美国太平洋西北国家实验室King, Jaelynne团队报道了，贫水溶剂的四聚体自组装实现氨基甲酸酯酸酐为基础的CO₂捕获化学，相关研究成果于2024年4月8日发表在《自然—化学》。

碳捕获、利用和储存是应对气候变化的一项关键但成本密集型技术。单组分贫水溶剂已成为燃烧后CO₂捕获的有前途的材料，但对其作用机制知之甚少。

该文中，研究人员对单组分贫水溶剂进行了实验和建模相结合的研究，发现CO₂的捕获伴随着溶液中反胶束状四聚团簇的自组装。这种自发聚集导致了具有高度对比的机制和热力学特征的逐步协同捕获现象。明确定义的超分子结构的出现显示出氢键内核，让人想起酶活性位点，使得能够形成含CO₂的分子物种，如氨基甲酸、氨基甲酸酐和烷氧基氨基甲酸酐。

该系统扩展了在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CO₂储存能力的材料开辟了道路，并为未来用于CO₂的寡聚或聚合成氨基甲酸酯提供了一种潜在的引发剂。

附：英文原文

Title: Tetrameric self-assembling of water-lean solvents enables carbamate anhydride-based CO2 capture chemistry

Author: Leclaire, Julien, Heldebrant, David J., Grubel, Katarzyna, Septavaux, Jean, Hennebelle, Marc, Walter, Eric, Chen, Ying, Bauelos, Jose Leobardo, Zhang, Difan, Nguyen, Manh-Thuong, Ray, Debmalya, Allec, Sarah I., Malhotra, Deepika, Joo, Wontae, King, Jaelynne

Issue&Volume: 2024-04-08

Abstract: 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.

DOI: 10.1038/s41557-024-01495-z

Source: https://www.nature.com/articles/s41557-024-01495-z