CN115845815A - Preparation method of Fe @ C/MXene-APTS magnetic composite material - Google Patents
Preparation method of Fe @ C/MXene-APTS magnetic composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a Fe @ C/MXene-APTS magnetic composite material, which comprises the steps of dispersing MXene suspension with a few-layer structure in an alkaline solution to obtain wrinkled MXene; dissolving polyvinyl pyrrolidone in diluted hydrochloric acid, and adding K 4 Fe(CN) 6 ·3H 2 O, pouring the solution into an ethanol solution dispersed with wrinkled MXene, dripping APTS into the mixed solution in an argon atmosphere, aging, centrifugally washing the precipitate for a plurality of times by using the ethanol solution, freeze-drying the product, and putting the product in a tubular furnace in an Ar-H (argon-hydrogen) furnace 2 Heat treatment in mixed atmosphere to obtain the Fe @ C/MXene-APTS composite material. The composite material prepared by the invention consists of ammonia functionalized folded MXene and hollow Fe @ C cubic nanoparticles,the former can adsorb rare earth elements efficiently, and the latter can recover the adsorbent by magnetic force and prolong the service life of the magnetic part under acidic condition.
Description
Technical Field
The invention belongs to the technical field of material synthesis and heavy metal pollution treatment, and particularly relates to a preparation method of a Fe @ C/MXene-APTS magnetic composite material.
Background
Due to the wide application of rare earth, some rare earth elements are inevitably released into wastewater and surface water, resulting in heavy metal water pollution. However, only 1% of the rare earth elements are recovered from these secondary sources, and recovery of rare earth elements from waste water is highly desirable due to surge in rare earth prices and short supply. Although various techniques such as electrochemistry, solvent extraction, precipitation, ion exchange and membrane filtration have been applied to the recovery and enrichment of rare earth elements from aqueous solutions, they are generally disposable high-consumption processes, and particularly, the recovery efficiency is low in the case of low-concentration rare earth solutions. In addition, some of these processes are accompanied by secondary pollution products, such as toxic solvents and hazardous sludges. Different from the method, the adsorption method has high recovery efficiency, recyclable absorbent, low commercial cost and convenient operation, and is the most cost-effective and eco-friendly method for recovering the rare earth element from the aqueous solution.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provide a preparation method of a Fe @ C/MXene-APTS magnetic composite material for recovering water-phase rare earth elements.
In order to achieve the aim, the invention provides a preparation method of a Fe @ C/MXene-APTS magnetic composite material for recovering water-phase rare earth elements, which comprises the following steps:
(1) Dispersing the MXene suspension with the less-layer structure in an alkaline solution for alkalization to obtain wrinkled MXene with high specific surface area, washing the wrinkled MXene, and ultrasonically dispersing in an ethanol solution for later use;
(2) Dissolving polyvinyl pyrrolidone in dilute hydrochloric acid, and adding K into the solution 4 Fe(CN) 6 ·3H 2 O, pouring the solution into an ethanol solution dispersed with wrinkled MXene, dripping a 3-Aminopropyltriethoxysilane (APTS) solution into the mixed solution under the argon atmosphere, magnetically stirring and aging, and centrifugally washing the precursor Fe-MOF/MXene-APTS for a plurality of times by using the ethanol solution;
(3) Freeze-drying the product obtained in the step (2), and placing the product in a tube furnace in Ar-H 2 And carrying out heat treatment in a mixed atmosphere to finally obtain the Fe @ C/MXene-APTS magnetic composite material.
Preferably, the MXene material used in step (1) comprises Ti 3 C 2 、Ti 2 C、Nb 2 C、V 2 C、Mo 2 One or more of C。
Preferably, the alkaline solution in step (1) comprises NaOH, KOH, ca (OH) 2 Ammonia water and Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 And one or more of ethylenediamine with the concentration of 0.1-10 wt%.
Preferably, in the step (1), the alkalization temperature is 10-70 ℃, the alkalization time is 1-10 h, and the volume ratio of the MXene suspension to the alkaline solution is 1.
