CN111518353A - MXene/polymer composite material and preparation method and application thereof - Google Patents
MXene/polymer composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an MXene/polymer composite material and a preparation method and application thereof, belonging to the field of preparation of nano functional materials. An MXene/polymer composite material is prepared from MXene nanosheets and poly (4-vinylpyridine)) Salt, and the MXene nanosheets are connected through poly (4-vinylpyridine) salt to form a three-dimensional network structure. The MXene/polymer composite material is obtained by performing electrostatic assembly on MXene nanosheets by utilizing negative charges on the surfaces of the MXene nanosheets and positive charges on the poly (4-vinylpyridine) salts. Cr is carried out by utilizing the adsorbent provided by the invention2O7 2‑The removal rate of the adsorption can reach 97 percent at most, and the adsorption method is simple to operate and environment-friendly.
Description
Technical Field
The invention relates to an MXene/polymer composite material and a preparation method and application thereof, belonging to the field of preparation of nano functional materials.
Background
With the rapid development of modern industrial production, the heavy metal pollution in water bodies is becoming more and more serious. Heavy metals cannot be biodegraded and are easily enriched in organisms and human bodies, and excessive heavy metals pose great threats to the ecological environment and human health. For example, the heavy metal Cr (VI) has strong carcinogenicity and mutagenicity and is one of three internationally recognized carcinogenic metal substances. Therefore, the method has important significance for treating heavy metal pollution in the water body by adopting an efficient method. The method for treating heavy metal pollution in water body mainly includes precipitation method, electrolytic method, ion exchange method, membrane separation method, microbiological method and adsorption method. Among them, the adsorption method has the advantages of simple and flexible operation, high adsorption efficiency, high selectivity, low cost, etc., and is widely used.
The two-dimensional transition metal carbide or nitride, namely MXene, is a novel two-dimensional layered structure material. In the aspect of adsorption application, as the MXene nanosheets have the characteristics of high specific surface area, abundant surface functional groups, hydrophilicity and the like, the MXene nanosheets are widely regarded as adsorption materials. MXene nanosheets are used as adsorbing materials for heavy metal Cu at present2+、Cd2+And Cr2O7 2-Has better removal effect. However, MXene nanosheets are easy to agglomerate and stack, so that adsorption active sites are reduced, and the adsorption performance is reduced; in addition, due to the small particle size of the MXene nanosheets, the MXene nanosheets are difficult to settle in water, difficult to separate and recover, and likely cause secondary pollution to a water body. Therefore, development of highly efficient, easily separable and recyclableThe functional MXene heavy metal adsorbent has important research value.
The polymer electrolyte is a polymer with ionizable groups on molecular chains, and has good water solubility due to charge interaction.
Disclosure of Invention
The invention aims to provide a high-performance heavy metal adsorbent and a preparation method thereof. The invention utilizes halide and poly (4-vinylpyridine) to carry out quaternary amination reaction to design and synthesize polyelectrolyte cations such as poly (4-vinylpyridine) salt, combines the characteristics of MXene nanosheet that the MXene nanosheet has good hydrophilicity and a negatively charged surface, and prepares the heavy metal adsorbent which has high adsorption efficiency, high selectivity and is easy to separate and recycle by compounding the poly (4-vinylpyridine) salt and the MXene nanosheet.
An MXene/polymer composite material is composed of MXene nanosheets and poly (4-vinylpyridine) salt, and the MXene nanosheets are connected through the poly (4-vinylpyridine) salt to form a three-dimensional network structure.
The MXene/polymer composite material is prepared by carrying out electrostatic assembly on MXene nano-sheets by utilizing negative charges on the surfaces of the MXene nano-sheets and positive charges on poly (4-vinylpyridine) salts.
The MXene/polymer composite material is obtained by self-assembling MXene nanosheets and poly (4-vinylpyridine) salts. The MXene/polymer composite material is subjected to electrostatic assembly by utilizing negative charges on the surface of the MXene nanosheet and positive charges on the poly (4-vinylpyridine) salt. The MXene nano-sheets are assembled in a three-dimensional mode to form a framework structure of a three-dimensional network, the MXene nano-sheets are connected with poly (4-vinylpyridine) salt, and the MXene nano-sheets are assembled randomly.
