CN114307941B - Aminated surface defect sphalerite material, preparation method and application thereof in degradation of perfluorinated compounds - Google Patents

Aminated surface defect sphalerite material, preparation method and application thereof in degradation of perfluorinated compounds Download PDF

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CN114307941B
CN114307941B CN202111208776.9A CN202111208776A CN114307941B CN 114307941 B CN114307941 B CN 114307941B CN 202111208776 A CN202111208776 A CN 202111208776A CN 114307941 B CN114307941 B CN 114307941B
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sphalerite
surface defect
aminated surface
aminated
degradation
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CN114307941A (en
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谷成
陈张浩
滕影
米娜
李晨
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Nanjing University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • 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
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • 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

Abstract

The invention discloses an aminated surface defect sphalerite material, a preparation method and application thereof in degradation of perfluorinated compounds, and belongs to the field of degradation of persistent pollutants. According to the invention, the surface of the sphalerite is aminated and induced to form surface crystal defects by adding the cationic surfactant in the synthesis process of the sphalerite, so that the novel sphalerite material with the aminated surface defects is obtained, and the material has extremely strong adsorptivity and extremely strong photoreductivity to perfluorinated compounds (PFCs), can greatly promote the degradation and defluorination of the PFCs when applied to perfluorinated polluted water, and solves the problems of low degradation efficiency, severe reaction conditions and the like in the existing perfluorinated compound degradation technology.

Description

Aminated surface defect sphalerite material, preparation method and application thereof in degradation of perfluorinated compounds
Technical Field
The invention belongs to the field of degradation of persistent pollutants, and particularly relates to an aminated surface defect sphalerite material, a preparation method and application thereof in degradation of perfluorinated compounds.
Background
As an emerging class of contaminants, perfluorinated compounds have attracted considerable attention in recent years due to their strong stability, potential toxicity (Giesy, j.p.; kannan, k.; perfluorochemical surfactants in) the environment.Environmental science&technology 2002,36,(7),146A-152A.Giesy,J.P.；Kannan,K.,Global distribution of perfluorooctane sulfonate in wildlife.Environmental Science&Technology 2001,35,(7),1339-1342.Paul,A.G.；Jones,K.C.；Sweetman,A.J.,A First Global Production,Emission,And Environmental Inventory For Perfluorooctane Sulfonate.Environmental science&technical 2009,43, (2), 386-392). Of these, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are the two most widely detected substances in the environment (Poothong, S.; thomsen, C.; padilla-Sanchez, J.A.; papanopoulou, E.; haug, L.S.; distribution of Novel and Well-Known Poly-and Perfluoroalkyl Substances (PFASs) in Human Serum, plasma, and white blood&technology 2017,51,(22),13388-13396.Lorber,M.；Egeghy,P.P.,Simple intake and pharmacokinetic modeling to characterize exposure of Americans to perfluoroctanoic acid,PFOA.Environmental science&technical 2011,45, (19), 8006-8014). Recently, in order to eliminate the adverse effects of such substances on the ecological environment and the human body, the international society has put PFOA and PFOS on the pollutant priority control lists of the stockholm convention, respectively. The national environmental protection agency of the United states also established that the PFOA and PFOS drinking water health risk index is 70ng L -1 (Xiao, l.; ling, y.; alsbaie, a.; li, c.; helbling, d.e.; dichtel, w.r.; beta-Cyclodextrin Polymer Network Sequesters Perfluorooctanoic Acid at Environmentally Relevant concentrations.j Am Chem Soc 2017,139, (23), 7689-7682.). Despite various efforts to reduce the environmental impact of such contaminants, the environmental problems associated with such contaminants continue to be endless.
