SERS Raman detection of the CO$_2$ Moisture Swing

TL;DR

This study uses SERS Raman spectroscopy to monitor humidity-driven ion exchange in moisture swing CO2 sorbents, providing real-time insights into the mechanisms and potential for optimizing carbon capture materials.

Contribution

It demonstrates the application of SERS as an operando diagnostic tool to observe reversible anion transformations in moisture swing sorbents under realistic conditions.

Findings

Humidity-dependent interconversion of carbonate, bicarbonate, and hydroxide ions

Spectral shifts confirm reversible hydrolysis reactions

SERS enables real-time monitoring of CO2 capture media

Abstract

The development of scalable, energy-efficient carbon dioxide capture technologies is critical for achieving net-zero emissions. Moisture swing sorbents offer a promising alternative to traditional thermal regeneration methods by enabling reversible CO$_2$ binding through humidity-driven ion hydrolysis. In this study, we investigate the anion speciation dynamics in two classes of MS materials, an anion-exchange resin with bicarbonate anion and activated carbon impregnated with potassium bicarbonate salt using both sorption measurements and in situ surface-enhanced Raman spectroscopy. Ni coated Ag nanowires were employed as SERS substrates to enhance signal intensity and enable the real-time detection of carbonate , bicarbonate , and hydroxide species under controlled humidity conditions in both air and nitrogen atmospheres. The results reveal humidity-dependent interconversion between anionic species, with significant spectral shifts confirming the reversible hydrolysis reactions that drive the MS mechanism. Under humid conditions, we observed the depletion of bicarbonate signals and a concurrent increase in carbonate species, consistent with moisture-induced desorption of CO$_2$. These findings not only validate the mechanistic models of humidity-driven anion exchange in moisture swing sorbents but also demonstrate the practical potential of SERS as an operando diagnostic tool for monitoring CO$_2$ capture media. The ability to resolve and quantify the reversible transformation of carbonate, bicarbonate, and hydroxide ions under realistic environmental conditions provides valuable insight for the rational design, performance optimization, and quality control of next-generation sorbent materials for direct air capture applications.