CN112978843A - Method for dispersing and recovering nano material in water phase based on environment response polymer - Google Patents
Method for dispersing and recovering nano material in water phase based on environment response polymer Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
Abstract
The invention discloses a method for dispersing and recovering a nano material in a water phase based on an environmental response polymer, belonging to the technical field of nano material dispersion and recovery. The method comprises the following steps: adding the nano material into an aqueous solution containing pollutants to obtain a mixed system; the environment response polymer is uniformly dispersed in the obtained mixed system to help the nano material to disperse, so as to obtain a uniform dispersion system; and (3) uniformly dispersing inorganic salt in the obtained uniform dispersion system, then carrying out environmental response treatment and oscillation treatment, and collecting after a floating layer appears on the surface of the aqueous solution, thereby realizing the recovery of the nano adsorption material in the aqueous phase. The processing method can improve the dispersibility of the nano material in the aqueous solution by utilizing the environment-responsive polymer and collect the nano material by utilizing the environment-responsive polymer, so that the processing method based on the environment-sensitive polymer for dispersing and recovering the nano material in the aqueous phase has the advantages of high collection efficiency, simple and rapid operation and low cost.
Description
Technical Field
The invention belongs to the technical field of nano material recovery, and relates to a method for dispersing and recovering a nano material in a water phase based on an environmental response polymer.
Background
With the rapid development of modern industry, fresh water resources are seriously damaged, and the survival and development of aquatic organisms and human beings are seriously threatened. And the residual pollutants in the environment have wide variety and complex and various components, thereby causing persistent pollution to water resources. The physical method, the biological method and the chemical method can effectively treat pollutants in the wastewater.
The adsorption method in the physical method is widely applied due to convenience, rapidness and low cost. Currently, the adsorbents suitable for water treatment are various, including alumina, activated carbon, and the like. The nano material is a material which has at least one dimension in a three-dimensional space in a nano size (1-100nm) or is formed by taking the nano material as a basic unit, the nano material has a large number of surface adsorption active sites due to small particles, and the characteristic determines that the nano material has super-strong adsorption capacity. However, since the surface energy of the nanomaterial is high and the interaction between particles is strong, the nanomaterial is liable to agglomerate, and thus the nanomaterial has a disadvantage of poor dispersibility when used. Generally, the surface modification of the nanomaterial can be carried out by physical methods such as ultrasound, and chemical methods such as addition of a surfactant, surface modification of the nanomaterial, and the like; in addition, since the particle size of the nanomaterial is small, it is difficult to separate and collect the nanomaterial from an aqueous solution by a common method such as filtration or centrifugation. The commonly used recovery method is to compound the nano material and the magnetic material, and then separate the nano material from the aqueous solution by using the magnetic field. However, different nano materials need different experimental processes to compound the magnetic material, and the process is complex.
These two disadvantages make the nano material have a limit in industrial application. Therefore, the dispersion and separation recovery of the nano-materials become a hot problem for research.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for dispersing and recovering a nano material based on an environment-responsive polymer in an aqueous phase, and solves the problems of low dispersibility and difficult separation and recovery of the existing nano material by a simple and efficient method.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a method for dispersing and recovering a nano material in a water phase based on an environmental response polymer, which comprises the following steps:
1) adding the nano material into an aqueous solution containing pollutants to obtain a mixed system; 2) uniformly dispersing the environmental response polymer in the mixed system obtained in the step 1) to help the nano material to disperse to obtain a uniform dispersion system; 3) and (3) uniformly dispersing inorganic salt in the uniform dispersion system obtained in the step 2), carrying out environmental response treatment and oscillation treatment, and collecting after a floating layer appears on the surface of the aqueous solution, so that the recovery of the nano adsorption material in the aqueous phase is realized.
Preferably, the nanomaterial is graphene, carbon nanotube or TiO2。
Preferably, the inorganic salt is sodium chloride.
Preferably, the environmentally responsive polymer is PDMAEMA or MAH- β -CD-co-PNIPAM.
Further preferably, the environment responsive treatment comprises a temperature controlled treatment or a pH change treatment.
Further preferably, the temperature of the temperature-controlled treatment is the lowest critical solution temperature of the environmentally responsive polymer.