In order to effectively control such contaminants, previous studies have invented a variety of techniques for removing perfluorocontaminants in water bodies, including carbon material-based adsorption techniques, electrochemical-based redox techniques, sulfate radical and hydrated electron-based radical removal techniques (McCleaf, p.; england, s.; ostlend, A.; lindegren, K.; wiberg, K.; ahrens, L.; removal efficiency of multiple poly-and perfluoroalkyl substances (PFASs) in drinking water using Granular Activated Carbon (GAC) and Anion Exchange (AE) column tests.Water Research 2017,120,77-87.Li, X.; chen, S.; quan, X.; zhang, Y.; enhanced Adsorption of PFOA and PFOS on Multiwalled Carbon Nanotubes under Electrochemical Assistant. Environmental Science & Technology 2011,45, (19), 8498-8505.Niu, J.; lin., H.; xu, J.; wu, H.; li, Y. Electronic mineralization of perfluorocarboxylic acids (PFs) by ce-doped modified porous nanocrystalline PbO2 film electronic device, environmental Science & Technology 2012,46,10191-10198. Truw wicz, M.; boujaka-Cjka K, J. Oside, U.S. F.; J. Lin., J.; lin. J.; J. Ev., J.; J.; lin. Electrical mineralization of perfluorocarboxylic acids (PFASs) by J. Electronic mineralization of perfluorocarboxylic acids (PFCAs) by way of U.S. Eventh.; chej. Electronic device, Y. 3749. Electronic device, Y. Face, Y. 2012,46,10191-10198. Trujawisz, M.; boujaw-cka-C. K. J, J-J cs. However, due to the hydrophobic and lipophobic properties of perfluorinated compounds and their structural stability, general activated carbon materials have low removal efficiency on such pollutants, biochemical techniques are almost ineffective on such pollutants, and electrochemical oxidation techniques and sulfate radical removal of such pollutants is not thorough.
In addition, although advanced reduction techniques based on hydrated electrons are believed to be capable of completely degrading and destroying perfluorinated contaminants, they are a potential application technique. However, the strong reducibility also makes the reaction based on the hydrated electrons extremely low in efficiency under the aerobic and neutral conditions, and the creation of chemical reaction environments (alkaline and anaerobic) favorable for the hydrated electrons can also greatly improve the use cost and the application difficulty of the technology.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem of low degradation efficiency of the existing perfluoro compound degradation technology, the invention provides an aminated surface defect sphalerite material, a preparation method and application thereof in degrading perfluoro compounds. According to the invention, the surface of the sphalerite is aminated and induced to form surface crystal defects by adding the cationic surfactant in the synthesis process of sphalerite, so that the aminated surface defect sphalerite material is obtained, and the material shows extremely strong adsorptivity and extremely strong photoreductivity to perfluorinated compounds. The material is applied to perfluorinated polluted water, can greatly improve the utilization rate of photo-generated electrons in the degradation process, simultaneously reduces side reactions caused by oxygen and protons, and effectively improves the degradation efficiency of perfluorinated compounds.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention discloses an aminated surface defect sphalerite material, which is characterized in that: contains primary or secondary amine groups and has surface zinc defects.
The invention relates to a preparation method of an aminated surface defect sphalerite material, which comprises the steps of respectively preparing a zinc sulfate solution A and a mixed solution B of sodium sulfide and a cationic surfactant; and then mixing the zinc sulfate solution A with the mixed solution B, stirring, and performing hydrothermal reaction to obtain the aminated surface defect sphalerite material.
Preferably, in the mixed solution B, the mass ratio of the sodium sulfide to the cationic surfactant is 82:1 to 82:5.
preferably, after mixing the zinc sulfate solution a with the mixed solution B, the mass ratio of the zinc sulfate, sodium sulfide and cationic surfactant is 74:82:1 to 74:82:5.
preferably, the cationic surfactant is a quaternary ammonium cationic surfactant including one or more of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
Preferably, the zinc sulfate solution A and the mixed solution B are mixed under the condition of stirring, stirred for 2-4 hours at 50-70 ℃, and then subjected to hydrothermal reaction for 15-17 hours at 140-160 ℃ to obtain the aminated surface defect sphalerite material.
