CN113135608A - Self-assembled micelle and method for treating perfluorinated compound polluted water body - Google Patents

Self-assembled micelle and method for treating perfluorinated compound polluted water body Download PDF

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CN113135608A
CN113135608A CN202110465919.8A CN202110465919A CN113135608A CN 113135608 A CN113135608 A CN 113135608A CN 202110465919 A CN202110465919 A CN 202110465919A CN 113135608 A CN113135608 A CN 113135608A
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self
hfpo
micelle
assembled micelle
assembled
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谷成
陈张浩
李晨
滕影
米娜
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Nanjing University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/32—Details relating to UV-irradiation devices
    • C02F2201/322—Lamp arrangement
    • C02F2201/3225—Lamps immersed in an open channel, containing the liquid to be treated
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone

Abstract

The invention discloses a self-assembled micelle and a method for treating a perfluorinated compound polluted water body, belonging to the field of degradation of persistent pollutants. According to the invention, hydroxyphenylacetic acid is used as a hydrated electron source substance, and the CTAB is used for inducing mutually exclusive HPA and HFPO-TA to form a ternary mixed self-assembled micelle, the self-assembled micelle can effectively reduce the interference of protons and oxygen outside the micelle on the reduction degradation reaction of the HFPO-TA inside the micelle, and obviously promote the degradation and defluorination of the HFPO-TA, so that the method is suitable for the reduction degradation of the novel perfluoro compound HFPO-TA under an aerobic condition and a wider pH value of 4-10, solves the problems of narrow reaction conditions and the like existing in the existing method for degrading the perfluoro compound by using hydrated electrons, and has a higher application prospect.

Description

Self-assembled micelle and method for treating perfluorinated compound polluted water body
Technical Field
The invention belongs to the field of degradation of persistent pollutants, and particularly relates to a self-assembled micelle and a method for treating a water body polluted by a perfluorinated compound.
Background
Perfluorinated compounds are a class of synthetic substances consisting of hydrophobic perfluoroalkyl chains and hydrophilic ionic heads (H.park, C.D.Vecitis, J.Cheng, W.Choi, B.T.Mader, M.R.Hoffmann, reduced defluorination of aqueous perfluorinated alkyl surfactants: Effects of ionic headgroup and chain length h.J.Phys.chem.A113(2009)690- > 696). PFCs have been widely used in various industrial and commercial fields in the past decades due to their superior chemical stability, fire resistance, hydrophobic lipophobicity (R.Renner, Evaporation of toxic effects and environmental impact of people sources, scientific research, technique.35 (2001),154A-160 A.J.P.Giesey, K.Kannan, Perfluorochemical research in the environmental research, Environ.Sci.technique.36 (2002)146A-152A.S.Wang, Q.Yang, F.Chen, J.Su.Luo, F.Yao, X.Yang, D.D.Li, X.G.G.Yang, Photic soil, F.Chen.F.Chen, J.Su, K.Luo, F.Yang, X.D.Wang.Li, G.G.Yang, P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.. Among these, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are the two best known PFCs. However, in recent years with The increasing awareness of The public and international organizations on their environmental persistence and toxicity, PFOA and PFOS have been banned from production and use (S.Nakayama, K.Harada, K.Inoue, K.Sasaki, B.Seery, N.Saito, A.Koizumi, Distributions of perfluorooctanoic acid (PFOA) and perfluoroactane sulfonate (PFOS) in Japan and of The microorganisms of environmental importance, Environ.Sci.12(2005)293-313. Steenaland T.Fletcher, D.A.Savitz, epidemic evaluation of The health benefits of fluorine acid (PCA) and P.E.P.Softula.122. P.12, P.E.7, P.J.10. environmental persistence, P.10.P.P.12, P.P.7. environmental and