Pore-Free Matrix with Cooperative Chelating of Hyperbranched Ligands for High-Performance Separation of Uranium

A new strategy combining a pore-free matrix and cooperative chelating was proposed in the present paper in order to effectively avoid undesired nonselective physical adsorption and intraparticle diffusion caused by pores and voids in porous sorbents, and to greatly enhance uranium-chelating capability based on hyperbranched amidoxime ligands on the surface of nanodiamond particles. Thus, a pore-free, amidoxime-terminated hyperbranched nanodiamond (ND-AO) was designed and synthesized. The experimental results demonstrate that the strategy endows the as-synthesized ND-AO with the following expected features: (1) distinctively high uranium selectivity (S_U = q_e-U/q_e-tol × 100%) from over 80% to nearly 100% over the whole weak acidity range (pH < 4.5); especially, the S_U can reach up to unprecedented >91% at pH 4.5, more than 20% of selectivity increment over any analogous sorbent materials reported so far, with a uranium sorption capacity of 121 mg/g in simulated nuclear industry effluent samples containing 12 coexistent nuclide ions; (2) superfast equilibrium sorption time of <30 s; and (3) one of the highest distribution coefficients (K_d) of ∼3 × 10⁶ mL/g for U(VI) as well as a fairly high sorption capacity of 212 mg/g at pH 4.5 in pure uranium solution. The strategy could also provide an optional approach for the design and fabrication of other new high-performance sorbing materials with prospective applications in selective separation of other interested metal ions.