Superparamagnetic MOF@GO Ni and Co based hybrid nanocomposites as efficient water pollutant adsorbents

A series of highly efficient adsorbents were developed using Ni₃(BTC)₂ and Co₃(BTC)₂ metal-organic frameworks (MOFs) and Fe₃O₄ magnetic nanoparticles (MNPs) to functionalize graphene oxide (GO). XRD results show high crystallinity of the prepared nanomaterials and the successful decoration of Ni₃(BTC)₂ and Co₃(BTC)₂ MOFs over the GO substrate (BTC = benzene-1,3,5-tricarboxylic acid). SEM and TEM imaging show the successful formation of nanoscale MOFs and Fe₃O₄ MNPs over GO. IR spectroscopy supports the characterization and successful preparation of the Fe₃O₄/MOF@GO hybrid composite nanoadsorbents. The prepared composite nanoadsorbents were used to sorb Methylene Blue (MB) as a model for common organic pollutants in water and common ions (Na⁺, Ca²⁺, Mg²⁺, SO₄²⁻, SiO₃²⁻) from a brackish water model. The adsorbed concentration at equilibrium of MB of the prepared composite nanoadsorbents increases by an average of 30.52 and 13.75 mg/g for the Co and Ni composite, respectively, when compared to the MOFs parent materials. The adsorbed amount of sulfate ions increases by 92.1 mg/g for the Co composite and 112.1 mg/g for the Ni composite, when compared to graphene oxide. This adsorption enhancement is attributed to suppressed aggregation through increased dispersive forces in the MOFs due to the presence of GO, formation of nanoscale MOFs over the GO platform, and the hindering of stacking of the graphene layers by the MOFs. Leaching tests show that the release of Co and Ni ions to water is reduced from 105.2 and 220 mg/L, respectively, in the parent MOF materials to 0.5 and 16.4 mg/L, respectively, in the composite nanoadsorbents. These findings show that the newly developed composite nanoadsorbents can sorb organic pollutants, and target sulfate and silicate anions, which makes them suitable candidates for water and wastewater treatments.