P.P.7. environmental persistence of health, P.7. environmental, P.7.E.7. environmental impact, P.10.7.E.7. environmental impact, P.7.E.A.A.A.A.A.A. Savieren. In order to meet the demand of industrial production, some novel PFCs available for PFOA and PFOS replacement include hexafluoropropylene oxide trimer acid (HFPO-TA), hexafluoropropylene oxide dimer acid (HFPO-DA), ammonium salt (GneX), 4, 8-dioxa-3-hydro-perfluorononanoic acid (ADONA), perfluoro-3, 5, 7-trioxaprylic acid (PFO3OA), etc. are synthesized in place of conventional PFCs (C.H.Li, X.M.ren, L.H.Guo, adoptive activity of oligomeric siloxane promoter-activated platelet oxide (perfluoroacetic acid) through reactor promoter-activated platelet additive paper, environ.Sci.53 (2019)3287-3295 Y.95 H.95, H.12. channel, W.768. moisture, W.768. W.W.768. moisture and J.W.W.76, W.76, W.768. moisture and W.W.768. sub.W.W.W.76, W.76, W.W.76, W.768. sub.W.W.W.76, W.W.76, W.76, W.W.768. sub.W.W.W.W.W.W.76, U.A. of PFCs, A. However, these novel PFCs have also been frequently detected in various water bodies, and recent studies have found that such contaminants are potentially cytotoxic and hepatotoxic (F. Heydefleck, J. Tang, Z. Xie, R. Ebinhaus, Alternative and legacy Perfluoroalkyl subsistents: differences between sources and devices/ideal systems. Environ. Sci. Techniol.49 (2015)8386-8395.Y.Pan, H.Zhang, Q.Cui, N.Sheng, L.W.Y.Young, Y.Guo, Y.Su, J.Dai, First to the environment and the moisture content, Y.S. Rice.20100.2017. moisture content, C.8. moisture content, III. moisture content, N.S. Ser. No. 8. moisture content, C.8. moisture content, N.7. moisture content, moisture content of No. 8. moisture content of No. 8. moisture content of No. 7. moisture content of No. 12 990). Since no legislation is currently established that can cover such contaminants, the concentration of such contaminants in the environment continues to rise. Therefore, there is a need to develop effective control techniques to eliminate such contaminants.
HFPO-TA is a novel class of PFCs widely used to replace PFOA/PFOS. Recently reported HFPO-TA in surface water pollution concentration from USA, Germany and China even reaches 70 mu g L-1(Pan, H.Zhang, Q.Cui, N.Sheng, L.W.Y.Yeung, Y.Sun, Y.Guo, J.Dai, Worldwide distribution of novel perfluor ether carboxylic and sulfonic acids in surface water. environmental. Sci.Technol.52(2018)7621-7629. F.Heydebrush, J.Tang, Z.Xie, R.Eghaus, organic and legacy perfluor alkyl residues: differences environmental impact and chip river/environmental systems, environmental impact. Sci.Sci.49. Anchor.86-95, Y.Sheng.K.Zhang, L.W.Y.Ye, Y.W.Y.Ye, Y.Su, Y.W.Y.J.yellow acid in surface water, Z.X.E. R.Eghaus, environmental and legacy sludge, C.E.E.C.E.E. No. 5. Sci.K. No. 5. III, K.E.E.E.E.E.E. No. 5, K. J.E.E.E.E.E.E.E.E.E.E.E.E.E. No. 7, J.E.E.E.E.E.E.E. 7. environmental impact, E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.A. No. K. No. 6.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.E.. Meanwhile, HFPO-TA is considered to have higher bioaccumulation in biological tissues, human serum samples, than PFOA/PFOS (N.Sheng, Y.Pan, Y.Guo, Y.Sun, J.Dai, hepatotoxin effects of hepatotoxin oxide trimer acid (HFPO-TA), alpha novel perfluoroctanoic acid (PFOA) alternative, on micro.environ.Sci.Technol.52 (2018)8005-8015.F.Allendorf, U.Berger, K.U.Goss, N.Ulrich, Partition coefficients of fluoroolefin copolymer bovine serum albumin (scientific) and Bovine Serum Albumin (BSA) supplement) 1859.1859). Like PFOA/PFOS, HFPO-TA exhibits resistance to almost all conventional water treatment technologies such as biofilters, activated carbon adsorption, advanced oxidation, etc. (m.sun, e.arevalo, m.strynar, a.lindstrom, m.richardson, b.kearns, a.pickett, c.smith, d.r.u.knappe, Legacy and engineering perfluoralkyl subsistence of arm organic solvents driving water conditioners in the cup feeder water washed of notr-Holady,E.R.V.Dickenson,Treatment of poly-and perfluoroalkyl substances in US full-scale water treatment systems.Water Res.51(2014)246-255)。
