Revealing the Intrinsic Restructuring of Bi₂O₃ Nanoparticles into Bi Nanosheets during Electrochemical CO₂ Reduction

Abstract

Bismuth is a catalyst material that selectively produces formate during the electrochemical reduction of CO 2 . While different synthesis strategies have been employed to create electrocatalysts with better performance, the restructuring of bismuth precatalysts during the reaction has also been previously reported. The mechanism behind the change has, however, remained unclear. Here, we show that Bi 2 O 3 nanoparticles supported on Vulcan carbon intrinsically transform into stellated nanosheet aggregates upon exposure to an electrolyte. Liquid cell transmission electron microscopy observations first revealed the gradual restructuring of the nanoparticles into nanosheets in the presence of 0.1 M KHCO 3 without an applied potential. Our experiments also associated the restructuring with solubility of bismuth in the electrolyte. While the consequent agglomerates were stable under moderate negative potentials (−0.3 V RHE ), they dissolved over time at larger negative potentials (−0.4 and −0.5 V RHE ). Operando Raman spectra collected during the reaction showed that under an applied potential, the oxide particles reduced to metallic bismuth, thereby confirming the metal as the working phase for producing formate. These results inform us about the working morphology of these electrocatalysts and their formation and degradation mechanisms.

Recent Developments in Single-Entity Electrochemistry

“…As highlighted above, SEE with nanoelectrodes can enable structural characterization of electrode immobilized entities before and after electrochemical experiments to determine morphological and compositional changes. Beyond such static snapshots, high-resolution optical microscopy ( vide infra ) and advances in Si x N y -based liquid cells that enable in situ transmission electron microscopy (TEM) provide routes to track operando electrochemical transformations of single particles in real time. − Examples of recent work in this aspect studied Cu, Cu 2 O nanocubes, and Bi 2 O 3 nanoparticles under CO 2 reduction conditions, capturing operando disintegration and structural evolution of nanocrystals to heterostructures. In both cases, although no direct electrochemical SEE response was recorded with liquid-cell TEM, the wealth of information gained through monitoring such transformations in situ is clear.…”