Abstract
Efficient CO(2) separation technologies are essential for mitigating climate change. Compared to traditional thermochemical methods, electrochemically mediated carbon capture using redox-tunable sorbents emerges as a promising alternative due to its versatility and energy efficiency. However, the undesirable linear free-energy relationship between redox potential and CO(2) binding affinity in existing chemistry makes it fundamentally challenging to optimise key sorbent properties independently via chemical modifications. Here, we demonstrate a design paradigm for electrochemically mediated carbon capture sorbents, which breaks the undesirable scaling relationship by leveraging intramolecular hydrogen bonding in isoindigo derivatives. The redox potentials of isoindigos can be anodically shifted by >350 mV to impart sorbents with high oxygen stability without compromising CO(2) binding, culminating in a system with minimised parasitic reactions. With the synthetic space presented, our effort provides a generalisable strategy to finetune interactions between redox-active organic molecules and CO(2), addressing a longstanding challenge in developing effective carbon capture methods driven by non-conventional stimuli.