CN108355627A - A kind of preparation method and application of polypyrrole modified magnetic nanocomposite - Google Patents

A kind of preparation method and application of polypyrrole modified magnetic nanocomposite Download PDF

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CN108355627A
CN108355627A CN201810205358.6A CN201810205358A CN108355627A CN 108355627 A CN108355627 A CN 108355627A CN 201810205358 A CN201810205358 A CN 201810205358A CN 108355627 A CN108355627 A CN 108355627A
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modified magnetic
polypyrrole modified
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magnetic nanocomposite
cofe
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郭永福
张振宗
赵宇豪
夏楷
朱鹤
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Suzhou University of Science and Technology
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Abstract

The invention belongs to Functional polymer materials technology fields.The preparation method of polypyrrole modified magnetic nanocomposite includes CoFe2O4(four oxygen, two cobalt ferrite) powder, coated silica, configuration polymerization reaction system, free radical polymerization and post-processing.The minimizing technology of water pollutant is that the polypyrrole modified magnetic nanocomposite is added in 2~10 solution containing pollutant in pH, after shaking 2 8h at normal temperatures, it is placed in external magnetic field, is detached with solution after being magnetized to polypyrrole modified magnetic nanocomposite using external magnetic field.The present invention provide composite material specific surface area prepared by technical method is high, adsorption capacity is big, with efficient compound adsorbent feature, prepare simple, easily operated, non-secondary pollution and with the good renewable ability of recycling.

Description

A kind of preparation method and application of polypyrrole modified magnetic nanocomposite
Technical field
The invention belongs to Functional polymer materials technology fields, and in particular to a kind of nano combined material of polypyrrole modified magnetic The preparation method and application of material.
Background technology
Water is Source of life, is that human society is able to one of important substance resource developed, the production and living of the mankind all from Not boiling water.With the industrialized rapid development in China, technology and management level are relatively low in addition, and discharged volume of industrial waste water is increasingly Greatly, water pollution problems is on the rise, the serious health and life security for endangering the mankind.
Industrial wastewater derives from a wealth of sources, often from metallurgy, mining, the industries such as printing and dyeing.The polluter type that it contains is numerous More, heavy metal is wherein most common, and one of most reluctant polluter.Heavy metal is not easy to be decomposed by organism, leads to It crosses after the modes such as food chain enter human body, less serious case will cause symptoms, the severe one such as headache, dizziness, insomnia, arthralgia will be to human body Digestive system, urinary system, nervous system etc. cause serious harm.For example, in common several heavy metal species, chromium can cause acute Kidney failure；Cadmium can causing bleeding property enterogastritis, liver, renal necrosis etc.；Serious Nausea and vomiting can be caused, spit by eating a large amount of copper The symptoms such as blood, severe patient have hepatitis, low blood pressure, stupor, haemolysis, acute renal failure, or even dead.Heavy metals in industrial wastewater Existing forms it is changeable, this also determines the intractable characteristic of heavy metal.
Mercury is a kind of heavy metal that toxicity is extremely strong, and the biology with persistence, property easy to migrate, high volatile and height is rich Collection property.Mercury is in water mainly with Hg2+Form exist, into human body after by the central nervous system for influencing people, reproductive system, regard Nethike embrane nervous system, internal organ etc. cause neurasthenia syndrome, infertile, kidney failure, visual impairment of people etc., to people's Body causes serious irreversible damage.
For increasingly serious heavy metal pollution problem, researcher has carried out a large amount of experimental work, works out various It is fruitful either physically or chemically solving the problems, such as heavy metal pollution of water body, common are bioanalysis, chemical precipitation method, Absorption method, membrane separation process, ion-exchange etc..Wherein, absorption method have it is at low cost, do not easily cause secondary pollution, removal efficiency The advantages that high, therefore be used widely in Practical Project.Conventional sorbing material such as activated carbon, clay, cellulose etc., it is right The adsorption efficiency of certain heavy metals is low, and lacks specificity, limits the development space of such material.
Nano material, is a kind of emerging water treatment absorbent, and huge answer has been shown in heavy metals removal field With potentiality and researching value.Often there is nano particle larger specific surface area, the specific surface area of every gram of solid can reach hundreds of Even thousands of square metres, this makes them can be used as the adsorbent of high activity.However, common nano adsorber is nano level because of its Size is difficult to be separated from solution, and the utilization rate of material is not high, and may cause secondary pollution to environment.
Magnetic Nano material, according to its own magnetic superior physical properties of tool, retaining, common nano material is excellent While performance, and solves the problems, such as its hardly possible separation, the recycling for realization material provides possibility, is a kind of economic ring The heavy-metal adsorption material of guarantor.
