对苯二酚在室温离子液体碳糊电极上电化学行为的半经验量子化学AM1研究

Theoretical Studies on Electrochemical Behavior of P-Diphenol at Carbon Paste Electrode of Room Temperature Ionic Liquid with Graphite Powder by AM1 Semiempirical Quantum Chemical Method

为了从理论上对对苯二酚在[BMIM]BF4室温离子液体及甲基硅油与石墨粉组成的碳糊电极上的电化学行为深入研究,以半经验分子轨道的AM1方法计算对[BMIM]BF4室温离子液体,甲基硅油和对苯二酚及其之间的分子相互作用的热力学参数如生成焓、电离能、分子间距离及能量.[BMIM]BF4室温离子液体与对苯二酚是以BF4-负离子为作用基点,而甲基硅油是以甲基碳作为作用基点,甲基硅油具有降低最高占有轨道能量,催化了对苯二酚的电化学氧化.[BMIM]BF4室温离子液体离子性质增加了极性水分子的渗透性,表现出较大的介电常数,给出了较大的充电电流.

In order to understand the electrochemiesl behavior of p-diphenol at carbon paste dectrodes composed of [BMIM] BF4 room temperature inonic liquid and methyl silicane with graphite powder theoretically, the thermodynamic parameters of molecular interactions between [BMIM] BF4, methyl silicane and p-diphenol were carried out by AM1 semiempirical quantum chemical method. The p-diphenol interacts with [ BMIM] BF4 molecue through the site of BF4 chation, while interacts with methyl silicane through the sites of methyl, which decreases the energy level of the HOMO orbital and catalyzes the oxidation of p-diphenol. [BMIM] BF4 increases the permeation of water molecules and increases the dielectric constant and shows a larger background current in CV plots.