CN112076734A - Preparation method of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material and application of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material in gallium recovery - Google Patents
Preparation method of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material and application of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material in gallium recovery Download PDFInfo
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Abstract
The invention relates to a preparation method of a salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material and application of the salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material in gallium recovery. Ultrasonically dispersing KIT-6 in a Tris-HCl buffer solution, then simultaneously adding dopamine and salicylaldoxime, adjusting the pH value of the solution, violently stirring the mixture at room temperature for a certain time, carrying out centrifugal separation on the obtained product, washing with deionized water, and drying in a vacuum drying oven to obtain the target product SOy/PDAx-KIT-6. The preparation method is simple, green and pollution-free, and the prepared adsorbent has high adsorption capacity on gallium and practical applicability.
Description
Technical Field
The invention belongs to the technical field of effective recovery of metal gallium and preparation of a silicon dioxide-based adsorbent material, and particularly relates to a preparation method of a three-dimensional mesoporous silicon dioxide-based adsorbent material, aiming at effectively adsorbing gallium from a solution containing metal ion gallium.
Background
The rare dispersion elements mainly comprise seven elements of gallium (Ga), indium (In), germanium (Ge), selenium (Se), tellurium (Te), rhenium (Re) and thallium (Tl), and have the characteristics of rare content and dispersion distribution on the earth. Currently, gallium and gallium compounds are increasingly favored, and among them, in terms of new energy and semiconductor materials, compounds formed by Ga and nitrogen (N), phosphorus (P), arsenic (As), and the like have semiconductor properties, and GaAs is most widely used As a semiconductor material. The GaAs material solar cell can still keep good photoelectric conversion performance under the high temperature condition (250 ℃), so the GaAs material solar cell can be used as a high-temperature concentrating solar cell and can be used as a reliable driving power supply in the aspects of spaceflight and military affairs.
With the development of new energy technology, the separation and enrichment of rare and scattered metal gallium becomes more important. Gallium is used more and more widely in various fields, but the reserves of gallium are very small, and independent ore deposits are hardly formed, so that the separation and extraction from roasting leachate and smelting waste liquid of associated ores are the main methods for obtaining gallium. The traditional separation methods mainly comprise a solvent extraction method, a solid phase extraction method, an ion exchange method, an electrodialysis method, an adsorption method and the like. The solvent extraction method and the solid phase extraction method have the problems of long extraction time, unsatisfactory separation effect and the like in practical application, and the extractant is generally flammable and volatile substance, which causes pollution to the environment, thereby limiting the further industrial development of the extractant. The ion exchange method and the electrodialysis method have excellent separation effect, but the application is limited due to higher cost. The adsorption method has the characteristics of high efficiency, simple operation, good adsorption selectivity and the like for separating the metal ions, and is a metal ion recovery method with a very promising prospect.
The mesoporous silica (KIT-6) has the advantages of moderate aperture size, highly ordered three-dimensional cubic pore channels, large specific surface area and the like, and is more and more concerned in the two traditional fields of adsorption and catalysis in recent years. The adsorbent prepared by modifying KIT-6 has excellent adsorption performance and has unusual significance for environmental protection.
Disclosure of Invention
The invention aims to design a preparation method of a salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material and application of the salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material in gallium recovery. The invention utilizes Dopamine (DA) to carry out oxidative autopolymerization reaction under certain weak base condition to obtain PDA with strong adhesive capacity, and in the process, DA can be rapidly adhered to the surfaces of almost all materials through autopolymerization to form a functional layer of PDA. Also, the PDA may serve as an adhesive layer to bond the two substances together to form a functionalized composite.
The invention is realized by the following technical scheme: a preparation method of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material comprises the following steps: 1) adopting a post-grafting method, taking sodium silicate as a silicon source, and synthesizing mesoporous silica KIT-6 by microwave assistance; 2) then adding Dopamine (DA) under alkaline conditions to enable the Dopamine (DA) to be rapidly attached to the surface of KIT-6, simultaneously adding Salicylaldoxime (SO), and obtaining a target product under vigorous stirring.