Esmail Mahmoudi etc. synthesize core-shell type Fe by the precipitation method3O4/ NiO nanocomposites, and have studied it To the absorption property of Cr in water (VI), highest adsorption capacity reaches 6.88mg/g, and absorption property is not ideal enough.
Abin Sebastian etc. use ferric chloride solution and coconut shell extract, synthesis semi-crystal Fe3O4Nano particle, And it is subjected to adsorption experiment to Cr (VI), adsorption capacity reaches 9.6mg/g, and absorption property is weaker.
The thermal oxide iron foil under different high-temperature vapors such as Faisal Budiman, respectively obtains the nanometer sheet of ferriferous oxide (NSs) and nano wire (NWs).The oxide on surface of NSs and NWs is by α-Fe2O3Composition, subscale is mainly by Fe3O4Group At.Two kinds of materials have been carried out adsorption experiment by researcher to Cr (VI) respectively, it is found that NSs is to the adsorbance of Cr (VI) 112mg/L, and the adsorbance of NWs is 200mg/L, absorption property is moderate, but synthesizes obtained material shape and performance controllability Poor, the scope of application is not wide.
The physical arrangements features such as specific surface area and hole of above-mentioned magnetic Nano material be can be seen that in above-mentioned example to inhale Attached heavy metal ion, adsorption capacity and scope of application etc. have significant limitation.Therefore, it is necessary to modified magnetic nanometer material Material, to improve the absorption property of magnetic Nano inorganic agent.Polypyrrole is a kind of C, N five-ring heterocycles conjugated type conducting polymer material Material, is usually formed by pyrrole by oxidation polymerization.Polypyrrole contains conjugated double bond, has preferable electric conductivity, antioxygen It is good to change performance, stablizes nontoxic, preparation process is simple, at low cost, is a kind of good ep-type material.With polypyrrole modified magnetic Pyrrole is aggregated in magnetic Nano material surface by nano material, utilizes a large amount of amino etc. pair in polypyrrole polymers chain Heavy metal ion has the group of chelation so that modified material puies forward the adsorption capacity of heavy metal ion significantly It rises.Many scholars place oneself in the midst of the study on the modification of polypyrrole functional magnetic nano-particle in recent years.
Pyrrole is aggregated on nickel oxide by Varsha Srivastava etc., synthesizes PPy/NiO, and be used for Sr2+Suction Attached research.It is 258mg/g to test obtained adsorption capacity, and absorption property is relatively low.
Nazia H.Kera etc. are in Fe3O4FeCl is added in solution3As oxidant, pyrroles (Py) and aniline are injected dropwise (ANI), PPy-PANI/Fe is made3O4Compound carries out adsorption experiment to Cr (VI).The result shows that the adsorption capacity in pH=2 Maximum is 303mg/g.Material is suitable for strong acid environment, and absorption property is weaker in neutral conditions, is not suitable for natural water, Actual application value is relatively low.
Xiangqian Peng etc. prepare Fe by chemical coprecipitation3O4, lauryl sodium sulfate is added under acid condition (SDS) and pyrroles, stirring simultaneously obtain Fe after interval is ultrasonically treated3O4/ PPy nanocomposites.Nanocomposite is investigated to Ag (I) adsorption capacity, maximum adsorption capacity 143.3mg/g, absorption property are weaker.It needs persistently to lead to nitrogen in its manufacturing process Gas, manufacturing cost are higher.
Nomcebo H etc. magnetize zeolite, with FeCl3For oxidant pyrrole polymerization, it is multiple magnetic zeolite-polypyrrole has been obtained Condensation material (MZ-PPY).Counterweight vanadium metal progress adsorption experiment, maximum adsorption capacity 74.97mg/g, absorption property are weaker.Material The regenerability of material is poor, and after tertiary recycling, adsorption capacity drops to 53%.
However, polypyrrole modified magnetic nano material is still in the stage of fumbling in the application of water process, and it is immature.Greatly The adsorption effect of most materials is poor, and regenerability is bad, narrow scope of application.And it is numerous in the prevalence of material preparation process Trivial, of high cost, operation requires high disadvantage, limits its application and popularization in Practical Project.
In recent years, there are also the applications of polypyrrole modified magnetic preparation method of nano material, such as Chinese patent both at home and abroad A kind of preparation method of polypyrrole coated magnetic reduced graphene nano material is given in CN104971703A, is mainly added Pyrrole monomer is aggregated to Fe by sodium peroxydisulfate solid (APS)3O4The surfaces /RGO, to prepare PPY/Fe3O4The method of/RGO.But The material preparation cost is higher, and wherein reduced graphene preparation process is complicated and finished product form is difficult to control.In addition, the patent is not Absorption property of the material to heavy metal in water is elaborated, the actual application value of material is unknown.