Preferably, the preparation method of the aminated surface defect sphalerite material comprises the following specific steps:
s10, respectively configuring 10.8 and 10.8g L -1 35mL of zinc sulfate heptahydrate solution as zinc sulfate solution a, and 9.9. 9.9g L -1 35mL of a mixed solution of sodium sulfide nonahydrate and 1.5mM cetyltrimethylammonium bromide as a mixed solution B;
s20, mixing the zinc sulfate solution A with the mixed solution B under the stirring condition, stirring for 2-4 hours at 50-70 ℃, and then carrying out hydrothermal reaction for 15-17 hours at 140-160 ℃ to obtain an aminated surface defect sphalerite material;
and S30, washing and freeze-drying the aminated surface defect sphalerite material obtained in the step S20.
The application of the aminated surface defect sphalerite material in degrading perfluorinated compounds comprises the steps of mixing the aminated surface defect sphalerite material with perfluorinated compounds, and then carrying out illumination on a mixed system of the aminated surface defect sphalerite material and perfluorinated compounds to realize photoreaction so as to degrade perfluorinated compounds.
Preferably, the mass ratio between the aminated surface defect sphalerite material and the perfluorinated compound is 10:1 to 10:10.
preferably, before the mixed system of the aminated surface defect sphalerite material and the perfluorinated compound is subjected to illumination, the pH value of the mixed system is adjusted to be 4-10.
Preferably, the reaction time of the photoreaction is 2 to 4 hours and the reaction temperature is 20 to 30 ℃.
Preferably, the mixed system of the aminated surface defect sphalerite material and the perfluorinated compound is illuminated by a high-pressure mercury lamp, wherein the high-pressure mercury lamp is a mercury lamp with the power of 500W.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the aminated surface defect sphalerite material, the surface of sphalerite is aminated by using Cetyl Trimethyl Ammonium Bromide (CTAB) based on wide forbidden band semiconductor sphalerite, and the aminated sphalerite can greatly promote the adsorption of perfluorinated pollutants;
(2) According to the preparation method of the aminated surface defect sphalerite material, CTAB aminated sphalerite is used, and meanwhile, introduced bromide ions can enable the sphalerite surface to form defects, so that the aminated surface defect sphalerite has stronger photoreductivity and photogenerated carrier separation efficiency, and the degradation efficiency of perfluoro pollutants adsorbed on the surface is greatly promoted;
(3) According to the aminated surface defect sphalerite material, the perfluoro pollutants can be rapidly enriched through electron rearrangement with the anionic head on the perfluoro pollutants, and the perfluoro pollutants adsorbed on the surface of the aminated surface defect sphalerite can be degraded and defluorinated by strong-light reductive photo-generated electrons generated by the aminated surface defect sphalerite, so that the rapid degradation and defluorination of the pollutants under aerobic and weak-acidic conditions are realized;
(4) The application of the aminated surface defect sphalerite material in degrading perfluorinated compounds does not need to add any cocatalyst or electron donor, and the perfluorinated pollutants adsorbed on the aminated surface defect sphalerite serve as an oxidant and a reducing agent at the same time.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of an aminated surface defect sphalerite material of the present invention;
FIG. 2 is a schematic diagram of the principle of degrading perfluorinated compounds by aminated surface defect sphalerite material according to the present invention;
FIG. 3 is a transmission electron microscope and surface micro-area analysis chart of an aminated surface defect sphalerite material of the present invention;
FIG. 4 is an electron paramagnetic resonance diagram of an aminated surface defect sphalerite material of the present invention;
FIG. 5 is an infrared spectrum of an aminated surface defect sphalerite material of the present invention;
FIG. 6 is a chloranil test chart of an aminated surface defect sphalerite material of the present invention;
FIG. 7 is an X-ray photoelectron spectrum of an aminated surface defect sphalerite material of the present invention;
FIG. 8 is an ultraviolet absorption diagram of an aminated surface defect sphalerite material of the present invention;
FIG. 9 is a fluorescent image of an aminated surface defect sphalerite material of the present invention;
FIG. 10 is a diagram of the adsorption kinetics of an aminated surface defect sphalerite material to PFOA according to the present invention;
FIG. 11 is a graph of adsorption kinetics of an aminated surface defect sphalerite material to PFOA according to the invention;
FIG. 12 is a graph of the degradation kinetics of an aminated surface defect sphalerite material of the present invention against PFOA;
FIG. 13 is a kinetic graph of pH impact on PFOA degradation system of an aminated surface defect sphalerite material of the present invention;
FIG. 14 is a graph of multiple recycles of the degradation PFOA of aminated surface defect sphalerite material of the present invention;
FIG. 15 is a graph of degradation kinetics of PFOS by an aminated surface defect sphalerite material of the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments.
