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多壁碳纳米管对林丹的吸附和催化转化

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杨吉睿, 孙红文. 多壁碳纳米管对林丹的吸附和催化转化[J]. 环境化学, 2016, 35(4): 629-638. doi: 10.7524/j.issn.0254-6108.2016.04.2015102302
引用本文: 杨吉睿, 孙红文. 多壁碳纳米管对林丹的吸附和催化转化[J]. 环境化学, 2016, 35(4): 629-638. doi: 10.7524/j.issn.0254-6108.2016.04.2015102302
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YANG Jirui, SUN Hongwen. Adsorption and catalytic transformation of lindane on multi-walled carbon nanotubes[J]. Environmental Chemistry, 2016, 35(4): 629-638. doi: 10.7524/j.issn.0254-6108.2016.04.2015102302
Citation: YANG Jirui, SUN Hongwen. Adsorption and catalytic transformation of lindane on multi-walled carbon nanotubes[J]. Environmental Chemistry, 2016, 35(4): 629-638. doi: 10.7524/j.issn.0254-6108.2016.04.2015102302
shu

多壁碳纳米管对林丹的吸附和催化转化

  • 1.

    南开大学环境科学与工程学院, 教育部环境污染过程与基准重点实验室, 天津, 300071

  • 基金项目:

    教育部创新团队发展计划(IRT13024)资助.

Adsorption and catalytic transformation of lindane on multi-walled carbon nanotubes

  • 1.

    MOE Key Laboratory on Pollution Processes and Environmental Criteria, College of Environmental Science and Engineering, Nankai University, Tianjin, 300071, China

  • Fund Project: Supported by the Program for Innovative Research Team in University (IRT13024).

  • 摘要: 进入环境的纳米材料对共存化学污染物的环境行为有重要影响.本文选择3种多壁碳纳米管,分别为石墨化多壁碳纳米管(G-MWCNT)、羟基化多壁碳纳米管(O-MWCNT)和氨基化多壁碳纳米管(N-MWCNT),通过批次实验研究其对林丹的吸附行为和催化转化作用.林丹在3种多壁碳纳米管上的吸附动力学符合准二级动力学模型(R2>0.997),吸附速率常数(k2)分别为0.73(G-MWCNT)、0.60(N-MWCNT)和0.28(O-MWCNT) g·mg-1·h-1.林丹在3种多壁碳纳米管上吸附的等温线符合Freundlich经验模型(R2>0.979),不同pH条件下,吸附系数(KF)分别为28.0—30.0(G-MWCNT)、21.3—24.6(N-MWCNT)和9.1—10.2(O-MWCNT)mg1-n·Ln·g-1.平衡浓度为8.5 mg·L-1,在不同pH条件下林丹在3种多壁碳纳米管上的分配常数(Kd)分别为12.7—14.4(G-MWCNT)、8.7—9.8(N-MWCNT)和3.9—4.2(O-MWCNT)L·g-1.林丹是非离子型有机化合物,疏水作用在吸附过程中起主导作用,表面引入亲水性强的氨基和羟基后,N-MWCNT和O-MWCNT的吸附作用相比具有疏水性表面的G-MWCNT明显减弱.溶液的pH值(5.0—9.0)对同种多壁碳纳米管的吸附作用影响不显著.均相溶液中,林丹发生β-消去反应的准一级动力学表观速率常数kobs(0.017—10.2 d-1)随溶液pH值(7.0—12.0)升高而增大.N-MWCNT对林丹发生β-消去反应起催化作用,这种催化作用随pH值(7.0—9.0)升高而增强.当N-MWCNT存在时,林丹的去除率分别增加了7.5%(pH=7.0)、29.3%(pH=8.0)和30.1%(pH=9.0).在均相溶液和N-MWCNT体系中都检测到γ-1,3,4,5,6-五氯环己烯、1,2,4-三氯苯和1,2,3-三氯苯转化产物.
    Abstract: Nanomaterials in the environment have great impacts on the environmental processes of co-existing chemistry contaminats. In this paper, three types of multi-walled carbon nanotubes (MWCNTs) including graphitized MWCNT (G-MWCNT), hydroxylated MWCNT (O-MWCNT) and aminated MWCNT (N-MWCNT) were studied for their adsorption and catalytic transformation of lindane using batch experiments. Adsorption kinetics of lindane on the three MWCNTs followed pseudo-second-order kinetic model (R2>0.997), and the adsorption rate constants (k2) of G-, N- and O-MWCNT were 0.73, 0.60 and 0.28 g·mg-1·h-1, respectively. Freundlich model could well describe the adsorption isotherms of lindane on the three MWCNTs (R2>0.979). The Freundlich affinity coefficients (KF) of G-, N- and O-MWCNT were 28.0—30.0, 21.3—24.6 and 9.1—10.2 mg1-n·Ln·g-1, respectively, under different pH. The distribution coefficients (Kd) of lindane on G-, N- and O-MWCNT were 12.7—14.4, 8.7—9.8 and 3.9—4.2 L·g-1, respectively, at lindane equilibrium concentration of 8.5 mg·L-1 under different pH. Lindane was a typical nonionic organic chemical, and hydrophobic interactions dominantly controlled its adsorption on MWCNTs. The adsorption of lindane by N- and O-MWCNTs with hydrophilic moieties was weaker than the graphitized MWCNT with higher surface hydrophobicity. Changing the pH value of solution from 5.0 to 9.0 didn't affect the adsorption of lindane significantly. The pseudo-first-order rate constant (kobs) of β-elimination in homogeneous aqueous solution increased from 0.017 to 10.2 d-1 with increasing pH in the range of 7.0—12.0. The N-MWCNT had catalytic effects on the β-elimination of lindane at moderate to slight alkaline pH values (7.0—9.0), and catalysis became faster with increasing pH value from 7.0 to 9.0. The removal rates of lindane were increased by 7.5%, 29.3% and 30.1% in the presence of N-MWCNT at pH value of 7.0, 8.0 and 9.0, respectively. Several transformation intermediates, 1,3,4,5,6-pentachlorocyclohexene, 1,2,4-trichlorobenzene, and 1,2,3-trichlorobenzene were detected as main products during the β-elimination of lindane in both homogeneous aqueous solution and N-MWCNT-water system.
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  • 收稿日期:  2015-10-23
  • 刊出日期:  2016-04-15

