炭基材料催化过氧化物降解水中有机污染物:表面作用机制  

Surface Mechanism of Carbon-Based Materials for Catalyzing Peroxide Degradation of Organic Pollutants in Water

作　　者：杨世迎[1,2,3] 张翱[1,3] 任腾飞[3] 张宜涛[3] 

机构地区：[1]海洋环境与生态教育部重点实验室,青岛266100 [2]山东省海洋环境地质工程重点实验室,青岛266100 [3]中国海洋大学环境科学与工程学院,青岛266100

出　　处：《化学进展》2017年第5期539-552,共14页Progress in Chemistry

基　　金：国家自然科学基金项目(No.21107101;21677135)资助~~

摘　　要：近几年来,利用传统炭材料(如活性炭(AC)、生物炭(BC)、活性炭纤维(ACF)与活性炭布(ACC))以及纳米碳材料(如碳纳米管(CNT)、石墨烯(GE)、有序介孔碳(OMC)),或其表面改性后的炭基材料,代替金属催化剂,来催化活化过氧化物(包括过氧化氢(H_2O_2)、过一硫酸氢盐(HSO_5^-,PMS)、过二硫酸盐(S_2O_8^(2-),PS))产生高活性羟基自由基(·OH)或硫酸根自由基(SO_4^(·-)),从而氧化去除水中难生物降解有机污染物,成为水处理领域研究热点。在炭表面富含很多起催化作用的官能团,如羟基、羧基、酮基、吡啶、吡咯等,同时具有丰富多样的缺陷形状、离域π电子、杂化C轨道等,能共同协作表现出非金属炭基催化剂的优良特性。因此,不同类型材料及其表面官能团、表面结构、电子密度等因素对炭基材料催化过氧化物的机理发挥显著作用。本文深入分析了上述炭基材料在吸附、络合中间体、电子转移过程中催化过氧化物产生强氧化性的自由基,并高效降解水中有机污染物的作用机理,综述了2010年以来该类高级氧化技术在水处理领域的研究进展,特别是通过总结炭基材料的氧化改性作用、氮化改性作用、多原子原位掺杂作用以及还原改性作用,系统阐述了表面物理化学性质对炭基材料催化过氧化物的表面作用机制的影响,并归纳了氧化剂对炭基材料的表面作用机制,对存在的问题提出了新的研究展望。In recent years,compared to metal catalysts,metal-free carbon-based catalysts including traditional carbon materials such as activated carbon（ AC）,biochar（ BC）,activated carbon fiber（ ACF） and activated carbon cloth（ ACC）,and newnano-carbon material such as carbon nanotubes（ CNT）,graphene（ GE）,ordered mesoporous carbon（ OMC）,and their surface modified materials are gradually investigated as a newperoxide activator. In the field of water treatment,the above carbon-based materials can be used to catalyze and activate peroxides such as hydrogen peroxide（ H2O2）,peroxymonosulfate（ HSO5-,PMS） or persulfate（ S2O82-,PS） to produce highly active hydroxyl radicals（ ·OH） or sulfate radicals（ SO4·-）,which can efficiently degrade organic contaminants through advance oxidation processes（ AOPs）. What ’s more,the surface structure of carbon-based materials is rich in functional groups,such as hydroxyl,carboxyl,ketone,pyridine,pyrrole,etc.,as well as abundant and varied defect shape,delocalized π electrons,hybrid C orbitals,and so on. They can work together and showthe excellent catalytic properties of metal-free carbon-based materials. Therefore,different types of materials and their surface functional groups,surface structure,electron density and other factors play a significant role in the mechanism of carbon-based materials catalyzing peroxides.Accordingly,the progress of this AOP since 2010 and the surface mechanism of the above carbon-based materials in catalyzing peroxide and then degrading organic pollutants in water through the process of adsorption,complexing intermediates and electron transfer are deeply reviewed. Especially,the effects of surface physical and chemical properties on catalyzing mechanisms by the way of oxidation,nitriding,polyatomic in-situ doping and reduction modification are summarized. In addition,the influence mechanism of oxidants on the surface of carbon-based materials is also studied. At the same time,the prospects of the existing problem

关 键 词：表面作用机制 炭基材料 表面官能团 表面结构 催化 过氧化物 

分 类 号：X131.2[环境科学与工程—环境科学] O643.3[理学—物理化学]