CN109206554B - Ion imprinted polymer material for photo-reduction of hexavalent chromium and preparation and application thereof - Google Patents

Ion imprinted polymer material for photo-reduction of hexavalent chromium and preparation and application thereof Download PDF

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CN109206554B
CN109206554B CN201710534799.6A CN201710534799A CN109206554B CN 109206554 B CN109206554 B CN 109206554B CN 201710534799 A CN201710534799 A CN 201710534799A CN 109206554 B CN109206554 B CN 109206554B
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hexavalent chromium
graphene oxide
ion imprinted
imprinted polymer
reduction
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CN109206554A (en
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沈先涛
陈志亮
刘小杰
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Huazhong University of Science and Technology
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Abstract

The invention discloses a preparation method of an ion imprinted polymer material for photo-reduction of hexavalent chromium, belonging to the field of new materials. The method uses potassium dichromate as a template, 2-vinylpyridine as a functional monomer, trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate as a cross-linking agent, toluene as a pore-foaming agent, and graphene oxide as a solid surfactant, and utilizes a Pickering emulsion technology to prepare the hexavalent chromium ion imprinted polymer material. Under the illumination condition, the graphene oxide provides reduction electrons, hexavalent chromium is reduced through valence conversion between trivalent and divalent states of an electron mediator (ferric ions), and the reduced product trivalent chromium is adsorbed by functional groups on the surface of the graphene oxide through the charge action. The method combines the ion imprinting technology and the photocatalysis technology, realizes the idea of integrating the absorption and reduction of hexavalent chromium ions, can selectively purify the hexavalent chromium ions in the water, and does not need to carry out secondary treatment on the generated trivalent chromium ions.

Description

Ion imprinted polymer material for photo-reduction of hexavalent chromium and preparation and application thereof
Technical Field
The invention relates to the field of new materials, relates to an ion imprinted polymer material, a preparation method and application thereof, and particularly relates to a chromium ion imprinted polymer material, a preparation method and application thereof.
Background
With the rapid development of the industry in China, the heavy metal pollution events emerge endlessly, which causes a series of environmental problems. The main reason for this is the random discharge and leakage of heavy metals. Chromium contaminants are mainly derived from mining, metal painting, wood preservation, dyes, leather and stainless steel making etc. (Dhal B, Thatoi HN, Das NN et al, chemical and microbiological re-registration of the hazardous chlorine from a contaminated soil and/or metallic soil: a review [ J ] Hazard Mater,2013, 250-. Chromium in the environment exists mainly in the form of trivalent chromium and hexavalent chromium, wherein trivalent chromium is involved in the metabolism of sugars and fats in humans and animals, but long-term exposure to trivalent chromium may lead to cumulative toxicity of chromium. Hexavalent chromium is a determined carcinogen of human beings, has the toxicity 10-100 times of trivalent chromium, can enter human bodies through skin, digestive tracts and respiratory tracts, and causes diseases such as anemia, dermatitis, rhinitis, nephritis, neuritis and the like, and can cause respiratory tract inflammation and induce lung cancer after long-term contact, and severe hexavalent chromium poisoning can cause death (Kanmanip, Aravin J, Preston D. Regulation of chromium conservation and Science [ J ]. International Journal of Environmental Science and technology,2011,9(1): 183-193; Zhang Han Chi, Zhang Jun, Liu Feng. harm and prevention and treatment of chromium [ J ], inner Mongolia petrochemical industry, 2003, 30: 72-73.). Trivalent chromium in water can cause inhibition of certain metalloenzyme systems inside plants, thereby inhibiting plant growth and causing toxicity to plants (Shanker A K, Cervantes C, Loza-Tavera H, et al. chromium toxicity in plants [ J ]. environmental International,2005,31(5): 739-. Therefore, the hexavalent chromium is reduced into trivalent chromium, and the trivalent chromium is removed, so that the method has important significance for treating chromium pollution in the environment and reducing chromium toxicity in the environment.
