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

Journal Article · · Chemistry of Materials
 [1];  [2];  [2];  [3];  [3];  [3];  [4];  [1];  [1];  [1];  [4];  [3];  [2];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Pennsylvania State Univ., University Park, PA (United States). Dept of Mechanical and Nuclear Engineering
  3. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science
  4. Univ. of Delaware, Newark, DE (United States). Dept. of Chemistry and Biochemistry
+ Show Author Affiliations

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 Bi(0)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/AgCI due to a similar to 4-10% thinning and a similar to 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 center dot center dot center dot[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 center dot center dot center dot[Im]+ complex through partial cathodic corrosion of the Bi film under conditions (potential and electrolyte composition) that favor the catalytic reduction of CO2 .

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231
OSTI ID:
1434934
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Vol. 30; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Few‐Layer Bismuthene with Anisotropic Expansion for High‐Areal‐Capacity Sodium‐Ion Batteries journal January 2019
Reaction mechanisms at the homogeneous–heterogeneous frontier: insights from first-principles studies on ligand-decorated metal nanoparticles journal January 2019
Conversion of CO 2 to value-added products mediated by ionic liquids journal January 2019

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Bismuth electrodes
CO2 reduction
cathodic corrosion
imidazolium ionic liquids