Preferably, the thickness of the wrinkled MXene after alkalization in the step (1) is 10-200 nm, the number of layers is 1-20, and the specific surface area is 50-1000 m 2 The diameter of the holes is 5-50 nm.
Preferably, the dosage of the polyvinyl pyrrolidone in the step (2) is 1-200 g, the concentration of the dilute hydrochloric acid is 0.01-2 mol/L, the volume of the dilute hydrochloric acid solution is 50-2000mL, and the K is 4 Fe(CN) 6 ·3H 2 The addition amount of O is 0.1-100 g.
Preferably, the amount of the folded MXene added in the step (2) is 0.02 to 10g, and the amount of the 3-aminopropyltriethoxysilane added is 0.01 to 8g.
Preferably, the aging time in the step (2) is 2-40 h, and the aging temperature is 40-90 ℃.
Preferably, the heat treatment conditions in step (3) are: the heat treatment temperature is 300-800 ℃, the heating rate is 1-10 ℃/min, and the calcination time is 1-10 h.
Preferably, after the Fe @ C/MXene-APTS magnetic field composite material adsorbs the rare earth in the step (3), the magnetic recovery separation and the elution of the rare earth by 0.1mol/L nitric acid are carried out, and then the magnetic recovery separation and the elution are used for adsorbing the rare earth again.
The invention concept of the invention is as follows:
the two-dimensional few-layer MXene material has a strong adsorption effect on rare earth ions, and a typical MXene material has Ti 3 C 2 、Ti 2 C、Nb 2 C、V 2 C、Mo 2 C and the like. The MXene material is obtained by etching and stripping MAX phase material by HF (or mixed solution of LiF and concentrated HCl) and the like, the etched MXene material has surface functional groups of-OH, -O, -F and the like, and the upper layer liquid after etching can be harvested littleThe MXene material of the layer, the bottom layer is the MXene material of the multilayer. The MXene-based adsorbent is alkalized and grafted with amino functional groups to improve the rare earth ion adsorption capacity of the MXene-based adsorbent, and can be used for recovering aqueous phase low-concentration rare earth elements.
In addition, the MXene-based adsorbent is recovered by traditional centrifugation or filtration, the operation is complicated, the material loss is large, and the adsorbent can be efficiently and simply separated by adding a magnetic material. Conventional magnetic materials such as elemental Fe or Fe 3 O 4 It is easily dissolved in an acidic solution, resulting in the failure of the adsorbent. Aiming at the defect that the MXene-based adsorbent is difficult to separate, the invention introduces the iron-based metal organic framework material which grows in situ and is based on Ar-H 2 The Kendall effect under the reducing atmosphere constructs hollow magnetic particles, and the carbon shell is utilized to protect Fe elements in the magnetic particles from being easily dissolved in an acid solution. Therefore, the super-strong adsorption effect of the Fe @ C/MXene-APTS composite material on various rare earth ions is realized, the adsorbent can be recycled for multiple times, and the cost is saved.
Compared with the prior art, the technical scheme adopted by the invention has the following advantages:
1. the invention uses alkalization to match amino functional group for grafting, and can be used for various heavy rare earth ions such as Ho 3+ 、Er 3+ 、Eu 3+ 、Lu 3 + 、Tm 3+ 、Y 3+ 、Yb 3+ The adsorption effect is more than 95 percent.
2. Through one-step reaction, an iron-based metal organic framework material grows on the alkalized MXene, and meanwhile, amino functional groups grow on the surface of the MXene.
3. The Fe @ C/MXene-APTS adsorbent prepared by the invention can be subjected to repeated cyclic adsorption through magnetic separation, and the adsorption rate of rare earth ions is still kept above 85% after 15 cycles.
Drawings
FIG. 1 is a TEM image of Fe @ C particulate material of example 1.
FIG. 2 is Fe @ C/Ti in example 1 3 C 2 SEM images of APTS composites.
FIG. 3 is Fe @ C/Ti in example 1 3 C 2 -magnetic separation diagram after adsorption of rare earths by APTS, (a) non-ferromagnetic adsorption material; (b) the magnetic material; and (c) the magnet migrates the magnetic material.
