苯并三氮唑及其羧酸酯衍生物对铜缓蚀机理的分子动力学模拟研究

用分子动力学(MD)方法, 模拟计算了5种铜缓蚀剂苯并三氮唑(BTA)、苯并三氮唑-5-羧酸甲酯(MBTC)、苯并三氮唑-5-羧酸丁酯(BBTC)、苯并三氮唑-5-羧酸己酯(HBTC)、苯并三氮唑-5-羧酸辛酯(OBTC)]与Cu₂O晶体的相互作用. 结果发现, 中性条件下缓蚀剂分子与Cu₂O晶体的结合能均大于酸性条件下的数值, 但两种条件下结合能的大小排序均为OBTC＞HBTC＞BBTC＞MBTC＞BTA. 对体系各种相互作用以及对关联函数g(r)的分析表明, 体系结合能主要由库仑作用提供, Cu₂O晶体中的Cu原子与缓蚀剂分子中的N原子之间形成了配位键. 在与Cu₂O(001)晶面结合过程中, BTA及其衍生物分子发生了扭曲变形, 但形变能远小于体系的非键相互作用能.

Molecular Dynamics Simulation of the Corrosion Inhibition Mechanism of Copper by Benzotriazole and Its Carboxylate Derivatives

The interactions between kinds of corrosion inhibitors, benzotriazole (BTA), methyl benzotria- zole-5-carboxylate (MBTC), butyl benzotriazole-5-carboxylate (BBTC), hexyl benzotriazole-5-carboxylate (HBTC), octyl benzotriazole-5-carboxylate (OBTC) and Cu2O crystal have been simulated by molecular dy- namics (MD). The results showed that the binding energies of corrosion inhibitors with Cu2O crystal in neu- tral medium were bigger than those in acidic medium, but the orders of binding energy were both as follows: OBTC>HBTC>BBTC>MBTC>BTA. The analysis of various interactions and pair correlation functions of all systems indicated that binding energies were mainly determined by coulomb interaction, and coordina- tion bonds were formed between the copper atoms in Cu2O crystal and the nitrogen atoms in corrosion in- hibitors. Benzotriazole and its derivatives were deformed during their combining with the (001) face of Cu2O crystal, but all the deformation energies were far less than respective nonbond interaction energies.