mechanistic insights from experimental and computational studies
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Document Title
Electrochemical oxidation of resorcinol: Mechanistic insights from experimental and computational studies
Author
Ngamchuea K., Tharat B., Hirunsit P., Suthirakun S.
Name from Authors Collection
Affiliations
School of Chemistry, Institute of Science, Suranaree University of Technology, 111 University Ave, Muang District, Nakhon Ratchasima, 30000, Thailand; National Nanotechnology Center, National Science and Technology Development Agency, 111 Thailand Science Park, Pathum Thani, 12120, Thailand; Research Network NANOTEC-SUT on Advanced Nanomaterials and Characterization, School of Chemistry, Suranaree University of Technology, Thailand
Type
Article
Source Title
RSC Advances
ISSN
20462069
Year
2020
Volume
10
Issue
47
Page
28454-28463
Open Access
Gold
Publisher
Royal Society of Chemistry
DOI
10.1039/d0ra06111e
Format
Abstract
This work investigates the mechanisms of resorcinol oxidation by density functional theory (DFT) calculation and cyclic voltammetry measurements. Complementary data from experimental and computational studies provide new insights into the reaction mechanisms. At both macro- and micro-electrodes, cyclic voltammetry of resorcinol is chemically and electrochemically irreversible over the whole pH range (1-14). Resorcinol molecules undergo a 1H+ 1e- oxidation at pH pKa2 to form radicals. The radicals then readily react to form dimers/polymers deposited on the electrode surface. All of the experimental findings are consistent with the proposed mechanisms, including the apparent transfer coefficient (β) of 0.6 ± 0.1, the slope of the peak potential (Ep) against pH of -54 mV pH-1, the peak-shaped responses at micro-electrodes, and the fouling of the electrodes upon the oxidation of resorcinol. DFT calculation of the reaction energy of elementary steps and the eigenvalues of the highest occupied molecular orbital (HOMO) of the radical intermediates confirms that the (1H+) 1e- oxidation is the energetically favorable pathway. In addition to mechanistic insights, an electrochemical sensor is developed for resorcinol detection at microelectrodes in low ionic strength samples with the sensitivity of 123 ± 4 nA μM-1 and the limit of detection (3 sB m-1) of 0.03 μM. This journal is © The Royal Society of Chemistry.
Industrial Classification
Knowledge Taxonomy Level 1
Knowledge Taxonomy Level 2
Knowledge Taxonomy Level 3
Funding Sponsor
National Science and Technology Development Agency; Suranaree University of Technology; National Nanotechnology Center
License
CC BY-NC
Rights
Author
Publication Source
Scopus
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Electrochemical oxidation of resorcinol Mechanistic insights from experimental and computational studiesDownload