CN114669200A - Nanofiltration membrane and preparation method and application thereof - Google Patents
Nanofiltration membrane and preparation method and application thereof Download PDFInfo
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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Abstract
The invention discloses a nanofiltration membrane, a preparation method and application thereof. A nanofiltration membrane comprising: graphene oxide and layered multi-metal hydroxide dispersed in the graphene oxide, wherein the graphene oxide and the layered multi-metal hydroxide are combined together through electrostatic interaction. The nanofiltration membrane can effectively separate and filter the quantum dot solution.
Description
Technical Field
The invention relates to the technical field of quantum dot light emitting display devices, in particular to a nanofiltration membrane, a preparation method and application.
Background
Quantum dots (Quantum dots) and Quantum Dot related materials and devices have been praised as one of the core scientific and technological engines in the current industrial 4.0 era. Because each small particle is a single crystal particle and the size has good tunability, the color filter has high color purity, wide color gamut, high crystal stability, narrow and symmetrical fluorescence emission spectrum and wide and continuous ultraviolet absorption spectrum, and thus the color filter is an ideal new material for flexible printed display.
It is well known that in electro-optical lighting and display devices, the purity requirements for the electro-optical starting material are very high. The introduction of trace and trace amount of reaction precursor substances not only affects the optical and electrical properties of the photoelectric material, but also irreversibly affects the electroluminescent efficiency, service life and the like of a quantum dot light emitting display device, such as the phenomenon of electric leakage quenching, so that the performance of the corresponding photoelectric material is greatly reduced. At present, most of semiconductor material quantum dots in the photoelectric field are synthesized and prepared by a hydrothermal method, and the quantum dots synthesized by the method often have cationic precursor and anionic precursor residues and can be used after being centrifuged or extracted for many times. And the two treatment methods are only primary separation and cannot ensure that the quantum dot product with higher purity is obtained.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a nanofiltration membrane, a preparation method and application thereof, and aims to solve the problem that the prior art cannot ensure that a quantum dot product with higher purity can be obtained.
A nanofiltration membrane comprising: graphene oxide and layered multi-metal hydroxide dispersed in the graphene oxide, wherein the graphene oxide and the layered multi-metal hydroxide are combined together through electrostatic interaction.
In the nanofiltration membrane, the number of layers of the graphene oxide is 10-20.
In the nanofiltration membrane, the interlayer spacing of the graphene oxide is 1-3 nm.
In the nanofiltration membrane, the coverage rate of oxygen-containing groups on the surface of the graphene oxide is 60-70%.
In the nanofiltration membrane, the layered multi-metal hydroxide comprises at least two metal elements, wherein the metal elements are metal elements with the number of electron layers being more than or equal to 4.
In the nanofiltration membrane, the at least two metal elements comprise: the electron beam comprises a first metal element, a second metal element and a third metal element, wherein the number of electron layers of the first metal element is 4, the number of electron layers of the second metal element is 5, and the number of electron layers of the third metal element is 6;
wherein the molar ratio of the first metal element to the second metal element to the third metal element is 2:1:1 to 9:2: 2.
In the nanofiltration membrane, the metal element is selected from one or more of potassium, calcium, scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, ruthenium, lanthanum, cerium, praseodymium, neodymium, europium and gadolinium.
In the nanofiltration membrane, the first metal element is selected from one or more of potassium, calcium, scandium, vanadium, chromium, manganese, iron, cobalt, nickel and copper;
the second metal element is selected from one or more of yttrium, zirconium, niobium, molybdenum and ruthenium;
the third metal element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, europium and gadolinium.
In the nanofiltration membrane, the mass ratio of the graphene oxide to the layered multi-metal hydroxide is 2: 1-3: 1.
A preparation method of a nanofiltration membrane comprises the following steps:
providing a layered multimetal hydroxide;
dispersing graphene oxide and layered multi-metal hydroxide into a dispersing agent to obtain a mixed solution;
and depositing the mixed solution to obtain the nanofiltration membrane.
In the preparation method of the nanofiltration membrane, the preparation method of the layered multi-metal hydroxide comprises the following steps:
providing a metal salt solution;
adding amide derivatives into the metal salt solution for reaction to obtain layered multi-metal hydroxide;
wherein the molar amount of the amide derivative is 1 to 2 times the molar amount of the metal salt.
In the preparation method of the nanofiltration membrane, the amide derivative is selected from one or more of urea, N-dimethylformamide, acrylamide, N-dimethylacetamide, stearic acid amide, erucamide and sulfonamide.
In the preparation method of the nanofiltration membrane, the reaction temperature is 130-180 ℃.