Further preferably, the formula of MAH-beta-CD-co-PNIPAM is:
Preferably, the concentration of the nano material is 0.05-2.5 mg/mL-1。
Preferably, the concentration of the environmentally responsive polymer is 1 mg-mL-1。
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a method for dispersing and recovering a nano material in a water phase based on an environmental response polymer. The polymer with the environmental response characteristic is used as a water phase collecting agent, and the nano material is recovered in the water phase by utilizing the phase transition property, so that the nano adsorption material can be used for adsorbing the nano adsorption material from a water sample containing pollutants, or the nano catalyst can be used for catalytic degradation when being applied to the water sample containing pollutants. Meanwhile, the environment-responsive polymer collecting agent is added into the system, so that the nano-material can be well dispersed to assist the nano-material to adsorb, the contact area of different material phase interfaces in the system is increased by adding inorganic salt and matching with temperature control treatment and oscillation treatment, a stable solid phase and a stable liquid phase are formed, and then the solid phase and the liquid phase can be separated by simple floating layer collection, so that the defect that the nano-adsorbing material is difficult to recover is overcome; improves the dispersibility of the nano adsorbent, and ensures high separation efficiency and simple and quick operation.
Furthermore, the selected inorganic salts are common salts, and the inorganic salts can effectively reduce the temperature of temperature control treatment, so that the temperature control energy consumption is reduced, the cost input of the treatment method can be effectively reduced, and the application benefit of the treatment method in practice is improved.
Further, the temperature of the selected temperature control treatment is near the lowest critical solution temperature of the environment response polymer, which is convenient and low in energy consumption.
Drawings
FIG. 1 is a schematic diagram of the synthesis route of MAH- β -CD-co-PNIPAM in the environmentally responsive polymer of the present invention;
FIG. 2 is a graph of the UV spectrum of the residual methylene blue in a water sample after adsorption according to an embodiment of the present invention;
FIG. 3 is a diagram of the ultraviolet spectra of the residual methylene blue in water samples after adsorption of different nano-adsorbent materials;
FIG. 4 is a UV standard spectrum of methylene blue;
FIG. 5 is a schematic diagram of the operation of the environmentally responsive polymer for recovering nanomaterials of the present invention;
FIG. 6 is a schematic diagram of the collection process of the environmental responsive polymer collector for the nanomaterials; wherein, (a) standing for 4h after uniform dispersion for pure carbon nanotube solution and carbon nanotube solution added with polymer; (b) a comparison graph of the two is obtained after the mixture is uniformly dispersed and is kept stand for 8 hours; (c) a comparison graph of the two after standing for 24 hours after uniform dispersion;
FIG. 7 is a schematic diagram of the dispersion of an environmentally responsive polymer collector into nanomaterials;
FIG. 8 is a graph of the kinetic detection of the dispersibility of the nanomaterial by UV spectrophotometry;
FIG. 9 is a comparative graph of a study of the recovery performance of an environmentally responsive polymer collector on nanomaterials.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses a method for dispersing and recovering a nano material in a water phase based on an environmental response polymer, which specifically comprises the following operation steps:
step 1, adding a nano material into a glass bottle containing a pollutant water sample, and performing adsorption or catalytic degradation treatment on pollutants;
step 2, adding the environment-responsive polymer into a glass bottle to help the nano material to form a water solution with good dispersibility, and assisting the nano material to adsorb pollutants or catalytically degrade the pollutants;
and 3, adding inorganic salt into the glass bottle, putting the glass bottle into a water bath kettle for environment response treatment and oscillation treatment (the oscillation treatment time is 5-10 s, so that the phase separation can be rapidly carried out, the separation efficiency is improved), and fishing out the glass bottle after the nano material in the aqueous solution floats to the surface and undergoes phase transition to realize the recovery of the nano adsorption material in the aqueous phase.
The nano material is graphene, carbon nano tube and TiO2And the like.
The inorganic salt is sodium chloride.
The above-described environmentally responsive polymers act as collectors. The environment response polymer comprises PDMAEMA or MAH-beta-CD-co-PNIPAM and the like.
Specifically, the concentration of the nano material is 0.05-2.5 mg/mL-1。
Specifically, the concentration of the environment-responsive polymer was 1 mg. multidot.mL-1。
Specifically, the contaminants are organic dyes and persistent organic contaminants.