A kind of polypyrrole/titanium dioxide compound adsorbent and its preparation are provided in Chinese patent CN104971703A, are answered With and regeneration method, specifically by polypyrrole and titanium dioxide occur In-situ reaction react made from adsorbent method.The absorption Agent preparation method is simple, can effectively adsorb the dyestuff in dye wastewater with high concentration, regenerability is also preferable, but is not suitable for Remove heavy metal in water removal.
Invention content
The present invention provides a kind of preparation method and application of polypyrrole modified magnetic nanocomposite, to solve mesh Preceding magnetic nanometer composite material there are adsorption capacities it is low, preparation method is complicated the problems such as.
In order to solve the above-mentioned technical problem, the technical scheme is that：The nano combined material of polypyrrole modified magnetic The preparation method of material, includes the following steps：
1) CoFe as core is prepared2O4(four oxygen, two cobalt ferrite) powder；
2) coated silica：By CoFe in step 1)2O4Powder realizes that silica (SiO2) wraps by basic hydrolysis It covers, obtains CoFe2O4@SiO2 nucleocapsid powder；
3) polymerization reaction system is configured：The CoFe2O4@SiO2 nucleocapsids powder and neopelex is taken to be dissolved in pure In water, after mixing by ultrasonic and mechanical agitation, pyrroles is added, obtains polymerization reaction system；
4) free radical polymerization：By Iron(III) chloride hexahydrate aqueous solution, it is added drop-wise in the polymerization reaction system, at room temperature 6~10h of mechanic whirl-nett reaction；
5) it post-processes：Product in step 4) is washed and dried, polypyrrole modified magnetic nanocomposite is obtained.
The present invention uses CoFe2O4As magnetic Nano nucleome material, with large specific surface area, superparamagnetism, Yi Congrong In liquid the features such as separation, hypotoxicity.
In addition, being first sufficiently mixed pyrroles and nucleocapsid powder, ferric trichloride is then added dropwise and carries out free radical polymerization, it is this anti- To the mode of dropwise addition, the content of pyrroles in product can be significantly increased, to significantly improve absorption property.
Optionally, in step 1), spent glycol makees reducing agent and reaction medium, and anhydrous sodium acetate and polyethylene glycol are surface Activating agent, divalent cobalt and trivalent iron salt, which react 8-10 hours for raw material under the conditions of 150-200 DEG C, is prepared CoFe2O4.With The ferroso-ferric oxide generally used is compared as nuclear structure, CoFe2O4Preparation temperature it is low, the reaction time is short, condition control letter Just, it is especially easy to get high-purity product, and often there are di-iron trioxide impurity in Fe 3 O 4 magnetic material, influence The quality of product.
It is pointed out that CoFe2O4After synthesis, required CoFe can be obtained using conventional post processing mode2O4It is magnetic Nano particle, such as：It is dry at 50~105 DEG C after washing 2~3 times.
Optionally, the divalent cobalt is selected from cobalt nitrate, cobaltous sulfate, cobalt chloride or acetylacetone cobalt, preferably cobalt nitrate, institute It states trivalent iron salt and is selected from ferric acetyl acetonade, ferric nitrate, ferric sulfate or iron chloride, preferably ferric acetyl acetonade.
Optionally, the step 1) each raw material component is as follows according to the mass fraction：
Optionally, in step 2), using cetyl trimethylammonium bromide as surfactant, hydrolysis material is silicate (ester) class compound, is hydrolyzed by reaction medium of water in CoFe2O4Surface coated silica, wherein cetyl front three Base ammonium bromide and CoFe2O4Mass ratio (0.15~0.8):(0.3~1.5)；Wherein CoFe2O4With silicate (ester) class compound Mass volume ratio be (0.3~1.5) g:(1~5) mL, reaction temperature are 50~100 DEG C, and the reaction time is 2~4h.Selection is suitable When surfactant, be equipped with suitable material rate, could be obtained under the appropriate reaction conditions compared with small particle, it is larger to compare table The nucleocapsid powder in face lays the foundation for the content of further polypyrrole and the absorption property of final product.
It should be pointed out that the post-processing after being covered to complete, can also use common method, wash and at 50~105 DEG C Lower drying puts into the next step again.
Optionally, silicate (ester) the class compound is selected from ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester or silicon Sour sodium, preferably ethyl orthosilicate.
Optionally, in step 3), the mass volume ratio of CoFe2O4@SiO2 nucleocapsids powder and pyrroles are (0.15~0.8) g: (0.25~1.3) mL；The mass volume ratio of CoFe2O4@SiO2 nucleocapsids powder and pure water is (0.15~0.8) g:(100~500) mL；The mass ratio of CoFe2O4@SiO2 nucleocapsids powder and neopelex is (0.15~0.8):(0.025~0.2).
