Adsorptive removal of aromatic diamines from water using metal-organic frameworks functionalized with a nitro group

Adsorptive removal of aromatic diamines such as methylenedianiline (MDA) and p-phenylenediamine (PPD) was firstly investigated with nitro-functionalized metal-organic frameworks (MOFs, MIL-101(Cr)-NO₂). The MIL-101(Cr)-NO₂ showed much better performances in the removal of MDA and PPD, in both adsorption capacity and kinetics, than any other adsorbents. For example, MIL-101(Cr)-NO₂ had a much higher maximum adsorption capacity for MDA (1111 mg·g^-1) than activated carbon (208 mg·g^-1) or a reported adsorbent (391 mg·g^-1). Based on experimental results, hydrogen bonding (especially, via the formation of a 6-membered ring (6-MR) between -NO₂ of the adsorbent and -NH₂ of the adsorbates) could be suggested as the main mechanism to interpret the noticeable adsorption of the diamines. Importantly, this is the first example to confirm that MOFs with nitro group can be a competitive adsorbent to remove organics composed of amino group, especially via making 6-MR through hydrogen bonding. Higher adsorption of MDA than that of PPD over MIL-101(Cr)-NO₂ might be explained with π-π interaction between aromatic rings (π-lean aromatics of MOF and π-rich aromatics of the adsorbates). Moreover, MIL-101(Cr)-NO₂ could be recycled after simple washing, suggesting the potential use of the MOF in adsorptive purification of contaminated water with organics with amino groups.