Electrifying Carbon Capture by Developing Nanomaterials at the Interface of Molecular and Process Engineering.

ConspectusCarbon capture is an indispensable step toward closing the anthropogenic carbon cycle. However, the large-scale implementation of conventional thermochemical carbon capture technologies is hindered by their low energy efficiency, limited sorbent stability, and complexity in infrastructure integration. A mechanistically different alternative, commonly known as electrochemically mediated carbon capture (EMCC), has garnered increasing research traction over the past few years and relies on electrochemical stimuli instead of thermal or pressure swings for the capture and release of carbon dioxide (CO 2 ). Compared to conventional methods, EMCC can be operated under mild conditions driven by intermittent renewable energy sources and has a flexible design to meet the multiscale demands of carbon capture, offering a potentially sustainable, energy-efficient, and cost-effective solution to CO 2 concentration from dilute mixtures or the ambient environment.Nanomaterials have played a crucial role in carbon capture research. For instance, nanoporous materials can provide increased free volumes, surface areas, and active sites for carbon capture through physical or chemical adsorption from the gaseous phase. In contrast, EMCC relies on chemical absorption via acid-base interactions using solubilized CO 2 in electrolytes. Therefore, most EMCC sorbents and mediators explored so far have been developed as molecules rather than nanomaterials. In recent years, our team has been focusing on electrifying the carbon capture processes at the molecular, materials, and process levels. We seek to address the most pressing issues associated with EMCC, either in fixed-bed or flow systems, that prevent their practical use. These issues include parasitic reactions with molecular oxygen, insufficient electrode capacity utilization, sorbent crossover, etc. To address these problems, there is an urgent need to develop rationally designed nanomaterials at the interface of molecular electrochemistry and device engineering. This Account provides an overview of recent progress on developing new chemistries and engineering batch/continuous processes for EMCC. We discuss the limitations of current EMCC technology and emphasize why nanomaterials are critical for electrifying carbon capture. First, we introduce the design principles for EMCC sorbents based on redox-active organic CO 2 carriers and discuss metrics for their performance evaluation. Second, we showcase how molecular design can tackle problems of sorbent solubility, oxygen stability, and electrolyte compatibility in EMCC. Third, we discuss the early results of nanomaterials as solid sorbents in fixed-bed systems, nonswelling membranes for flow systems, and high-surface-area gas-liquid contactors. Finally, building on the foundation we established through our prior work, we offer perspectives on future directions for nanomaterials to help address the challenges in EMCC.