Optionally, in step 4), a concentration of 0.06~1.5g/mL of the Iron(III) chloride hexahydrate aqueous solution, and six water Closing ferric chloride aqueous solutions is made it completely dissolved through ultrasound after being mixed with water by Iron(III) chloride hexahydrate.
The present invention also provides a kind of minimizing technologies of water pollutant comprising following steps：Contain 2~10 in pH Above-mentioned polypyrrole modified magnetic nanocomposite is added in pollutant solution, after shaking 2-8h at normal temperatures, is placed in extraneous magnetic In, detached with solution after being magnetized to polypyrrole modified magnetic nanocomposite using external magnetic field.
Optionally, the pollutant is heavy metal ion or organic matter, and the heavy metal ion is Hg2+、Pb2+、As(V)、 Cr(VI)、Ni2+And/or Cd2+, organic matter is phenol.
Optionally, pollutant concentration is 10~100mg/L in the solution containing pollutant, and per 50-100mL containing pollution The amount that polypyrrole modified magnetic nanocomposite is added in object solution is 5-10mg.
Compared with prior art, technical solution provided by the invention has the advantage that：
1) advantage that specific surface area is high, adsorption capacity is big, can be to the huge sum of money that is coexisted in water under the conditions of lower solid-to-liquid ratio Belong to ion and realizes higher removal efficiency；
2) there is efficient compound adsorbent feature, (such as mercury Hg of contents of many kinds of heavy metal ion in water can be adsorbed simultaneously2+, chromium Cr (VI), lead Pb2+, nickel2+, cadmium Cd2+Deng) and organic matter (such as phenol) adaptive surface and application surface it is wider；
3) prepare it is simple, easily operated, it is not high to equipment requirement.Material preparation cost and energy consumption are relatively low；Used material Material belongs to non-toxic or low-toxic material, and processing safety is higher, manufacture craft and adsorption process, green non-secondary pollution；
4) can be under the action of externally-applied magnetic field, Magnetic Isolation comes out from water, can be realized for material by parsing-absorption The recycling of material, have the good renewable ability of recycling, improve the utilization rate of material, to reduce use at This.
Description of the drawings
Fig. 1 is the SEM figures of polypyrrole modified magnetic nanocomposite prepared by embodiment 1；
Fig. 2 is the TEM figures of polypyrrole modified magnetic nanocomposite prepared by embodiment 1；
Fig. 3 is the nitrogen adsorption desorption figure of polypyrrole modified magnetic nanocomposite prepared by embodiment 1；
Fig. 4 is the infrared FTIR figures of polypyrrole modified magnetic nanocomposite prepared by embodiment 1；
Fig. 5 is the hysteresis graph of polypyrrole modified magnetic nanocomposite prepared by embodiment 1；
Fig. 6 is that polypyrrole modified magnetic nanocomposite prepared by embodiment 1 is imitated in the magnetism outside plus under magnetic fields Fruit display diagram；
Fig. 7 is to recycle design sketch by 5 cycle parsings in embodiment 12.
Specific implementation mode
In order to make it easy to understand, with reference to embodiment illustrate polypyrrole modified magnetic nanocomposite preparation method and Using, it should be appreciated that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
The implementation condition used in embodiment can do further adjustment according to the actual conditions of producer, the reagent being not specified Usually conventional commercial commodity.
The preparation method of 1 polypyrrole modified magnetic nanocomposite of embodiment
(1) 2g cobalt nitrates, 5g ferric acetyl acetonades, 3g anhydrous sodium acetates and 1g polyethylene glycol are weighed respectively is dissolved in 50mL second two It in alcohol, is stirred until homogeneous, moves in reaction kettle and react 8h at 150 DEG C, the product washed is simultaneously dry at 60 DEG C, obtains CoFe2O4Powder；
(2) 0.15g cetyl trimethylammonium bromide ultrasounds is soluble in water, preparation in 0.3g steps 1) is added CoFe2O4Powder, 1mL ethyl orthosilicates and 1.5mL ammonium hydroxide (25%) react 3h at 60 DEG C, the product washed and at 60 DEG C Lower drying obtains CoFe2O4@SiO2 nucleocapsid powder；
(3) 0.15g CoFe are taken2O4- SiO2 nucleocapsids powder and 0.025g neopelexes are dissolved in 100mL pure water In, ultrasonic 30min simultaneously after mechanical agitation 30min, is slowly added to 0.25mL pyrroles；
(4) it weighs 3g ferric chloride (FeCl36H2O)s to be dissolved in 10mL pure water, ultrasound is slowly dropped to reaction system to being completely dissolved In, continued mechanical is stirred to react 6h.