Preferably, the poly (4-vinylpyridine) salt is prepared by the following process: mixing poly (4-vinylpyridine) and methanol in a mass ratio of 1: 5-1: 20, and stirring at room temperature until the poly (4-vinylpyridine) is completely dissolved; dropwise adding halide into a poly (4-vinylpyridine) solution according to the molar ratio of the halide to a 4-vinylpyridine monomer of 1: 1-3: 1; after the dropwise addition, stirring and reacting for 48-96 h at 0-60 ℃, soaking the obtained precipitate with anhydrous ether, and then drying in vacuum to obtain poly (4-vinylpyridine) salt,
wherein the halide is hydrochloric acid, bromoethane, 1-bromobutane, 1-bromohexane or 1-bromooctane.
Further, the poly (4-vinylpyridine) has a weight average molecular weight of MW＝60000g/mol。
Further, after the dropwise addition is finished, stirring and reacting at 0-60 ℃ for 48-96 h, pouring the reaction liquid into a large amount of anhydrous ether, soaking the precipitate with the anhydrous ether for three times, and drying the product in vacuum to obtain the poly (4-vinylpyridine) salt.
Preferably, the MXene nanosheets are prepared by the following method: adding LiF into 6-9M hydrochloric acid according to the proportion of 8g to 100ml, and stirring for dissolving; after complete dissolution, Ti is added3AlC2Powder, stirring and reacting for 24-72 h at 20-40 ℃, and Ti3AlC2The mass ratio of the powder to the LiF is 1: 1-1: 3; after the reaction is finished, obtaining Ti through centrifugation, washing, ultrasound, centrifugation and drying3C2Phase MXene nanoplatelets.
And further, after the reaction is finished, repeatedly performing operations of centrifuging and washing with deionized water for 6-10 times, dispersing the centrifuged product with deionized water, performing ultrasonic treatment for 1-4 hours, centrifuging and performing vacuum drying to obtain the MXene nanosheet.
Preferably, Ti is added3C2Dispersing the MXene nanosheets in deionized water to prepare 5-20 mg/ml of dispersion liquid; dropwise adding a poly (4-vinylpyridine) salt aqueous solution into the MXene nanosheet dispersion liquid under the atmosphere of nitrogen or argon, wherein the mass ratio of the MXene nanosheets to the poly (4-vinylpyridine) salt is 1: 1-1: 5; and after the dropwise addition, stirring at the room temperature of 600-1000 rpm for reaction for 3 hours, centrifuging, washing, and performing vacuum drying on a product to obtain the MXene/polymer composite material.
The invention also aims to provide a preparation method of the MXene/polymer composite material.
A preparation method of MXene/polymer composite material comprises the following process steps:
(1) LiF is added according to the proportion of 8g to 100mlProportionally adding the mixture into 6-9M hydrochloric acid, stirring and dissolving; after complete dissolution, Ti is added3AlC2Powder, stirring and reacting for 24-72 h at 20-40 ℃, and Ti3AlC2The mass ratio of the powder to the LiF is 1: 1-1: 3; after the reaction is finished, obtaining Ti through centrifugation, washing, ultrasound, centrifugation and drying3C2Phase MXene nanosheets;
(2) mixing poly (4-vinylpyridine) and methanol in a mass ratio of 1: 5-1: 20, and stirring at room temperature until the poly (4-vinylpyridine) is completely dissolved; dropwise adding halide into a poly (4-vinylpyridine) solution according to the molar ratio of the halide to a 4-vinylpyridine monomer of 1: 1-3: 1; after the dropwise addition is finished, stirring and reacting at 0-60 ℃ for 48-96 h, soaking the obtained precipitate with anhydrous ether, and then drying in vacuum to obtain poly (4-vinylpyridine) salt, wherein the halide is hydrochloric acid, bromoethane, 1-bromobutane, 1-bromohexane or 1-bromooctane;
(3) mixing Ti3C2Dispersing the MXene nanosheets in deionized water to prepare 5-20 mg/ml of dispersion liquid; dropwise adding a poly (4-vinylpyridine) salt aqueous solution into the MXene nanosheet dispersion liquid under the atmosphere of nitrogen or argon, wherein the mass ratio of the MXene nanosheets to the poly (4-vinylpyridine) salt is 1: 1-1: 5; and after the dropwise addition, stirring at the room temperature of 600-1000 rpm for reaction for 3 hours, centrifuging, washing, and performing vacuum drying on a product to obtain the MXene/polymer composite material.