The existing hexavalent chromium wastewater treatment method mainly comprises a physical-chemical method and a biological method, and the main mechanism is to reduce hexavalent chromium into trivalent chromium by utilizing reducing substances. The physicochemical method has the disadvantages of high operation cost and raw material cost, poor selectivity, large sludge production amount and easy secondary pollutionAnd the like, but the biological method has the problems of low reducing capability, long treatment and repair time, biological safety and the like (Romanenko VI),Koren'kov VN.Pure culture of bacteria usingchromates and bichromates as hydrogen acceptors during development underanaerobic conditions[J]Mikrobiologiia,1977,46(3): 414-417; methods for removing Cr (VI) from water, Tou Jie, Lu Xiao Shu, et al, review [ J]2011, chinese scientific paper online). Ion imprinting technology and photocatalytic technology have been widely applied to the adsorption and removal of heavy metal ions, and ion imprinted polymer materials and photocatalytic materials designed for hexavalent chromium are also emerging (Ren Z, Kong D, Wang K, et al].Journal of Materials Chemistry A,2014,2(42):17952-17961；Waldmann N.S.,Paz Y.Photocatalytic reduction of Cr(VI)by titaniumdioxide coupled to functionalized CNTs:An example of counterproductive chargeseparation[J]The Journal of Physical Chemistry C,2010,114(44): 18946-. However, the ion imprinted polymer in the materials only aims at the specific adsorption of hexavalent chromium, and the hexavalent chromium is only transferred without reducing the toxicity of the hexavalent chromium; the photocatalytic material is only directed at the reduction of metal ions, but is not selective for the reduction of hexavalent chromium, and secondly the reduction product, trivalent chromium, is not treated. Therefore, the development of a novel material which can selectively carry out the photoreduction of hexavalent chromium and can timely treat the trivalent chromium which is a reduction product is of great significance.
Disclosure of Invention
Aiming at the problems that the existing material for treating hexavalent chromium only specifically adsorbs hexavalent chromium without reducing the toxicity of the material or only reduces metal ions without specifically adsorbing the hexavalent chromium or does not treat the reduction product trivalent chromium and the like, the invention aims to provide the ion imprinted polymer material for photo-reducing the hexavalent chromium, the preparation method and the application thereof, so that the ion imprinted polymer material has the characteristics of specifically adsorbing and photo-reducing the hexavalent chromium, simultaneously adsorbing the reduction product trivalent chromium and the like, and overcomes the defects of the prior art.
The specific scheme for realizing the invention is as follows:
the ion imprinted polymer material for photo-reduction of hexavalent chromium provided by the invention is of a spherical or sphere-like structure, the inner layer of the spherical or sphere-like structure is a hexavalent chromium ion imprinted hole, the whole outer surface of the spherical or sphere-like structure is coated by graphene oxide and is called a graphene layer, and a cross-linked complex is formed between the graphene layer and the inner layer formed by the hexavalent chromium ion imprinted hole and is called a cross-linked complex layer.
The invention provides a photo-reduction hexavalent chromium ion imprinted polymer material, which is prepared by taking potassium dichromate as a template molecule, 2-vinylpyridine as a functional monomer, trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate as a cross-linking agent, toluene as a pore-forming agent, graphene oxide as a solid surfactant, forming oil-in-water emulsion microspheres by using a Pickering (Pickering) emulsion method (Chevalier Y, Bolzinger M A. emulsions stabilized with dissolved nanoparticles: Pickering emulsions [ J ]. gels and Surfaces A: physical and engineering industries, 2013,439:23-34.), adding an initiator azobisisobutyronitrile to initiate polymerization reaction to obtain an ion imprinted polymer precursor, the precursor is firstly washed by tetrahydrofuran, then washed by sodium hydroxide-acetonitrile mixed solution to remove template molecule potassium dichromate, and then washing the mixture with deionized water to be neutral, and carrying out vacuum drying at 40-60 ℃ to obtain the ion imprinted polymer material of the photo-reduced hexavalent chromium.