(5) it post-processes：It is dry at 60 DEG C after washing 2-3 times, obtain product PPy-CoFe2O4@SiO2。
A series of performance tests are carried out to the composite material of preparation, concrete condition is as follows：
As shown in Figure 1, passing through polypyrrole modification and SiO2The formation of shell, the PPy-CoFe of preparation2O4@SiO2Magnetic Nano The dispersibility of composite material substantially improves, and surface is smooth and presents spherical.In addition grain diameter is smaller, in 90~140nm.
As shown in Fig. 2, the PPy-CoFe prepared2O4@SiO2The magnetic core of magnetic nanometer composite material, internal black is CoFe2O4, by external translucent SiO2It is wrapped up with PPy shells, shows PPy-CoFe2O4@SiO2Magnetic nanometer composite material has There is apparent nucleocapsid structure.
As shown in figure 3, the PPy-CoFe prepared2O4@SiO2The specific surface area of magnetic nanometer composite material is up to 218.56m2/g。
As shown in figure 4, being located at 1552cm-1C=C stretching vibration peaks show PPy on magnetic nanometer composite material at Work(synthesizes, 1088cm-1Si-O-Si stretching vibration peaks show SiO2The presence of shell.
As shown in figure 5, the PPy-CoFe prepared2O4@SiO2Magnetic nanometer composite material, saturation magnetic strength are 44.8emu/ G has higher Magneto separate characteristic.
As shown in fig. 6, the PPy-CoFe prepared2O4@SiO2Magnetic nanometer composite material has preferable Magneto separate characteristic.
The preparation method of 2 polypyrrole modified magnetic nanocomposite of embodiment
(1) 4g acetylacetone cobalts, 10g ferric nitrates, 6g anhydrous sodium acetates and 2g polypropylene glycols are weighed respectively is dissolved in 100mL second It in glycol, is stirred until homogeneous, moves in reaction kettle and react 10h at 200 DEG C, the product washed is simultaneously dry at 80 DEG C, obtains To CoFe2O4Powder；
(2) 0.3g cetyl trimethylammonium bromide ultrasounds is soluble in water, 0.6g CoFe are added2O4The positive silicon of powder, 2mL Sour methyl esters and 1mL sodium hydroxide solutions (1M) react 4h at 100 DEG C, and the product washed is simultaneously dry at 80 DEG C, obtains CoFe2O4@SiO2Powder；
(3) 0.3g CoFe are taken2O4@SiO2It is dissolved in 200mL pure water with 0.05g neopelexes, ultrasonic 30min And after mechanical agitation 30min, it is slowly added to 0.5mL pyrroles；
(4) it weighs 6g ferric chloride (FeCl36H2O)s to be dissolved in 20mL pure water, ultrasound is slowly dropped to reaction system to being completely dissolved In, continued mechanical is stirred to react 8h；
(5) it post-processes：It is dry at 80 DEG C after washing 2~3, obtain product PPy-CoFe2O4@SiO2。
The preparation method of 3 polypyrrole modified magnetic nanocomposite of embodiment
(1) 10g cobalt chlorides, 25g ferric sulfate, 15g anhydrous sodium acetates and 5g polyethylene glycol are weighed respectively is dissolved in 300mL second two It in alcohol, is stirred until homogeneous, moves in reaction kettle and react 8h at 150 DEG C, the product washed is simultaneously dry at 105 DEG C, obtains CoFe2O4Powder；
(2) 0.8g cetyl trimethylammonium bromide ultrasounds is soluble in water, 1.5g CoFe are added2O4Powder, 5mL silicic acid Sodium and 3mL ammonium hydroxide (25%) react 2h at 100 DEG C, and the product washed is simultaneously dry at 105 DEG C, obtains CoFe2O4@SiO2 Powder；
(3) 0.8g CoFe are taken2O4@SiO2It is dissolved in 500mL pure water with 0.2g neopelexes, ultrasonic 30min And after mechanical agitation 30min, it is slowly added to 1.3mL pyrroles；
(4) it weighs 15g ferric chloride (FeCl36H2O)s to be dissolved in 50mL pure water, ultrasound is slowly dropped to reactant to being completely dissolved In system, continued mechanical is stirred to react 8h；
(5) it post-processes：It is dry at 105 DEG C after washing, obtain product PPy-CoFe2O4@SiO2。
4 polypyrrole modified magnetic nanocomposite of embodiment is to heavy metal Hg in water2+Removal
Take 50mL, the heavy metal Hg containing 25.1mg/L2+Solion is placed in the conical flask of 250mL, with nitric acid or hydrogen-oxygen Change the PPy-CoFe that sodium etc. adjusts the preparation of embodiment 1 that 5mg is added after pH is 82O4@SiO2, will be upper after shaking 4h at normal temperatures It states conical flask to be placed in external magnetic field, be detached with solution after being magnetized to sorbing material using external magnetic field.After separation Supernatant using ICP-OES to remaining heavy metal Hg in solution2+Ion concentration is detected, and testing result is preceding molten with absorption Hg in liquid2+After the initial concentration of ion is compared, by the way that polypyrrole modified magnetic nanocomposite is calculated to a huge sum of money Belong to Hg2+Adsorption capacity be 210.4mg/g, at this time to heavy metal Hg2+Removal efficiency be 83.8%.