Still another object of the present invention is to provide the use of the MXene/polymer composite as Cr (vi) adsorbent.
A method for adsorbing Cr (VI) includes such steps as dispersing MXene/polymer composite in the solution containing Cr ions, and stirring at 25 deg.C and pH 5.
Preferably, the method further comprises a filtration step after adsorption, and the MXene/polymer composite material after adsorption is filtered by a 0.22 mu m filter membrane to realize solid-liquid separation.
The invention has the beneficial effects that: the MXene/polymer composite material prepared by the invention utilizes the negative charges on the surface of the MXene nano-sheet and the positive charges on the positive charges of the polyelectrolyte cation on the basis of obtaining the MXene nano-sheet and the polyelectrolyte cationAnd (3) performing electrostatic self-assembly to obtain the MXene/polymer composite material with a stable three-dimensional network structure. On one hand, the stable three-dimensional network structure can effectively prevent agglomeration of the MXene nanosheets, expose more adsorption active sites and improve the adsorption performance of the MXene nanosheets; on the other hand, the introduction of polyelectrolyte cation enables the MXene/polymer composite adsorbent to have the advantages of easy separation and recovery, environmental friendliness and the like. Cr is carried out by utilizing the adsorbent provided by the invention2O7 2-The removal rate of the adsorption can reach 97 percent at most, and the adsorption method is simple to operate and environment-friendly. When the single MXene nanosheet is used as an adsorbing material to be dispersed in a water body, an MXene colloidal aqueous solution is formed for adsorption, and after the adsorption is finished, the MXene nanosheet is difficult to separate and recover through operations such as centrifugation or filtration; and after compounding the MXene nanosheets and the polymer, adsorbing the MXene nanosheets in a powder particle state in a water body, and after adsorption is finished, separating and recovering the MXene/polymer composite material through simple operations such as precipitation, filtration and the like.
Drawings
Fig. 1 is an SEM image of MXene nanoplates prepared in example 3 of the present invention.
FIG. 2 is a FT-IR chart of the synthesis of poly (4-vinylpyridine) salts and poly (4-vinylpyridine) used in example 3 of the present invention.
Fig. 3 is an SEM image of MXene nanosheet/poly (4-vinylpyridine) salt composite adsorbent prepared in example 3 of the present invention.
FIG. 4 shows the adsorbent prepared in examples 1 to 6 of the present invention and comparative example 1 against Cr (VI) (in K) having a concentration of 100ppm2Cr2O7As a Cr (vi) source) aqueous solution. As can be seen from fig. 4, the adsorbent prepared in example 3 has a Cr (vi) removal rate as high as 97%.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the following examples, the weight average molecular weight of the poly (4-vinylpyridine) is MW＝60000g/mol。
Example 1
(1) Adding 8g LiF into 100ml of 9M hydrochloric acid, and stirring for dissolving; after complete dissolution, 4g of Ti were added3AlC2Stirring the powder at 20 ℃ to react for 72 hours; after the reaction is finished, repeatedly performing centrifugation and washing for 10 times by using deionized water, dispersing the centrifuged product by using the deionized water, performing ultrasonic treatment for 1h, centrifuging and performing vacuum drying to obtain Ti3C2Phase MXene nanoplatelets.
(2) 5g of poly (4-vinylpyridine) is mixed with 50g of methanol and stirred at room temperature until the poly (4-vinylpyridine) is completely dissolved; after the solution is stirred uniformly, 3.96ml of 12M hydrochloric acid is added into the solution drop by drop after the solution is stirred uniformly; after the dropwise addition, stirring at 0 ℃ for reaction for 96 hours, pouring the reaction liquid into a large amount of anhydrous ether, soaking the precipitate with the anhydrous ether for three times, and drying the product in vacuum to obtain the poly (4-vinylpyridine) salt.
(3) Taking Ti3C20.3g of phase MXene nano-sheet is dispersed in deionized water to prepare dispersion liquid with the concentration of 10 mg/ml; dropwise adding 30ml of 2 wt% poly (4-vinylpyridine) salt aqueous solution into the MXene nanosheet dispersion under a nitrogen atmosphere; after the dropwise addition, stirring at the room temperature of 800rpm for reaction for 3 hours, centrifuging, washing, and drying the product in vacuum to obtain the MXene nanosheet/poly (4-vinylpyridine) salt composite adsorbent.
