Carbon capture, utilization and storage is a key yet cost-intensive technology for the fight against climate change. Single-component water-lean solvents have emerged as promising materials for post-combustion CO₂ capture, but little is known regarding their mechanism of action. Here we present a combined experimental and modelling study of single-component water-lean solvents, and we find that CO₂ capture is accompanied by the self-assembly of reverse-micelle-like tetrameric clusters in solution. This spontaneous aggregation leads to stepwise cooperative capture phenomena with highly contrasting mechanistic and thermodynamic features. The emergence of well-defined supramolecular architectures displaying a hydrogen-bonded internal core, reminiscent of enzymatic active sites, enables the formation of CO₂-containing molecular species such as carbamic acid, carbamic anhydride and alkoxy carbamic anhydrides. This system extends the scope of adducts and mechanisms observed during carbon capture. It opens the way to materials with a higher CO₂ storage capacity and provides a means for carbamates to potentially act as initiators for future oligomerization or polymerization of CO₂.

碳捕获、利用和储存是应对气候变化的关键但成本密集型技术。单组分贫水溶剂已成为燃烧后CO ₂捕获的有前途的材料，但对其作用机制知之甚少。在这里，我们提出了单组分贫水溶剂的组合实验和建模研究，我们发现CO ₂捕获伴随着溶液中反胶束状四聚体簇的自组装。这种自发聚集导致逐步协同捕获现象，具有高度对比的机械和热力学特征。明确的超分子结构的出现显示出氢键内部核心，让人想起酶活性位点，使得能够形成含CO ₂的分子种类，例如氨基甲酸、氨基甲酸酐和烷氧基氨基甲酸酐。该系统扩展了碳捕获过程中观察到的加合物和机制的范围。它为具有更高CO ₂存储能力的材料开辟了道路，并为氨基甲酸酯提供了一种可能充当未来CO ₂低聚或聚合引发剂的方法。