The preparation method of the ion imprinted polymer material for photo-reduction of hexavalent chromium provided by the invention comprises the following steps:
the method comprises the following steps: putting excessive template molecule potassium dichromate into a centrifuge tube, adding a functional monomer 2-vinylpyridine, a crosslinking agent trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate and a pore-foaming agent toluene, uniformly mixing by shaking, then adding a graphene oxide aqueous solution, adding deionized water, and uniformly mixing by shaking the solution to obtain a Pickering (Pickering) emulsion system containing oil-in-water type emulsion microspheres; wherein the template molecule is saturated in the water phase and enters the organic phase, and the template molecule entering the organic phase is coordinated with the functional monomer; 2-vinylpyridine, trimethylolpropane trimethylpropaneThe mol ratio of the alkenoic acid ester to the ethylene glycol dimethacrylate to the toluene to the deionized water is 1: 0.2-0.5: 4-8: 3-7: 10-20; the concentration is 8-20 mg mL-1The volume ratio of the added volume of the graphene oxide aqueous solution to the added volume of the deionized water is 1: 3-6;
step two: adding an initiator azobisisobutyronitrile into the Pickering emulsion system prepared in the first step, introducing nitrogen to remove oxygen, wherein the molar ratio of 2-vinylpyridine to azobisisobutyronitrile is 1: 0.5-2, shaking and uniformly mixing the solution, and reacting for 8-15 hours in a water bath at 65-75 ℃ to obtain an ion imprinted polymer material precursor, wherein the precursor is prepared by using L with the concentration of 12mol-1Washing with tetrahydrofuran, and washing off the template molecule potassium dichromate by using a sodium hydroxide-acetonitrile mixed solution with a volume ratio of 1-5: 1, wherein the concentration of sodium hydroxide is 0.05-0.2 mol L-1Acetonitrile concentration of 19mol L-1And then washing the mixture to be neutral by using deionized water, and drying the mixture in vacuum at 40-60 ℃ to obtain the ion imprinted polymer material for photo-reduction of hexavalent chromium.
The concentration of the graphene oxide aqueous solution in the preparation method is 8-20 mg mL-1The graphene oxide aqueous solution can be prepared by a Hummers (Hummers) method, and the method for preparing the graphene oxide aqueous solution by the Hummers (Hummers) method comprises the following steps: placing a reaction vessel such as a triangular flask in an ice-water bath, sequentially adding graphite powder and potassium nitrate, slowly adding sulfuric acid, stirring, slowly adding potassium permanganate, and continuing stirring; removing the ice water bath, placing the reaction vessel in an oil bath, heating to 30-40 ℃, stirring for 1-2 hours, then adding warm distilled water, heating to 95-100 ℃ again, stirring for 1-1.5 hours, then adding warm distilled water and 30% hydrogen peroxide again, continuing stirring for 10-15 min and stopping the reaction; and washing the obtained reaction product with a hydrochloric acid solution, then washing with distilled water, centrifuging to remove a supernatant, and stopping washing until the pH value of the solution is greater than 5 to obtain the graphene oxide aqueous solution. [ the method for preparing the graphene oxide aqueous solution by the Hummers (Hummers) method can be referred to as follows: preparation of a graphic oxide, journal of the American Chemical Society,80(6),1339-1339.]。
The invention also provides a method for producing the sameThe adsorption capacity of the original hexavalent chromium ion imprinted polymer material to hexavalent chromium is 0.613mg g-1The imprinting factor reaches 1.5 times, can reduce hexavalent chromium under the condition of illumination and adsorb the reduced product trivalent chromium, and can be used for treating chromium pollution in the environment and reducing the chromium toxicity in the environment.
The invention also provides a process method for photo-reducing hexavalent chromium by using the ion imprinted polymer material, which comprises the following specific steps:
taking a proper amount of prepared ion imprinted polymer, dispersing the ion imprinted polymer in an acidic aqueous solution containing hexavalent chromium, and adding a proper amount of ferric ions into the solution, wherein the concentration of the ion imprinted polymer is 1-5 mg mL-1The concentration of hexavalent chromium is 1-12 mg L-1The pH value of the acidic solution is 1-5, and the concentration of ferric ions is 3-10 mg L-1. Stirring the mixed solution for adsorption reaction for 30-60 min, carrying out illumination, and monitoring the change of hexavalent chromium in the supernatant solution in real time, wherein the illumination intensity is 90000-110000 lux, and the incident wavelength is less than 500 nm.