Detailed Description
The invention is further described below by means of specific embodiments for a better understanding of the invention, without the examples being set forth to limit the scope of the invention.
The invention provides a preparation method of a Fe @ C/MXene-APTS magnetic composite material, which comprises the following steps:
(1) Dispersing the MXene suspension with the less-layer structure in an alkaline solution for alkalization to obtain wrinkled MXene with high specific surface area, washing the wrinkled MXene, and ultrasonically dispersing the wrinkled MXene in an ethanol solution for later use. The thickness of the alkalized wrinkled MXene in the step (1) is 10-200 nm, the number of layers is 1-20, and the specific surface area is 50-1000 m 2 The diameter of the holes is 5-50 nm.
(2) Dissolving polyvinyl pyrrolidone in dilute hydrochloric acid, and adding K into the solution 4 Fe(CN) 6 ·3H 2 And O, pouring the solution into an ethanol solution in which wrinkled MXene is dispersed, dropwise adding a 3-aminopropyltriethoxysilane solution into the mixed solution under an argon atmosphere, magnetically stirring and aging, and centrifugally washing the precursor Fe-MOF/MXene-APTS for several times by using the ethanol solution. In the precursor Fe-MOF/MXene-APTS in the step (2), the particle size of the Fe metal organic framework material Fe-MOF is 50-500 nm, the Fe metal organic framework material Fe-MOF is in the shape of coarse solid cubes, and edges and corners are formed at the top points of the cubes, so that the particles are favorably attached to MXene and are not easy to separate.
(3) Freeze-drying the product obtained in the step (2), and placing the product in a tube furnace in Ar-H 2 And carrying out heat treatment in a mixed atmosphere to finally obtain the Fe @ C/MXene-APTS magnetic composite material. In the step (3), the particle size of the Fe @ C/MXene-APTS composite material is 0.1-500 μm, the Fe content is 1-10 wt.%, the carbon content is 3-40 wt.%, the thickness of the MXene layer is 10-200 nm, and the specific surface area is 50-900 m 2 The diameter of the holes is 5-50 nm. In the Fe @ C/MXene-APTS composite material, the particle diameter of Fe @ C particles is 50-500 nm, the particles are rough hollow cubes, fe is distributed in the hollow carbon shell, edges and corners are arranged at the tops of the cubes, and the particles haveAnd (4) magnetism.
Example 1
A preparation method of Fe @ C/MXene-APTS magnetic composite material for recovering water phase rare earth elements comprises the following specific steps:
(1) 2ml of a small layer of Ti 3 C 2 The suspension was added to 5ml of 4wt% K 2 CO 3 Stirring at 25 deg.C for 5 hr for alkalizing, and collecting the obtained corrugated Ti 3 C 2 Washing with deionized water for 5 times to obtain corrugated Ti 3 C 2 The thickness is 50nm, the number of layers is 3, and the specific surface area is 380m 2 The diameter of holes is distributed between 5 and 30nm, and the holes are dispersed in an ethanol solution by ultrasonic waves for standby;
(2) 100g of polyvinyl pyrrolidone is dissolved in 500ml of 1mol/L dilute hydrochloric acid, and 20g K is added into the solution 4 Fe(CN) 6 ·3H 2 O, pouring the solution until 0.1g of folded Ti is dispersed 3 C 2 In the ethanol solution, 5g of APTS solution is dripped into the mixed solution under the argon atmosphere, the mixture is magnetically stirred and aged for 10h at the temperature of 80 ℃, and the precipitated precursor Fe-MOF/Ti is added into the ethanol solution 3 C 2 -APTS is centrifugally washed for several times, and the particle size of Fe-MOF contained in the precursor is 100-200 nm;
(3) Precursor Fe-MOF/Ti 3 C 2 -APTS freeze-dried, placed in a tube furnace under Ar-H 2 In mixed atmosphere (Ar: H) 2 The volume ratio is 9:1) is heated to 400 ℃ at the heating rate of 2 ℃/min, the calcination time is 5h, and finally Fe @ C/Ti is obtained 3 C 2 APTS composite material, see FIG. 2, with particle size ranging from 1 to 10 μm, fe content of 4wt.%, carbon content of 30wt.%, ti 3 C 2 The layer thickness is 100nm, the specific surface area is 300m 2 The pore diameter is distributed between 5 and 30nm. The particle diameter of Fe @ C particles in the composite material is 100-200 nm, and the particles have magnetism, please refer to FIG. 1.
