【摘要】：本論文合成了一類新型的1,2,3-三唑(1,2,3-Tz)類配體,該類配體難溶于水,可溶于氯仿等傳統(tǒng)有機溶劑以及咪唑類離子液體。1,2,3-三唑類化合物富含給電子的氮原子,易與具有軟酸性質(zhì)的鈀(II)形成穩(wěn)定的配合物,我們將該類化合物用于鈀的萃取研究。分別研究了接觸時間、萃取劑結(jié)構(gòu)和濃度、水相酸度、硝酸根離子(NO3-)濃度對萃取Pd~(2+)的影響。我們選擇了兩種性能較好的1,2,3-三唑類萃取劑Tz1和Tz2,研究其在離子液和氯仿中萃取Pd~(2+)的情況,結(jié)果表明該萃取過程能較快的達(dá)到萃取平衡,該類萃取劑在離子液中的萃取能力強于在氯仿中,溶液酸性越強,萃取效果越好。并對這兩種萃取劑在離子液和氯仿中萃取Pd~(2+)的機理做了詳細(xì)的研究,通過斜率法和摩爾比法,推測1,2,3-三唑類萃取劑在離子液和氯仿中與Pd~(2+)主要形成1:1的萃合物;利用傅里葉變換紅外光譜分析法(FTIR)和電噴霧質(zhì)譜分析法(ESI-MS)對萃取Pd~(2+)形成的萃合物進(jìn)行了表征,推測出1,2,3-三唑類萃取劑是通過三唑環(huán)的氮原子和吡啶環(huán)上的氮原子與Pd~(2+)配位;在離子液中主要通過中性溶劑化作用萃取Pd~(2+),水相酸度較高時還存在少量的陰離子交換作用,而在氯仿中的萃取過程僅存在中性溶劑化作用。此外,我們對這兩種配體萃取Pd~(2+)的選擇性做了研究,結(jié)果表明1,2,3-三唑類萃取劑在離子液中可以將Pd~(2+)從含多種金屬離子的混合溶液中分離出來,而對混合溶液中的其它金屬離子,如堿金屬、堿土金屬、鑭系、錒系等元素的金屬離子基本沒有萃取。我們還對反萃體系做了研究,結(jié)果表明較低酸度的硝酸溶液和低酸度酸化的硫脲溶液都可以把Pd~(2+)從離子液中反萃出來。我們對兩種萃取劑在離子液中萃取Pd~(2+)的熱力學(xué)也做了探討,通過實驗和計算得到了該萃取反應(yīng)的熱力學(xué)參數(shù)(ΔH,ΔS和ΔG),結(jié)果說明1,2,3-三唑類萃取劑對Pd~(2+)的萃取過程是一個吸熱的自發(fā)萃取過程。
[Abstract]:A new class of 1,2,3- three azole (1,2,3-Tz) ligands, which are difficult to dissolve in water, can be dissolved in the traditional organic solvents such as chloroform, and the imidazole ionic liquid.1,2,3- three azole compounds are rich in electron nitrogen atoms. It is easy to form a stable complex with palladium (II) with the properties of soft acid. We use this compound to be used in palladium. The effects of contact time, structure and concentration of extractants, water phase acidity and nitrate ion (NO3-) concentration on the extraction of Pd~ (2+) were studied. Two kinds of 1,2,3- three azole extractants, Tz1 and Tz2, were selected to study the extraction of Pd~ (2+) in ionic liquid and chloroform. The results showed that the extraction process could be faster. The extraction ability of this kind of extractant in ionic liquid is stronger than in chloroform. The better the solution is, the better the extraction effect is. The mechanism of the extraction of Pd~ (2+) in the ionic liquid and the chloroform of these two extractants is studied in detail. By the slope method and the molar ratio method, it is speculated that the 1,2,3- three azole extractants are in the ionic liquid and chloroform. Pd~ (2+) is mainly formed with Pd~ (2+), the extraction of Pd~ (2+) is characterized by Fourier transform infrared spectroscopy (FTIR) and electrospray ionization mass spectrometry (ESI-MS). It is conjectured that the 1,2,3- three azole extractant is the nitrogen atom of the three azole ring and the nitrogen atom of the pyridine ring with the Pd~ (2+) coordination; and in the ionic liquid. In order to extract Pd~ (2+) by neutral solvation, there is a small amount of anion exchange when the acidity of the aqueous phase is high, and the extraction process in chloroform only has neutral solvation. In addition, we have studied the selectivity of these two ligands for the extraction of Pd~ (2+). The results show that the 1,2,3- three azole extractants can make Pd~ in the ionic liquid. 2+) separates from a mixed solution containing a variety of metal ions, and the metal ions of other metal ions in the mixed solution, such as alkali metal, alkaline earth metal, lanthanide, actinide, etc., are basically not extracted. We have also studied the stripping system. The results show that the low acid nitrate solution and the low acidity acidified thiourea solution are all available. The Pd~ (2+) is extracted from the ionic liquid. The thermodynamics of the extraction of Pd~ (2+) in the ionic liquid of the two extractants is also discussed. The thermodynamic parameters (delta H, Delta S and delta G) of the extraction reaction are obtained by experiments and calculations. The results show that the extraction process of 1,2,3- three azolics is a spontaneous extraction process of the endothermic process.
【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O658.2;O614.823

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