The environment response treatment comprises temperature control treatment or pH value change treatment, wherein the temperature of the temperature control treatment is the low critical solution temperature of the temperature-sensitive polymer (generally controlled at about 37 ℃, which is convenient and has low energy consumption).
Specifically, the temperature of the temperature control treatment is 60-70 ℃.
Specifically, the structural formula of the MAH-beta-CD-co-PNIPAM is as follows:
Specifically, the preparation method of the MAH-beta-CD-co-PNIPAM comprises the following operations:
a. the dried beta-cyclodextrin (beta-CD) and maleic anhydride were dissolved in N, N-Dimethylformamide (DMF), and the solution was stirred at 80 ℃ for 12 hours to obtain maleic anhydride-modified cyclodextrin (MAH-beta-CD). And precipitating the obtained product MAH-beta-CD by using trichloromethane, and washing the product MAH-beta-CD by using acetone for multiple times to obtain the high-purity MAH-beta-CD.
Wherein the mass ratio of the beta-cyclodextrin to the maleic anhydride is 1: 1.
b. MAH- β -CD and N-isopropylacrylamide (NIPAM) were dissolved in DMF and Azobisisobutyronitrile (AIBN) was added to obtain a suspension. The resulting suspension is placed in N2Stirring for 8-24 hours at 70-80 ℃ under the atmosphere and anhydrous and anaerobic conditions to carry out copolymerization reaction. And after the copolymerization reaction is finished, obtaining a product mixed system, pouring the solution of the product mixed system into a 2000Da dialysis bag for dialysis for two days, and then carrying out freeze drying treatment to obtain a purified copolymer product (MAH-beta-CD-co-PNIPAM) of maleic anhydride modified cyclodextrin and N-isopropylacrylamide, namely the environment-responsive (temperature-sensitive) polymer collecting agent. The synthetic route for the environmentally responsive (temperature sensitive) polymeric collector of the present invention is shown in figure 1.
Wherein the ratio of the amount of the reacted substance of MAH-beta-CD and NIPAM is 1: 10 to 20.
Wherein the amount of AIBN added is 1.5% of the sum of the mass of the monomers used.
The method for dispersing and recovering the environment-responsive polymer-based nanomaterial in the aqueous phase according to the present invention is described in further detail below with reference to the following specific examples and the accompanying drawings.
Example 1
A method for preparing an environmentally responsive (temperature sensitive) polymer collector:
a. dried beta-CD (beta-cyclodextrin, 5.68g, 0.05mol) and maleic anhydride (0.49g, 0.05mol) were dissolved in DMF (30mL), and the solution was stirred at 80 ℃ for 12h to give maleic anhydride modified cyclodextrin (MAH-beta-CD). And precipitating the obtained product MAH-beta-CD by using trichloromethane, and washing the product MAH-beta-CD by using acetone for multiple times to obtain the high-purity MAH-beta-CD.
b. MAH-. beta. -CD (1.249g, 1mmol) and NIPAM (1.695g, 15mmol) were dissolved in 10mL of DMF, and AIBN (0.044g) was added to give a suspension. The resulting suspension is placed in N2The mixture was stirred at 70 ℃ for 24 hours under an atmosphere to conduct copolymerization. And (3) obtaining a product mixed system after the copolymerization reaction is finished, pouring the solution of the product mixed system into a 2000Da dialysis bag for dialysis for two days, and then carrying out freeze drying treatment to obtain the MAH-beta-CD-co-PNIPAM, namely the environment-responsive (temperature-sensitive) polymer collecting agent.
Example 2
A method for preparing an environmentally responsive (temperature sensitive) polymer collector:
MAH-. beta. -CD was prepared as described in step a of example 1.
MAH-. beta. -CD (1.249g, 1mmol) and NIPAM (1.13g, 10mmol) were dissolved in 10mL DMF and AIBN (0.035g) was added to give a suspension. The resulting suspension is placed in N2The mixture was stirred at 70 ℃ for 24 hours under an atmosphere to conduct copolymerization. Obtaining a product mixed system after the copolymerization reaction is finished, pouring the solution of the product mixed system into a 2000Da dialysis bag for two-day dialysis, and then carrying out freeze drying treatment to obtain MAH-beta-CD-co-PNIPAM, an environmental response (temperature sensitive) polymer collector was obtained.
