Initialising ...
Initialising ...
Initialising ...
Initialising ...
Initialising ...
Initialising ...
Initialising ...
Micheau, C.; 上田 祐生; 元川 竜平; 阿久津 和宏*; 山田 悟史*; 山田 雅子*; Moussaoui, S. A.*; Makombe, E.*; Meyer, D.*; Berthon, L.*; et al.
Journal of Molecular Liquids, 401, p.124372_1 - 124372_12, 2024/05
Supramolecular organization of extractant molecules impacts metal ions separation behavior. Probing bulk and interfacial structures of the relevant systems is expected to provide key insights into the metal ion selectivity and kinetic aspects. The supramolecular features of two solvent extraction systems based on malonamide extractants, N,N,N′,N′-tetrahexylmalonamide (THMA) in toluene and N,N′-dimethyl-N,N′-dibutyl-2-tetradecylmalonamide (DBMA) in n-heptane, were studied using small-angle X-ray scattering for the organic bulk phases, as well as interfacial tension and neutron reflectivity measurements for the interfaces. In the bulk solution, THMA forms dimeric/trimeric associates but no aggregates in toluene, while DBMA forms large aggregates in n-heptane. On the other hand, THMA accumulates in a diffuse layer at the interface at high THMA concentration, whereas DBMA forms a compact but thinner layer. After Pd(II) extraction, the thickness of interfacial layers decreases in the case of THMA, and totally vanishes in the case of DBMA. Based on these new structural information, two mechanisms are proposed for Pd(II) and Nd(III) extraction with malonamides. In toluene, THMA associates slightly accumulate in the vicinity of the interface, then coordinate Pd(II) and diffuse into the organic bulk phase. In n-heptane, DBMA aggregates adsorb at the interface then pick up Nd(III) cations in their polar cores and finally diffuse into the bulk.
Tamain, C.*; Bonato, L.*; Aupiais, J.*; Dumas, T.*; Guillaumont, D.*; Barkleit, A.*; Berthon, C.*; Solari, P. L.*; 池田 篤史; Guilbard, P.*; et al.
European Journal of Inorganic Chemistry, 2020(14), p.1331 - 1344, 2020/04
被引用回数：3 パーセンタイル：23.3(Chemistry, Inorganic & Nuclear)水溶液中における三価アメリシウム(Am(III))とクエン酸(Citric acid)の配位・錯形成反応について、可視吸収分光, NMR, X戦吸収分光(EXAFS), TRLFS、及び電気泳動測定を実施し、溶液中に生成している化学種の数、種類、及びその配位・錯形成状態についての検討を行った。当該実験結果はさらに量子化学計算の結果とも組み合わせ、生成化学種の詳細な配位・錯体構造について検討した。
Micheau, C.; 上田 祐生; 元川 竜平; Moussaoui, S.*; Makombe, E.*; Daniel, M.*; Berthon, L.*; Bourgeois, D.*; 阿久津 和宏*
no journal, ,
The DIAMEX process aims to separate minor f-elements using malonamide as extractant molecules such as N,N'-dimethyl-N,N'-dibutyl-tetradecyl-malonamide (DBMA). Recently, Poirot studied the effect of n-heptane and toluene on the selectivity of DBMA between Pd and Nd and have conclude that Pd extraction is driven by coordination whereas Nd extraction is driven by extractant aggregation. More recently, a specific study on tetrahexylmalonamide (THMA) in toluene demonstrated a superior selectivity for Pd compared to DBMA. THMA molecular structure suggests poor aptitude for aggregation compared with DBMA, and has been much less characterized. Supramolecular features of two different solvent extraction systems based on malonamide extractants, THMA in toluene and DBMA in heptane, have been studied using characterization techniques dedicated to bulk organic phase organisation, ie. small angle X-ray scattering, and to interface characterization, ie. neutron reflectivity and interfacial tension.