(4) Taking 16mg MXene nanosheet/poly (4-vinylpyridine) salt composite material adsorbent, and taking 100ppm Cr (VI) (by K)2Cr2O720ml of aqueous solution of Cr (VI) as a source) was stirred at 25 ℃ for 24 hours at 600rpm at pH 5, and then filtered through a 0.22 μm filter to rapidly separate the solid from the liquid, and the concentration of Cr (VI) in the filtrate after adsorption was measured with an atomic absorption spectrophotometer to obtain a Cr (VI) removal rate of 83% at a concentration of 28 ppm.
Example 2
(1) Adding 8g LiF into 100ml of 6M hydrochloric acid, and stirring for dissolving; after complete dissolution, 6g of the mixture was addedTi3AlC2Stirring the powder at 30 ℃ to react for 72 hours; after the reaction is finished, repeatedly performing centrifugation and washing (with deionized water) for 8 times, dispersing the centrifuged product with the deionized water, performing ultrasonic treatment for 3 hours, centrifuging and performing vacuum drying to obtain Ti3C2Phase MXene nanoplatelets.
(2) 5g of poly (4-vinylpyridine) is mixed with 25g of methanol and stirred at room temperature until the poly (4-vinylpyridine) is completely dissolved; after the solution is stirred uniformly, 3.96ml of 12M hydrochloric acid is added into the solution drop by drop after the solution is stirred uniformly; after the dropwise addition, stirring at 0 ℃ for reaction for 48 hours, pouring the reaction liquid into a large amount of anhydrous ether, soaking the precipitate with the anhydrous ether for three times, and drying the product in vacuum to obtain the poly (4-vinylpyridine) salt.
(3) Taking Ti3C20.2g of phase MXene nano-sheet is dispersed in deionized water to prepare dispersion liquid with the concentration of 5 mg/ml; dropwise adding 10ml of 2 wt% poly (4-vinylpyridine) salt aqueous solution into the MXene nanosheet dispersion under a nitrogen atmosphere; after the dropwise addition, stirring at the room temperature of 800rpm for reaction for 3 hours, centrifuging, washing, and drying the product in vacuum to obtain the MXene nanosheet/poly (4-vinylpyridine) salt composite adsorbent.
(4) Taking 16mg MXene nanosheet/poly (4-vinylpyridine) salt composite material adsorbent, and taking 100ppm Cr (VI) (by K)2Cr2O720ml of aqueous solution of Cr (VI) as a source) was stirred at 25 ℃ for 24 hours at 600rpm at pH 5, and then filtered through a 0.22 μm filter to rapidly separate the solid from the liquid, and the concentration of Cr (VI) in the filtrate after adsorption was measured with an atomic absorption spectrophotometer to obtain a Cr (VI) removal rate of 90% at a concentration of 37 ppm.
Example 3
(1) Adding 8g LiF into 100ml of 9M hydrochloric acid, and stirring for dissolving; after complete dissolution, 5g of Ti were added3AlC2Stirring the powder at 35 ℃ to react for 48 hours; after the reaction is finished, repeatedly performing centrifugation and washing (with deionized water) for 9 times, dispersing the centrifuged product with the deionized water, performing ultrasonic treatment for 2 hours, centrifuging and performing vacuum drying to obtain Ti3C2Phase MXene nanoplatelets.
(2) 5g of poly (4-vinylpyridine) is mixed with 50g of methanol and stirred at room temperature until the poly (4-vinylpyridine) is completely dissolved; after the solution is stirred uniformly, 3.96ml of 12M hydrochloric acid is added into the solution drop by drop after the solution is stirred uniformly; after the dropwise addition, stirring at 15 ℃ for reaction for 72 hours, pouring the reaction liquid into a large amount of anhydrous ether, soaking the precipitate with the anhydrous ether for three times, and drying the product in vacuum to obtain the poly (4-vinylpyridine) salt.
(3) Taking Ti3C20.1g of phase MXene nano-sheet is dispersed in deionized water to prepare dispersion liquid with the concentration of 10 mg/ml; dropwise adding 10ml of 2 wt% poly (4-vinylpyridine) salt aqueous solution into the MXene nanosheet dispersion under a nitrogen atmosphere; after the dropwise addition, stirring at room temperature and 1000rpm for reaction for 3h, centrifuging, washing, and vacuum-drying the product to obtain the MXene nanosheet/poly (4-vinylpyridine) salt composite adsorbent.