Example 3
A method for preparing an environmentally responsive (temperature sensitive) polymer collector:
MAH-. beta. -CD was prepared as described in step a of example 1.
MAH-. beta. -CD (1.249g, 1mmol) and NIPAM (2.26g, 20mmol) were dissolved in 30mL of DMF, and AIBN (0.053g) was added to give a suspension. The resulting suspension is placed in N2The mixture was stirred at 70 ℃ for 24 hours under an atmosphere to conduct copolymerization. And (3) obtaining a product mixed system after the copolymerization reaction is finished, pouring the solution of the product mixed system into a 2000Da dialysis bag for dialysis for two days, and then carrying out freeze drying treatment to obtain the MAH-beta-CD-co-PNIPAM, namely the environment-responsive (temperature-sensitive) polymer collecting agent.
Example 4
A method for preparing an environmentally responsive (temperature sensitive) polymer collector:
MAH-. beta. -CD was prepared as described in step a of example 1.
MAH-. beta. -CD (1.249g, 1mmol) and NIPAM (2.034g, 18mmol) were dissolved in 25mL of DMF and AIBN (0.049g) was added to give a suspension. The resulting suspension is placed in N2The mixture was stirred at 70 ℃ for 24 hours under an atmosphere to conduct copolymerization. And (3) obtaining a product mixed system after the copolymerization reaction is finished, pouring the solution of the product mixed system into a 2000Da dialysis bag for dialysis for two days, and then carrying out freeze drying treatment to obtain the MAH-beta-CD-co-PNIPAM, namely the environment-responsive (temperature-sensitive) polymer collecting agent.
Example 5
A method for preparing an environmentally responsive (temperature sensitive) polymer collector:
MAH-. beta. -CD was prepared as described in step a of example 1.
MAH-. beta. -CD (1.249g, 1mmol) and NIPAM (1.469g, 13mmol) were dissolved in 20mL of DMF, and AIBN (0.041g) was added to give a suspension. The resulting suspension is placed in N2The mixture was stirred at 70 ℃ for 24 hours under an atmosphere to conduct copolymerization. The copolymerization reaction is connectedAnd finally, obtaining a product mixed system, pouring the solution of the product mixed system into a 2000Da dialysis bag for dialysis for two days, and then carrying out freeze drying treatment to prepare the MAH-beta-CD-co-PNIPAM, namely obtaining the environmental response (temperature sensitive) polymer collecting agent.
Example 6
A method for preparing an environment-responsive (temperature and pH dual-response) polymer collector comprises the following steps:
DMAEMA (dimethylaminoethyl methacrylate, 3.36mL, 0.02mol) which had been subjected to the double evaporation to remove impurities and AIBN (0.0080g) were dissolved in toluene (20mL), and the solution was stirred at 80 ℃ for 8 hours to effect copolymerization. And (3) obtaining a product mixed system after the reaction is finished, performing rotary evaporation on the obtained product mixed system to remove most of the solvent, and performing vacuum drying to obtain the PDMAEMA, namely obtaining the polymer collecting agent with environmental response (temperature and pH dual response).
The invention is described in detail below with reference to application-related tests:
example 7
The application of the environmental response (temperature sensitive) polymer collector prepared in the example 1 as a water phase recovery agent of a nano adsorption material is a method for recovering a nano material in a water phase based on the phase transition property of the environmental response (temperature sensitive) polymer, so that the method for dispersing and recovering the nano material in the water phase based on the environmental response polymer is realized, and comprises the following steps:
1. transfer 5mL of 40 mg. L-1Putting the organic methylene blue aqueous solution into a 5mL glass bottle, and adding 0.75mg of nano-adsorption material carbon nano-tubes into the glass bottle to adsorb the methylene blue pollutant; wherein the concentration of the carbon nano tube is 0.15 mg/mL-1
2.5mg of an environmental response (temperature sensitive) polymer collector MAH-beta-CD-co-PNIPAM is added into a glass bottle to form a water solution with good dispersibility of the nano adsorbent carbon nano tube so as to assist the nano adsorbent carbon nano tube in adsorption. The polymer concentration was 1 mg. multidot.mL-1；
3. After the pollutants are adsorbed for 24 hours, adding 1g of sodium chloride into the mixed solution, putting the mixed solution into a water bath kettle at 70 ℃ after shaking, fishing out the nano material after the nano material is observed to suspend on the liquid surface along with the environmental response (temperature sensitive) polymer collecting agent, and detecting the residual methylene blue by using an ultraviolet visible spectrophotometer.
