Defect-Engineered MOF-801/Sodium Alginate Aerogel Beads for Boosting Adsorption of Pb(II)

Metal-organic frameworks (MOFs) are attractive adsorbents for heavy metal capture due to their superior stability, easy modification, and adjustable pore size. However, their inherent microporous structure poses challenges in achieving a higher adsorption capacity. Defect engineering is considered a simple method to create hierarchical MOFs with larger pores. Here, we employed l-aspartic acid as a mixed linker to bind Zr⁴⁺ clusters in competition with fumaric acid of MOF-801 to create defects, and the pore size was increased from 4.66 to 15.65 nm. Mercaptosuccinic acid was subsequently used as a postexchange ligand to graft the resultant MOF-801 by acid-ammonia condensation to further expand the pore size to 22.73 nm. Notably, the -NH₂, -COOH, and -SH groups contributed by these two ligands increased the adsorption sites for Pb(II). The obtained defective MOF-801 with larger pores was thereafter loaded onto sodium alginate to form aerogel beads as adsorbents, and an adsorption capacity of 375.48 mg/g for Pb(II) was achieved, which is ∼51 times that of pristine MOF-801. The aerogel beads also exhibited outstanding reusability with a removal efficiency of ∼90.23% after 5 cycles of use. The adsorption mechanism of Pb(II) included ion-exchange interaction, as well as chelation interactions of Pb-O, Pb-NH₂, and Pb-S. The versatile combination of defect engineering and composite beads provides novel inspirations for MOF modification for boosting heavy metal adsorption.