Hydrated electrons are an active species with strong reducibility that has been shown to be effective in degrading and defluorinating PFCs under anaerobic conditions (Z.Song, H.Tang, N.Wang, L.Zhu, reduced defluorination of perfluorinated organic acids by Hydrated electrons in a subfile-medium UV photochemical system.J.Hazard.Mater.262(2013)332-338.Y.Gu, T.Liu, H.Wang, H.Han, W.Dong, hydrogenated electron based composition of perfluorinated organic sulfonic acid (PFOS) in the VUV/sulfate system.Sci.Total Environment software.548 (2017)). I is-、SO3 2-And indole substances and the like are developed to be used as hydration electron source substances to degrade PFCs. However, hydrated electrons are low in utilization rate in an environmental state (oxygen-rich, neutral, room temperature), and are easily quenched by oxygen, protons, and the like. Previous studies we developed a self-assembled micelle based on indoleacetic acid (3-IAA) to achieve Efficient degradative removal of PFOA/PFOS (Z.Chen, C.Li, J.Gao, H.Dong, Y.Chen, B.Wu, C.Gu, effective reduction of volatile substructures unit selected-allocated microorganism communication. Environment.Sci.technol.54 (2020)5178-5185.Z.Chen, N.Mi, C.Li, Y.Tec.Chen, C.Gu, Effects of volatile on photostructure of volatile acid in selected-oil system.Sci.438 (438)). However, in the research, the self-assembled micelle formed by the 3-IAA is found to have obviously reduced performance under alkaline conditions, and the 3-IAA used in the system as an odorous plant hormone possibly brings certain application risks. Therefore, the self-assembled micelle system described above still needs to be further improved.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that the existing method for degrading the perfluorinated compounds has narrow reaction conditions and the degradation treatment effect needs to be further improved, the invention provides the self-assembled micelle and the method for treating the water body polluted by the perfluorinated compounds. According to the invention, hydroxyphenylacetic acid is used as a hydrated electron source substance, a novel self-assembly micelle system is developed to be applied to stable and efficient degradation of perfluorinated compounds, the self-assembly micelle system can reduce and degrade the perfluorinated compounds under aerobic conditions and a wider pH value of 4-10, the problem of narrow reaction conditions in the prior art is solved, and the application prospect is high.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the self-assembled micelle for treating the water body polluted by the perfluorinated compounds comprises a cationic surfactant, hydroxyphenylacetic acid (HPA) and hexafluoropropylene oxide trimer (HFPO-TA).
Preferably, the molar ratio of the cationic surfactant to the hydroxyphenylacetic acid to the hexafluoropropylene oxide trimer is 20-200: 1: 7.
preferably, the molar ratio between the cationic surfactant, hydroxyphenylacetic acid and hexafluoropropylene oxide trimer is 50: 1: 7.
preferably, the cationic surfactant is cetyltrimethylammonium bromide (CTAB).
Preferably, the self-assembled micelle is specifically produced by mixing the cationic surfactant, hydroxyphenylacetic acid and hexafluoropropylene oxide trimer and stirring to obtain the ternary mixed self-assembled micelle.
Preferably, the cationic surfactant, the hydroxyphenylacetic acid and the hexafluoropropylene oxide trimer are mixed and stirred for 10-30 min, and the stirring speed is 50-300 rpm.
The invention relates to a method for treating a water body polluted by perfluorinated compounds, which comprises the following steps:
s10, mixing the cationic surfactant, the hydroxyphenylacetic acid and the hexafluoropropylene oxide trimer, and stirring to obtain a ternary mixed self-assembled micelle;
s20, illuminating the ternary mixed self-assembled micelle obtained in the step S10 to realize photoreaction so as to degrade hexafluoropropylene oxide trimer.
Preferably, before the illumination of the ternary mixed self-assembled micelle in the step S20, the pH value of the ternary mixed self-assembled micelle is adjusted to 4-10.