The environment-responsive polymer is a high molecular polymer that can recognize and respond to changes in the external environment. The external environment stimulus includes temperature, pH, ions, solvents, light, electric field, etc. When an environmentally responsive polymer is subjected to such a stimulus, it responds rapidly and causes changes in physical structure and chemical properties. For example, the solubility of a temperature sensitive polymer changes when the temperature changes from ambient temperature. The mechanism of this responsiveness is generally believed to be related to the hydrophilic and hydrophobic groups in the polymer. When the environmental temperature is lower, the hydrophilic groups in the polymer are interacted with water molecules, so that the polymer is well dissolved in water; when the environmental temperature is higher, the interaction between the hydrophilic group and water molecules can be destroyed, so that the hydrophobic acting force of the polymer is enhanced, the solubility of the polymer in water is influenced, and the phase change is shown. This Temperature at which the phase transition of the polymer occurs is referred to as the Lower Critical Solution Temperature (LCST). In the environment-responsive (temperature-sensitive) polymer solution containing the nano-adsorption material, when the environment temperature is higher than LCST, the polymer and the nano-adsorption material have hydrophobic acting force, so that the nano-adsorption material can be separated from the mixed solution.
In the experiment, methylene blue is used as a probe molecule to characterize the collection performance of an environmental response (temperature sensitive) polymer collector MAH-beta-CD-co-PNIPAM on the nano material in the water body. The nano adsorbent carbon nano tube is added into the methylene blue aqueous solution to adsorb the methylene blue aqueous solution, so that the methylene solution is observed to be blue, namely the nano adsorbent cannot be well dispersed, and the adsorption of the nano adsorbent to pollutants is not facilitated under the condition; after the environmental response polymer is added, the nano adsorption material can be observed to be well dispersed in the methylene blue aqueous solution to form a homogeneous solution; after heating at 70 ℃ and adding inorganic salt, the solid-liquid two-phase separation can be observed, a black solid-phase substance (a solid-phase substance formed after methylene blue is adsorbed by the carbon nano tube and the polymer) is chromatographed on the solution, and the solution becomes colorless. Therefore, the environmental response polymer collector can assist the nano adsorbent carbon nano tube to completely adsorb the pollutant methylene blue in the water body at the temperature of 70 ℃, and the collection of the pollutant methylene blue is completed.
The method for recovering the nano material in the water phase based on the phase transition property of the environment-responsive polymer uses different organic pollutants and nano materials, and has different adsorption amounts. When the organic pollutant is methyl orange and the nano adsorbent is graphene, the adsorption capacity can reach 95.00mg g-1(ii) a When the organic pollutant is methyl orange and the nano adsorbent is carbon nano tube, the adsorption capacity can reach 50.71mg g-1(ii) a When the organic pollutant is methylene blue and the nano adsorbent is graphene, the adsorption capacity can reach 29.00mg g-1(ii) a When the organic pollutant is methylene blue and the nano adsorbent is carbon nano tube, the adsorption capacity can reach 52.37mg g-1. For example, fig. 2 is an ultraviolet spectrogram of the residual methylene blue in the water sample after the carbon nano tube adsorbs the methylene blue, fig. 3 is an ultraviolet spectrogram of the residual methylene blue in the water sample after different nano adsorbents adsorb, and fig. 4 is an ultraviolet standard spectrogram of the methylene blue. The position and shape of the absorption peak of the sample are consistent with those of the standard, and fig. 5 shows the whole operation process of the environmental response polymer for recovering the nano-adsorption material, which illustrates that the environmental response polymer collecting agent provided by the invention can utilize the phase transition property thereof to recover the nano-material in the water phase.