5 polypyrrole modified magnetic nanocomposite of embodiment is to heavy metal Pb in water2+Removal
Take 50mL, the heavy metal Pb containing 18.2mg/L2+Solion is placed in the conical flask of 250mL, with nitric acid or hydrogen-oxygen Change the PPy-CoFe that sodium etc. adjusts the preparation of embodiment 1 that 5mg is added after pH is 42O4@SiO2, will be upper after shaking 4h at normal temperatures It states conical flask to be placed in external magnetic field, be detached with solution after being magnetized to sorbing material using external magnetic field.After separation Supernatant using ICP-OES to remaining heavy metal Pb in solution2+Ion concentration is detected, and testing result is preceding molten with absorption Pb in liquid2+After the initial concentration of ion is compared, by the way that polypyrrole modified magnetic nanocomposite is calculated to a huge sum of money Belong to Pb2+Adsorption capacity be 166.1mg/g, at this time to heavy metal Pb2+Removal efficiency be 91.2%.
Removal of the 6 polypyrrole modified magnetic nanocomposite of embodiment to heavy metal As (V) in water
50mL, heavy metal As (V) solion containing 16.7mg/L is taken to be placed in the conical flask of 250mL, with nitric acid or hydrogen Sodium oxide molybdena etc., which is adjusted, is added PPy-CoFe prepared by the embodiment 1 of 5mg after pH is 62O4@SiO2, will after shaking 5h at normal temperatures Above-mentioned conical flask is placed in external magnetic field, is detached with solution after being magnetized to sorbing material using external magnetic field.Separation Supernatant afterwards is detected remaining heavy metal As (V) ion concentration in solution using ICP-OES, testing result and absorption After the initial concentration of As (V) ion is compared in preceding solution, by the way that polypyrrole modified magnetic nanocomposite is calculated Adsorption capacity to heavy metal As (V) is 156.4mg/g, is at this time 93.7% to the removal efficiency of heavy metal As (V).
Removal of the 7 polypyrrole modified magnetic nanocomposite of embodiment to heavy metal Cr in water (VI)
50mL, heavy metal Cr (VI) solion containing 29.8mg/L is taken to be placed in the conical flask of 250mL, with nitric acid or hydrogen Sodium oxide molybdena etc., which is adjusted, is added PPy-CoFe prepared by the embodiment 1 of 5mg after pH is 52O4@SiO2, will after shaking 5h at normal temperatures Above-mentioned conical flask is placed in external magnetic field, is detached with solution after being magnetized to sorbing material using external magnetic field.Separation Supernatant afterwards is detected remaining heavy metal Cr (VI) ion concentration in solution using ICP-OES, testing result and suction After the initial concentration of Cr (VI) ion is compared in attached preceding solution, by the way that the nano combined material of polypyrrole modified magnetic is calculated Expect that the adsorption capacity of heavy metal Cr (VI) be 273.2mg/g, is at this time 91.7% to the removal efficiency of heavy metal Cr (VI).
8 polypyrrole modified magnetic nanocomposite of embodiment is to heavy metal Ni in water2+Removal
Take 50mL, the heavy metal Hg containing 14.1mg/L2+Solion is placed in the conical flask of 250mL, with nitric acid or hydrogen-oxygen Change the PPy-CoFe that sodium etc. adjusts the preparation of embodiment 1 that 4mg is added after pH is 72O4@SiO2, will be upper after shaking 4h at normal temperatures It states conical flask to be placed in external magnetic field, be detached with solution after being magnetized to sorbing material using external magnetic field.After separation Supernatant using ICP-OES to remaining heavy metal Ni in solution2+Ion concentration is detected, and testing result is preceding molten with absorption Ni in liquid2+After the initial concentration of ion is compared, by the way that polypyrrole modified magnetic nanocomposite is calculated to a huge sum of money Belong to Ni2+Adsorption capacity be 147.8mg/g, at this time to heavy metal Ni2+Removal efficiency be：83.9%.