(4) Taking 16mg MXene nanosheet/poly (4-vinylpyridine) salt composite material adsorbent, and taking 100ppm Cr (VI) (by K)2Cr2O720ml of aqueous solution of Cr (VI) as a source) was stirred at 25 ℃ for 24 hours at 600rpm at pH 5, and then filtered through a 0.22 μm filter to rapidly separate the solid from the liquid, and the concentration of Cr (VI) in the filtrate after adsorption was measured with an atomic absorption spectrophotometer to obtain a Cr (VI) removal rate of 97% at a concentration of 3 ppm.
Example 4
(1) Adding 8g LiF into 100ml of 6M hydrochloric acid, and stirring for dissolving; after complete dissolution, 2.7g of Ti were added3AlC2Stirring the powder at 40 ℃ to react for 24 hours; after the reaction is finished, repeatedly performing centrifugation and washing (with deionized water) for 6 times, dispersing the centrifuged product with the deionized water, performing ultrasonic treatment for 4 hours, centrifuging and performing vacuum drying to obtain Ti3C2Phase MXene nanoplatelets.
(2) 5g of poly (4-vinylpyridine) is mixed with 100g of methanol and stirred at room temperature until the poly (4-vinylpyridine) is completely dissolved; after the solution was stirred uniformly, 20.03ml of 1-bromohexane was added dropwise to the solution; after the dropwise addition, stirring at 60 ℃ for reaction for 72h, pouring the reaction liquid into a large amount of anhydrous ether, soaking the precipitate with anhydrous ether for three times, and drying the product in vacuum to obtain the poly (4-vinylpyridine) salt.
(3) Taking Ti3C20.2g of phase MXene nano-sheet is dispersed in deionized water to prepare a dispersion liquid with the concentration of 20 mg/ml; dropwise adding 40ml of 2 wt% poly (4-vinylpyridine) salt aqueous solution into the MXene nanosheet dispersion under a nitrogen atmosphere; after the dropwise addition, stirring at 600rpm at room temperature for reaction for 3h, centrifuging, washing, and vacuum-drying the product to obtain the MXene nanosheet/poly (4-vinylpyridine) salt composite adsorbent.
(4) Taking 16mg MXene nanosheet/poly (4-vinylpyridine) salt composite material adsorbent, and taking 100ppm Cr (VI) (by K)2Cr2O720ml of aqueous solution of Cr (VI) as a source) was stirred at 25 ℃ for 24 hours at 600rpm at pH 5, and then filtered through a 0.22 μm filter to rapidly separate the solid from the liquid, and the concentration of Cr (VI) in the filtrate after adsorption was measured with an atomic absorption spectrophotometer to obtain a Cr (VI) removal rate of 84% at a concentration of 16 ppm.
Example 5
(1) Adding 8g LiF into 100ml of 9M hydrochloric acid, and stirring for dissolving; after complete dissolution, 5g of Ti were added3AlC2Stirring the powder at 35 ℃ to react for 48 hours; after the reaction is finished, repeatedly performing centrifugation and washing for 10 times by using deionized water, dispersing the centrifuged product by using the deionized water, performing ultrasonic treatment for 4 hours, centrifuging and performing vacuum drying to obtain Ti3C2Phase MXene nanoplatelets.
(2) 5g of poly (4-vinylpyridine) is mixed with 50g of methanol and stirred at room temperature until the poly (4-vinylpyridine) is completely dissolved; after the solution is stirred uniformly, 3.96ml of 12M hydrochloric acid is added into the solution drop by drop after the solution is stirred uniformly; after the dropwise addition, stirring at 15 ℃ for reaction for 96 hours, pouring the reaction liquid into a large amount of anhydrous ether, soaking the precipitate with the anhydrous ether for three times, and drying the product in vacuum to obtain the poly (4-vinylpyridine) salt.
(3) Taking Ti3C20.2g of phase MXene nano-sheet is dispersed in deionized water to prepare dispersion liquid with the concentration of 10 mg/ml; dropwise adding 2 wt% poly (4-vinylpyridine) salt aqueous solution into MXene nanosheet dispersion under nitrogen atmosphere10 ml; after the dropwise addition, stirring at room temperature and 1000rpm for reaction for 3h, centrifuging, washing, and vacuum-drying the product to obtain the MXene nanosheet/poly (4-vinylpyridine) salt composite adsorbent.