The ion imprinted polymer material for photo-reducing hexavalent chromium photo-reduces hexavalent chromium in an acid solution, and the reduction rate of hexavalent chromium in the solution can reach 60-90%. In the photoreduction process, graphene oxide serves as an electron donor to provide reduction electrons, ferric ions serve as an electron mediator to rapidly transfer the reduction electrons to hexavalent chromium through valence conversion between the trivalent state and the divalent state, and the reduction product trivalent chromium is adsorbed by functional groups on the surface of the graphene oxide through the action of charges.
Compared with the traditional Pickering emulsion method, the preparation process of the invention proves that the metal ions can also be used as the template to synthesize the corresponding imprinted polymer material by applying the Pickering emulsion method. And secondly, the preparation process breaks through the concept that the template is polymerized in the soluble phase in the traditional method, and the imprinting process is completed by using a small amount of template entering the insoluble phase after the soluble phase is saturated by adopting a method of adding excessive template. Compared with the traditional hexavalent chromium ion imprinted polymer material, the imprinted polymer material prepared by the method not only can specifically adsorb hexavalent chromium, but also can carry out photoreduction on the hexavalent chromium.
Compared with the traditional hexavalent chromium photocatalytic material, the material does not contain traditional photocatalysts such as titanium dioxide and zinc oxide, can specifically carry out photoreduction aiming at hexavalent chromium, and can simultaneously adsorb and treat a reduction product trivalent chromium.
In the process of photoreduction, the invention selects the trivalent iron ions which are rich in nature and non-toxic as the electron mediator, and the trivalent iron ions enable electrons to be more easily transferred to hexavalent chromium through the valence conversion between the trivalent and the divalent states. The material realizes the idea of integrating hexavalent chromium adsorption and reduction, can selectively and thoroughly purify hexavalent chromium in water, and does not need secondary treatment on generated trivalent chromium. In the material, graphene oxide is a solid surfactant for stabilizing Pickering emulsion, an electron donor in a photoreduction process, and an adsorbent for an electron mediator ferric iron ion and a reduction product trivalent chromium.
Drawings
FIG. 1 is a schematic diagram of the synthesis of the ion imprinted polymer material for photo-reduction of hexavalent chromium according to the present invention (1), and a schematic diagram of the process (2) and mechanism of photo-reduction of hexavalent chromium (3).
Fig. 2 is an electron micrograph of the ion imprinted polymer (a) and the non-ion imprinted polymer (blank) (b), with the inset being graphene oxide on the surface of the polymer.
FIG. 3 is an isothermal adsorption curve for hexavalent chromium ions for an ionically imprinted polymer and a non-ionically imprinted polymer (blank).
FIG. 4 is a graph showing the adsorption kinetics of hexavalent chromium ions by the ion imprinted polymer and the non-ion imprinted polymer (blank).
FIG. 5 shows the selective reduction performance of the ionic imprinted polymer and the nonionic imprinted polymer (blank) for hexavalent chromium ions under the illumination condition.
FIG. 6 is a graph of the distribution of hexavalent chromium and total chromium in solution during the selective photo-reduction of hexavalent chromium with an ionically imprinted polymer and a non-ionically imprinted polymer (blank).
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1: preparation of ion imprinted polymer material for photo-reduction of hexavalent chromium (Pickering) emulsion method
The method for preparing the product with the concentration of 16.5mg mL by using Hummers (Hummers)-1The aqueous solution of graphene oxide of (1). 0.45g of potassium dichromate, 0.15mL of commercially available 2-vinylpyridine, 0.15mL of commercially available trimethylolpropane trimethacrylate, 1.5mL of commercially available ethylene glycol dimethacrylate and 0.8mL of commercially available toluene were placed in a 15mL centrifuge tube and mixed by shaking. Simultaneously, 1.0mL of the prepared graphene oxide aqueous solution (16.5mg mL) was added-1) The solution was shaken and mixed with 4.0mL of deionized water. Adding 20mg of azodiisobutyronitrile into the mixture, introducing nitrogen for 5min, vigorously shaking the mixture into uniform emulsion, and reacting for 10h under the condition of 70 ℃ water bath; the resulting polymer was washed with commercial tetrahydrofuran to remove unreacted organic reagent, and then 0.1mol L-1And (3) washing the template by using a sodium hydroxide-acetonitrile (1:1, v/v) mixed solution, finally washing the template to be neutral by using water, and performing vacuum drying at 50 ℃ to obtain the ion imprinted polymer prepared by a Pickering emulsion method. The preparation of the nonionic imprinted polymer (blank) by Pickering emulsion method was as described above except that no template potassium dichromate was added during the preparation.
