Analysis of the Mechanism of Choline Chloride-oxalate Action on Zinc Oxide Leaching Based on First Principles
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摘要:
这是一篇冶金工程领域的文章。为探究氯化胆碱-草酸对含锌尘泥中氧化锌的浸出机理，运用量子力学手段，模拟氯化胆碱-草酸1∶1、1∶2低共熔溶剂在氧化锌表面相互作用，通过实验对模拟结果进行验证。结果表明，氯化胆碱-草酸形成的分子间氢键对低共熔溶剂稳定性起到重要作用，电子得失情况为Ch+得到电子，OA、Cl-失去电子。ZnO(001)面为氧化锌完全解理面，氧与锌原子形成四面体结构，在与外界发生反应过程中氧原子容易得电子，锌原子容易失去电子。氯化胆碱-草酸和氧化锌相互作用过程中氧化锌失去电子，氯化胆碱-草酸得到电子。ChCl-2OA和ZnO相互作用能$ \Delta \mathrm{E} $=-819.6896Ha较小，说明氧化锌更容易与ChCl-2OA发生反应。径向分布函数表明氯化胆碱-草酸在与氧化锌相互作用过程中主要以化学吸附为主，物理吸附为辅，化学吸附形成的Cl-Zn比O-Zn贡献较大。通过纯矿物实验验证可知，ChCl-2OA对氧化锌的浸出效果较好，验证了利用分子模拟氯化胆碱-草酸与氧化锌相互作用机理的准确性，为低共熔溶剂浸出含锌尘泥提供理论基础。
Abstract:This is an article in the field of metallurgical engineering. In order to explore the leaching mechanism of zinc oxide from zinc-containing dust by choline chloride and oxalic acid, the interaction of choline chloride and oxalic acid with 1∶1 and 1∶2 eutectic solvent on zinc oxide surface was simulated by means of quantum mechanics, and the simulation results were verified by experiments. The results show that the intermolecular hydrogen bond formed by choline chloride and oxalic acid plays an important role in the stability of eutectic solvent. Ch+ gains electrons, OA and Cl- lose electrons. ZnO(001) surface is the complete cleavage surface of zinc oxide, oxygen and zinc atoms form tetrahedral structure, oxygen atom is easy to gain electrons and zinc atom is easy to lose electrons during the reaction with the outside world. The zinc oxide loses electrons during the interaction between cholinergic chloride-oxalic acid and zinc oxide, and cholinergic chloride-oxalic acid gains electrons. The interaction energy △E=-819.6896Ha between ChCl-2OA and ZnO is small, indicating that zinc oxide is more likely to react with ChCl-2OA. The radial distribution function shows that the chemical adsorption is the main factor in the interaction between choline chloride and oxalic acid and zinc oxide, and the physical adsorption is the secondary factor. The contribution of Cl-Zn formed by chemical adsorption is greater than that of O-Zn. Through the pure mineral test, it can be verified that ChCl-2OA has a better leaching effect on zinc oxide, which verifies the accuracy of molecular simulation of the interaction mechanism between choline chloride and oxalic acid and zinc oxide, and provides a theoretical basis for the leaching of zinc-containing dust with eutectic solvent.
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表 1 两种比例氯化胆碱-草酸电荷布居/e
Table 1. Charge distribution of choline chloride and oxalic acid in two proportions
ChCl-OA ChCl-2OA Ch+ +0.728 +0.752 Cl- -0.569 -0.564 OA -0.159 -0.188 其中+代表得到电子，-代表失去电子 
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表 2 氧化锌常见解理面表面能/(J/m2)
Table 2. Common surface energy of metal oxides
单矿物 001 011 111 101 110 ZnO 0.8177 3.9275 3.9271 2.0852 2.4053
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表 3 原子层数对表面能的影响
Table 3. Influence of atomic layer number on surface energy
完全解理面 原子层数 原子数 表面能J/m2
ZnO(001)2 8 1.5438 3 12 1.5908 4 16 1.6079 5 20 1.6088 6 24 1.6093
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表 4 氧化锌各原子电荷布居
Table 4. Atomic charge population of zinc oxide
原子 各轨道布居数 总数 电荷数 s轨道 p轨道 d轨道 O 1.86 4.97 - 6.82 -0.83 Zn 0.48 0.72 9.97 11.18 0.83
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表 5 两种比例氯化胆碱-草酸和氧化锌前线分子轨道能量
Table 5. Frontier molecular orbital energy of choline chloride - oxalic acid and zinc oxide in two proportions
HOMO LUMO △E1 △E2 ChCl-OA -0.2023 -0.0679 0.1734 0.0941 ChCl-2OA -0.2118 -0.1154 0.1897 0.0771 ZnO -0.1625 -0.0221 其中ΔE1=|HOMODES−LUMOZnO|、△E2=|HOMOZnO−LUMODES|
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表 6 两种比例氯化胆碱-草酸与氧化锌相互作用能/Ha
Table 6. Interaction energy between choline chlorine-oxalic acid and zinc oxide in two proportions
低共熔溶剂 EA EB EAB △E ChCl-OA 101.2460 - 448581.5872 - 449217.2274 - 736.8862 ChCl-2OA 130.9856 - 448581.5872 - 449267.8158 - 817.2142
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