Detection of an Unstable Intermediate in Br Electro-oxidation to Br3 on a Platinum Electrode in Nitrobenzene by Scanning Electrochemical Microscopy

Jinho Chang, Brent Bennett, Allen J. Bard

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

We report the detection of an unstable intermediate generated during Br oxidation to Br3 in nitrobenzene by scanning electrochemical microscopy (SECM), and we attempt to simulate the collection of the intermediate using a proposed mechanism of Br oxidation to Br3 . At a distance of ∼ 3.5 μm between the tip and the substrate electrode in the SECM experiment, we observed two waves as we measured the collection efficiency, Nss, while holding the tip at an anodic potential and scanning the substrate toward cathodic potentials. The second wave obtained at more negative substrate potentials was associated with the collection of Br3 , and the first wave was associated with the collection of an intermediate generated in Br oxidation to Br3 . The Nss as a function of d, estimated at the constant substrate potential of 0.27 V vs. TMPD/TMPD+·, abruptly increased as d was brought below 2.5 μm. We simulated this approach curve by using the following mechanism of Br oxidation to Br3 : (1) Br + e ⇋ Br·, (2) 2Br· ⇋ Br2, (3) Br· + Br ⇋ Br2 ·, (4) Br2 · + e ⇋ Br2, and (5) Br2 + Br ⇋ Br3 .

Original languageEnglish
Pages (from-to)74-80
Number of pages7
JournalElectrochimica Acta
Volume238
DOIs
StatePublished - 2017 Jun 1

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Nitrobenzene
Electrooxidation
Platinum
Microscopic examination
Scanning
Oxidation
Electrodes
Substrates
nitrobenzene
Experiments

Keywords

  • bromine
  • cyclic voltammetry
  • digital simulation
  • electrochemistry
  • intermediate detection
  • nitrobenzene
  • reaction mechanism
  • scanning electrochemical microscopy

Cite this

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title = "Detection of an Unstable Intermediate in Br− Electro-oxidation to Br3 − on a Platinum Electrode in Nitrobenzene by Scanning Electrochemical Microscopy",
abstract = "We report the detection of an unstable intermediate generated during Br− oxidation to Br3 − in nitrobenzene by scanning electrochemical microscopy (SECM), and we attempt to simulate the collection of the intermediate using a proposed mechanism of Br− oxidation to Br3 −. At a distance of ∼ 3.5 μm between the tip and the substrate electrode in the SECM experiment, we observed two waves as we measured the collection efficiency, Nss, while holding the tip at an anodic potential and scanning the substrate toward cathodic potentials. The second wave obtained at more negative substrate potentials was associated with the collection of Br3 −, and the first wave was associated with the collection of an intermediate generated in Br− oxidation to Br3 −. The Nss as a function of d, estimated at the constant substrate potential of 0.27 V vs. TMPD/TMPD+·, abruptly increased as d was brought below 2.5 μm. We simulated this approach curve by using the following mechanism of Br− oxidation to Br3 −: (1) Br− + e ⇋ Br·, (2) 2Br· ⇋ Br2, (3) Br· + Br− ⇋ Br2 −·, (4) Br2 −· + e ⇋ Br2, and (5) Br2 + Br− ⇋ Br3 −.",
keywords = "bromine, cyclic voltammetry, digital simulation, electrochemistry, intermediate detection, nitrobenzene, reaction mechanism, scanning electrochemical microscopy",
author = "Jinho Chang and Brent Bennett and Bard, {Allen J.}",
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Detection of an Unstable Intermediate in Br Electro-oxidation to Br3 on a Platinum Electrode in Nitrobenzene by Scanning Electrochemical Microscopy. / Chang, Jinho; Bennett, Brent; Bard, Allen J.

In: Electrochimica Acta, Vol. 238, 01.06.2017, p. 74-80.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Detection of an Unstable Intermediate in Br− Electro-oxidation to Br3 − on a Platinum Electrode in Nitrobenzene by Scanning Electrochemical Microscopy

AU - Chang, Jinho

AU - Bennett, Brent

AU - Bard, Allen J.

PY - 2017/6/1

Y1 - 2017/6/1

N2 - We report the detection of an unstable intermediate generated during Br− oxidation to Br3 − in nitrobenzene by scanning electrochemical microscopy (SECM), and we attempt to simulate the collection of the intermediate using a proposed mechanism of Br− oxidation to Br3 −. At a distance of ∼ 3.5 μm between the tip and the substrate electrode in the SECM experiment, we observed two waves as we measured the collection efficiency, Nss, while holding the tip at an anodic potential and scanning the substrate toward cathodic potentials. The second wave obtained at more negative substrate potentials was associated with the collection of Br3 −, and the first wave was associated with the collection of an intermediate generated in Br− oxidation to Br3 −. The Nss as a function of d, estimated at the constant substrate potential of 0.27 V vs. TMPD/TMPD+·, abruptly increased as d was brought below 2.5 μm. We simulated this approach curve by using the following mechanism of Br− oxidation to Br3 −: (1) Br− + e ⇋ Br·, (2) 2Br· ⇋ Br2, (3) Br· + Br− ⇋ Br2 −·, (4) Br2 −· + e ⇋ Br2, and (5) Br2 + Br− ⇋ Br3 −.

AB - We report the detection of an unstable intermediate generated during Br− oxidation to Br3 − in nitrobenzene by scanning electrochemical microscopy (SECM), and we attempt to simulate the collection of the intermediate using a proposed mechanism of Br− oxidation to Br3 −. At a distance of ∼ 3.5 μm between the tip and the substrate electrode in the SECM experiment, we observed two waves as we measured the collection efficiency, Nss, while holding the tip at an anodic potential and scanning the substrate toward cathodic potentials. The second wave obtained at more negative substrate potentials was associated with the collection of Br3 −, and the first wave was associated with the collection of an intermediate generated in Br− oxidation to Br3 −. The Nss as a function of d, estimated at the constant substrate potential of 0.27 V vs. TMPD/TMPD+·, abruptly increased as d was brought below 2.5 μm. We simulated this approach curve by using the following mechanism of Br− oxidation to Br3 −: (1) Br− + e ⇋ Br·, (2) 2Br· ⇋ Br2, (3) Br· + Br− ⇋ Br2 −·, (4) Br2 −· + e ⇋ Br2, and (5) Br2 + Br− ⇋ Br3 −.

KW - bromine

KW - cyclic voltammetry

KW - digital simulation

KW - electrochemistry

KW - intermediate detection

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KW - reaction mechanism

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