(4) Taking 16mg MXene nanosheet/poly (4-vinylpyridine) salt composite material adsorbent, and taking 100ppm Cr (VI) (by K)2Cr2O720ml of aqueous solution of Cr (VI) as a source) was stirred at 25 ℃ for 24 hours at 600rpm at pH 5, and then filtered through a 0.22 μm filter to rapidly separate the solid from the liquid, and the concentration of Cr (VI) in the filtrate after adsorption was measured with an atomic absorption spectrophotometer to give a Cr (VI) removal rate of 93% at a concentration of 7 ppm.
Example 6
(1) Adding 8g LiF into 100ml of 6M hydrochloric acid, and stirring for dissolving; after complete dissolution, 3g of Ti were added3AlC2Stirring the powder at 30 ℃ to react for 72 hours; after the reaction is finished, repeatedly performing centrifugation and washing (with deionized water) for 9 times, dispersing the centrifuged product with the deionized water, performing ultrasonic treatment for 2 hours, centrifuging and performing vacuum drying to obtain Ti3C2Phase MXene nanoplatelets.
(2) 5g of poly (4-vinylpyridine) is mixed with 50g of methanol and stirred at room temperature until the poly (4-vinylpyridine) is completely dissolved; after the solution is stirred uniformly, 7.92ml of 12M hydrochloric acid is added into the solution drop by drop after the solution is stirred uniformly; after the dropwise addition, stirring at 15 ℃ for reaction for 72 hours, pouring the reaction liquid into a large amount of anhydrous ether, soaking the precipitate with the anhydrous ether for three times, and drying the product in vacuum to obtain the poly (4-vinylpyridine) salt.
(3) Taking Ti3C20.1g of phase MXene nano-sheet is dispersed in deionized water to prepare dispersion liquid with the concentration of 10 mg/ml; under nitrogen atmosphere, dropwise adding 15ml of 2 wt% poly (4-vinylpyridine) salt aqueous solution into MXene nanosheet dispersion; after the dropwise addition, stirring at room temperature and 1000rpm for reaction for 3h, centrifuging, washing, and vacuum-drying the product to obtain the MXene nanosheet/poly (4-vinylpyridine) salt composite adsorbent.
(4) Taking 16mg MXene nanosheet/poly (4-vinylpyridine) salt composite material adsorbent, and taking 100ppm Cr (VI) (by K)2Cr2O720ml of aqueous solution of Cr (VI) as a source) was stirred at 25 ℃ for 24 hours at 600rpm at pH 5, and then filtered through a 0.22 μm filter to rapidly separate the solid from the liquid, and the concentration of Cr (VI) in the filtrate after adsorption was measured with an atomic absorption spectrophotometer to obtain a Cr (VI) removal rate of 88% at a concentration of 12 ppm.
Comparative example 1
(1) Adding 8g LiF into 100ml of 9M hydrochloric acid, and stirring for dissolving; after complete dissolution, 5g of Ti were added3AlC2Stirring the powder at 35 ℃ to react for 48 hours; after the reaction is finished, repeatedly performing centrifugation and washing for 10 times by using deionized water, dispersing the centrifuged product by using the deionized water, performing ultrasonic treatment for 4 hours, centrifuging and performing vacuum drying to obtain Ti3C2Phase MXene nanoplatelets.
(2) Taking 16mg MXene nano-sheet, the concentration is 100ppm Cr (VI) (by K)2Cr2O720ml of an aqueous solution of Cr (VI) as a source) was stirred at 25 ℃ for 24 hours at 600rpm at pH 5, and then the filtrate was filtered through a 0.22 μm filter to easily clog the filter, thereby making the filtration difficult and slow (difficult to separate solid from liquid), and the concentration of Cr (VI) in the filtrate after adsorption was measured with an atomic absorption spectrophotometer to obtain a Cr (VI) removal rate of 80% at a concentration of 20 ppm.
Claims (10)
1. An MXene/polymer composite characterized by: the MXene/polymer composite material is composed of MXene nanosheets and poly (4-vinylpyridine) salts, and the MXene nanosheets are connected through the poly (4-vinylpyridine) salts to form a three-dimensional network structure.