Preferably, in step S20, the reaction temperature of the photoreaction is 20 to 30 ℃ and the reaction time is 8 to 14 hours.
Preferably, in step S20, the ternary mixed self-assembled micelle is irradiated with light using a 36W low-pressure mercury lamp.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the self-assembled micelle comprises CTAB, HPA and HFPO-TA, and the CTAB is used for inducing mutually exclusive HPA and HFPO-TA to form a ternary mixed self-assembled micelle, so that the formation of the self-assembled micelle effectively reduces the interference of protons and oxygen outside the micelle on the reductive degradation reaction of the HFPO-TA inside the micelle, and obviously promotes the degradation and defluorination of the HFPO-TA;
(2) according to the self-assembled micelle disclosed by the invention, the interference of protons and oxygen outside the micelle on the reduction degradation reaction of HFPO-TA inside the micelle is reduced, so that a perfluorinated compound can be degraded under a wide range of reaction conditions;
(3) the method for treating the perfluorinated compound polluted water body adopts the ternary mixed self-assembled micelle formed by mutually exclusive HPA and HFPO-TA induced by CTAB, has good tolerance to pH, can maintain efficient degradation and defluorination to the HFPO-TA within the range of pH4-10, and has higher tolerance to natural organic matters commonly coexisting in the polluted water body.
Drawings
FIG. 1 is a schematic diagram of the self-assembled micelle system of the present invention degrading perfluorochemicals;
FIG. 2 is a schematic diagram of a photo-reactor apparatus used in the method for treating a water body contaminated with a perfluoro compound according to the present invention;
fig. 3a and 3b show the degradation and defluorination of HFPO-TA by different HPA self-assembled micellar systems of the invention, respectively;
FIGS. 4a and 4b are the polarized light microscope images of 2-HPA/HFPO-TA and CTAB/2-HPA/HFPO-TA, respectively; FIGS. 4c and 4d are cryo-electron micrographs of 2-HPA/HFPO-TA and CTAB/2-HPA/HFPO-TA, respectively;
FIGS. 5a-b show the dynamic light scattering particle size plot (a) and zeta potential plot (b) for different HPA self-assembled ternary micelle systems of the present invention; FIGS. 5c-d are schematic diagrams of self-assembled micelle structures of CTAB/2-HPA/HFPO-TA and CTAB/4-HPA/HFPO-TA, respectively;
FIG. 6a is a transient spectral scan of different HPA self-assembled micelle systems of the present invention; FIGS. 6b-c are transient absorption attenuation diagrams of different HPA self-assembled micelle systems of the present invention, respectively;
FIG. 7 is a photograph of the CTAB/2-HPA/HFPO-TA self-assembled micelle system of the present invention after reaction;
FIGS. 8a-f are HFPO-TA degradation and defluorination profiles of different HPA self-assembled micelle systems of the present invention at different pH's (2-HPA, a-b; 3-HPA, c-d; 4-HPA, e-f);
FIGS. 9a-d are graphs showing the effect of natural organic substances on the degradation and defluorination of the CTAB/2-HPA/HFPO-TA self-assembled micellar system of the invention (fulvic acid FA, a-b; humic acid HA, c-d);
in the figure: 100. a stirrer; 200. a magneton; 300. a reaction tube; 400. a UV light source.
Detailed Description
The invention is further described with reference to specific examples.
The self-assembled micelle for treating the perfluorinated compound polluted water body comprises a cationic surfactant, hydroxyphenylacetic acid and a hexafluoropropylene oxide trimer, wherein the molar ratio of the cationic surfactant to the hydroxyphenylacetic acid to the hexafluoropropylene oxide trimer is 20-200: 1: 7; preferably the molar ratio between the cationic surfactant, hydroxyphenylacetic acid and hexafluoropropylene oxide trimer is 50: 1: 7; more preferably the cationic surfactant is cetyltrimethylammonium bromide.
