The development of robust and thin CO 2 separation membranes that allow fast and selective permeation of CO 2 will be crucial for rebalancing the global carbon cycle. Hydrogels are attractive membrane materials because of their tunable chemical properties and exceptionally high diffusion coefficients for solutes. However, their fragility prevents the fabrication of thin defect-free membranes suitable for gas separation. Here, we report the assembly of defect-free hydrogel nanomembranes for CO 2 separation. Such membranes can be prepared by coating an aqueous suspension of colloidal hydrogel microparticles (microgels) onto a flat, rough, or micropatterned porous support as long as the pores are hydrophilic and the pore size is smaller than the diameter of the microgels. The deformability of the microgel particles enables the autonomous assembly of defect-free 30−50 nm-thick membrane layers from deformed ∼15 nm-thick discoidal particles. Microscopic analysis established that the penetration of water into the pores driven by capillary force assists the assembly of a defect-free dense hydrogel layer on the pores. Although the dried films did not show significant CO 2 permeance even in the presence of amine groups, the permeance dramatically increased when the membranes are adequately hydrated to form a hydrogel. This result indicated the importance of free water in the membranes to achieve fast diffusion of bicarbonate ions. The hydrogel nanomembranes consisting of amine-containing microgel particles show selective CO 2 permeation (850 GPU, α CO2/N2 = 25) against post-combustion gases. Acid-containing microgel membranes doped with amines show highly selective CO 2 permeation against post-combustion gases (1010 GPU, α CO2/N2 = 216) and direct air capture (1270 GPU, α CO2/N2 = 2380). The membrane formation mechanism reported in this paper will provide insights into the self-assembly of soft matters. Furthermore, the versatile strategy of fabricating hydrogel nanomembranes by the autonomous assembly of deformable microgels will enable the large-scale manufacturing of high-performance separation membranes, allowing low-cost carbon capture from postcombustion gases and atmospheric air.

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