As shown in FIG. 1, the preparation method of the aminated surface defect sphalerite material comprises the following steps:
s10, respectively preparing a zinc sulfate solution A and a mixed solution B of sodium sulfide and a cationic surfactant; wherein the cationic surfactant is a quaternary ammonium salt cationic surfactant and comprises one or more of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide; and in the mixed solution B, the mass ratio of the sodium sulfide to the cationic surfactant is 82:1 to 82:5, a step of;
s20, mixing a zinc sulfate solution A with a mixed solution B under the condition of stirring, wherein the mass ratio of substances among zinc sulfate, sodium sulfide and a cationic surfactant is 74:82:1 to 74:82:5, a step of; and the mixture is stirred for 2 to 4 hours under the temperature of 50 to 70 ℃ in a hydrothermal way, and the stirring speed is controlled to be 50 to 100rmp; transferring the reactant into a Teflon reaction kettle with the volume of 100mL for hydrothermal reaction, wherein the reaction temperature of the hydrothermal reaction is 140-160 ℃, the reaction time of the hydrothermal reaction is 15-17 hours, and obtaining a solid precipitate after the reaction;
s30, performing centrifugal separation on the solid precipitate, respectively washing for eight times by using 100mL of methanol and ultrapure water to obtain an aminated surface defect sphalerite material, and collecting and freeze-drying for later use.
The method for degrading the perfluorinated compounds by adopting the aminated surface defect sphalerite material comprises the steps of mixing the aminated surface defect sphalerite material with the perfluorinated compounds, wherein the mass ratio of the aminated surface defect sphalerite material to the perfluorinated compounds is 10:1 to 10:10, and adjusting the pH value of a mixed system of the aminated surface defect sphalerite material and the perfluorinated compound to be 4-10; the mixed system was then charged into a cylindrical quartz photoreaction tube (specifically d=1cm, h=15cm), and the mixed system was irradiated with light using a photoreaction instrument equipped with a 500W high-pressure mercury lamp to effect photoreaction for degrading perfluorinated compounds, wherein the reaction time of photoreaction was controlled to 2 to 4 hours and the reaction temperature was 20 to 30 ℃.
In the synthesis process of sphalerite, a certain amount of quaternary ammonium salt cationic surfactant is added, so that the cationic surfactant is used for carrying out surface amination on sphalerite and inducing formation of surface crystal defects to obtain the aminated sphalerite material with the surface defects. As shown in fig. 2, the aminated surface defect sphalerite material exhibits two advantages: on the one hand, the aminated surface defect sphalerite can realize rapid enrichment of perfluoro pollutants in an aqueous solution by electron rearrangement with an anion head on a perfluoro compound; on the other hand, the photo-generated electrons generated by the aminated surface defect sphalerite show stronger light reducibility and stronger carrier separation efficiency, so that the utilization efficiency of the photo-generated electrons is greatly improved, and the rapid degradation and defluorination of PFASs under aerobic and weak acid conditions can be realized.
