Abstract
To develop high-performance activated carbons (ACs) for adsorption heat pumps (AHPs), it is important to characterize the adsorption behaviors of the refrigerant molecules in the pores of ACs. Not only pore structures, such as pore size and shape, but also surface functionalities strongly influences the adsorption behaviors, especially for polar molecules, such as water and ethanol, which are typical refrigerants for AHP. In this study, we examined the influence of surface functional groups on the adsorption behaviors of ethanol molecules in carbon micropores using model ACs with different amounts of oxygen-containing surface functional groups but comparable porosities. For the AC with an increased amount of surface functional groups, ethanol adsorption/desorption isotherms showed significant decreases in the adsorption amounts and shortened adsorption equilibrium times compared to those with less surface functional groups throughout the entire relative pressure region. This suggests diffusional hindrance of ethanol molecules in micropores with abundant surface functional groups. To verify our hypothesis, we examined the influence of surface functional groups on the adsorption behavior of ethanol molecules using a solid-state NMR technique. The NMR results revealed that the hydroxyl group of ethanol molecules strongly interacts with the surface functional groups, giving rise to an oriented adsorption of ethanol molecules in the micropores with oxygen-containing surface functional groups. Furthermore, electrochemical analyses confirmed that diffusion resistance of electrolyte ions in the micropores increases after the introduction of oxygen-containing surface functional groups, which supports our hypothesis.
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