胆碱类低共熔溶剂与氧化锌吸附分子动力学模拟  

First Principles Calculation and Analysis of Adsorption ofCholine Deep with Zinc Oxide

作　　者：张晋霞 杨超 高淑玲[2] 牛福生 信晓飞[3] ZHANG Jinxia;YANG Chao;GAO Shuling;NIU Fusheng;XIN Xiaofei(College of Mining Engineering,North China University of Science and Technology,Tangshan 063009,Hebei,China;School of Resources and Civil Engineering,Northeastern University,Shenyang 110819,Liaoning,China;No.2 Geological Brigade of Hebei Geology and Mineral Exploration Bureau,Tangshan 063000,Hebei,China)

机构地区：[1]华北理工大学矿业工程学院,河北唐山063009 [2]东北大学资源与土木工程学院,辽宁沈阳110819 [3]河北省地矿局第二地质大队,河北唐山063000

出　　处：《矿产综合利用》2024年第3期179-186,192,共9页Multipurpose Utilization of Mineral Resources

基　　金：国家自然科学基金项目(51904106);河北省自然科学基金资助项目(E2018209085);唐山市基础创新团队项目(19130207C)。

摘　　要：这是一篇冶金工程领域的论文。为了更好实现含锌尘泥中氧化锌的浸出,采用基于密度泛函理论的Materials Studio软件模拟优化氧化锌晶体结构以及三种胆碱类低共熔溶剂结构,并对两者相互吸附模型进行计算。计算结果表明:ZnO(001)面为完全解理面,在费米能级附近最高占据态向左发生偏移,且最高占据态的波峰增加,峰值升高,在最高占据态中O的p轨道以及Zn的d轨道活性较大,为ZnO(001)面反应活性位点。对三种胆碱类低共熔溶剂优化发现氯化胆碱与三种不同氢键供体形成以氯原子为中心的多重分子间氢键。运用Forcite模块对低共熔溶剂与氧化锌吸附模型计算结果表明,氧化锌与三种胆碱类低共熔溶剂相互作用强弱为Chcl-MA>Chcl-Urea>Chcl-Eg。径向分布函数得出丙二酸使得氯化胆碱中的Cl更容易与Zn发生化学吸附,三种氢键供体中与Zn形成化学键的氧原子官能团活泼性为C=O、N-O、C-O,由此说明丙二酸中的C=O使得Chcl-MA与ZnO结合更稳定。通过实验验证发现Chcl-MA在浸出温度为70℃、液固比为10∶1、浸出时间1 h条件下可将氧化锌单矿物几乎完全浸出,浸出效果远远大于Chcl-Urea、Chcl-Eg两种药剂,从而证明了分子模拟的准确性,为胆碱类低共熔溶剂浸出含锌尘泥提供了理论指导。This is an article in the field of metallurgical engineering.In order to better realize the leaching of zinc oxide from zinc-containing dust,Materials Studio software based on density functional theory was used to simulate and optimize the crystal structure of zinc oxide and the structure of three kinds of choline deep eutectic solvents,and the mutual adsorption model of the two was calculated.The calculated results show that the ZnO(001)plane is a complete cleavage plane,and the highest occupied state near the Fermi level shifts to the left,and the peak of the highest occupies state increases,and the p orbital of O and the d orbital of Zn are more active,which are the active sites of the ZnO(001)plane.Optimization of three choline hyper eutectic solvent shows that choline chloride forms multiple intermolecular hydrogen bonds with three different hydrogen bond donors centered on chlorine atom.The adsorption model of deep eutectic solvents and zinc oxide was calculated using Forcite module.The results shows that the interaction strength of zinc oxide with three choline deep eutectic solvent is Chcl-MA>Chcl-Urea>Chcl-Eg.The radial distribution function shows that malonic acid makes it easier for Cl in choline chloride to chemisorb with Zn.In the three kinds of hydrogen bond donors,the activity of oxygen atomic functional groups forming chemical bonds with Zn is C=O,N-O and C-O,indicating that C=O in malonic acid makes the combination of Chcl-MA and ZnO more stable.Results show that the leaching temperature of Chcl-MA is 70℃and the liquid-solid ratio is 10∶1.Under the condition of leaching time of 1 h for 60 min,single mineral zinc oxide can be almost completely leached,and the leaching effect is far greater than that of Chcl-Urea and Chcl-Eg,thus proving the accuracy of molecular simulation and providing theoretical guidance for the leaching of zinc-containing dust in choline deep eutectic solvent.

关 键 词：冶金工程 低共熔溶剂 氧化锌 完全解理面 相互作用能 化学吸附 

分 类 号：TD952[矿业工程—选矿]