Example 8
The environment-responsive (temperature-sensitive) polymer collector MAH-beta-CD-co-PNIPAM provided by the invention can help the nano material to form a good dispersion liquid to assist in adsorbing pollutants while collecting the nano adsorbent.
The nano-adsorption material with the environmental response (temperature sensitive) polymer collector is dispersed more uniformly and is kept for a longer time.
A method for an environmentally responsive (temperature sensitive) material polymer to aid in the dispersion of nanomaterials comprising the acts of:
1. carbon nanotubes (1 mg. mL) were added to two 5mL glass bottles, respectively-1) In A, the temperature-sensitive polymer collecting agent is not added, and in B, the temperature-sensitive polymer collecting agent (1 mg. mL) is added-1) Respectively adding 5mL of deionized water;
2. performing ultrasonic treatment for 3h to uniformly disperse the two;
3. the mixture was taken out and left to stand for several hours, and the dispersibility of the mixture was observed.
Referring to fig. 6, which is a schematic diagram of the dispersion of the environment-responsive (temperature-sensitive) polymer collector on the nano-adsorbent in the application test, it can be seen that (a) is a pure carbon nanotube solution and a carbon nanotube solution added with the environment-responsive (temperature-sensitive) polymer collector, which are left to stand for 4 hours after being uniformly dispersed; (b) is a comparison graph of the two after standing for 8 hours after uniform dispersion; (c) and (4) a comparison graph of the two after standing for 24 hours after uniform dispersion. It can be seen that the carbon nanotubes with the addition of the environmentally responsive (temperature sensitive) polymer collector are more uniformly dispersed and the dispersion time is longer.
Example 9
Kinetic measurements using ultraviolet spectrophotometry to explore the effect of the presence or absence of added environmental response (temperature sensitive) polymer collectors on nanomaterial dispersibility
An aqueous solution of 2.5mg/mL Carbon Nanotubes (CNTs) was subjected to assisted dispersion using an environmental response (temperature sensitive) polymer collector MAH- β -CD-co-PNIPAM (1mg/mL) and ultrasonic waves (1h), respectively, and the resulting dispersed solution was immediately subjected to kinetic measurement of absorbance at a wavelength of 500nm using a UV-Vis (ultraviolet spectrophotometer). As can be seen from fig. 7, the deposition rate of CNTs by the ultrasound-free environmental-response (temperature-sensitive) polymer collector-assisted dispersion was much lower than that by the ultrasound-assisted dispersion, and they all had good stability within 45min without significant agglomeration. While the CNTs dispersed using ultrasonic wave assistance are rapidly deposited within 16.50min, and then the CNTs therein are largely aggregated, because the uniformity of the nanomaterial aqueous solution itself is deteriorated, resulting in frequent and large fluctuations in absorbance. It can be seen that the environmentally responsive (temperature sensitive) polymeric collector can provide good and stable dispersion of various nanomaterials.
Example 10
Exploration of recovery performance of environment-responsive (temperature-sensitive) polymer collector on nano materials
0.5 mg/mL was used-1For CNT (carbon nanotube) aqueous solution of 0.1 mg/mL-1Adsorbing with methylene blue aqueous solution, shaking for 3 hr, and adding 10mg of environment responsive (temperature sensitive) polymer (1 mg. mL)-1) The collector recovers the nanomaterial (procedure as in example 7). And desorbing the nano material by using ethanol, putting the nano material into subunit methyl blue aqueous solution with the same concentration for re-adsorption after the nano material is completely eluted, and detecting the adsorption efficiency of the nano material used twice by using an ultraviolet-visible spectrum to explore the recovery performance of the collector on the nano material. As can be seen from fig. 8, the first carbon nanotube adsorbs 100% of methylene blue in the aqueous solution; 87.37% of methylene blue in the aqueous solution is adsorbed for the second time, which shows that the environment response (temperature sensitive) polymer collector can well recover the nano adsorbent, the process is simple and easy to operate, and the nano material can be recovered without synthesis steps.
