Synthesis of ZnO nanoparticle-anchored biochar composites for the selective removal of perrhenate, a surrogate for pertechnetate, from radioactive effluents.

Pertechnetate (TcO4-) is a component of low-activity waste (LAW) fractions of legacy nuclear waste, and the adsorption removal of TcO4- from LAW effluents would greatly benefit the site remediation process. However, available adsorbent materials lack the desired combination of low cost, radiolytic stability, and high selectivity. In this study, a ZnO nanoparticle-anchored biochar composite (ZBC) was fabricated and applied to potentially separate TcO4- from radioactive effluents. The as-synthesized material exhibited γ radiation resistance and superhydrophobicity, with a strong sorption capacity of 25,916 mg/kg for perrhenate (ReO4-), which was used in this study as a surrogate for radioactive pertechnetate (TcO4-). Additionally, the selectivity for ReO4- exceeded that for the competing ions I-, NO2-, NO3-, SO42-, PO43-, Cu2+, Fe3+, Al3+, and UO22+. These unique features show that ZBC is capable of selectively removing ReO4- from Hanford LAW melter off-gas scrubber simulant effluent. This selectivity stems from the synergistic effects of both the superhydrophobic surface of the sorbent and the inherent nature of sorbates. Furthermore, density functional theory (DFT) calculations indicated that ReO4- can form stable complexes on both the (100) and (002) planes of ZnO, of which, the (002) complexes have greater stability. Electron transfer from ReO4- on (002) was greater than that on (100). These phenomena may be because (002) has a lower surface energy than (100). Partial density of state (PDOS) analysis further confirms that ReO4- is chemisorbed on ZBC, which agrees with the findings of the Elovich kinetic model. This work provides a feasible pathway for scale-up to produce high-efficiency and cost-effective biosorbents for the removal of radionuclides.