And (3) testing the adsorption performance: using Y (NO) 3 ) 3 Is formulated to contain Y 3+ Ionic solution by addition of 1g/L of Y at room temperature 3+ 10mL of the solution was added 10mgFe @ C/Ti 3 C 2 APTS adsorbent for Y 3+ Absorption Capacity determination and Rapid filtration Using 0.22 μm Filter and determination of Y in aqueous phase Using inductively coupled plasma emission Spectroscopy (ICP) 3+ The ion residual concentration is calculated, so that the adsorption capacity of the element Y adsorbed by Fe @ C/MXene-APTS reaches 100.3mg/g.
Applying 0.1mol/L nitric acid solution to the loaded Y 3+ Desorbing the adsorbent material, placing the adsorbed material in nitric acid solution with the same volume, reacting at normal temperature (298K) for 60min in a shaking table with the rotating speed of 180rpm, separating the solid phase from the liquid phase by using a 0.22 mu m water phase needle filter after desorption, continuously adsorbing the Y element by using the adsorbent after separation, and adsorbing and desorbing the Y element for 15 times 3+ The adsorption retention of ions is still 90%.
Example 2
A preparation method of Fe @ C/MXene-APTS magnetic composite material for recovering water phase rare earth elements comprises the following specific steps:
(1) 3ml of the mixture is reduced into a layer V 2 Adding the suspension C into 5ml of ethylenediamine solution with the concentration of 8wt%, stirring for 3h at 60 ℃ for alkalization, and after the alkalization process is finished, carrying out the obtained wrinkled V 2 C washing with deionized water for 5 times, and pleating V 2 C has a thickness of 100nm, 13 layers and a specific surface area of 270m 2 The diameter of holes is 5-50 nm, and the holes are ultrasonically dispersed in an ethanol solution for later use;
(2) 130g of polyvinyl pyrrolidone is dissolved in 800ml of dilute hydrochloric acid with the concentration of 2mol/L, and 60g K is added into the solution 4 Fe(CN) 6 ·3H 2 O, pour this solution until 1g of wrinkles V are dispersed 2 C, dripping 6g of APTS solution into the mixed solution in the argon atmosphere, magnetically stirring, aging at 60 ℃ for 20h, and precipitating a precursor Fe-MOF/V by using the ethanol solution 2 C-APTS is centrifugally washed for several times, and the particle size of Fe-MOF contained in the precursor is 200-300 nm;
(3) The precursor Fe-MOF/V is put in 2 After C-APTS freeze-drying, placing in a tube furnace in Ar-H 2 In a mixed atmosphere (Ar: H) 2 The volume ratio is 9:1) is heated to 800 ℃ at the heating rate of 6 ℃/min, the calcination time is 3h, and finally Fe @ C/V is obtained 2 C-APTS composite material, the particle size range of the material is 1-10 μm, the Fe content is 4wt.%, the carbon content is 20wt.%, V 2 The thickness of the C layer is 120nm, and the specific surface area is 210m 2 The pore diameter is distributed between 5 and 50nm. The grain diameter of Fe @ C particles in the composite material is 200-300 nm, and the particles have magnetism.
And (3) testing the adsorption performance: using Ho (NO) 3 ) 3 Is prepared to contain Ho 3+ Ionic solution by addition of 1g/L Ho at room temperature 3 + 10mL of the solution was added 10mgFe @ C/V 2 C-APTS adsorbent for Ho 3+ Absorption Capacity determination and Rapid filtration Using 0.22 μm Filter and determination of Ho in the aqueous phase Using inductively coupled plasma emission Spectroscopy (ICP) 3+ The residual concentration of ions, thereby calculating Fe @ C/V 2 The adsorption capacity of the C-APTS for adsorbing Ho element reaches 100.3mg/g.