The aminated surface defect sphalerite is utilized to treat the water body polluted by the perfluorinated compounds with extremely strong adsorptivity and extremely strong photoreductivity, so that the degradation efficiency of the PFASs in an environmental state is effectively improved, the existing application technology system is simplified, green and environment-friendly treatment is realized, and the aminated surface defect sphalerite has higher application value for degrading the perfluorinated compounds.
Example 1
The preparation method of the aminated surface defect sphalerite material comprises the following steps:
s10, respectively configuring 10.8 and 10.8g L -1 35mL of the zinc sulfate heptahydrate solution is zinc sulfate solution A,9.9g L -1 And 35mL of a mixed solution of 1.5mM sodium sulfide nonahydrate and cetyltrimethylammonium bromide (CTAB) is a mixed solution B in which the mass ratio of sodium sulfide to cationic surfactant is 82:3, a step of;
s20, mixing a zinc sulfate solution A with a mixed solution B under the condition of stirring, wherein the mass ratio of substances among zinc sulfate, sodium sulfide and a cationic surfactant is 74:82:3, a step of; and the mixture is stirred for 3 hours under the temperature of 60 ℃ in a hydrothermal way, and the stirring speed is controlled to be 50-100 rmp; transferring the reactant into a 100mL Teflon reaction kettle for hydrothermal reaction, wherein the reaction temperature of the hydrothermal reaction is 150 ℃, the reaction time of the hydrothermal reaction is 16 hours, and obtaining a solid precipitate after the reaction;
s30, performing centrifugal separation on the solid precipitate, respectively washing for eight times by using 100mL of methanol and ultrapure water to obtain an aminated surface defect sphalerite material, and collecting and freeze-drying for later use.
Comparative example 1
The basic content of this comparative example is the same as in example 1, except that: in the synthesis process of sphalerite, cetyl trimethyl ammonium bromide cationic surfactant is not added.
The preparation method of the common zinc blende of the comparative example comprises the following steps:
s10, respectively matchPut 10.8g L -1 35mL of the zinc sulfate heptahydrate solution is zinc sulfate solution A,9.9g L -1 35mL of sodium sulfide nonahydrate solution as solution B;
s20, mixing the zinc sulfate solution A and the zinc sulfate solution B under the stirring condition, and carrying out hydrothermal stirring for 3 hours at the temperature of 60 ℃, wherein the stirring speed is controlled to be 50-100 rmp; transferring the reactant into a 100mL Teflon reaction kettle for hydrothermal reaction, wherein the reaction temperature of the hydrothermal reaction is 150 ℃, the reaction time of the hydrothermal reaction is 16 hours, and obtaining a solid precipitate after the reaction;
s30, performing centrifugal separation on the solid precipitate, respectively washing for eight times by using 100mL of methanol and ultrapure water to obtain a common zinc blende material, and collecting and freeze-drying for later use.
Example 2
In the embodiment, the aminated surface defect sphalerite is characterized by a transmission electron microscope, and the method comprises the following steps:
(1) The aminated surface defect sphalerite material of example 1 was dispersed in ethanol at a concentration of 100mg L -1 After ultrasonic dispersion, 10 mu L of the solution is dripped on a carbon net and is dried naturally for standby. The same procedure was used to prepare a sample of the conventional sphalerite of comparative example 1.
(2) And (3) placing the sample prepared in the step (1) into a transmission electron microscope for shooting, wherein the shooting picture is shown in fig. 3. Fig. 3a and 3c show a transmission electron microscope image and a surface micro-area analysis image of a general sphalerite material, respectively, and fig. 3b and 3d show a transmission electron microscope image and a surface micro-area analysis image of an aminated surface defect sphalerite material, respectively.
From this it can be concluded that: the common sphalerite has stronger agglomeration, and the aminated surface defect sphalerite has better dispersibility. In addition, surface structure analysis found that the aminated surface defect sphalerite surface had defect properties.