2. The material of claim 1, wherein: the MXene/polymer composite material is obtained by performing electrostatic assembly on MXene nanosheets by utilizing negative charges on the surfaces of the MXene nanosheets and positive charges on the poly (4-vinylpyridine) salts.
3. The material of claim 1, wherein: the poly (4-vinylpyridine) salt is prepared by the following method: mixing poly (4-vinylpyridine) and methanol in a mass ratio of 1: 5-1: 20, and stirring at room temperature until the poly (4-vinylpyridine) is completely dissolved; dropwise adding halide into a poly (4-vinylpyridine) solution according to the molar ratio of the halide to a 4-vinylpyridine monomer of 1: 1-3: 1; after the dropwise addition, stirring and reacting for 48-96 h at 0-60 ℃, soaking the obtained precipitate with anhydrous ether, and then drying in vacuum to obtain poly (4-vinylpyridine) salt,
wherein the halide is hydrochloric acid, bromoethane, 1-bromobutane, 1-bromohexane or 1-bromooctane.
4. The material of claim 1, wherein: the poly (4-vinylpyridine) has a weight average molecular weight of MW＝60000g/mol。
5. The material of claim 1, wherein: the MXene nanosheet is prepared by the following method: adding LiF into 6-9M hydrochloric acid according to the proportion of 8g to 100ml, and stirring for dissolving; after complete dissolution, Ti is added3AlC2Powder, stirring and reacting for 24-72 h at 20-40 ℃, and Ti3AlC2The mass ratio of the powder to the LiF is 1: 1-1: 3; after the reaction is finished, obtaining Ti through centrifugation, washing, ultrasound, centrifugation and drying3C2Phase MXene nanoplatelets.
6. The material of claim 5, wherein: mixing Ti3C2Dispersing the MXene nanosheets in deionized water to prepare 5-20 mg/ml of dispersion liquid; dropwise adding a poly (4-vinylpyridine) salt aqueous solution into the MXene nanosheet dispersion liquid under the atmosphere of nitrogen or argon, wherein the mass ratio of the MXene nanosheets to the poly (4-vinylpyridine) salt is 1: 1-1: 5; and after the dropwise addition, stirring at the room temperature of 600-1000 rpm for reaction for 3 hours, centrifuging, washing, and performing vacuum drying on a product to obtain the MXene/polymer composite material.
7. The method for preparing MXene/polymer composite material of claim 1, wherein: the method comprises the following process steps:
(1) adding LiF according to the proportion of 8g to 100mlAdding the mixture into 6-9M hydrochloric acid, and stirring and dissolving; after complete dissolution, Ti is added3AlC2Powder, stirring and reacting for 24-72 h at 20-40 ℃, and Ti3AlC2The mass ratio of the powder to the LiF is 1: 1-1: 3; after the reaction is finished, obtaining Ti through centrifugation, washing, ultrasound, centrifugation and drying3C2Phase MXene nanosheets;
(2) mixing poly (4-vinylpyridine) and methanol in a mass ratio of 1: 5-1: 20, and stirring at room temperature until the poly (4-vinylpyridine) is completely dissolved; dropwise adding halide into a poly (4-vinylpyridine) solution according to the molar ratio of the halide to a 4-vinylpyridine monomer of 1: 1-3: 1; after the dropwise addition is finished, stirring and reacting at 0-60 ℃ for 48-96 h, soaking the precipitate obtained from the oyou in anhydrous ether, and then drying in vacuum to obtain poly (4-vinylpyridine) salt, wherein the halide is hydrochloric acid, bromoethane, 1-bromobutane, 1-bromohexane or 1-bromooctane;
(3) mixing Ti3C2Dispersing the MXene nanosheets in deionized water to prepare 5-20 mg/ml of dispersion liquid; dropwise adding a poly (4-vinylpyridine) salt aqueous solution into the MXene nanosheet dispersion liquid under the atmosphere of nitrogen or argon, wherein the mass ratio of the MXene nanosheets to the poly (4-vinylpyridine) salt is 1: 1-1: 5; and after the dropwise addition, stirring at the room temperature of 600-1000 rpm for reaction for 3 hours, centrifuging, washing, and performing vacuum drying on a product to obtain the MXene/polymer composite material.
8. Use of a material according to any one of claims 1 to 6 as a Cr (vi) adsorbent.
9. A Cr (VI) adsorption method is characterized in that: dispersing the MXene/polymer composite material of any one of 1 to 6 in a solution containing Cr ions, and stirring at 25 ℃ at a pH of 5.
