Detection of the Sn(III) intermediate and the mechanism of the Sn(IV)/Sn(II) electroreduction reaction in bromide media by cyclic voltammetry and scanning electrochemical microscopy

Jinho Chang, Allen J. Bard

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Abstract

Fast-scan cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM) were used to investigate the reduction of Sn(IV) as the hexabromo complex ion in a 2 M HBr-4 M NaBr medium. CV at scan rates to 100 V/s and SECM indicated the reaction pathway involves ligand-coupled electron transfer via an ECEC-DISP process: (1) one-electron reduction of SnIVBr 6 2- to SnIIIBr6 3-; (2) bromide dissociation of the reduced SnIIIBr6 3- to SnIIIBr5 2-; (3) disproportionation of the reduced 2SnIIIBr5 2- to SnIVBr 5 - and SnIIBr5 3-; (4) one-electron reduction of SnIIIBr5 2- to Sn IIBr5 3-; (5) bromide dissociation from Sn IIBr5 to SnIIBr4 2-. The intermediate Sn(III) species was confirmed by SECM3-, where the Sn(III) generated at the Au tip was collected on a Au substrate in the tip generation/substrate collection mode when the distance between the tip and substrate was a few hundred nanometers.

Original languageEnglish
Pages (from-to)311-320
Number of pages10
JournalJournal of the American Chemical Society
Volume136
Issue number1
DOIs
StatePublished - 2014 Jan 8

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Electrochemical Scanning Microscopy
Bromides
Cyclic voltammetry
Microscopic examination
Electrons
Scanning
Substrates
Ligands
Ions

Cite this

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title = "Detection of the Sn(III) intermediate and the mechanism of the Sn(IV)/Sn(II) electroreduction reaction in bromide media by cyclic voltammetry and scanning electrochemical microscopy",
abstract = "Fast-scan cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM) were used to investigate the reduction of Sn(IV) as the hexabromo complex ion in a 2 M HBr-4 M NaBr medium. CV at scan rates to 100 V/s and SECM indicated the reaction pathway involves ligand-coupled electron transfer via an ECEC-DISP process: (1) one-electron reduction of SnIVBr 6 2- to SnIIIBr6 3-; (2) bromide dissociation of the reduced SnIIIBr6 3- to SnIIIBr5 2-; (3) disproportionation of the reduced 2SnIIIBr5 2- to SnIVBr 5 - and SnIIBr5 3-; (4) one-electron reduction of SnIIIBr5 2- to Sn IIBr5 3-; (5) bromide dissociation from Sn IIBr5 to SnIIBr4 2-. The intermediate Sn(III) species was confirmed by SECM3-, where the Sn(III) generated at the Au tip was collected on a Au substrate in the tip generation/substrate collection mode when the distance between the tip and substrate was a few hundred nanometers.",
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T1 - Detection of the Sn(III) intermediate and the mechanism of the Sn(IV)/Sn(II) electroreduction reaction in bromide media by cyclic voltammetry and scanning electrochemical microscopy

AU - Chang, Jinho

AU - Bard, Allen J.

PY - 2014/1/8

Y1 - 2014/1/8

N2 - Fast-scan cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM) were used to investigate the reduction of Sn(IV) as the hexabromo complex ion in a 2 M HBr-4 M NaBr medium. CV at scan rates to 100 V/s and SECM indicated the reaction pathway involves ligand-coupled electron transfer via an ECEC-DISP process: (1) one-electron reduction of SnIVBr 6 2- to SnIIIBr6 3-; (2) bromide dissociation of the reduced SnIIIBr6 3- to SnIIIBr5 2-; (3) disproportionation of the reduced 2SnIIIBr5 2- to SnIVBr 5 - and SnIIBr5 3-; (4) one-electron reduction of SnIIIBr5 2- to Sn IIBr5 3-; (5) bromide dissociation from Sn IIBr5 to SnIIBr4 2-. The intermediate Sn(III) species was confirmed by SECM3-, where the Sn(III) generated at the Au tip was collected on a Au substrate in the tip generation/substrate collection mode when the distance between the tip and substrate was a few hundred nanometers.

AB - Fast-scan cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM) were used to investigate the reduction of Sn(IV) as the hexabromo complex ion in a 2 M HBr-4 M NaBr medium. CV at scan rates to 100 V/s and SECM indicated the reaction pathway involves ligand-coupled electron transfer via an ECEC-DISP process: (1) one-electron reduction of SnIVBr 6 2- to SnIIIBr6 3-; (2) bromide dissociation of the reduced SnIIIBr6 3- to SnIIIBr5 2-; (3) disproportionation of the reduced 2SnIIIBr5 2- to SnIVBr 5 - and SnIIBr5 3-; (4) one-electron reduction of SnIIIBr5 2- to Sn IIBr5 3-; (5) bromide dissociation from Sn IIBr5 to SnIIBr4 2-. The intermediate Sn(III) species was confirmed by SECM3-, where the Sn(III) generated at the Au tip was collected on a Au substrate in the tip generation/substrate collection mode when the distance between the tip and substrate was a few hundred nanometers.

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