Water confined in nanoscopic pores is essential in determining the energetics of many physical and chemical systems. Herein, we report a recently discovered unconventional, reversible chemical reaction driven by water quantities in nanopores. The reduction of the number of water molecules present in the pore space promotes the hydrolysis of CO32- to HCO3- and OH-. This phenomenon led to a nano-structured CO2 sorbent that binds CO2 spontaneously in ambient air when the surrounding is dry, while releasing it when exposed to moisture. The underlying mechanism is elucidated theoretically by computational modeling and verified by experiments. The free energy of CO32- hydrolysis in nanopores reduces with a decrease of water availability. This promotes the formation of OH-, which has a high affinity to CO2. The effect is not limited to carbonate/bicarbonate, but is extendable to a series of ions. Humidity-driven sorption opens a new approach to gas separation technology. The presence of water confined in nanoscopic pores was shown to control the equilibrium between CO2 and bicarbonate on adsorbent surfaces. This control allowed for facile sequestration of CO2 from the air, and may influence the design of other adsorbent materials.
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© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
- air-water interfaces
- CO capture
- free energy
- ion hydration
- molecular dynamics