Extraction Performance of a Fluorous Phosphate for Zr(IV) from HNO3 Solution: Comparison with Tri-n-Butyl Phosphate
Extraction Performance of a Fluorous Phosphate for Zr(IV) from HNO3 Solution: Comparison with Tri-n-Butyl Phosphate
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氟磷酸盐从 HNO3 溶液中萃取 Zr(IV) 的性能：与磷酸三正丁酯的比较
DOI：
10.1080/07366299.2019.1638015
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发表时间：
2019
影响因子：
2
通讯作者：
Motokawa Ryuhei
中科院分区：
文献类型：
--
作者：
Ueda Yuki;Kikuchi Kei;Sugita Tsuyoshi;Motokawa Ryuhei
比较了新型萃取剂磷酸氟三(4，4，5，5，6，6，7，7，7，7-九氟庚基)磷酸(TFP)在氟化稀释剂全氟己烷中与传统有机萃取剂磷酸三正丁酯(TBP)在正辛烷中对Zr(IV)的萃取性能。令人惊讶的是，将TBP氟化为TFP可以改善萃取性能，因为通常情况下，将烃类取代基氟化在中性萃取剂上会降低萃取强度。通过对TFP提取过程中化学反应的平衡分析，探讨了TFP提取性能优异的原因。与TFP的平衡反应为：⇌的平衡反应为：ZrNO34aq+3TFP Flu；与⇌的平衡反应为：ZrNO34aq+2TBPorg。P-31核磁共振和红外光谱测量表明，TFP和TBP在P原子上的电子密度和TeP=O基团的振动模相似，这意味着它们与Zr(IV)的配位相似。此外，采用电感耦合等离子体质谱、离子色谱和卡尔-费歇尔滴定等方法对萃取后氟相和有机相中所有组分(Zr(IV)、HNO3和水)的浓度进行了测定。在萃取过程中，水和HNO_3分子在氟相中的浓度变低，表明水和HNO_3分子并不比正辛烷中的Zr(NO_3)_4(TBP)_2优先与水和HNO_3分子相互作用。推测这种优异的性能源于Zr(NO_3)_4(TFP)_3在氟相中的稳定性。因此，TFP有望作为TBP的替代萃取剂。
We compare the extraction performance of new extractant, fluorous phosphate tris(4,4,5,5,6,6,7,7,7-nonafluoroheptyl) phosphate (TFP) in the fluorinated diluent perfluorohexane, for Zr(IV) with a conventional organic extractant, tri-n-butyl phosphate (TBP) inn-octane. It is surprising that fluorinating TBP to TFP improved the extraction performance, as normally fluorinating the hydrocarbon substituents on neutral extractants tends to decrease the extraction strength. We examined the origin of the superior extraction performance of TFP by analyzing the equilibrium of the chemical reaction during the extraction. The equilibrium reaction of Zr(IV) with TFP is ZrNO34aq+3TFPflu ⇌ZrNO34TFP3flu, whereas that with TBP is ZrNO34aq+2TBPorg ⇌ZrNO34(TBP)2org. Phosphorus-31 nuclear magnetic resonance and infrared spectroscopy measurements of TFP and TBP showed similar electron densities at the phosphorus atom and vibration modes of theP=O group, implying similar coordination to Zr(IV). In addition, the concentrations of all components (Zr(IV), HNO3, and water) in the fluorous and organic phases after solvent extraction were evaluated by inductively coupled plasma-mass spectrometry, ion chromatography, and Karl-Fischer titration. The concentrations of water and HNO3molecules in the fluorous phase become low during the Zr(NO3)4(TFP)3extraction, indicating that water and HNO3molecules do not preferentially interact with Zr(NO3)4(TFP)3in contrast to Zr(NO3)4(TBP)2inn-octane We speculate that the excellent performance originated from the stability of Zr(NO3)4(TFP)3in the fluorous phase. Hence, TFP is expected to be used as an alternative extractant to TBP.
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Purex 工艺中沉淀形成磷酸锆-二丁基络合物。
影响因子：
1.2
作者：
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通讯作者：
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氟溶剂和相关介质
DOI：
10.1002/3527603905.ch3
发表时间：
2005
期刊：
ChemInform
影响因子：
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作者：
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通讯作者：
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DOI：
--
发表时间：
1964
期刊：
影响因子：
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作者：
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通讯作者：
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影响因子：
1.8
作者：
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通讯作者：
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影响因子：
0.9
作者：
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