Covalent organic frameworks functionalized electrodes for simultaneous removal of UO22+ and ReO4- with fast kinetics and high capacities by electro-adsorption

Abstract

The recovery of radioactive ions from high salinity low-level radioactive wastewater (LLRW) is important for the sustainable utilization of nuclear energy. Previous work primarily focuses on developing adsorbents that remove individual types of ions via physicochemical adsorption. Here, we report a new strategy for the simultaneous recovery of uranium (UO22+) and rhenium (ReO4-) as a non-radioactive surrogate of technetium from LLRW via electro-adsorption. Carboxyl functionalized covalent organic frameworks (COF-1) and cationic covalent organic frameworks (COF-2) were prepared as cathode and anode materials, respectively. The adsorption capacities were 411 mg U/g for COF-1 and 984 mg Re/g for COF-2 under 1.2 direct-current (DC) volts, 2.5 and 2.1 times higher than the capacities of the same adsorbents obtained by physicochemical adsorption. We also found that the electro-adsorption of uranium and rhenium follows pseudo-second-order kinetics with the adsorption rates of 0.45 and 1.05 g/mg/h at pH 7.0 and 298.15 K, again two times faster than those measured in physicochemical adsorption. Therefore, electro-adsorption improves both adsorption capacity and kinetics by maximizing the utility of available active sites in adsorbents and facilitating ion migration towards the adsorbents. The adsorption efficiencies for uranium and rhenium reached 65.9% and 89.2%, respectively, after electro-adsorption for 2 h. The high efficiencies can be maintained after five adsorption-desorption cycles. Furthermore, the electrodes showed high selectivity for uranium(VI) and rhenium(VII) and excellent salt resistance even in 1 mol/L NaCl solution. XPS studies revealed that covalent bonds were formed between uranium(VI) and carboxyl groups on COF-1, and rhenium(VII) was bound to cationic COF-2 through electrostatic interaction. Our asymmetric electrodes design can be extended to simultaneously and efficiently remove other types of radioactive or heavy metal ions from wastewater.