An alkali-resistant metal-organic framework as halogen bond donor for efficient and selective removing of ReO 4 - /TcO 4 .

99 Tc is one of the most problematic nuclear fuel products due to its long half-life and high environmental mobility. Direct removal of TcO 4 - from the highly alkaline solution of nuclear fuel is a serious and challenging environmental issue. In this work, the first efficient synthetic approach introducing halogens into a two-dimensional metal-organic framework, named Mn-MOF, is established using MnCl 2 ·4H 2 O coordinating with neutral nitrogen-donor ligand, showing ultrahigh stability in alkaline aqueous even under 1 M NaOH. The luxuriant Mn-Cl bonds and ordered hydrophobic pore channels enable the Mn-MOF to have an efficient adsorption capacity for ReO 4 - with a large capacity (403 mg g -1 ), which is higher than most MOF adsorbents. More importantly, the Mn-MOF shows an excellent selectivity toward ReO 4 - in high-density competitive anions, such as NO 3 - and SO 4 2- . Moreover, the outstanding performance of Mn-MOF in removing ReO 4 - endowed it successfully separated ReO 4 - from the simulated Savannah River Site (SRS) high-level waste (HLW) stream with high removal of 66.84% at the phase ratio of 10. The adsorption mechanism is further demonstrated by FT-IR, XPS analysis, and DFT calculation, showing that the ReO 4 - can selectively interact with Mn-Cl bonds and imidazole groups, forming unique halogen bonds Cl-O-Re, and a series of hydrogen bonds, respectively. This work suggests a new approach to the removal of TcO 4 - from nuclear fuel.