Example 3
The embodiment characterizes aminated surface defect sphalerite through electron paramagnetic resonance, and comprises the following steps:
(1) 0.1g of the ordinary sphalerite of comparative example 1 and the aminated surface defect sphalerite of example 1 were weighed into a quartz tube having an inner diameter of 0.5mm, respectively;
(2) The two samples obtained in step (1) were each passed through an electron paramagnetic resonance test, as shown in fig. 4.
From this it can be concluded that: the normal sphalerite has no defects formed, whereas the aminated surface defect sphalerite has a pronounced zinc defect signal.
Example 4
The embodiment characterizes aminated surface defect sphalerite by infrared spectrum, which comprises the following steps:
(1) Respectively weighing 10mg of CTAB and aminated surface defect sphalerite of example 1, mixing with KBr, and tabletting;
(2) The two samples obtained in the step (1) are pressed into tablets for detection by using infrared spectrum, and the test result is shown in fig. 5.
From this it can be concluded that: CTAB in aminated surface defect sphalerite synthesized by a self-assembly method is converted into primary amine or secondary amine.
Example 5
In the embodiment, the aminated surface defect sphalerite is characterized by chloranil test, and the steps are as follows:
(1) 10mg of CTAB and the aminated surface defect sphalerite of example 1 were weighed separately;
(2) The two samples in the step (1) are respectively poured into 10mL of mixed solution containing 3mM of acetaldehyde and 3mM of chloroaniline, and photographed after shaking, and the result is shown in FIG. 6, wherein a left test tube is CTAB solution, and a right test tube is amination defect sphalerite dispersion liquid.
From this it can be concluded that: CTAB in aminated surface defect sphalerite synthesized by a self-assembly method is converted into primary amine or secondary amine.
Example 6
The embodiment characterizes aminated surface defect sphalerite by X-ray photoelectron spectroscopy, which comprises the following steps:
(1) A small amount of the ordinary sphalerite of comparative example 1 and the aminated surface defect sphalerite of example 1 were weighed separately, and the samples were pressed on an indium foil;
(2) The spectrum of the sample in step (1) was then collected using an X-ray photoelectron spectrometer, and the collected spectrum was corrected with a C1s peak, and the test results are shown in fig. 7.
From this it can be concluded that: primary amine or secondary amine functional groups are formed in aminated surface defect sphalerite synthesized by a self-assembly method.
Example 7
In the embodiment, the optical absorption performance of the aminated surface defect sphalerite is tested by a solid ultraviolet spectrophotometer, and the method comprises the following steps:
(1) A small amount of the ordinary sphalerite of comparative example 1 and the aminated surface defect sphalerite of example 1 were respectively taken and smeared in a sample cell filled with barium sulfate as a reference background;
(2) The two samples obtained in step (1) were tested by a solid uv spectrophotometer, as shown in particular in fig. 8.
From this it can be concluded that: the aminated surface defect sphalerite has stronger ultraviolet absorption compared with the common sphalerite, and the light absorption range is shifted towards red light.
Example 8
In the embodiment, the fluorescence emission intensity of the aminated surface defect sphalerite is tested by solid fluorescence, and the method comprises the following steps:
(1) Respectively taking a small amount of the common sphalerite of the comparative example 1 and the aminated surface defect sphalerite of the example 1, and smearing the sphalerite in a fluorescence test sample cell;
(2) The two samples obtained in step (1) were tested by a solid state fluorescence tester, as shown in fig. 9.
From this it can be concluded that: the intensity of the aminated fluorescence emission is reduced, which indicates that the separation efficiency of the sphalerite photogenerated carriers of the aminated surface defects is improved.
Example 9
The embodiment mainly examines the adsorption thermodynamic of the aminated surface defect sphalerite to PFOA, and comprises the following steps of;
(1) Preparation of initial concentration of 0 to 600mg L -1 Respectively adding 7.5mg of two different sphalerite (the common sphalerite of comparative example 1 and the aminated surface defect sphalerite of example 1) into 10mL of each of the PFOA solutions, sealing, vibrating for 12 hours at room temperature, centrifuging, taking the supernatant, and measuring the PFOA concentration;
(2)adsorption isotherms for PFOA were fitted using the langmuir model, model q e ＝(K L ×C max ×C e )/(1+K L ×C e ) The maximum adsorption amount of PFOA on normal sphalerite was obtained as Ce (mmol/kg) =0.0502, and the maximum adsorption amount of PFOA on aminated surface defect sphalerite was obtained as Ce (mmol/kg) =0.201, as shown in fig. 10.