9 polypyrrole modified magnetic nanocomposite of embodiment is to heavy metal Cd in water2+Removal
Take 50mL, the heavy metal Cd containing 35.0mg/L2+Solion is placed in the conical flask of 250mL, with nitric acid or hydrogen-oxygen Change the PPy-CoFe that sodium etc. adjusts the preparation of embodiment 1 that 10mg is added after pH is 52O4@SiO2, will be upper after shaking 5h at normal temperatures It states conical flask to be placed in external magnetic field, be detached with solution after being magnetized to sorbing material using external magnetic field.After separation Supernatant using ICP-OES to remaining heavy metal Cd in solution2+Ion concentration is detected, and testing result is preceding molten with absorption Cd in liquid2+After the initial concentration of ion is compared, by the way that polypyrrole modified magnetic nanocomposite is calculated to a huge sum of money Belong to Cd2+Adsorption capacity be 166.3mg/g, at this time to heavy metal Cd2+Removal efficiency be：95.0%.
10 polypyrrole modified magnetic nanocomposite of embodiment is to mixture-metal Hg in water2+, Cr (VI) and Cd2+'s It removes simultaneously
It takes 100mL, contain Hg2+, Cr (VI) and Cd2+Concentration be that 10mg/L solution is placed in the conical flask of 250mL, use Nitric acid or sodium hydroxide etc., which are adjusted, is added PPy-CoFe prepared by the embodiment 1 of 6mg after pH is 72O4@SiO2, shake at normal temperatures After 8h, above-mentioned conical flask is placed in external magnetic field, is divided with solution after being magnetized to sorbing material using external magnetic field From.Supernatant after separation is using ICP-OES to remaining heavy metal Hg in solution2+, Cr (VI) and Cd2+Ion concentration carries out Detection, testing result and Hg solution before absorption2+, Cr (VI) and Cd2+After the initial concentration of ion is compared, pass through calculating Obtain sulfhydryl modified CoFe2O4@SiO2Nanocomposite is to heavy metal Hg2+, Cr (VI) and Cd2+Adsorption capacity 139.4mg/ g、147.8mg/g、142.5mg/g.At this time to heavy metal Hg2+, Cr (VI) and Cd2+Removal efficiency be respectively：83.6%, 88.7%, 85.5%, the total removal rate to three heavy metal species is 85.9%.
Removal of the 11 polypyrrole modified magnetic nanocomposite of embodiment to phenol in water
It takes 100mL phenol solution of the concentration containing 10mg/L in the conical flask of 250mL, adjusts after pH is 6 and be added 4.0mg's PPy-CoFe prepared by embodiment 12O4@SiO2, after 4h is shaken in water-bath at normal temperatures, above-mentioned conical flask is placed in external magnetic field, It is detached with solution after being magnetized to sorbing material using external magnetic field.Supernatant after separation uses uv-spectrophotometric Meter is detected remaining phenol concentration in solution, and polypyrrole modified magnetic nanocomposite pair can be obtained by calculating The adsorption capacity 207.7mg/g of phenol, the at this time removal efficiency 83.1% of Pyrogentisinic Acid.
The parsing of embodiment 12 recycles
(1) resolving
It takes 100mL 1M HCl solutions in 250mL conical flasks, the material recycled after adsorbing, shaking table is added in embodiment 4 40min is shaken in middle room temperature water-bath, after pickling is parsed, by drying for standby after material pure water.
(2) adsorption process after parsing
Adsorption experiment is carried out after being parsed again.Take 50mL, the heavy metal Hg containing 25.3mg/L2+Solion is placed in In the conical flask of 250mL, it is 8 to adjust pH with nitric acid or sodium hydroxide etc., and water-bath at normal temperatures shakes 3h and carries out adsorption experiment.Such as Shown in Fig. 7, its adsorption capacity is the 91.7% of initial adsorption ability after 3 parsing-absorption, its adsorption energy after 5 parsing-absorption Power is the 82.3% of initial adsorption ability.It can be seen that the regeneration rate of the material is higher, use cost is relatively low.
The parsing of embodiment 13 recycles
(1) resolving
It takes 100mL absolute ethyl alcohols in 250mL conical flasks, the material recycled after 11 adsorbing phenol of embodiment, shaking table is added 60min is shaken in middle room temperature water-bath, spare after being dried with 105 DEG C after material pure water after the completion of elution.
(2) adsorption process after parsing
Adsorption experiment is carried out after being parsed again.Take 100mL, the phenol solution containing 10mg/L in the conical flask of 250mL In, it is 6 to adjust pH, and water-bath at normal temperatures shakes 4h and carries out adsorption experiment, its adsorption capacity is initial inhales after 5 parsing-absorption The 83.3% of attached ability shows that material has parsing regenerability well, and application cost is relatively low, and application prospect is preferable.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations.Although Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used To modify to the technical solution recorded in previous embodiment, either which part or all technical features are equal It replaces, and these modifications or substitutions, the model for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution It encloses.