The Ho is loaded by using 0.1mol/L nitric acid solution 3+ Desorbing the adsorbent material, placing the adsorbed material in nitric acid solution with the same volume, reacting at normal temperature (298K) for 60min in a shaking table with the rotating speed of 180rpm, separating the solid phase from the liquid phase by using a 0.22 mu m water phase needle filter after desorption, continuously adsorbing the Ho element by using the adsorbent after separation, and adsorbing and desorbing Ho for 15 times 3+ The adsorption retention of ions is still 89%.
Comparative example 1
Using less Ti 3 C 2 Direct application of material to rare earth Y 3+ Adsorbing with an adsorption capacity of 78.1mg/g and 0.1mol/L nitric acid solution to adsorb Y 3+ Ti of (A) 3 C 2 After desorption, the adsorbent is centrifugally washed and separated, the loss rate of the adsorbent reaches 30 percent, and the subsequent adsorption experiment is difficult to continue.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of Fe @ C/MXene-APTS magnetic composite material for recovering water-phase rare earth elements is characterized by comprising the following steps:
(1) Dispersing the MXene suspension with the less-layer structure in an alkaline solution for alkalization to obtain wrinkled MXene with high specific surface area, washing the wrinkled MXene, and ultrasonically dispersing the wrinkled MXene in an ethanol solution for later use;
(2) Dissolving polyvinyl pyrrolidone in dilute hydrochloric acid, and adding K into the solution 4 Fe(CN) 6 ·3H 2 O, pouring the solution into an ethanol solution dispersed with wrinkled MXene, dripping a 3-aminopropyltriethoxysilane solution into the mixed solution under the argon atmosphere, magnetically stirring and aging, and centrifugally washing the precursor Fe-MOF/MXene-APTS for a plurality of times by using the ethanol solution;
(3) Freeze-drying the product obtained in the step (2), and placing the product in a tube furnace in Ar-H 2 And carrying out heat treatment in the mixed atmosphere to finally obtain the Fe @ C/MXene-APTS magnetic composite material.
2. The method of claim 1, wherein the MXene material used in step (1) comprises Ti 3 C 2 、Ti 2 C、Nb 2 C、V 2 C、Mo 2 C.
3. The method of claim 1, wherein the alkaline solution in step (1) comprises NaOH, KOH, ca (OH) 2 Ammonia water and Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 And one or more of ethylenediamine with the concentration of 0.1-10 wt%.
4. The preparation method according to claim 1, wherein in the step (1), the alkalization temperature is 10-70 ℃, the alkalization time is 1-10 h, and the volume ratio of the MXene suspension to the alkaline solution is 1.1-1.
5. The method of claim 1, wherein the step of preparing the composition comprisesThe thickness of the wrinkled MXene after alkalization in the step (1) is 10-200 nm, the number of layers is 1-20, and the specific surface area is 50-1000 m 2 The diameter of the holes is 5-50 nm.
6. The method according to claim 1, wherein the polyvinylpyrrolidone used in the step (2) is 1 to 200g, the diluted hydrochloric acid has a concentration of 0.01 to 2mol/L, the volume of the diluted hydrochloric acid solution is 50 to 2000mL, K is 4 Fe(CN) 6 ·3H 2 The addition amount of O is 0.1-100 g.
7. The method according to claim 1, wherein the amount of MXene added in the step (2) is 0.02 to 10g and the amount of 3-aminopropyltriethoxysilane added is 0.01 to 8g.
8. The process according to claim 1, wherein the aging time in the step (2) is 2 to 40 hours and the aging temperature is 40 to 90 ℃.
9. The production method according to claim 1, wherein the heat treatment conditions in the step (3) are: the heat treatment temperature is 300-800 ℃, the heating rate is 1-10 ℃/min, and the calcination time is 1-10 h.
10. The method according to claim 1, wherein the Fe @ C/MXene-APTS magnetic composite material in the step (3) is used for adsorbing rare earth again after magnetic recovery separation and elution of rare earth with 0.1mol/L nitric acid after adsorbing rare earth.
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