The polymer material obtained by the method is spherical or spheroidal as seen in an electron microscope image, and graphene oxide is coated on the surface of the polymer material (see fig. 2). The adsorption capacity of the ion imprinted polymer material to hexavalent chromium reaches 0.613mgg-1The adsorption capacity of the nonionic imprinted polymer material is only 0.396mgg-1It was shown that imprinted sites specifically recognizing hexavalent chromium have been prepared (see fig. 3). Due to the existence of residual imprinting sites after the removal of template ions, the imprinted polymer can reach adsorption equilibrium within 30min, and shows better adsorption efficiency (see fig. 4).
Example 2: application example of ion imprinted polymer material for photo-reduction of hexavalent chromium
50mL of a pH4 aqueous solution (containing 3mg L of hexavalent chromium)-1Ferric iron concentration 5mg L-1) Placing in a crystalAdding prepared 50mg of ionic imprinted polymer and nonionic imprinted polymer into the solution respectively in a dish (diameter is 90mm), stirring and adsorbing for 30min, illuminating (illumination intensity is 90000lux, incident wavelength is 440nm), taking supernatant liquid when illuminating for 30,60,90,120 and 180min, measuring the content of hexavalent chromium in the supernatant liquid by adopting a national standard method, and monitoring the change of hexavalent chromium in the supernatant liquid.
Due to the existence of imprinted recognition sites in the ion imprinted polymer, the ion imprinted polymer can adsorb more hexavalent chromium compared to non-imprinted polymers, so that the hexavalent chromium is more available for electrons to be reduced (see fig. 5). In the process of photo-reducing hexavalent chromium, the concentration of hexavalent chromium in the solutions of the ion imprinted polymer and the non-ion imprinted polymer is substantially consistent with the total chromium concentration, so that it can be determined that the trivalent chromium ion as a reduction product is not dissociated in the solution, but is adsorbed on the surface of the polymer (see fig. 6).
Example 3: influence of pore-foaming agent volume on adsorption performance of ion imprinted polymer material
An ion imprinted polymer material was prepared as in example 1, except that different volumes (0.4, 0.6, 0.8, 1.0, 1.2mL) of toluene were used as porogens and the effect of porogen volume on the adsorption performance of the ion imprinted polymer material was examined. Through the investigation of the adsorption performance of the ion imprinted polymer material on hexavalent chromium ions, the structure shows that the adsorption performance of the ion imprinted polymer material prepared when the volume of the pore-foaming agent toluene is 0.8mL is the highest.
Example 4: preparation of graphene oxide aqueous solution by Hummers method
A250 mL Erlenmeyer flask was placed in an ice-water bath, and 0.5g of graphite powder and 0.5g of potassium nitrate were added, followed by slow addition of 23mL of 18.4mol L-1Stirring the sulfuric acid for 5min, slowly adding 3g of potassium permanganate, and stirring for 10 min; removing the ice water bath, placing the Erlenmeyer flask in an oil bath, heating to 35 ℃, stirring for 1.5h, then adding 40mL of 45 ℃ distilled water, heating to 98 ℃ again, stirring for 1h, then adding 50mL of 45 ℃ distilled water and 15mL of 30% hydrogen peroxide, and continuing stirring for 10 min; washing the obtained reaction product with 5% hydrochloric acid solution, washing with distilled water, and separatingRemoving the supernatant from the core, and stopping cleaning until the pH value is more than 5, wherein the cleaning is stopped when the pH value is 5 by the method, so that the graphene oxide aqueous solution with the volume of 180mL and the concentration of 16.25mg mL is obtained-1. The preparation method of the embodiment refers to the following documents: graphene oxide-ironcomplex synthesis, catalysis and visible-light-driven photochemical analysis, journal of Materials Chemistry A,1(3), 644.