Further, the preparation method comprises the following steps:
1) putting P123 into a conical flask, adding deionized water and concentrated hydrochloric acid, stirring until the deionized water and the concentrated hydrochloric acid are dissolved, adding n-butyl alcohol, stirring and reacting for 0.5-2h in a water bath kettle at 30-40 ℃, slowly dropwise adding sodium silicate, continuously stirring for 5-6h, transferring the obtained mixed solution into a microwave reaction tank, reacting by using a microwave reaction synthesizer, sequentially washing with ethanol and water until the solution is neutral, drying, and roasting in a muffle furnace to remove a template agent P123 to obtain mesoporous silica KIT-6;
2) ultrasonically dispersing the obtained mesoporous silica KIT-6 in a Tris-HCl buffer solution, then simultaneously adding Dopamine (DA) and Salicylaldoxime (SO), adjusting the pH value of the solution to be alkaline, violently stirring the obtained mixture at room temperature for 1-2h, then carrying out centrifugal separation on the obtained product, washing with deionized water, and carrying out vacuum drying to obtain the salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material.
Further, in the above preparation method, in step 1), the reaction conditions using the microwave reaction synthesizer are as follows: reacting for 4 hours at the temperature of 95 ℃ under the condition of 400W; the conditions for firing in the muffle furnace were: roasting at 550 ℃ for 8 h.
Further, in the above preparation method, step 2), DA: KIT-6 is 1:0.5-2 by mass ratio.
Further, in the above preparation method, step 2), KIT-6: SO ═ 1:2-6 by mass ratio.
Further, in the above preparation method, step 2), the pH of the solution is adjusted to 7 to 9.
Further, in the preparation method, step 2), the vacuum drying is carried out for 12-36h at 40-80 ℃.
The salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material is used as an adsorbent in gallium adsorption. The method comprises the following steps: in a solution containing gallium ions, adjusting the pH value of the solution to 3-12, and adding a salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material.
The invention has the beneficial effects that:
1) in the invention, mesoporous silica KIT-6 is used as a matrix of the adsorbent, and has the characteristics of high specific surface area, ordered and adjustable pore diameter structure, hydrothermal stability, mechanical stability, easy surface modification and the like, so that the reaction sites of the adsorbent can be increased, and the stability of the adsorbent can be enhanced.
2) In the present invention, the DA may form a functional layer of the PDA by self-polymerization, and the PDA may serve as an adhesive layer to bond two substances together to form a functionalized composite material.
3) In the present invention, SO was grafted onto the surface of KIT-6 using PDA as a binder to obtain SOy/PDAx-KIT-6 composite material. Gallium can generate ion exchange and chelation with the phenolic hydroxyl and the oximino functional groups on the surface of SOy/PDAx-KIT-6, and the adsorption capacity to gallium can be obviously enhanced by utilizing the synergistic effect of the phenolic hydroxyl and the oximino bifunctional groups.
4) The adsorbent prepared by the invention has the maximum adsorption capacity of 136.40mg g for gallium under the conditions that the addition amount of DA is 50mg and the addition amount of SO is 200mg and the pH value is 10-1。
5) The invention adopts specific reaction conditions and raw materials, and the material obtained by microwave hydrothermal has good effect on the gallium adsorption capacity, and the preparation method is simple and has low cost. Easy to realize industrial production.
In conclusion, the adsorbent prepared by the invention has better gallium adsorption capacity, simple synthesis method and practical and reliable applicability. The invention utilizes the modified KIT-6 adsorbent to carry out deep research on the high-efficiency separation of low-content gallium in the wastewater by adopting an adsorption method, prepares the adsorbent which is green, low in cost and high in selectivity, and has wide application prospect.
Drawings
FIG. 1 is a schematic representation of the preparation of SOy/PDAx-KIT-6 of the present invention.
FIG. 2 is an XRD pattern of SO200/PDA50-KIT-6 and KIT-6 in example 1.
FIG. 3 is an infrared spectrum of SO200/PDA50-KIT-6 and KIT-6 of example 1.
FIG. 4 is a graph of the performance of SO200/PDA50-KIT-6 on gallium adsorption at different acidity levels in example 1.
FIG. 5 is the adsorption isotherm of SO200/PDA50-KIT-6 on gallium in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, but is not limited thereto.
