Water Adsorption Property of Hierarchically Nanoporous Detonation Nanodiamonds.

The detonation nanodiamonds form the aggregate having interparticle voids, giving a marked hygroscopic property. As the relationship between pore structure and water adsorption of aggregated nanodiamonds is not well understood yet, adsorption isotherms of N2 at 77 K and of water vapor at 298 K of the well-characterized aggregated nanodiamonds were measured. HR-TEM and X-ray diffraction showed that the nanodiamonds were highly crystalline and their average crystallite size was 4.5 nm. The presence of the graphitic layers on the nanodiamond particle surface was confirmed by the EELS examination. The pore size distribution analysis showed that nanodiamonds had a few ultramicropores with predominant mesopores of 4.5 nm in average size. The water vapor adsorption isotherm of IUPAC Type V indicates the hydrophobicity of the nanodiamond aggregates, with the presence of hydrophilic sites. Then the hygroscopic nature of nanodiamonds should be associated with the surface functionalities of the graphitic shell and the ultramicropores on the mesopore walls.

Pore-Mouth Structure of Highly Agglomerated Detonation Nanodiamonds.

Detonation nanodiamond aggregates contain water that is removed by thermal treatments in vacuo, leaving available pores for the adsorption of target molecules. A hard hydrogel of detonation nanodiamonds was thermally treated at 423 K for 2 h, 10 h, and 52 h in vacuo to determine the intensive water adsorption sites and clarify the hygroscopic nature of nanodiamonds. Nanodiamond aggregates heated for long periods in vacuo agglomerate due to the removal of structural water molecules through the shrinkage and/or collapse of the pores. The agglomerated nanodiamond structure that results from long heating periods decreases the nitrogen adsorption but increases the water adsorption by 40%. Nanodiamonds heated for long times possess ultramicropores <0.4 nm in diameter in which only water molecules can be adsorbed, and the characteristic mouth-shaped mesopores adsorb 60% more water than nitrogen. The pore mouth controls the adsorption in the mesopores. Long-term dehydration partially distorts the pore mouth, decreasing the nitrogen adsorption. Furthermore, the nitrogen adsorbed at the pore mouth suppresses additional nitrogen adsorption. Consequently, the mesopores are not fully accessible to nitrogen molecules because the pore entrances are blocked by polar groups. Thus, mildly oxidized detonation nanodiamond particles can show a unique molecular sieving behavior.

Unusual hygroscopic nature of nanodiamonds in comparison with well-known porous materials.

Nanodiamond aggregates have interparticle pores of 4.5 nm on average, exhibiting porous nature involved in their water storage. This work studies the hygroscopic nature of porous nanodiamond aggregates by water absorption based on liquid water droplets. Nanodiamond aggregates show hydrophobicity from the water vapor adsorption. Surprisingly, porous nanodiamond aggregates quickly absorb water droplets at the bulk scale. The volume of absorbed liquid water is comparable to that of the water-absorbing clay Montmorillonite and higher than those of zeolites ZSM-5 and molecular sieve 5A. This hygroscopic nature of nanodiamonds is ascribed to the micro- and mesoporous structure of their aggregates and the special core-shell structure of each nanodiamond particle (wrapped by graphene-like carbon). The absorption rate of liquid water in the porous nanodiamonds is influenced by the surface wettability, while the hygroscopic capacity depends mainly on the hierarchical porosity.