Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO2 Reduction

Jonnathan Medina-Ramos, Weiwei Zhang, Kichul Yoon, Peng Bai, Ashwin Chemburkar, Wenjie Tang, Abderrahman Atifi, Sang Soo Lee, Timothy T. Fister, Brian J. Ingram, Joel Rosenthal, Matthew Neurock, Adri Van Duin, Paul Fenter

Research output: Contribution to journalArticle

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Abstract

Bismuth electrodes undergo distinctive electrochemically induced structural changes in nonaqueous imidazolium ([Im]+)-based ionic liquid solutions under cathodic polarization. In situ X-ray reflectivity (XR) studies have been undertaken to probe well-ordered Bi (001) films which originally contain a native Bi2O3 layer. This oxide layer gets reduced to Bi0 during the first cyclic voltammetry (CV) scan in acetonitrile solutions containing 1-butyl-3-methylimidazolium ([BMIM]+) electrolytes. Approximately 60% of the Bi (001) Bragg peak reflectivity is lost during a potential sweep between -1.5 and -1.9 V vs Ag/AgCl due to a ∼ 4-10% thinning and a ∼40% decrease in lateral size of Bi (001) domains, which are mostly reversed during the anodic scan. Repeated potential cycling enhances the thinning and roughening of the films, suggesting that partial dissolution of Bi ensues during negative polarization. The mechanism of this behavior is understood through molecular dynamics simulations using ReaxFF and density functional theory (DFT) calculations. Both approaches indicate that [Im]+ cations bind to the metal surface more strongly than tetrabutylammonium (TBA+) as the potential and the charge on the Bi surface become more negative. ReaxFF simulations predict a higher degree of disorder for a negatively charged Bi (001) slab in the presence of the [Im]+ cations and substantial migration of Bi atoms from the surface. DFT simulations show the formation of Bi···[Im]+ complexes that lead to the dissolution of Bi atoms from step edges on the Bi (001) surface at potentials between -1.65 and -1.95 V. Bi desorption from a flat terrace requires a potential of approximately -2.25 V. Together, these results suggest the formation of a Bi···[Im]+ complex through partial cathodic corrosion of the Bi film under conditions (potential and electrolyte composition) that favor the catalytic reduction of CO2.

Original languageEnglish (US)
Pages (from-to)2362-2373
Number of pages12
JournalChemistry of Materials
Volume30
Issue number7
DOIs
StatePublished - Apr 10 2018

Fingerprint

Ionic Liquids
Bismuth
Ionic liquids
Electrolytes
Corrosion
Density functional theory
Cations
Dissolution
Positive ions
Atoms
Cathodic polarization
Acetonitrile
Oxides
Cyclic voltammetry
Molecular dynamics
Desorption
Metals
Polarization
X rays
Electrodes

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Medina-Ramos, J., Zhang, W., Yoon, K., Bai, P., Chemburkar, A., Tang, W., ... Fenter, P. (2018). Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO2 Reduction. Chemistry of Materials, 30(7), 2362-2373. https://doi.org/10.1021/acs.chemmater.8b00050
Medina-Ramos, Jonnathan ; Zhang, Weiwei ; Yoon, Kichul ; Bai, Peng ; Chemburkar, Ashwin ; Tang, Wenjie ; Atifi, Abderrahman ; Lee, Sang Soo ; Fister, Timothy T. ; Ingram, Brian J. ; Rosenthal, Joel ; Neurock, Matthew ; Van Duin, Adri ; Fenter, Paul. / Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO2 Reduction. In: Chemistry of Materials. 2018 ; Vol. 30, No. 7. pp. 2362-2373.
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abstract = "Bismuth electrodes undergo distinctive electrochemically induced structural changes in nonaqueous imidazolium ([Im]+)-based ionic liquid solutions under cathodic polarization. In situ X-ray reflectivity (XR) studies have been undertaken to probe well-ordered Bi (001) films which originally contain a native Bi2O3 layer. This oxide layer gets reduced to Bi0 during the first cyclic voltammetry (CV) scan in acetonitrile solutions containing 1-butyl-3-methylimidazolium ([BMIM]+) electrolytes. Approximately 60{\%} of the Bi (001) Bragg peak reflectivity is lost during a potential sweep between -1.5 and -1.9 V vs Ag/AgCl due to a ∼ 4-10{\%} thinning and a ∼40{\%} decrease in lateral size of Bi (001) domains, which are mostly reversed during the anodic scan. Repeated potential cycling enhances the thinning and roughening of the films, suggesting that partial dissolution of Bi ensues during negative polarization. The mechanism of this behavior is understood through molecular dynamics simulations using ReaxFF and density functional theory (DFT) calculations. Both approaches indicate that [Im]+ cations bind to the metal surface more strongly than tetrabutylammonium (TBA+) as the potential and the charge on the Bi surface become more negative. ReaxFF simulations predict a higher degree of disorder for a negatively charged Bi (001) slab in the presence of the [Im]+ cations and substantial migration of Bi atoms from the surface. DFT simulations show the formation of Bi···[Im]+ complexes that lead to the dissolution of Bi atoms from step edges on the Bi (001) surface at potentials between -1.65 and -1.95 V. Bi desorption from a flat terrace requires a potential of approximately -2.25 V. Together, these results suggest the formation of a Bi···[Im]+ complex through partial cathodic corrosion of the Bi film under conditions (potential and electrolyte composition) that favor the catalytic reduction of CO2.",
author = "Jonnathan Medina-Ramos and Weiwei Zhang and Kichul Yoon and Peng Bai and Ashwin Chemburkar and Wenjie Tang and Abderrahman Atifi and Lee, {Sang Soo} and Fister, {Timothy T.} and Ingram, {Brian J.} and Joel Rosenthal and Matthew Neurock and {Van Duin}, Adri and Paul Fenter",
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Medina-Ramos, J, Zhang, W, Yoon, K, Bai, P, Chemburkar, A, Tang, W, Atifi, A, Lee, SS, Fister, TT, Ingram, BJ, Rosenthal, J, Neurock, M, Van Duin, A & Fenter, P 2018, 'Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO2 Reduction', Chemistry of Materials, vol. 30, no. 7, pp. 2362-2373. https://doi.org/10.1021/acs.chemmater.8b00050

Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO2 Reduction. / Medina-Ramos, Jonnathan; Zhang, Weiwei; Yoon, Kichul; Bai, Peng; Chemburkar, Ashwin; Tang, Wenjie; Atifi, Abderrahman; Lee, Sang Soo; Fister, Timothy T.; Ingram, Brian J.; Rosenthal, Joel; Neurock, Matthew; Van Duin, Adri; Fenter, Paul.

In: Chemistry of Materials, Vol. 30, No. 7, 10.04.2018, p. 2362-2373.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO2 Reduction

AU - Medina-Ramos, Jonnathan

AU - Zhang, Weiwei

AU - Yoon, Kichul

AU - Bai, Peng

AU - Chemburkar, Ashwin

AU - Tang, Wenjie

AU - Atifi, Abderrahman

AU - Lee, Sang Soo

AU - Fister, Timothy T.

AU - Ingram, Brian J.

AU - Rosenthal, Joel

AU - Neurock, Matthew

AU - Van Duin, Adri

AU - Fenter, Paul

PY - 2018/4/10

Y1 - 2018/4/10

N2 - Bismuth electrodes undergo distinctive electrochemically induced structural changes in nonaqueous imidazolium ([Im]+)-based ionic liquid solutions under cathodic polarization. In situ X-ray reflectivity (XR) studies have been undertaken to probe well-ordered Bi (001) films which originally contain a native Bi2O3 layer. This oxide layer gets reduced to Bi0 during the first cyclic voltammetry (CV) scan in acetonitrile solutions containing 1-butyl-3-methylimidazolium ([BMIM]+) electrolytes. Approximately 60% of the Bi (001) Bragg peak reflectivity is lost during a potential sweep between -1.5 and -1.9 V vs Ag/AgCl due to a ∼ 4-10% thinning and a ∼40% decrease in lateral size of Bi (001) domains, which are mostly reversed during the anodic scan. Repeated potential cycling enhances the thinning and roughening of the films, suggesting that partial dissolution of Bi ensues during negative polarization. The mechanism of this behavior is understood through molecular dynamics simulations using ReaxFF and density functional theory (DFT) calculations. Both approaches indicate that [Im]+ cations bind to the metal surface more strongly than tetrabutylammonium (TBA+) as the potential and the charge on the Bi surface become more negative. ReaxFF simulations predict a higher degree of disorder for a negatively charged Bi (001) slab in the presence of the [Im]+ cations and substantial migration of Bi atoms from the surface. DFT simulations show the formation of Bi···[Im]+ complexes that lead to the dissolution of Bi atoms from step edges on the Bi (001) surface at potentials between -1.65 and -1.95 V. Bi desorption from a flat terrace requires a potential of approximately -2.25 V. Together, these results suggest the formation of a Bi···[Im]+ complex through partial cathodic corrosion of the Bi film under conditions (potential and electrolyte composition) that favor the catalytic reduction of CO2.

AB - Bismuth electrodes undergo distinctive electrochemically induced structural changes in nonaqueous imidazolium ([Im]+)-based ionic liquid solutions under cathodic polarization. In situ X-ray reflectivity (XR) studies have been undertaken to probe well-ordered Bi (001) films which originally contain a native Bi2O3 layer. This oxide layer gets reduced to Bi0 during the first cyclic voltammetry (CV) scan in acetonitrile solutions containing 1-butyl-3-methylimidazolium ([BMIM]+) electrolytes. Approximately 60% of the Bi (001) Bragg peak reflectivity is lost during a potential sweep between -1.5 and -1.9 V vs Ag/AgCl due to a ∼ 4-10% thinning and a ∼40% decrease in lateral size of Bi (001) domains, which are mostly reversed during the anodic scan. Repeated potential cycling enhances the thinning and roughening of the films, suggesting that partial dissolution of Bi ensues during negative polarization. The mechanism of this behavior is understood through molecular dynamics simulations using ReaxFF and density functional theory (DFT) calculations. Both approaches indicate that [Im]+ cations bind to the metal surface more strongly than tetrabutylammonium (TBA+) as the potential and the charge on the Bi surface become more negative. ReaxFF simulations predict a higher degree of disorder for a negatively charged Bi (001) slab in the presence of the [Im]+ cations and substantial migration of Bi atoms from the surface. DFT simulations show the formation of Bi···[Im]+ complexes that lead to the dissolution of Bi atoms from step edges on the Bi (001) surface at potentials between -1.65 and -1.95 V. Bi desorption from a flat terrace requires a potential of approximately -2.25 V. Together, these results suggest the formation of a Bi···[Im]+ complex through partial cathodic corrosion of the Bi film under conditions (potential and electrolyte composition) that favor the catalytic reduction of CO2.

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