As shown in figure 1, through mixing positively charged hexadecyl trimethyl ammonium bromide with negatively charged hydroxyphenylacetic acid and hexafluoropropylene oxide trimer and stirring at 50-300 rpm for 10-30 min, HPA and HFPO-TA which are mutually exclusive are induced by utilizing the electrostatic action of CTAB to form a compact ternary mixed self-assembled micelle, the formed self-assembled micelle effectively reduces the interference of protons and oxygen outside the micelle on the reduction degradation reaction of the HFPO-TA inside the micelle, remarkably promotes the degradation and defluorination of the HFPO-TA, thereby realizing the rapid degradation defluorination of the HFPO-TA under ultraviolet illumination and showing the degradation stability of the HFPO-TA within a wider pH4-10 range.
As shown in fig. 2, a method for treating a water body polluted by a perfluorinated compound of the present invention comprises the following steps:
s10, mixing the components in a molar ratio of 20-200: 1: 7 (preferably 50: 1: 7), mixing a cationic surfactant cetyl trimethyl ammonium bromide, hydroxyphenylacetic acid and a hexafluoropropylene oxide trimer, and stirring for 10-30 min at a stirring speed of 50-300 rpm to obtain a ternary mixed self-assembled micelle;
s20, loading the 300mL ternary mixed self-assembled micelle obtained in the step S10 into a reaction tube, adjusting the pH value of the ternary mixed self-assembled micelle to 4-10 by using 0.1mM NaOH, and uniformly stirring under the action of a stirrer 100 and magnetons 200; and then, using an ultraviolet light source 400, preferably a 36W low-pressure mercury lamp to illuminate the ternary mixed self-assembled micelle, and realizing a photoreaction to degrade the hexafluoropropylene oxide trimer, wherein the reaction temperature of the photoreaction is 20-30 ℃, the reaction time is 8-14 hours, and the reaction atmosphere is an ambient atmosphere. The ternary mixed self-assembled micelle realizes the rapid degradation and defluorination of HFPO-TA under the ultraviolet illumination.
Example 1
This example tests the effect of different HPA self-assembled micelle systems on HFPO-TA degradation and defluorination, and the steps are:
(1) 300mL of a mixture containing 1mM of different HPAs (including 2-HPA, 3-HPA and 4-HPA), 10mg of L-1HFPO-TA and 50mg L-1Stirring the mixed system of CTAB for 10min under 200rmp to obtain a mixed self-assembled micelle solution, wherein the molar ratio of CTAB to HPA to HFPO-TA is 50: 1: 7; photolysis experiments of HFPO-TA alone and HFPO-TA photolysis experiments with/without CTAB added were set as control groups;
(2) and (2) respectively filling the mixed self-assembly micelle solution obtained in the step (1) and the control solution into a cylindrical quartz photoreaction tube (d is 1cm, h is 15cm), adjusting the pH value to 6, and putting the tube into a photoreactor with a 36W low-pressure mercury lamp as a light source for reaction. The reaction temperature is controlled at 25 +/-1 ℃ and the reaction time is 8 hours.
The sampling time is set to be 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h and 8h respectively. The sample was divided into two portions, one portion was extracted with 2 volumes of acetonitrile and the remaining HFPO-TA content was measured by LC-MS/MS, and the other portion was filtered and the F formed was measured by Ion Chromatography (IC)-The degradation rate and defluorination rate of HFPO-TA were calculated based on the content, and the specific degradation and defluorination curves are shown in FIGS. 3 a-b.
From this it can be concluded that: the CTAB/HPAs/HFPO-TA mixed self-assembly micelle system formed by different HPAs can effectively degrade and defluorinate the HFPO-TA, wherein the 4-HPA has the best efficiency on the degradation and defluorination of the HFPO-TA.
Example 2
The self-assembled micelle generated by the characterization of the polarized light microscope and the cryoelectron microscope in the embodiment comprises the following steps:
(1) 300mL of a solution containing 1mM 2-HPA and 10mg L-1HFPO-TA and 50mg L-1Stirring the mixed system of CTAB for 10min under 200rmp to obtain a mixed self-assembled micelle solution, wherein the molar ratio of CTAB to HPA to HFPO-TA is 50: 1: 7; the HFPO-TA photolysis experiment without the CTAB group was set as a control group;
(2) adjusting the pH value of the mixed self-assembly micelle solution obtained in the step (1) and the control solution to 6, respectively dripping 100 mu L of the two solutions on a glass slide, and observing under a polarized light microscope. And dripping 10 μ L of the above two solutions on two different lace carbon films, quickly inserting into liquid nitrogen-cooled ethane liquid for cooling, and taking the cooled sample film in a cryoelectron microscope, as shown in FIGS. 4 a-d.