Claims (10)

1. a kind of preparation method of polypyrrole modified magnetic nanocomposite, which is characterized in that include the following steps：
1) CoFe as core is prepared2O4(four oxygen, two cobalt ferrite) powder；
2) coated silica：By CoFe in step 1)2O4Powder realizes that silica (SiO2) coats by basic hydrolysis, obtains Obtain CoFe2O4@SiO2 nucleocapsid powder；
3) polymerization reaction system is configured：The CoFe2O4@SiO2 nucleocapsids powder and neopelex is taken to be dissolved in pure water In, after mixing by ultrasonic and mechanical agitation, pyrroles is added, obtains polymerization reaction system；
4) free radical polymerization：Iron(III) chloride hexahydrate aqueous solution is added drop-wise in the polymerization reaction system, it is mechanical at room temperature It is stirred to react 6~10h；
5) it post-processes：Product in step 4) is washed and dried, polypyrrole modified magnetic nanocomposite is obtained.
2. the preparation method of polypyrrole modified magnetic nanocomposite according to claim 1, which is characterized in that step 1) In, spent glycol makees reducing agent and reaction medium, and anhydrous sodium acetate and polyethylene glycol are surfactant, divalent cobalt and trivalent Molysite, which reacts 8-10 hours for raw material under the conditions of 150-200 DEG C, is prepared CoFe2O4。
3. the preparation method of polypyrrole modified magnetic nanocomposite according to claim 2, which is characterized in that described two Valence cobalt salt is selected from cobalt nitrate, cobaltous sulfate, cobalt chloride or acetylacetone cobalt, preferably cobalt nitrate, and the trivalent iron salt is selected from levulinic Ketone iron, ferric nitrate, ferric sulfate or iron chloride, preferably ferric acetyl acetonade.
4. the preparation method of polypyrrole modified magnetic nanocomposite according to claim 2, which is characterized in that the step It is rapid 1) in each raw material component it is as follows according to the mass fraction：
5. the preparation method of polypyrrole modified magnetic nanocomposite according to claim 1, which is characterized in that step 2) In, using cetyl trimethylammonium bromide as surfactant, hydrolysis material is silicate (ester) class compound, is anti-with water Medium is answered to be hydrolyzed in CoFe2O4Surface coated silica, wherein cetyl trimethylammonium bromide and CoFe2O4Quality Than (0.15~0.8):(0.3~1.5)；Wherein CoFe2O4With the mass volume ratio of silicate (ester) class compound be (0.3~ 1.5)g:(1~5) mL, reaction temperature are 50~100 DEG C, and the reaction time is 2~4h.
6. the preparation method of polypyrrole modified magnetic nanocomposite according to claim 5, which is characterized in that the silicon Hydrochlorate (ester) class compound is selected from ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester or sodium metasilicate, preferably ethyl orthosilicate.
7. the preparation method of polypyrrole modified magnetic nanocomposite according to claim 1, which is characterized in that step 3) In, the mass volume ratio of CoFe2O4@SiO2 nucleocapsids powder and pyrroles are (0.15~0.8) g:(0.25~1.3) mL； The mass volume ratio of CoFe2O4@SiO2 nucleocapsids powder and pure water is (0.15~0.8) g:(100~500) mL；CoFe2O4@ The mass ratio of SiO2 nucleocapsids powder and neopelex is (0.15~0.8):(0.025~0.2).
8. the preparation method of polypyrrole modified magnetic nanocomposite according to claim 1, which is characterized in that step 4) In, a concentration of 0.06~1.5g/mL of the Iron(III) chloride hexahydrate aqueous solution, and Iron(III) chloride hexahydrate aqueous solution is to pass through Iron(III) chloride hexahydrate makes it completely dissolved after being mixed with water through ultrasound.
9. a kind of minimizing technology of water pollutant, which is characterized in that include the following steps：In pH 2~10 containing pollutant Any polypyrrole modified magnetic nanocomposite of claim 1~8 is added in solution, after shaking 2-8h at normal temperatures, It is placed in external magnetic field, divides with solution after being magnetized to polypyrrole modified magnetic nanocomposite using external magnetic field From.
10. the minimizing technology of water pollutant according to claim 9, which is characterized in that dirty in the solution containing pollutant A concentration of 10~100mg/L of object is contaminated, and it is nano combined that polypyrrole modified magnetic is added in every 50-100mL solution containing pollutant The amount of material is 5-10mg.
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