Accessibility control of Cu sites to enhance adsorption capacity of ultra-low-concentration methyl mercaptan

Methyl mercaptan (MM) is a typical malodorous gas and low-concentration MM makes human uncomfortable. Adsorption is applied in industry to remove MM. However, adsorptive-site agglomeration results in that adsorbent is not fully utilized. In this work, pore size and unsaturated-site amount of Cu-based metal-organic frameworks (MOFs) were regulated by using different ligands to increase adsorptive-site accessibility for MM. As a result, when Cu²⁺ sites were imbedded in MOFs network, these sites were inaccessible for MM; when Cu²⁺ sites were occupied by none-network organics, these sites were accessible for MM after simple activation; when Cu²⁺ sites were occupied by water, these sites were the most effective for MM removal among above site species. Furthermore, with the increase of bonding sites in ligands, channel pore size of MOFs was increased. Both pore size and unsaturated-site amount were important to MM removal. When above MOFs were used in purification of ultra-low-concentration MM, the regulated MOFs with a big pore size (11 and 5 Å) and water-occupied sites showed a best removal capacity of 160.3 mg g^-1. The main result of this work is in favor of understanding structure-efficiency relationship in MOFs. This work also helps to develop effective adsorbents for ultra-low-concentration pollutants.