Phosphorylated covalent organic framework/graphene composites for photoelectrothermal integrated collaborative reduction of uranium

Photocatalytic reduction is becoming an effective method to remove UVI from uranium mine wastewater. Herein, 1,3,5-benzotrialdehyde (Tb) and 4,4′-diaminobiphenyl (BD) used as monomers of covalent organic framework (COF) are in situ growth on graphene oxide (GO) surfaces to obtain Tb-BD/rGO. Then, Tb-BD/rGO is converted into Tb-BD-P/rGO by asymmetric hydrogen phosphorylation, which is served as a new material for photocatalytic reduction of uranium via photoelectrothermal synergy. Benefiting from the transformation of dynamic imine bonds into irreversible carbon–nitrogen single bonds, Tb-BD-P/rGO expresses remarkable chemical and thermal stability. The introduction of phosphate groups improve the electronegativity and hydrophilicity of Tb-BD-P/rGO, which contribute to rapid transportation of uranium. In addition, the introduction of rGO achieves excellent photothermal conversion, accelerating the adsorption kinetics of uranium. Meanwhile, the π-π interaction between Tb-BD-P and rGO promotes inter-interfacial electron transfer and reduces the complexation of electron-hole pairs during the photocatalytic process, further improving photocatalytic performance. Therefore, Tb-BD-P/rGO demonstrates exceptional removal uranium rates (>95 %) in uranium mine wastewater by synergistically photoelectrothermal integration, offering a pathway for developing multifunctional and integrated photocatalysts.