ic8b00099_si_001.pdf (3.26 MB)
Porous Anionic Uranyl–Organic Networks for Highly Efficient Cs+ Adsorption and Investigation of the Mechanism
journal contribution
posted on 2018-03-23, 19:04 authored by Jing Ai, Fang-Yuan Chen, Chao-Ying Gao, Hong-Rui Tian, Qing-Jiang Pan, Zhong-Ming SunExploitation
of new materials for the removal of long-lived and highly radioactive
actinides and their fission products produced in the nuclear fuel
cycle is crucial for radionuclide management. Here, two rare porous
anionic uranyl–organic frameworks (UOFs) have been successfully
synthesized by a judicious combination of the tetratopic carboxylate
ligand 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) and D3h-symmetrical triangular [UO2(COO)3]−. The resulting two compounds exhibit different architectures, albeit
with similar coordination modes. Of interest is that they have excellent
adsorption performance on Cs+ from aqueous solution. The
high removal efficency would make them promising in applications of
radioactive waste management. Notably, the framework of compound 2, [(CH3)2NH2]4[(UO2)4(TBAPy)3]·22DMF·37H2O is sufficiently robust to allow the accessibility of intriguing
single crystals of a Cs+-adsorbed derivative, which helps
to elucidate the adsorption mechanism. The structural, bonding, and
spectroscopic properties of the above compounds are examined using
relativistic density functional theory (DFT). It is found that the
adsorption toward cesium on UOFs is energetically favored, which features
largely ionic bonds and is dominated by electrostatic attraction.