A preparation method of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material comprises the following steps:
1) placing P123 in a conical flask, adding deionized water and concentrated hydrochloric acid, stirring until the deionized water and the concentrated hydrochloric acid are dissolved, adding n-butyl alcohol, stirring and reacting for 0.5-2h in a water bath kettle at 30-40 ℃, slowly dropwise adding sodium silicate, continuously stirring for 5-6h, transferring the obtained mixed solution into a microwave reaction tank, reacting for 4h under the conditions of 400W and 95 ℃ by using a microwave reaction synthesizer, then sequentially washing with ethanol and water until the solution is neutral, drying, and roasting for 8h at 550 ℃ in a muffle furnace to remove a template agent P123, thus obtaining KIT-6;
2) ultrasonically dispersing KIT-6 in a Tris-HCl buffer solution, then simultaneously adding dopamine DA and salicylaldoxime SO, adjusting the pH value of the solution to 7-9, violently stirring the obtained mixture for 1-2h at room temperature, centrifuging the obtained product, washing with deionized water, and vacuum-drying at 40-80 ℃ for 12-36h to obtain the salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material named SOy/PDAx-KIT-6, wherein x represents the dosage of DA, and y represents the dosage of SO.
Further, according to the mass ratio, DA: KIT-6 is 1: 0.5-2.
Further, KIT-6: SO-1: 2-6 by mass ratio.
Example 1
Preparation of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material (SO200/PDA50-KIT-6)
1. Preparation of KIT-6: 4.0g of 4.0g P123 was placed in a 250mL Erlenmeyer flask, 120g of deionized water and 20mL of concentrated hydrochloric acid were added, the mixture was stirred until dissolved, and 4.0g of n-butanol was added dropwise to the clear solution. Stirring and reacting for 1h in a water bath kettle at 35 ℃, slowly dripping 11.73g of sodium silicate, continuously stirring for 6h, transferring the obtained mixed solution into a microwave reaction tank after self-assembly is finished, and reacting for 4h at the temperature of 95 ℃ under the condition of 400W by using a microwave reaction synthesizer. Washing with ethanol/water to neutrality, drying, and roasting at 550 deg.C in muffle furnace for 8 hr to obtain KIT-6.
2. Preparation of SO200/PDA 50-KIT-6: 50mg of KIT-6 was ultrasonically dispersed in 30mL of Tris-HCl buffer solution (10mM), 50mg of DA and 200mg of SO were then simultaneously added to adjust the pH of the solution to 8.5, and the mixture was vigorously stirred at room temperature for 2 h. And carrying out centrifugal separation on the obtained product, washing the product with deionized water, and drying the product in a vacuum drying oven at 60 ℃ for 24 hours to obtain the salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material named SO200/PDA 50-KIT-6.
(II) detection
FIG. 2 is a small angle XRD pattern of SO200/PDA50-KIT-6 and KIT-6 from example 1. As can be seen from FIG. 2, the DA and SO loaded material still maintains the original ordered structure of KIT-6. However, in contrast to KIT-6 alone, the intensity of the diffraction peak decreased with DA and SO loading. This indicates that the introduction of DA and SO has some influence on the channel properties of KIT-6.
FIG. 3 is an infrared spectrum of SO200/PDA50-KIT-6 and KIT-6 in example 1. As can be seen in FIG. 3, at 2977cm-1The peak at (A) belongs to the stretching vibration of the C-H bond in DA and SO. At 1658cm-1And 1392cm-1The peak belongs to the vibration peak of the benzene ring, which indicates that polydopamine is successfully adhered to the surface of KIT-6. 1658cm in the spectrum of SO200/PDA50-KIT-6 after SO loading-1The peak intensity is increased because the characteristic peak of C ═ N in salicylaldoxime appears in the vicinity, and coincides with the vibration peak of benzene ring at 965cm-1The peak of N-O bond appears, which indicates that the oxime functional group is successfully grafted on the surface of the material.
(III) adsorption of gallium by SO200/PDA50-KIT-6 at different acidity
The method comprises the following steps: 10mg of SO200/PDA50-KIT-6 was weighed out and put in a shaker bottle, and 10mL ( pH 1, 2, 3, 10, 11, 12) of 20 mg. L was added-1Shaking the gallium solution uniformly, placing the shaking bottle in a constant-temperature shaking box, shaking at the rotation speed of 180rpm at 30 ℃ for 24 hours, filtering, and measuring the concentration of gallium ions in the solution before and after adsorption by using an ultraviolet spectrophotometry. The adsorption rate a% at different pH was calculated by the following formula.
