Covalent bonding confining polyoxometalates in covalent organic frameworks for efficiently capturing uranium.

• TFHH-POM was developed by using amino-modified polyoxometalates embedded in covalent organic framework pores. • The covalent bond connection between TFHH and POM improves the stability of POM. • Covalent bonding and internal confined improve the mass transfer from TFHH to POM. • TFHH-POM exhibits a notably elevated photoreduction capacity of U(VI). To achieve sustainable nuclear energy and environmental protection, capturing uranium from mining wastewater is imperative. Herein, as an extraction composite of U(VI), TFHH-POM was developed by using a highly conjugated polyaromatic ether-based covalent organic framework (TFHH) as the carrier with amino-modified polyoxometalates (POM) embedded in its pores through amide bonds. The highly conjugated structure of TFHH facilitates charge transport, and in combination with the charge density contrast between POM and TFHH, along with the constraining effect of POM within TFHH channels, jointly enhances charge separation efficiency. As a result, the photoreduction efficiency of U(VI) is substantially increased. Simultaneously, the oxygen-containing groups in POM and carboxyl groups in TFHH could selectively adsorb U(VI), while Mo(V) in POM effectively reduces U(VI) to U(IV), synergistically promoting U(VI) capture. Hence, TFHH-POM exhibits remarkable U(VI) extraction efficiency through enhanced mass transfer, improved diffusion, and introduced chemical reduction. The U(VI) extraction capacity of TFHH-POM reaches 489.2 mg/g, surpassing those of POM and TFHH by 3.2 and 1.6 times, respectively. The reduced U(IV) remains stable after 30 days of storage with no reoxidation observed. Moreover, TFHH-POM demonstrates selective U(VI) capture from mining wastewater, highlighting its vast potential for environmentally sustainable uranium mining. [ABSTRACT FROM AUTHOR]