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超声强化金刚石膜电极电化学降解效率的机制
摘要点击 2361  全文点击 1648  投稿时间:2007-09-07  修订日期:2007-10-10
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中文关键词  电化学氧化  金刚石膜电极  超声  传质  吸附量  平均电化学氧化能量利用率
英文关键词  electrochemical oxidation  BDD electrode  ultrasound  mass transport  adsorption amount  average electrochemical oxidation energy efficiency
作者单位
沈世豪 同济大学化学系上海 200092 
赵国华 同济大学化学系上海 200092 
吴梅芬 同济大学化学系上海 200092 
雷燕竹 同济大学化学系上海 200092 
刘梅川 同济大学化学系上海 200092 
中文摘要
      从电化学氧化的传质过程、吸附与脱附、电极反应3个步骤,考察了超声强化金刚石膜电极(BDD)电化学降解效率的机制.超声对上述3个步骤都有显著影响.超声增强了污染物的传质过程,苯酚和邻苯二甲酸的传质系数分别由5.410-6 m/s和6.710-6 m/s增大至2.010-5 m/s,提高了270%和199%.污染物在BDD电极表面的电化学吸附特性决定了超声对吸附与脱附过程的作用.苯酚的吸附量大,但中间产物难于脱附,超声虽然使得吸附量由6.4910-10 mol/cm2减小至1.3910-10 mol/cm2,但促进了产物的脱附,产生了正效应,有利于直接氧化,氧化峰电流提高了32%;邻苯二甲酸的吸附能力弱,超声使得吸附量由1.2510-11 mol/cm2进一步减小至3.1110-12 mol/cm2,产生了负效应,导致直接氧化消失.超声可以显著提高BDD电极的降解效率,而且对苯酚降解的促进作用更为明显.苯酚的平均电化学氧化能量利用率提高了287%,高于邻苯二甲酸的224%,这主要是因为超声可以同时强化苯酚的直接氧化和间接氧化,但对于邻苯二甲酸,间接氧化得到了加强,却不发生直接氧化.
英文摘要
      Mass transport process, adsorption and desorption, and electrochemical reaction were analyzed to investigate the mechanism of enhancement on boron-doped diamond (BDD) electrode electrochemical degradation efficiency by ultrasound (US). US has considerable influences on the above steps of electrochemical oxidation. Mass transport coefficients of Ph and PA reach 2.010-5 m/s with US, from 5.410-6 m/s and 6.710-6 m/s in EC process, increasing by 270% and 199%, respectively. The effect of US on adsorption and desorption has relationship with electrochemical adsorption properties of pollutants on BDD electrode surface. The adsorption amount of Ph decreases from 6.4910-10 mol/cm2 to 1.3910-10 mol/cm2, with the desorption of polymer intermediates promoted, so US makes positive effect with benefit to direct oxidation and oxidation peak current increases by 32%. For PA, the adsorption amount decreases from 1.2510-11 mol/cm2 to 3.1110-12 mol/cm2 with US, and no direct oxidation happens in US-EC process. US can improve degradation efficiency of BDD electrode and the enhancement on Ph degradation is more effective. Average electrochemical oxidation energy efficiency (AEE) of Ph increases by 287%, more than 224% of PA. This is because both direct and indirect oxidation for Ph can be enhanced by US, while for PA, direct oxidation almost disappears.

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