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  1. Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO 2 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 (TBAPF 6 or TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi 2O 3) and metallic bismuth (Bi 0), and that the reduction of oxidized bismuth speciesmore » to Bi 0 is fully achieved under potentials at which CO 2 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 CO 2 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 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 CO 2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. By contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO 2 reduction. In conclusion, 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, changes in roughness and near-surface viscosity.« less

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