Claims (7)

1. A photo-reduction hexavalent chromium ion imprinted polymer material is of a spherical or sphere-like structure, the inner layer of the spherical or sphere-like structure is a hexavalent chromium ion imprinted hole, the whole outer surface of the spherical or sphere-like structure is coated by graphene oxide and is called a graphene layer, and a cross-linked complex is formed between the graphene layer and the inner layer formed by the hexavalent chromium ion imprinted hole; the graphene oxide layer is used to provide reducing electrons as an electron donor.
2. The photo-reducible hexavalent chromium ion imprinted polymeric material according to claim 1, for treating chromium contamination in an environment to reduce chromium toxicity in the environment.
3. Use of the photo-reducible hexavalent chromium ion imprinted polymeric material of claim 1 to reduce hexavalent chromium and adsorb the reduction product trivalent chromium under light conditions; the reduction is carried out in an acidic solution containing ferric ions, which are used as electron transfer mediators.
4. The method of preparing an ion imprinted polymer material of claim 1, comprising the steps of:
the method comprises the following steps: putting excessive template molecule potassium dichromate into a centrifuge tube, adding a functional monomer 2-vinylpyridine, a crosslinking agent trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate and a pore-foaming agent toluene, uniformly mixing by shaking, adding a graphene oxide aqueous solution, adding deionized water, and uniformly mixing by shaking to obtain pickering (Picker) containing oil-in-water type emulsion microspheresing) an emulsion system; wherein the template molecule is saturated in the water phase and enters the organic phase, and the template molecule entering the organic phase is coordinated with the functional monomer; the molar ratio of 2-vinylpyridine, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, toluene and deionized water is 1: 0.2-0.5: 4-8: 3-7: 10-20; the concentration is 8-20 mg mL-1The volume ratio of the added volume of the graphene oxide aqueous solution to the added volume of the deionized water is 1: 3-6;
step two: adding an initiator azobisisobutyronitrile into the Pickering emulsion system prepared in the first step, introducing nitrogen to remove oxygen, wherein the molar ratio of 2-vinylpyridine to azobisisobutyronitrile is 1: 0.5-2, shaking and uniformly mixing the solution, and reacting for 8-15 hours in a water bath at 65-75 ℃ to obtain an ion imprinted polymer material precursor, wherein the precursor is prepared by using L with the concentration of 12mol-1Washing with tetrahydrofuran, and washing off the template molecule potassium dichromate by using a sodium hydroxide-acetonitrile mixed solution with a volume ratio of 1-5: 1, wherein the concentration of sodium hydroxide is 0.05-0.2 mol L-1Acetonitrile concentration of 19mol L-1And then washing the mixture to be neutral by using deionized water, and drying the mixture in vacuum at 40-60 ℃ to obtain the ion imprinted polymer material for photo-reduction of hexavalent chromium.
5. The preparation method according to claim 4, wherein the concentration of the graphene oxide aqueous solution is 8-20 mg mL-1。
6. The method according to claim 4 or 5, wherein the aqueous graphene oxide solution is prepared by Hummers (Hummers) method.
7. The method according to claim 6, wherein the specific method for preparing the graphene oxide aqueous solution by using the Hummers (Hummers) method comprises: placing the reaction vessel in an ice-water bath, sequentially adding graphite powder and potassium nitrate, slowly adding sulfuric acid, stirring, slowly adding potassium permanganate, and continuing stirring; removing the ice water bath, placing the reaction vessel in an oil bath, heating to 30-40 ℃, stirring for 1-2 hours, then adding warm distilled water, heating to 95-100 ℃ again, stirring for 1-1.5 hours, then adding warm distilled water and 30% hydrogen peroxide again, continuing stirring for 10-15 min and stopping the reaction; and washing the obtained reaction product with a hydrochloric acid solution, then washing with distilled water, centrifuging to remove a supernatant, and stopping washing until the pH value of the solution is greater than 5 to obtain the graphene oxide aqueous solution.
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