Example 11
The application of the environmental response (temperature and pH dual response) Polymer (PDMAEMA) collector prepared in example 6 as a recovery agent of a nano-material water phase is a method for recovering nano-materials in the water phase based on the principle that the dual response polymer generates phase transition after being stimulated by the outside, and comprises the following steps:
1. accurately weigh 1mg of the nanomaterial TiO2And 20mg of collecting agent PDMAEMA in a 20mL colorimetric tube, and adding 20mL of deionized water to obtain TiO2The dispersion is uniform. The same mixed solution was prepared in duplicate, numbered A and B. Nano TiO 22Has a concentration of 0.05 mg/mL-1The polymer concentration was 1 mg. multidot.mL-1；
2. Dispersing to obtain TiO2And the absorbance of the polymer solution was measured immediately using a UV-Vis (ultraviolet spectrophotometer) at a wavelength of 305nm to TiO dispersed in an aqueous solution2Carrying out detection;
3. original TiO after completion of detection2After the concentration, 3g of sodium chloride was added to each of the mixed solutions of A and B. 1 mol. L was used for the mixed solution A-1The pH value of the NaOH aqueous solution is adjusted to 10, the NaOH aqueous solution is shaken by hand to be fully mixed, and the No. B mixed solution is shaken by hand and then is put into a 70 ℃ water bath kettle. Nano TiO is observed in both A and B colorimetric tubes2With the dual response polymer collector suspended on the liquid surface, absorbance measurements were taken at a wavelength of 305nm using a UV-Vis (ultraviolet spectrophotometer) immediately after the suspended solid phase was fished out, and the remaining TiO dispersed in the aqueous solution was analyzed2And (6) detecting. As shown in FIG. 9, 59.20% of TiO remained after the pH was changed2Is recovered by the dual response polymer; after changing the temperature, 53.92% of TiO was present2Recovered by the dual response polymer.
The invention provides a method for dispersing and recovering a nano material in a water phase based on an environment response polymer, which is a method for recovering the nano material in the water phase based on the phase transition property of an environment response polymer collecting agent. Thus, treatment of contaminants, such as organic dyes and persistent organic contaminants, in aqueous solutions containing the contaminants can be achieved. The method has high collection efficiency and low price, and provides a simple and efficient recovery and separation method for the nano material.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. A method for dispersing and recovering a nano material based on an environment-responsive polymer in an aqueous phase is characterized by comprising the following steps:
1) adding the nano material into an aqueous solution containing pollutants to obtain a mixed system;
2) uniformly dispersing the environmental response polymer in the mixed system obtained in the step 1) to help the nano material to disperse to obtain a uniform dispersion system;
3) and (3) uniformly dispersing inorganic salt in the uniform dispersion system obtained in the step 2), carrying out environmental response treatment and oscillation treatment, and collecting after a floating layer appears on the surface of the aqueous solution, so that the recovery of the nano adsorption material in the aqueous phase is realized.
2. The method for dispersing and recovering the nano-material based on the environment-responsive polymer in the aqueous phase as claimed in claim 1, wherein the nano-material is graphene, carbon nano-tube or TiO2。
3. The method for dispersing and recovering an environmental-responsive polymer-based nanomaterial in an aqueous phase according to claim 1, wherein the inorganic salt is sodium chloride.
4. The method for dispersing and recovering the nano-material in the aqueous phase based on the environment-responsive polymer as claimed in claim 1, wherein the environment-responsive polymer is PDMAEMA or MAH-beta-CD-co-PNIPAM.
5. The method for dispersing and recovering the nano-materials based on the environment-responsive polymer in the water phase as claimed in claim 4, wherein the environment-responsive treatment comprises a temperature-controlled treatment or a pH-value change treatment.
6. The method as claimed in claim 4, wherein the temperature of the temperature-controlled treatment is the lowest critical solution temperature of the environment-responsive polymer.
7. The method for dispersing and recovering the nano-material in the aqueous phase based on the environment-responsive polymer as claimed in claim 4, wherein the structural formula of MAH-beta-CD-co-PNIPAM is as follows:
8. The method for dispersing and recovering the nano-materials based on the environmental response polymers in the water phase as claimed in claim 1, wherein the concentration of the nano-materials is 0.05-2.5 mg-mL-1。
9. The method for dispersing and recovering the nano-material in the aqueous phase based on the environment-responsive polymer as claimed in claim 1, wherein the concentration of the environment-responsive polymer is 1 mg-mL-1。
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