10. The material of claim 9, wherein: the method also comprises a filtering step after adsorption, and the MXene/polymer composite material after adsorption is filtered by a 0.22 mu m filter membrane to realize solid-liquid separation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112599851A (en) * | 2020-12-14 | 2021-04-02 | 中科(马鞍山)新材料科创园有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN113340947A (en) * | 2021-05-21 | 2021-09-03 | 东莞理工学院 | Preparation method of polyaniline hollow sphere/MXene composite ammonia gas-sensitive material |
| CN113398327A (en) * | 2021-06-18 | 2021-09-17 | 福州大学 | Preparation method of MXene/bioglass microsphere composite material with high biological activity |
| CN113984849A (en) * | 2021-10-29 | 2022-01-28 | 东莞理工学院 | Water-soluble polyaniline/MXene composite flexible ammonia gas sensor and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102672195A (en) * | 2012-01-04 | 2012-09-19 | 河南科技大学 | Preparation method of gold nanoparticles |
| CN104183830A (en) * | 2014-08-19 | 2014-12-03 | 中南大学 | Preparation method of two-dimensional inorganic layered compound/graphene composite material |
| CN107583627A (en) * | 2017-08-31 | 2018-01-16 | 同济大学 | A kind of Au nano particles/graphene oxide composite material and its preparation method and application |
| CN108379876A (en) * | 2018-05-08 | 2018-08-10 | 东莞理工学院 | A method of adsorbing lithium salts using adsorbent |
| CN109796016A (en) * | 2019-02-26 | 2019-05-24 | 北京化工大学 | A method of regulation MXene nanoscale twins spacing |
| CN110514712A (en) * | 2019-09-24 | 2019-11-29 | 辽宁大学 | A kind of polymeric ionic liquid modification MXene nanocomposite and its preparation method and application |
| WO2020096366A1 (en) * | 2018-11-07 | 2020-05-14 | 성균관대학교산학협력단 | Mxene-conductive polymer composite material and supercapacitor comprising same |
-
2020
- 2020-05-18 CN CN202010419074.4A patent/CN111518353B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102672195A (en) * | 2012-01-04 | 2012-09-19 | 河南科技大学 | Preparation method of gold nanoparticles |
| CN104183830A (en) * | 2014-08-19 | 2014-12-03 | 中南大学 | Preparation method of two-dimensional inorganic layered compound/graphene composite material |
| CN107583627A (en) * | 2017-08-31 | 2018-01-16 | 同济大学 | A kind of Au nano particles/graphene oxide composite material and its preparation method and application |
| CN108379876A (en) * | 2018-05-08 | 2018-08-10 | 东莞理工学院 | A method of adsorbing lithium salts using adsorbent |
| WO2020096366A1 (en) * | 2018-11-07 | 2020-05-14 | 성균관대학교산학협력단 | Mxene-conductive polymer composite material and supercapacitor comprising same |
| CN109796016A (en) * | 2019-02-26 | 2019-05-24 | 北京化工大学 | A method of regulation MXene nanoscale twins spacing |
| CN110514712A (en) * | 2019-09-24 | 2019-11-29 | 辽宁大学 | A kind of polymeric ionic liquid modification MXene nanocomposite and its preparation method and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112599851A (en) * | 2020-12-14 | 2021-04-02 | 中科(马鞍山)新材料科创园有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN113340947A (en) * | 2021-05-21 | 2021-09-03 | 东莞理工学院 | Preparation method of polyaniline hollow sphere/MXene composite ammonia gas-sensitive material |
| CN113340947B (en) * | 2021-05-21 | 2022-08-26 | 东莞理工学院 | Preparation method of polyaniline hollow sphere/MXene composite ammonia gas-sensitive material |
| CN113398327A (en) * | 2021-06-18 | 2021-09-17 | 福州大学 | Preparation method of MXene/bioglass microsphere composite material with high biological activity |
| CN113398327B (en) * | 2021-06-18 | 2022-05-10 | 福州大学 | Preparation method of MXene/bioglass microsphere composite material with high biological activity |
| CN113984849A (en) * | 2021-10-29 | 2022-01-28 | 东莞理工学院 | Water-soluble polyaniline/MXene composite flexible ammonia gas sensor and preparation method thereof |
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