From this it can be concluded that: self-assembled micelles are not formed in a system only containing 2-HPA and HFPO-TA, and the self-assembled micelles are formed after CTAB is added.
Example 3
The micelle particle size and zeta potential generated by the dynamic light scattering test of the embodiment comprises the following steps:
(1) 100mL of a mixture containing 1mM of different HPAs (including 2-HPA, 3-HPA and 4-HPA), 10mg of L-1HFPO-TA and 50mg L-1Stirring the mixed system of CTAB for 10min under 200rmp to obtain a mixed self-assembled micelle solution, wherein the molar ratio of CTAB, HPAs and HFPO-TA is 50: 1: 7; HPA and HFPO-TA mixed solution without CTAB addition was set as a control group;
(2) the pH value of the mixed self-assembly micelle solution obtained in the step (1) and the control solution is adjusted to 6, and then 1mL of the mixed self-assembly micelle solution is taken to test the particle size of the mixed self-assembly micelle solution, and the specific figure is shown in figures 5 a-d.
From this it can be concluded that: CTAB induces HPA and HFPO-TA to form a compact self-assembled micelle after being added.
Example 4
This example examines the generation and decay of hydrated electrons of different HPAs systems and includes the steps of;
(1) 300mL of a mixture containing 1mM of different HPAs (including 2-HPA, 3-HPA and 4-HPA), 10mg of L-1HFPO-TA and 50mg L-1Stirring the mixed system of CTAB for 10min under 200rmp to obtain a mixed self-assembled micelle solution, wherein the molar ratio of CTAB to HPA to HFPO-TA is 50: 1: 7; before preparing the solution, the ultrapure water used is exposed to N2Carrying out deoxidization treatment;
(2) and (2) adjusting the pH value of the mixed self-assembly micelle solution obtained in the step (1) to 6, and then respectively taking 3mL of the three self-assembly micelle solutions and detecting the hydrated electron condition generated in 3 systems by using a laser flash photolysis instrument probe. The 266nm laser excited 3 solutions were first scanned in the 500-800nm range to determine the relative yield of hydrated electrons in different systems, followed by transient absorption decay tests at 700nm, see in particular fig. 6 a-d.
From this it can be concluded that: the hydrated electron yield of the self-assembled micelle system formed by different HPAs is ordered as 4-HPA >3-HPA > 2-HPA. The 2-HPA system produces the fastest decay of hydrated electrons, followed by 3-HPA and finally 4-HPA.
Example 5
In this embodiment, the change of the CTAB/HPA/HFPO-TA self-assembled micelle system after reaction is examined, taking CTAB/2-HPA/HFPO-TA as an example, the steps are as follows:
(1) 300mL of a solution containing 1mM 2-HPA, 10mg L-1HFPO-TA and 50mg L-1Stirring the mixed system of CTAB for 10min under 200rmp to obtain a mixed self-assembled micelle solution, wherein the molar ratio of CTAB to HPA to HFPO-TA is 50: 1: 7, photolysis of HFPO-TA alone and photolysis experiments of HFPO-TA with/without CTAB group were set as control group;
(2) and (2) respectively filling the mixed self-assembly micelle solution obtained in the step (1) and the control solution into a cylindrical quartz photoreaction tube (d is 1cm, h is 15cm), adjusting the pH value to 6, and putting the tube into a photoreactor with a 36W low-pressure mercury lamp as a light source for reaction. The reaction temperature is controlled at 25 +/-1 ℃ and the reaction time is 8 hours. After the reaction, photographs were taken. The left side of FIG. 7 shows a photograph immediately after the reaction is completed, and the right side shows a photograph after 1 hour of sedimentation.
From this it can be concluded that: the CTAB/HPA/HFPO-TA self-assembled micelle generates phase change after being irradiated by ultraviolet light, and finally forms precipitate.