A％＝(Ci-Ce)/Ci*100％，CiAnd CeRespectively represents the rhenium concentration (mg. L) in the solution before and after adsorption-1)。
FIG. 4 is a graph of the analytical performance of SO200/PDA50-KIT-6 in example 1 on gallium at different acidity levels. As can be seen from fig. 4, as the pH increases, the adsorption performance of the adsorbent to ga (iii) gradually increases, reaching a maximum at pH 10, and then its adsorption rate significantly decreases at pH 12, because KIT-6 decomposes at pH greater than 12, resulting in a decrease in adsorption rate.
FIG. 5 is the adsorption isotherm of SO200/PDA50-KIT-6 on gallium in example 1. As can be seen from FIG. 5, the adsorption process of the adsorbent SO200/PDA50-KIT-6 to Ga (III) conforms to the Langmuir adsorption isotherm model (R)2Closest to 1), indicating that the active sites for adsorption are uniformly distributed on the surface of the adsorbent, which adsorption is a monolayer adsorption. The calculation shows that the maximum adsorption quantity of the SO200/PDA50-KIT-6 to the gallium is 136.40mg g under the condition that the pH value is 10-1。
Example 2
Preparation of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material (SO250/PDA50-KIT-6)
1. Preparation of KIT-6: 4.0g of 4.0g P123 was placed in a 250mL Erlenmeyer flask, 120g of deionized water and 20mL of concentrated hydrochloric acid were added, the mixture was stirred until dissolved, and 4.0g of n-butanol was added dropwise to the clear solution. Stirring and reacting for 1h in a water bath kettle at 35 ℃, slowly dripping 11.73g of sodium silicate, continuously stirring for 6h, transferring the obtained mixed solution into a microwave reaction tank after self-assembly is finished, and reacting for 4h at the temperature of 95 ℃ under the condition of 400W by using a microwave reaction synthesizer. Washing with ethanol/water to neutrality, drying, and roasting at 550 deg.C in muffle furnace for 8 hr to obtain KIT-6.
2. Preparation of SO250/PDA 50-KIT-6: 50mg of KIT-6 was ultrasonically dispersed in 30mL of Tris-HCl buffer solution (10mM), 50mg of DA and 250mg of SO were then simultaneously added to adjust the pH of the solution to 8.5, and the mixture was vigorously stirred at room temperature for 2 h. And carrying out centrifugal separation on the obtained product, washing the product with deionized water, and drying the product in a vacuum drying oven at 60 ℃ for 24 hours to obtain the salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material named SO250/PDA 50-KIT-6.
Adsorption of gallium by SO250/PDA50-KIT-6
The method comprises the following steps: 10mg of SO250/PDA50-KIT-6 was weighed out and put in a shaker bottle, and 10mL ( pH 1, 2, 3, etc.),10. 11, 12) of 20 mg.L-1Shaking the gallium solution uniformly, placing the shaking bottle in a constant-temperature shaking box, shaking at the rotation speed of 180rpm at 30 ℃ for 24 hours, filtering, and measuring the concentration of gallium ions in the solution before and after adsorption by using an ultraviolet spectrophotometry. The adsorption rate a% at different pH was calculated by the following formula.
A％＝(Ci-Ce)/Ci*100％，CiAnd CeRespectively represents the rhenium concentration (mg. L) in the solution before and after adsorption-1)。
The calculation shows that the maximum adsorption quantity of the SO250/PDA50-KIT-6 to the gallium is 136.25mg g under the condition that the pH value is 10-1。
Example 3
Preparation of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material (SO300/PDA50-KIT-6)
1. Preparation of KIT-6: 4.0g of 4.0g P123 was placed in a 250mL Erlenmeyer flask, 120g of deionized water and 20mL of concentrated hydrochloric acid were added, the mixture was stirred until dissolved, and 4.0g of n-butanol was added dropwise to the clear solution. Stirring and reacting for 1h in a water bath kettle at 35 ℃, slowly dripping 11.73g of sodium silicate, continuously stirring for 6h, transferring the obtained mixed solution into a microwave reaction tank after self-assembly is finished, and reacting for 4h at the temperature of 95 ℃ under the condition of 400W by using a microwave reaction synthesizer. Washing with ethanol/water to neutrality, drying, and roasting at 550 deg.C in muffle furnace for 8 hr to remove template agent to obtain KIT-6.
