HA和HNAPO萃取锌的密度泛函分析

doi:10.12034/j.issn.1009-606X.218157

摘要/Abstract

摘要： 为从微观层面分析从锌氨溶液中萃取Zn(II)的反应机理，采用密度泛函(DFT) B3LYP/6-31G+(d, p)理论对萃取剂1-苯基-1,3癸二酮(Mextral54-100，HA)和2-羟基-5-壬酰基苯甲酮肟(Lix84I，HNAPO)及Zn(II)萃合物的几何结构、红外光谱、原子轨道贡献率和电荷分布等进行研究。结果表明，在HA与锌形成萃合物的过程中，HA烯醇式上的O和C原子、HNAPO肟基上的C和N原子及苯酚上的O原子对分子轨道的贡献率最高；HA上的C=C双键的伸缩振动峰在萃取反应后发生红移，HNAPO肟基上的C=N双键的伸缩振动峰强度发生改变，酚羟基的摇摆振动峰消失，表明烯醇式、肟基和酚羟基为萃取反应的活性中心，键长和键角均发生了改变；Zn(II)取代烯醇式上的氢与氧原子形成配位键，C=O双键在形成萃合物后键长增大。HNAPO与锌形成萃合物的过程中，Zn(II)取代酚羟基上的氢与氧和氮原子形成配位键，且苯环和锌离子处于一个平面上；萃取剂HA的分子轨道差值和电负性均低于HNAPO，化学势高于HNAPO，理论预测HA萃取锌的反应活性大于HNAPO，与实验结果吻合。

关键词: 溶剂萃取, 密度泛函理论, Mextral54-100, Lix84I

Abstract: In order to analyse extraction mechanism of Zn(II) from ammonia/ammoniacal solution, density function theory (DFT) calculation at the level of B3LYP/6-31G+(d, p) were used to predict the geometry structures, vibrational frequencies, frontier orbitals energy, chemical potential and charge distribution of the 1-phennyl-1,3-sebacic-diketone (Mextral54-100, HA), 2-hydroxy-5-nonylacetophenone dioxime(Lix84I, HNAPO) and corresponding Zn(II) extracted complexes. The DFT calculation results were used to predict the extraction ability and compared with the experiment values. The results showed that during the process of extracting zinc by HA and HNAPO, the O and C atoms on enol-form of HA, the C and N atoms on oxime, the O atom on phenol of HNAPO, which accounting for the highest contribution to the molecular frontier orbitals. In the infrared spectrum of extractants and complexes, the stretching vibration peak of the C=C double bond on the HA showed red-shifted, the intensity of the distortion vibration peak of the C=N double bond on the oxime group changed, and the characteristic absorption peak of the phenolic hydroxyl group on the HNAPO disappeared after extraction reaction, indicating that the enol form, oximido and phenolic hydroxyl group were the active centers during extraction process. After extracted zinc, the bond molecule length and molecule angle changed, Zn(II) replaced enol-form hydrogen and with oxygen atom to form coordination bond, the C=O double bond stretched during zinc extraction process by HA. Besides, Zn(II) replaced phenolic hydroxyl H atom and reacted with O and N atoms to form coordination bonds, the benzene and Zn(II) were on the same plane of zinc extracted HNAPO molecule. The ΔE (ΔELUMO–HOMO) and electronegativity of HA were lower than HNAPO. The chemical potential was higher than HNAPO, which indicated that the extraction capacity was in the order of HA>HNAPO. The experimental results were in good agreement with the theoretical prediction results.

Key words: solvent extraction, density functional theory, Mextral54-100, Lix84I

罗兴国魏昶李兴彬邓志敢庄子宇李存兄. HA和HNAPO萃取锌的密度泛函分析[J]. 过程工程学报, 2019, 19(1): 151-158.

Xingguo LUO Chang WEI Xingbin LI Zhigan DENG Ziyu ZHUANG Cunxiong LI. Density functional analysis on extracting of zinc by HA and HNAPO[J]. Chin. J. Process Eng., 2019, 19(1): 151-158.

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