Example 6
This example investigates the degradation and defluorination of HFPO-TA of different HPA self-assembled micelle systems at different pH's by the following steps:
(1) 300mL of a mixture containing 1mM of different HPAs (including 2-HPA, 3-HPA and 4-HPA), 10mg of L-1HFPO-TA and 50mg L-1Stirring the mixed system of CTAB for 10min under 200rmp to obtain a mixed self-assembled micelle solution, wherein the molar ratio of CTAB to HPA to HFPO-TA is 50: 1: 7; sequentially adjusting the pH of the self-assembled micelle system containing different HPAs to 4, 6, 8 and 10;
(2) and (2) filling the mixed self-assembly micelle solution obtained in the step (1) into cylindrical quartz photoreaction tubes (d is 1cm, h is 15cm), adjusting the pH value to 6, and putting the tubes into a photoreactor with a 36W low-pressure mercury lamp as a light source for reaction. The reaction temperature is controlled at 25 +/-1 ℃ and the reaction time is 8 hours.
The sampling time is set to be 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h and 8h respectively. The sample was divided into two portions, one portion was extracted with 2 volumes of acetonitrile and the remaining HFPO-TA content was measured by LC-MS/MS, and the other portion was filtered and the F formed was measured by Ion Chromatography (IC)-The content of HF is calculated by thisThe degradation rate and defluorination rate of PO-TA, and specific degradation and defluorination curves are shown in FIGS. 8 a-f.
From this it can be concluded that: the CTAB/2-HPA/HFPO-TA self-assembled micelle system has the strongest capability of resisting pH influence.
Example 7
In this example, the effect of natural organic matters on the degradation and defluorination of CTAB/2-HPA/HFPO-TA self-assembled micelle system is examined, and the steps are as follows:
(1) 300mL of a solution containing 1mM 2-HPA, 10mg L-1HFPO-TA and 50mg L-1Stirring the mixed system of CTAB for 10min under 200rmp to obtain a mixed self-assembled micelle solution, wherein the molar ratio of CTAB to HPA to HFPO-TA is 50: 1: 7; then adding a certain amount of Fulvic Acid (FA) or Humic Acid (HA) into the system and controlling the concentration range to be 0.1-10mg L-1Then adjusting the pH value of the system to 6;
(2) the mixed self-assembled micelle solution obtained in the step (1) and the control solution (2-HPA/HFPO-TA) were separately loaded into a cylindrical quartz photoreaction tube (d 1cm, h 15cm), and then placed into a photoreactor using a 36W low-pressure mercury lamp as a light source for reaction. The reaction temperature is controlled at 25 +/-1 ℃ and the reaction time is 8 hours.
The sampling time is set to be 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h and 8h respectively. The sample was divided into two portions, one portion was extracted with 2 volumes of acetonitrile and the remaining HFPO-TA content was measured by LC-MS/MS, and the other portion was filtered and the F formed was measured by Ion Chromatography (IC)-The degradation rate and defluorination rate of HFPO-TA were calculated based on the contents, and the specific degradation and defluorination curves are shown in FIGS. 9 a-d.
From this it can be concluded that: the CTAB/2-HPA/HFPO-TA self-assembled micelle system has certain anti-interference capability. Only at 10mg L-1Degradation and defluorination of HFPO-TA in the presence of FA or HA of (A) is slightly reduced.
The present invention and its embodiments have been described above schematically, the description is not restrictive, the data used are only one of the embodiments of the present invention, and the actual data combination is not limited to this. Therefore, if the person skilled in the art receives the teaching, the embodiments and examples similar to the above technical solutions shall not be designed in an inventive manner without departing from the spirit of the present invention, and shall fall within the protection scope of the present invention.

Claims (10)

1. A self-assembled micelle for treating a perfluorinated compound-contaminated water body, comprising: comprising a cationic surfactant, hydroxyphenylacetic acid and a hexafluoropropylene oxide trimer.
2. The self-assembled micelle of claim 1, wherein: the molar ratio of the cationic surfactant to the hydroxyphenylacetic acid to the hexafluoropropylene oxide trimer is 20-200: 1: 7.
