期刊
INORGANIC CHEMISTRY
卷 52, 期 19, 页码 10904-10911出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic400895d
关键词
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资金
- National Natural Science Foundation of China [21201166, 21101157, 11105162, 21261140335]
- Major Research Plan Breeding and Transmutation of Nuclear Fuel in Advanced Nuclear Fission Energy System of Natural Science Foundation of China [91026007, 91126006]
- Strategic Priority Research Program of the Chinese Academy of Sciences [XDA03010401, XDA03010403]
A series of extraction complexes of Eu(III) and Am(III) with CMPO (n-octyl(phenyl)-N,N-diisobutyl-methylcarbamoyl phosphine oxide) and its derivative Ph2CMPO (diphenyl-N,N-diisobutyl carbamoyl phosphine oxide) have been studied using density functional theory (DFT). It has been found that for the neutral complexes of 2:1 and 3:1 (ligand/metal) stoichiometry, CMPO and Ph2CMPO predominantly coordinate with metal cations through the phosphoric oxygen atoms. Eu(III) and Am (III) prefer to form the neutral 2:1 and 3:1 type complexes in nitrate-rich acid solutions, and in the extraction process the reactions of [M(NO3)(H2O)(7)](2+) + 2NO(3)(-) + nL -> MLn(NO3)(3) + 7H(2)O (M = Eu, Am; n = 2, 3) are the dominant complexation reactions. In addition, CMPO and Ph2CMPO show similar extractability properties. Taking into account the solvation effects, the metal-ligand binding energies are obviously decreased, i.e., the presence of solvent may have an significant effect on the extraction behavior of Eu(III) and Am(III) with CMPOs. Moreover, these CMPOs reagents have comparable extractability for Eu(III) and Am(111), confirming that these extractants have little lanthanide/actinide selectivity in acidic media.
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