2. Preparation of SO300/PDA 50-KIT-6: 50mg of KIT-6 was ultrasonically dispersed in 30mL of Tris-HCl buffer solution (10mM), then 50mg of DA and 300mg of SO were simultaneously added to adjust the pH of the solution to 8.5, and the mixture was vigorously stirred at room temperature for 2 h. The resulting product was centrifuged and washed with deionized water and dried in a vacuum oven at 60 ℃ for 24 h. The salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material is obtained and named as SO300/PDA 50-KIT-6.
Adsorption of gallium by SO300/PDA50-KIT-6
The method comprises the following steps: 10mg of SO300/PDA50-KIT-6 was weighed out and put in a shaker bottle, and 10mL ( pH 1, 2, 3, 10, 11, 12) of 20 mg. L was added-1Shaking the gallium solution, and placing the shaking bottle at constant temperatureAnd (3) oscillating for 24 hours at 30 ℃ in an oscillation box at the rotating speed of 180rpm, filtering, and measuring the concentration of gallium ions in the solution before and after adsorption by using an ultraviolet spectrophotometry. The adsorption rate a% at different pH was calculated by the following formula.
A％＝(Ci-Ce)/Ci*100％，CiAnd CeRespectively represents the rhenium concentration (mg. L) in the solution before and after adsorption-1)。
The calculation shows that the maximum adsorption quantity of the SO300/PDA50-KIT-6 to the gallium is 132.53mg g under the condition that the pH value is 10-1。
Claims (9)
1. A preparation method of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material is characterized by comprising the following steps: 1) adopting a post-grafting method, taking sodium silicate as a silicon source, and synthesizing mesoporous silica KIT-6 by microwave assistance; 2) and then adding dopamine DA under an alkaline condition to enable the dopamine DA to be rapidly attached to the surface of KIT-6, simultaneously adding salicylaldoxime SO, and obtaining a target product under vigorous stirring.
2. The method of claim 1, comprising the steps of:
1) putting P123 into a conical flask, adding deionized water and concentrated hydrochloric acid, stirring until the deionized water and the concentrated hydrochloric acid are dissolved, adding n-butyl alcohol, stirring and reacting for 0.5-2h in a water bath kettle at 30-40 ℃, slowly dropwise adding sodium silicate, continuously stirring for 5-6h, transferring the obtained mixed solution into a microwave reaction tank, reacting by using a microwave reaction synthesizer, sequentially washing with ethanol and water until the mixed solution is neutral, drying, and roasting in a muffle furnace to obtain mesoporous silica KIT-6;
2) ultrasonically dispersing the obtained mesoporous silica KIT-6 in a Tris-HCl buffer solution, then simultaneously adding dopamine DA and salicylaldoxime SO, adjusting the pH value of the solution to be alkaline, violently stirring the obtained mixture at room temperature for 0.5-1h, then carrying out centrifugal separation on the obtained product, washing with deionized water, and carrying out vacuum drying to obtain the salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material.
3. The method according to claim 2, wherein the reaction conditions in step 1) using a microwave reaction synthesizer are: reacting for 4 hours at the temperature of 95 ℃ under the condition of 400W; the conditions for firing in the muffle furnace were: roasting at 550 ℃ for 8 h.
4. The preparation method according to claim 2, wherein in the step 2), DA: KIT-6 is 1:0.5-2 by mass ratio.
5. The method according to claim 2, wherein, in step 2), KIT-6: SO-1: 2-6 is added by mass.
6. The method according to claim 2, wherein in the step 2), the pH of the solution is adjusted to 7 to 9.
7. The method according to claim 2, wherein the vacuum drying in step 2) is performed at 40-80 ℃ for 12-36 h.
8. Use of a salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material prepared according to the method of any of claims 1 to 7 as an adsorbent for adsorbing gallium.
9. Use according to claim 8, characterized in that the method is as follows: in a solution containing gallium ions, adjusting the pH value of the solution to 3-12, and adding a salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material.
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Application publication date: 20201215 |