3. the self-assembled micelle of claim 1, wherein: the molar ratio of the cationic surfactant to the hydroxyphenylacetic acid to the hexafluoropropylene oxide trimer is 50: 1: 7.
4. the self-assembled micelle of claim 1, wherein: the cationic surfactant is cetyl trimethyl ammonium bromide.
5. The self-assembled micelle of any one of claims 1-4, wherein: the specific production step of the self-assembled micelle is to mix and stir a cationic surfactant, hydroxyphenylacetic acid and a hexafluoropropylene oxide trimer to obtain the ternary mixed self-assembled micelle.
6. The self-assembled micelle of claim 5, wherein: and mixing the cationic surfactant, the hydroxyphenylacetic acid and the hexafluoropropylene oxide trimer, and stirring for 10-30 min at the rotation speed of 50-300 rpm.
7. A method for treating a perfluorinated compound-contaminated water body, comprising the steps of:
s10, mixing the cationic surfactant, the hydroxyphenylacetic acid and the hexafluoropropylene oxide trimer, and stirring to obtain a ternary mixed self-assembled micelle;
s20, illuminating the ternary mixed self-assembled micelle obtained in the step S10 to realize photoreaction so as to degrade hexafluoropropylene oxide trimer.
8. The method as claimed in claim 7, wherein the pH of the ternary mixed self-assembled micelle is adjusted to 4-10 before the ternary mixed self-assembled micelle is illuminated in step S20.
9. The method as claimed in claim 7, wherein the step of treating the body of water contaminated with the perfluorinated compound comprises the steps of: in step S20, the reaction temperature of the photoreaction is 20-30 ℃ and the reaction time is 8-14 hours.
10. The method as claimed in claim 7, wherein the step of treating the body of water contaminated with the perfluorinated compound comprises the steps of: in step S20, the ternary mixed self-assembled micelle is illuminated with a 36W low-pressure mercury lamp.
CN202110465919.8A 2021-04-28 2021-04-28 Self-assembled micelle and method for treating perfluorinated compound polluted water body Pending CN113135608A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115321635A (en) * 2022-07-11 2022-11-11 南京大学 Interface adsorption method for efficiently removing perfluorinated compounds in water body

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104492378A (en) * 2014-11-13 2015-04-08 华中科技大学 Magnetic nano composite capable of absorbing perfluorochemicals and preparation method thereof
US20150360975A1 (en) * 2014-03-26 2015-12-17 Beijing Normal Univeristy Method for removing perfluorinated compounds by concentration and separation
CN111153462A (en) * 2020-01-14 2020-05-15 南京大学 Method for degrading perfluorinated compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150360975A1 (en) * 2014-03-26 2015-12-17 Beijing Normal Univeristy Method for removing perfluorinated compounds by concentration and separation
CN104492378A (en) * 2014-11-13 2015-04-08 华中科技大学 Magnetic nano composite capable of absorbing perfluorochemicals and preparation method thereof
CN111153462A (en) * 2020-01-14 2020-05-15 南京大学 Method for degrading perfluorinated compounds
US20210047256A1 (en) * 2020-01-14 2021-02-18 Nanjing University Method for degrading perfluorinated compounds

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEN ZHANGHAO ET AL.: "Effects of different variables on photodestruction of", 《SCIENCE OF THE TOTAL ENVIRONMENT》 *
CHEN ZHANGHAO ET AL.: "Efficient Reductive Destruction of Perfluoroalkyl Substances under", 《ENVIRONMENT SCIENCE & TECHNOLOGY》 *
HANS-INGO JOSCHEK ET AL.: "Optical Generation of Hydrated Electrons from Aromatic Compounds", 《JOURNAL OF AMERICAN CHEMICAL SOCIETY》 *
杨晓辉: "《环境功能材料对有机污染物的界面催化降解》", 31 December 2019, 中国环境出版集团 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115321635A (en) * 2022-07-11 2022-11-11 南京大学 Interface adsorption method for efficiently removing perfluorinated compounds in water body
CN115321635B (en) * 2022-07-11 2023-11-17 南京大学 Interfacial adsorption method for efficiently removing perfluorinated compounds in water body

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