多壁碳纳米管对林丹的吸附和催化转化

  • 1. 南开大学环境科学与工程学院, 教育部环境污染过程与基准重点实验室, 天津, 300071
  • 收稿日期:  2015-10-23
基金项目:

教育部创新团队发展计划(IRT13024)资助.

摘要: 进入环境的纳米材料对共存化学污染物的环境行为有重要影响.本文选择3种多壁碳纳米管,分别为石墨化多壁碳纳米管(G-MWCNT)、羟基化多壁碳纳米管(O-MWCNT)和氨基化多壁碳纳米管(N-MWCNT),通过批次实验研究其对林丹的吸附行为和催化转化作用.林丹在3种多壁碳纳米管上的吸附动力学符合准二级动力学模型(R2>0.997),吸附速率常数(k2)分别为0.73(G-MWCNT)、0.60(N-MWCNT)和0.28(O-MWCNT) g·mg-1·h-1.林丹在3种多壁碳纳米管上吸附的等温线符合Freundlich经验模型(R2>0.979),不同pH条件下,吸附系数(KF)分别为28.0—30.0(G-MWCNT)、21.3—24.6(N-MWCNT)和9.1—10.2(O-MWCNT)mg1-n·Ln·g-1.平衡浓度为8.5 mg·L-1,在不同pH条件下林丹在3种多壁碳纳米管上的分配常数(Kd)分别为12.7—14.4(G-MWCNT)、8.7—9.8(N-MWCNT)和3.9—4.2(O-MWCNT)L·g-1.林丹是非离子型有机化合物,疏水作用在吸附过程中起主导作用,表面引入亲水性强的氨基和羟基后,N-MWCNT和O-MWCNT的吸附作用相比具有疏水性表面的G-MWCNT明显减弱.溶液的pH值(5.0—9.0)对同种多壁碳纳米管的吸附作用影响不显著.均相溶液中,林丹发生β-消去反应的准一级动力学表观速率常数kobs(0.017—10.2 d-1)随溶液pH值(7.0—12.0)升高而增大.N-MWCNT对林丹发生β-消去反应起催化作用,这种催化作用随pH值(7.0—9.0)升高而增强.当N-MWCNT存在时,林丹的去除率分别增加了7.5%(pH=7.0)、29.3%(pH=8.0)和30.1%(pH=9.0).在均相溶液和N-MWCNT体系中都检测到γ-1,3,4,5,6-五氯环己烯、1,2,4-三氯苯和1,2,3-三氯苯转化产物.

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