We investigated the effects of supercritical-CO2 treatment on the pore structure and consequent H2 adsorption behavior of single-walled carbon nanohorns (SWCNHs) and SWCNH aggregates. High-resolution transmission electron microscopy and adsorption characterization techniques were employed to elucidate the alterations in the SWCNH morphology and aggregate pore characteristics induced by supercritical-CO2 treatment. Our results confirm that supercritical-CO2 treatment reduces the interstitial pore surface area and volume of SWCNH aggregates, notably affecting the adsorption of N2 (77 K), CO2 (273 K), and H2 (77 K) gasses. The interstitial porosity strongly depends on the supercritical-CO2 pressure. Supercritical-CO2 treatment softens the individual SWCNHs and opens the core of SWCNH aggregates, producing a partially orientated structure with interstitial ultramicropores. These nanopores are formed by the diffusion and intercalation of CO2 molecules during treatment. An increase in the amount of H2 adsorbed per interstitial micropore of the supercritically modified SWCNHs was observed. Moreover, the increase in the number and volume of ultramicropores enable the selective adsorption of H2 and CO2 molecules. This study reveals that supercritical-CO2 treatment can modulate the pore structure of SWCNH aggregates and provides an effective strategy for tailoring the H2 adsorption properties of nanomaterials.

The importance of nanopore structures of carbons is shown in terms of interaction potential for various molecules including supercritical gases such as H2 and CH4. The key factors for adsorption of supercritical H2 and CH4 are shown for single wall carbon nanohorn, single wall carbon nanotube, and double wall carbon nanotube. The cluster formation of molecules is a key process for water adsorption on hydrophobic carbon nanopores. The X-ray absorption spectroscopic examination elucidates an explicit dehydration structure of ions confined in carbon nanopores.