Structural dynamics and evolution of bismuth electrodes during electrochemical reduction of CO2 in imidazolium-based ionic liquid solutions

Jonnathan Medina-Ramos; Sang Soo Lee; Timothy T. Fister; Aude A. Hubaud; Robert L. Sacci; David R. Mullins; John L. DiMeglio; Rachel C. Pupillo; Stephanie M. Velardo; Daniel A. Lutterman; Joel Rosenthal; Paul Fenter

doi:10.1021/acscatal.7b01370

Structural dynamics and evolution of bismuth electrodes during electrochemical reduction of CO₂ in imidazolium-based ionic liquid solutions

Jonnathan Medina-Ramos, Sang Soo Lee, Timothy T. Fister, Aude A. Hubaud, Robert L. Sacci, David R. Mullins, John L. DiMeglio, Rachel C. Pupillo, Stephanie M. Velardo, Daniel A. Lutterman, Joel Rosenthal, Paul Fenter

Research output: Contribution to journal › Article › peer-review

45 Scopus citations

Abstract

Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO₂ into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM), and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM]⁺) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF₆ and TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi₂O₃) and metallic bismuth (Bi⁰) and that the reduction of oxidized bismuth species to Bi⁰ is fully achieved under potentials at which CO₂ activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO₂ reduction near −1.75 V vs Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM]⁺ solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates that extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than −1.6 V vs Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO₂. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. In contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO₂ reduction. Overall, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM]⁺-based electrolytes, including the reduction of bismuth oxide to bismuth metal and changes in roughness and near-surface viscosity.

Original language	English
Pages (from-to)	7285-7295
Number of pages	11
Journal	ACS Catalysis
Volume	7
Issue number	10
DOIs	https://doi.org/10.1021/acscatal.7b01370
State	Published - Oct 6 2017
Externally published	Yes

Funding

This material is based upon work supported as part of the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science (SC), and Office of Basic Energy Sciences (BES). Use of the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory (BNL) for XAS measurements was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-98CH10886, with additional support through the Synchrotron Catalysis Consortium under Grant DE-FG02-05ER15688. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The X-ray reflectivity work was carried out at the Advanced Photon Source, sectors 12-ID-D (Hua Zhou), 33-BM-C (Evguenia Karapetrova), and 33-ID-D (Zhan Zhang). Special thanks to Ahmet Uysal (Argonne) for training J.M.R. on graphene growth and to Brian J. Ingram (Argonne) for allowing A.A.H. access to the sputtering chamber for Bi thin film deposition.

Funders	Funder number
Synchrotron Catalysis Consortium	DE-FG02-05ER15688
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-AC02-98CH10886
Argonne National Laboratory	DE-AC02-06CH11357

Keywords

Bismuth electrocatalyst
EQCM
EXAFS
Electrochemical CO2 reduction
Electrode restructuring
Ionic liquid
X-ray reflectivity
XANES

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acscatal.7b01370

Cite this

Medina-Ramos, J., Lee, S. S., Fister, T. T., Hubaud, A. A., Sacci, R. L., Mullins, D. R., DiMeglio, J. L., Pupillo, R. C., Velardo, S. M., Lutterman, D. A., Rosenthal, J., & Fenter, P. (2017). Structural dynamics and evolution of bismuth electrodes during electrochemical reduction of CO₂ in imidazolium-based ionic liquid solutions. ACS Catalysis, 7(10), 7285-7295. https://doi.org/10.1021/acscatal.7b01370

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title = "Structural dynamics and evolution of bismuth electrodes during electrochemical reduction of CO2 in imidazolium-based ionic liquid solutions",

abstract = "Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM), and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM]+) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF6 and TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi2O3) and metallic bismuth (Bi0) and that the reduction of oxidized bismuth species to Bi0 is fully achieved under potentials at which CO2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO2 reduction near −1.75 V vs Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM]+ solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates that extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than −1.6 V vs Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. In contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO2 reduction. Overall, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM]+-based electrolytes, including the reduction of bismuth oxide to bismuth metal and changes in roughness and near-surface viscosity.",

keywords = "Bismuth electrocatalyst, EQCM, EXAFS, Electrochemical CO2 reduction, Electrode restructuring, Ionic liquid, X-ray reflectivity, XANES",

author = "Jonnathan Medina-Ramos and Lee, {Sang Soo} and Fister, {Timothy T.} and Hubaud, {Aude A.} and Sacci, {Robert L.} and Mullins, {David R.} and DiMeglio, {John L.} and Pupillo, {Rachel C.} and Velardo, {Stephanie M.} and Lutterman, {Daniel A.} and Joel Rosenthal and Paul Fenter",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acscatal.7b01370",

language = "English",

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Medina-Ramos, J, Lee, SS, Fister, TT, Hubaud, AA, Sacci, RL, Mullins, DR, DiMeglio, JL, Pupillo, RC, Velardo, SM, Lutterman, DA, Rosenthal, J & Fenter, P 2017, 'Structural dynamics and evolution of bismuth electrodes during electrochemical reduction of CO₂ in imidazolium-based ionic liquid solutions', ACS Catalysis, vol. 7, no. 10, pp. 7285-7295. https://doi.org/10.1021/acscatal.7b01370

TY - JOUR

T1 - Structural dynamics and evolution of bismuth electrodes during electrochemical reduction of CO2 in imidazolium-based ionic liquid solutions

AU - Medina-Ramos, Jonnathan

AU - Lee, Sang Soo

AU - Fister, Timothy T.

AU - Hubaud, Aude A.

AU - Sacci, Robert L.

AU - Mullins, David R.

AU - DiMeglio, John L.

AU - Pupillo, Rachel C.

AU - Velardo, Stephanie M.

AU - Lutterman, Daniel A.

AU - Rosenthal, Joel

AU - Fenter, Paul

PY - 2017/10/6

Y1 - 2017/10/6

N2 - Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM), and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM]+) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF6 and TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi2O3) and metallic bismuth (Bi0) and that the reduction of oxidized bismuth species to Bi0 is fully achieved under potentials at which CO2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO2 reduction near −1.75 V vs Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM]+ solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates that extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than −1.6 V vs Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. In contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO2 reduction. Overall, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM]+-based electrolytes, including the reduction of bismuth oxide to bismuth metal and changes in roughness and near-surface viscosity.

AB - Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM), and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM]+) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF6 and TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi2O3) and metallic bismuth (Bi0) and that the reduction of oxidized bismuth species to Bi0 is fully achieved under potentials at which CO2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO2 reduction near −1.75 V vs Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM]+ solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates that extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than −1.6 V vs Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. In contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO2 reduction. Overall, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM]+-based electrolytes, including the reduction of bismuth oxide to bismuth metal and changes in roughness and near-surface viscosity.

KW - Bismuth electrocatalyst

KW - EQCM

KW - EXAFS

KW - Electrochemical CO2 reduction

KW - Electrode restructuring

KW - Ionic liquid

KW - X-ray reflectivity

KW - XANES

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U2 - 10.1021/acscatal.7b01370

DO - 10.1021/acscatal.7b01370

M3 - Article

AN - SCOPUS:85032725936

SN - 2155-5435

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JO - ACS Catalysis

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IS - 10

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