Operando spectroelectrochemical identification of peroxide intermediate in molten carbonate CO₂-to-carbon electroreduction.

Abstract

Electrolysis of CO₂ in molten salts promises efficient carbon capture, but the underlying reaction mechanisms remain incompletely understood, as research thus far has been limited by a lack of tools for operando investigations. Here, we use a high-temperature operando Raman spectroelectrochemical system to look for signatures of reaction intermediates and study the evolution of carbon structures over electrolysis time. The analysis reveals the existence of O₂^2- concurrently with the deposition of carbon on Au, W, Inconel, and Ni electrode materials, pointing to a common reaction mechanism with O₂^2- as an intermediate. Secondly, the G peak of the as-deposited carbon experiences a noticeable blue-shift as the material is cooled down and purified, suggesting either a growth in crystallite size even after the electrolysis is stopped or lithium deintercalation. Elucidating the cathodic carbon deposition mechanism could help create greater value-added products and increase the economic viability of carbon capture.