Degradation of Tetrabromobisphenol A with Surfactant-Enhanced PAC-Pd/Fe Nanoparticles
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摘要: Pd/Fe纳米材料对卤代有机污染物有较强的降解能力，但四溴双酚A的强疏水性会阻碍污染物与Pd/Fe的有效接触.为促进四溴双酚A的降解，考察了不同表面活性剂对PAC-Pd/Fe纳米颗粒降解四溴双酚A的影响，结果表明：少量阴离子表面活性剂SDS对四溴双酚A的降解有明显的促进作用，反应速率可提高1.7~2.5倍；非离子表面活性剂TX-100对四溴双酚A降解的促进效果不明显，当其质量浓度超过临界胶束浓度时，甚至表现出抑制作用；阳离子表面活性剂CTAB对四溴双酚A的降解起抑制作用，且质量浓度越大，其抑制效果越明显；PAC-Pd/Fe纳米颗粒对四溴双酚A的降解是连续脱溴反应，四溴双酚A和其中间产物三溴双酚A、二溴双酚A和一溴双酚A的表观降解速率常数分别为0.466 2、0.435 6、0.338 0和0.271 1 min-1，与苯环上溴原子的数目成正比.
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关键词:
- 表面活性剂 /
- PAC-Pd/Fe纳米颗粒 /
- 四溴双酚A /
- 降解 /
- 动力学
Abstract: Pd/Fe nanoparticles are considered effective agents for the degradation of halogenated organic compounds (HOCs). However, the high hydrophobicity of tetrabromobisphenol A (TBBPA) hinders its degradation owing to the inefficient contacts of TBBPA and Pd/Fe nanoparticles. To promote the degradation of TBBPA, the effects of different surfactants on TBBPA degradation with PAC-Pd/Fe nanoparticles were investigated. The results show that the anionic surfactant SDS had the best promoting effect on TBBPA degradation and the rate of reaction increased by 1.7-2.5 times. The nonionic surfactant TX-100 had little enhancement in TBBPA degradation. It even exerted an inhibitive effect as its concentration went above the critical micelle concentration. The cationic surfactant CTAB displayed the most inhibitive effect on TBBPA degradation, and the inhibition was stronger as the surfactant concentration increased. The degradation of TBBPA with PAC-Pd/Fe nanoparticles was a consecutive debromination reaction. The corresponding degradation rate constants of parent TBBPA and its intermediates tri-BBPA, di-BBPA and mono-BBPA were 0.466 2, 0.435 6, 0.338 0 and 0.271 1 min-1, respectively, which were proportional to the amount of bromide atoms on benzene rings.-
Key words:
- surfactant /
- PAC-Pd/Fe nanoparticles /
- tetrabromobisphenol A /
- degradation /
- kinetics
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图 1 不同类型和质量浓度的表面活性剂对四溴双酚A降解的影响
注：CMC1、CMC2、CMC3分别为SDS、CTAB、TX-100的临界胶束浓度，表 2同.
Figure 1. The effects of various surfactants on the degradation of TBBPA with PAC-Pd/Fe nanoparticles
图 2 不同质量浓度CTAB溶液中PAC-Pd/Fe纳米颗粒的Zeta电位和粒径分布
Figure 2. The Zeta-potentials and size diameter distribution of PAC-Pd/Fe nanoparticles in CTAB aqueous solutions with various concentrations
图 3 SDS溶液(1.0CMC1)中PAC-Pd/Fe纳米颗粒降解四溴双酚A的产物变化情况
Figure 3. The varieties of products from TBBPA degradation with PAC-Pd/Fe nanoparticles in SDS solution (1.0CMC1)
图 4 SDS溶液(1.0CMC1)中四溴双酚A降解产物的动力学拟合
Figure 4. The kinetics fitting of products from TBBPA degradation in SDS solution (1.0CMC1)
表 1 表面活性剂的性质
Table 1. The properties of the surfactants
表面活性剂 类型 分子式 相对分子量 CMC/(g·L-1) 化学结构 CTAB 阳离子 C19H42BrN 364.5 0.36 
SDS 阴离子 C12H25O4SNa 288.6 2.36 
TX-100 非离子 C34H62O11 647.0 0.13 
注：表中CMC数据引自文献[11]. 
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表 2 四溴双酚A降解反应的一级动力方程拟合参数
Table 2. The fitting parameters of first-order kinetic equation for TBBPA degradation reaction
表面活性剂 质量浓度 Kobs/min-1 R2 无 - 0.188 2 0.995 1 SDS 0.5CMC1 0.321 2 0.991 3 1.0CMC1 0.466 2 0.986 4 3.0CMC1 0.281 1 0.998 5 5.0CMC1 0.251 6 0.998 4 CTAB 0.5CMC2 0.141 6 0.994 2 1.0CMC2 0.106 6 0.993 5 3.0CMC2 0.095 1 0.987 8 5.0CMC2 0.083 9 0.989 4 TX-100 0.5CMC3 0.216 6 0.993 6 1.0CMC3 0.246 4 0.997 9 3.0CMC3 0.154 1 0.996 0 5.0CMC3 0.132 5 0.993 9
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