Amidoxime‐based Star Polymer Adsorbent with Ultra‐High Uranyl Affinity for Extremely Fast Uranium Extraction from Natural Seawater

Polymer adsorbents functionalized with amidoxime groups are widely considered to have the most industrial potential for uranium extraction from seawater. However, the entanglement upon the collapse of polymer chain in seawater greatly reduces the utilization ratio of amidoxime ligands. Herein, a novel star‐shaped molecular brush adsorbent (β‐CD‐g‐PAO) is obtained by densely grafting polyamidoxime (PAO) chains from β‐cyclodextrin (β‐CD). Experimental and theoretical results reveal that, in contrast to conventional linear polymer adsorbents, the star polymer adsorbent with a high grafting density of PAO side chains enables strong steric repulsion between the polymer chains, leading to increased persistence length and disentanglement of side chains. As a result, the star polymer adsorbent shows higher accessibility of the adsorption ligands with lower adsorption energy, achieving an adsorption capacity of up to 944.75 mg g−1 in uranium‐spiked seawater, surpassing that of conventional linear PAO by 3.2 times. Remarkably, this star polymer adsorbent demonstrates an extraordinarily adsorption capacity of 10.9 mg−1 g−1 in only 1 day in natural seawater, coupled with excellent affinity for uranyl ions (K = 0.31 pM). The unique topological structure design provides a new approach to solving the problem of low utilization ratio of functional ligands in polymer adsorbents. Benefiting from the unique topological structure of molecular brushes, the side chains of this star polymer adsorbent can fully extend, resulting in high ligand utilization ratio. Coupled with a remarkably high AO density, this star polymer adsorbent exhibits exceptional affinity for uranyl ions and demonstrates an extraordinarily fast adsorption rate of uranium in natural seawater.