中文摘要：

采用动态激光光散射（DLS）、Fourier变换红外光谱（FTIR）、核磁共振波谱（^31P-/^1H NMR）等谱学技术,研究了TBP-Pd（Ⅱ）-HCl萃取有机相中微乳的形成以及溶液聚集态结构的变化。结果表明：（1）伴随钯的萃取,TBP萃取有机相中形成微乳。（2）萃取有机相中酸含量的变化导致溶液结构发生相应改变：胶团聚集体平均流体力学半径随有机相中酸含量的增加先增大而后又减小。微乳“内核水”的O—H伸缩振动吸收谱带逐渐宽化,与邻近的C—H伸缩振动区形成交迭,且有机相含酸量越高,交迭程度越大。水分子O—H—O弯曲变角振动吸收峰形也发生很大变化。TBP的PO伸缩振动明显向低频移动。核磁共振^31P化学位移与活泼氢1H化学位移变化行为相反,说明TBP分子与酸和水分子发生缔合,形成RP=O·H^＋或RP=O·H3O^＋,并与PdCl4^2-存在相互作用。（3）有机相形成微乳水团后,由于大量H^＋的进入,微乳水团中酸浓度表现出明显的“增浓效应”。微乳水池内部微观环境的改变是导致钯萃取行为变化的主要原因。

英文摘要：

The formation of W/O microemulsions in the extraction system TBP-Pd（Ⅱ）-HCl was investigated. The solution structural evolution of the palladium loaded organic phases, with the variation in the content of acid into the organic phases, was characterized by various spectroscopic techniques such as DLS, FTIR and ^31P-/^1H NMR. The results indicated that （1） the extraction behaviors of palladium was related to the formation of W/O microemulsion structure in the loaded organic solutions. Because of the co-extraction of hydrochloric acid, there formed the microscopic aggregates in the loaded organic phases. （2） The variation in the HCl content in organic phase resulted in corresponding changes in solution structure. With the increase in the HCl content, the average radii of nanoscopic aggregates in the organic phases increased and then decreased. The extraction of HCl into the organic phase exhibited a distinct impact on the O—H stretching vibration and O—H—O bending vibration of water molecules in the microscopic W/O micelles. FTIR spectra of the organic phase saturated with acids show that the broad band of O—H stretching vibration of water extended to a very wide range and overlaped with the C—H stretching vibration bands. The higher the acid concentration in the organic phase was, the greater the overlapping. On the other hand, it was also observed that a remarkable change appeared in the O—H—O bending vibration of water and the stretching vibration of PO in TBP molecules shifted to lower frequency. With the increase in acid content in the TBP organic phases, the observed ^31P NMR chemical shifts decreased and varied to up-field; whereas the ^1H NMR chemical shift of H^＋ increased and even became larger than that of deuterium chloride-d at a lower frequency field. The changes in δ^31P to opposite direction of δH^＋ means that TBP molecules were associated with acid protons and water molecules in microemulsion pools to form RP=O·H^＋ or RP=O·H3O^＋, and then interacted with PdCl4^