The application of the nanofiltration membrane or the nanofiltration membrane prepared by the preparation method of the nanofiltration membrane in filtering quantum dot solution is provided.
Has the advantages that: the nanofiltration membrane contains graphene oxide and layered multi-metal hydroxide dispersed in the graphene oxide, and can remove residual cation precursors and anion precursors in a quantum dot solution, so that a quantum dot product with high purity is obtained.
Detailed Description
The invention provides a nanofiltration membrane, a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Graphene is a two-dimensional sheet material with a honeycomb-like structure and is formed by sp2The hybridized carbon atom consists of only one atomic layer thickness and has ultrahigh strength. Graphene Oxide (GO) is a graphene derivative, and the surface of the graphene oxide contains rich oxygen-containing groups, such as hydroxyl, carboxyl and epoxy groups. Due to the abundant oxygen-containing functional groups, the graphene oxide has good hydrophilicity, and the graphene oxide nanosheets can be stacked into a compact layered structure due to the strong hydrogen bonding effect. In addition, the graphene oxide has high mechanical strength and good flexibility, can resist acid and alkali and organic solvents, and is easy to obtain.
Wherein, the structural formula of the single-layer graphene oxide is as follows:
the layered multi-metal hydroxide is a metal hydroxide composed of two or more metal elements, and the structure of the layered multi-metal hydroxide is formed by overlapping laminated plates and interlayer anions, and specifically, the layered multi-metal hydroxide is formed by orderly assembling positively charged laminated plates and interlayer exchangeable anions.
The embodiment of the invention provides a nanofiltration membrane, which comprises: graphene oxide and layered multimetal hydroxides dispersed in the graphene oxide, the graphene oxide and the layered multimetal hydroxides being bonded together by electrostatic interaction.
The nanofiltration membrane provided by the embodiment of the invention contains graphene oxide and layered multi-metal hydroxide dispersed in the graphene oxide, wherein the graphene oxide and the layered multi-metal hydroxide can form a coordination compound or remove residual cation precursors and anion precursors in a quantum dot solution in an electrostatic manner, so that a quantum dot product with higher purity is obtained.
Specifically, the graphene oxide surface contains abundant oxygen-containing groups and is negatively charged, and residual metal cations in the quantum dot solution can be removed by forming a coordination compound or by electrostatic attraction, for example, the oxygen-containing groups can be hydroxyl, carboxyl, epoxy groups and the like, and the residual metal cations in the quantum dot solution can be zinc ions, cadmium ions, lead ions, indium ions and the like, that is, the oxygen-containing groups such as the hydroxyl, carboxyl, epoxy groups and the like can form coordination compounds with the residual metal cations such as zinc ions, cadmium ions, lead ions, indium ions and the like in various quantum dot solutions or the residual metal cations can be removed by electrostatic attraction.
The layered multimetal hydroxide is a two-dimensional cationic material, namely, the layered multimetal hydroxide has a large amount of hydroxyl and positive charges on the surface, and can form a complex with the residual polymer or nano particles in the quantum dot solution, for example, the layered multimetal hydroxide removes the residual anions in the quantum dot solution in an electrostatic attraction manner, and specifically removes the residual ions such as sulfur ions, selenium ions, arsenic ions and the like in the quantum dot solution.
In the nanofiltration membrane, electrostatic interaction is generated between the positively charged layered multi-metal hydroxide and the negatively charged graphene oxide nanosheet, so that the stability of the membrane structure can be enhanced. That is, the layered multi-metal hydroxide has an effect of increasing the structural stability of graphene oxide.
In one embodiment of the present invention, the number of graphene oxide layers is 10 to 20. On one hand, the number of layers of the graphene oxide is 10-20, so that a good filtering rate can be guaranteed, and on the other hand, the number of layers of the graphene oxide is 10-20, so that impurities in the quantum dot solution can be effectively removed. Specifically, when the number of graphene oxide layers is less than 10, the number of graphene oxide layers is not easy to control, and the filtration rate is too high, which causes a problem of poor impurity removal. When the number of graphene oxide layers is greater than 20, the number of graphene oxide layers is too complex to prepare, the filtration rate is too low, and the loss of quantum dots can be caused. In one embodiment of the invention, the coverage rate of the oxygen-containing groups on the surface of the graphene oxide is 60-70%, the graphene oxide has enough negative charges to combine with cationic impurities in the quantum dot solution, and also has enough negative charges to perform electrostatic interaction with the layered metal hydroxide, so that the insertion effect of the layered metal hydroxide is realized.