From this it can be concluded that: the adsorption capacity of the aminated surface defect sphalerite to PFOA is remarkably improved.
Example 10
The method mainly examines the adsorption efficiency of the aminated surface defect sphalerite to PFOA, and comprises the following steps of;
a series of initial concentrations of 10mg L were prepared -1 7.5mg of two different sphalerites (the normal sphalerite of comparative example 1 and the aminated surface defect sphalerite of example 1) were added respectively to 10mL of each of the PFOA solutions, the mixture was shaken at room temperature after sealing, and after 10min, two parts of the mixture were taken out as parallel samples and centrifuged to obtain supernatants, and the PFOA concentration was measured, as shown in fig. 11.
From this it can be concluded that: the adsorption rate of the aminated surface defect sphalerite to PFOA is significantly enhanced.
Example 11
The method mainly examines degradation kinetics of aminated surface defect sphalerite on PFOA, and comprises the following steps:
(1) Respectively prepare and contain 10mg L -1 PFOA of (a) and 0.75. 0.75g L -1 The pH of the reaction solution was adjusted to 6 with NaOH of different concentrations;
(2) The reaction solution obtained in the step (1) was charged into a cylindrical quartz photoreaction tube (d=1cm, h=15cm), and photoreaction was performed using an XPA-7 photoreaction instrument equipped with a 500W high-pressure mercury lamp as a trigger. The reaction temperature is controlled at 25+/-2 ℃ and the reaction time is 3 hours. Sampling times were set to 0h,0.5h,1h,1.5h,2h,3h, respectively. Three photoreaction tubes were taken out at each time point to measure the degradation rate and defluorination rate of PFOA, as shown in fig. 12.
From this it can be concluded that: aminated surface defect sphalerite significantly promotes degradation and defluorination of PFOA.
Example 12
The influence of pH on degradation of PFOA by aminated surface defect sphalerite is mainly examined in the embodiment, and the method comprises the following steps:
(1) Preparation of the composition containing 10mg L -1 PFOA of (a) and 0.75. 0.75g L -1 The initial pH of the reaction solution was adjusted to 4,6,8, 10 with NaOH of different concentrations in the aminated surface defect sphalerite mixed solution of example 1;
(2) The reaction solution obtained in the step (1) was charged into a cylindrical quartz photoreaction tube (d=1cm, h=15cm), and photoreaction was performed using an XPA-7 photoreaction instrument equipped with a 500W high-pressure mercury lamp. The reaction temperature is controlled at 25+/-2 ℃ and the reaction time is 3 hours. Sampling times were set to 0h,0.5h,1h,1.5h,2h,3h, respectively. Three photoreaction tubes were taken out at each time point to measure the degradation rate and defluorination rate of PFOA, as shown in FIG. 13.
From this it can be concluded that: under the acidic condition, the degradation and defluorination rate of PFOA in the aminated surface defect sphalerite are slightly reduced, which is probably due to the fact that the photo-generated electrons generated on the aminated surface defect sphalerite are quenched by high-concentration protons, and the utilization efficiency of the photo-generated electrons is reduced.
Example 13
The method mainly examines the repeated recycling efficiency of degrading PFOA by aminated surface defect sphalerite, and comprises the following steps:
(1) Preparation of the composition containing 10mg L -1 PFOA of (a) and 0.75. 0.75g L -1 The mixed solution of aminated surface defect sphalerite of the example 1 was adjusted to an initial pH of 6 with NaOH of different concentrations;
(2) The reaction solution obtained in the step (1) was charged into a cylindrical quartz photoreaction tube (d=1cm, h=15cm), and photoreaction was performed using an XPA-7 photoreaction instrument equipped with a 500W high-pressure mercury lamp. The reaction temperature is controlled at 25+/-2 ℃, three photoreaction tubes are taken out after the reaction is carried out for 3 hours, and the degradation rate and defluorination rate of PFOA are measured;
(3) The liquid after the reaction in the step (2) is centrifuged to collect a precipitate, and the reaction is repeated according to the steps (1) and (2) after the liquid is alternately washed with methanol and water, respectively, and the concentration of the parent substance of PFOA and the concentration of fluoride ions in the system are monitored, and the result is shown in FIG. 14.
From this it can be concluded that: the aminated surface defect sphalerite has strong stability, and the five-time recycling still shows strong degradation and defluorination efficiency on PFOA.
Example 14
The degradation kinetics of the aminated surface defect sphalerite on the PFOS is mainly examined in the embodiment, and the steps are as follows:
(1) Respectively prepare and contain 10mg L -1 PFOS and 0.75. 0.75g L of (c) -1 The pH of the reaction solution was adjusted to 6 with NaOH of different concentrations;
(2) The reaction solution obtained in the step (1) was charged into a cylindrical quartz photoreaction tube (d=1cm, h=15cm), and photoreaction was performed using an XPA-7 photoreaction instrument equipped with a 500W high-pressure mercury lamp as a trigger. The reaction temperature is controlled at 25+/-2 ℃ and the reaction time is 3 hours. Sampling times were set to 0h,0.5h,1h,1.5h,2h,3h, respectively. Three photoreaction tubes were taken out at each time point to measure the degradation rate and defluorination rate of PFOS, as shown in fig. 15.
From this it can be concluded that: aminated surface defect sphalerite significantly promotes PFOS degradation and defluorination.
The invention and its embodiments have been described above schematically, without limitation, and the data used is only one of the embodiments of the invention, and the actual data combination is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the invention should not be construed as being limited to the embodiments and examples similar to the technical solutions without departing from the spirit of the invention.

Claims (5)

1. The application of aminated surface defect sphalerite material in degrading perfluorinated compounds is characterized in that: mixing an aminated surface defect sphalerite material with a perfluorinated compound, and then carrying out illumination on the mixed system of the aminated surface defect sphalerite material and the perfluorinated compound to realize photoreaction so as to degrade the perfluorinated compound;
the preparation method of the aminated surface defect sphalerite material comprises the steps of respectively preparing a zinc sulfate solution A and a mixed solution B of sodium sulfide and a cationic surfactant; then mixing the zinc sulfate solution A with the mixed solution B, wherein the mass concentration ratio of substances among the zinc sulfate, the sodium sulfide and the cationic surfactant is 74:82: 1-74: 82:5, stirring for 2-4 hours at 50-70 ℃, and carrying out hydrothermal reaction for 15-17 hours at 140-160 ℃.
2. The use of an aminated surface defect sphalerite material according to claim 1, for degrading perfluorinated compounds, characterized in that: the cationic surfactant is a quaternary ammonium salt cationic surfactant and is selected from one or more of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
3. The use of an aminated surface defect sphalerite material according to claim 1, for degrading perfluorinated compounds, characterized in that: the mass concentration ratio of the aminated surface defect sphalerite material to the perfluorinated compound is 10: 1-10: 10.
4. the use of an aminated surface defect sphalerite material according to claim 1, for degrading perfluorinated compounds, characterized in that: before the mixed system of the aminated surface defect sphalerite material and the perfluorinated compound is subjected to illumination, the pH value of the mixed system is adjusted to be 4-10.
5. The use of an aminated surface defect sphalerite material according to claim 1, for degrading perfluorinated compounds, characterized in that: the reaction time of the photoreaction is 2-4 hours, and the reaction temperature is 20-30 ℃.
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