The aperture of the channel in the nanofiltration membrane is in the nanometer level, the aperture of the channel in the nanofiltration membrane can be adjusted through the layered multi-metal hydroxide, the size of the quantum dot corresponds to that of the quantum dot, and the ligand falling off from the surface of the quantum dot can be blocked and separated.
The pore channels of the graphene oxide are gaps formed among the sheet layers, and the distance between the graphene oxide layers not only provides a transfer channel of water, but also has a steric hindrance effect on small molecules. Although the graphene oxide layers have certain gaps, the distance between the graphene oxide layers cannot be increased, and the distance between the graphene oxide layers and the graphene oxide layers can be increased by introducing foreign substances, so that the filtering speed of the quantum dot solution is improved. The research of the invention also finds that the common metal hydroxide can not be inserted into the graphene oxide lamella with a small quantity, and the layered metal hydroxide can realize the effective insertion between the graphene oxide lamella. Based on this, the embodiment of the invention realizes the regulation and control of the graphene oxide layer spacing by inserting the layered multi-metal hydroxide into the graphene oxide. In one embodiment of the present invention, the layered metal hydroxide can increase the interlayer distance by 0.5 to 1nm based on the original graphene oxide. Optionally, the interlayer spacing of graphene oxide in the nanofiltration membrane is 1-3 nm, in other words, the interlayer spacing of the nanofiltration membrane is 1-3 nm, so that the quantum dot solution has a higher filtration speed and a high-purity quantum dot solution can be obtained.
Specifically, the embodiment of the invention utilizes the electrostatic action of the layered multi-metal hydroxide and the graphene oxide to realize the regulation and control of the distance between the graphene oxide layers. Specifically, when a metal atom with a large number of inserted electron layers (for example, 4 electron layers or more) is inserted, the interlayer distance between the graphene oxides can be increased appropriately, and the larger the number of electron layers of the metal element is, the larger the increased interlayer distance is. In one embodiment of the present invention, the layered multimetal hydroxide comprises at least two metal elements, wherein the metal element is a metal element having 4 or more layers of electrons. Optionally, the metal element is selected from one or more of potassium, calcium, scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, ruthenium, lanthanum, cerium, praseodymium, neodymium, europium, gadolinium.
In addition, the larger the number of electron layers of the metal element is, the stronger the binding capacity to anions is, and the anion impurities remained in the quantum dot solution can be better removed. Meanwhile, the metal element with more electron layers is used, so that the using amount of the metal element can be reduced, and the effect of removing impurities is ensured and the cost is saved. The invention controls the number of channels and the aperture size in the nanofiltration membrane by changing the type of the layered multi-metal hydroxide in the nanofiltration membrane. In one embodiment of the present invention, the at least two metal elements include: the electron beam comprises a first metal element, a second metal element and a third metal element, wherein the number of electron layers of the first metal element is 4, the number of electron layers of the second metal element is 5, and the number of electron layers of the third metal element is 6; wherein the molar ratio of the first metal element to the second metal element to the third metal element is 2:1:1 to 9:2: 2. The research shows that when the molar ratio of the first metal element to the second metal element to the third metal element is less than 2:1:1, the effect of increasing the interlayer spacing of the nanofiltration membrane is difficult to achieve, and the filtration speed of the quantum dot solution is difficult to improve; when the molar ratio of the first metal element to the second metal element to the third metal element is greater than 9:2:2, the distance between graphene oxide layers is too large, and the effect of filtering impurities is poor. In the embodiment of the invention, the molar ratio of the first metal element to the second metal element to the third metal element is 2:1: 1-9: 2:2, so that the distance between graphene oxide layers can be properly increased, and the electropositivity of the layered multi-metal compound can be flexibly regulated. Optionally, the molar ratio of the first metal element, the second metal element, and the third metal element is 4:2: 1.
In one embodiment of the present invention, the first metal element is selected from one or more of potassium, calcium, scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper;
the second metal element is selected from one or more of yttrium, zirconium, niobium, molybdenum and ruthenium;
the third metal element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, europium and gadolinium.
The invention controls the number of channels and the aperture size in the nanofiltration membrane by changing the content of the layered multi-metal hydroxide in the nanofiltration membrane. In one embodiment of the present invention, the mass ratio of the graphene oxide to the layered multimetal hydroxide is 2:1 to 3: 1. Researches show that the larger the content of the layered multi-metal hydroxide in the nanofiltration membrane is, the larger the layer distance of the nanofiltration membrane is, namely, the larger the aperture of a two-dimensional channel for filtering the quantum dot solution is. The mass ratio of the graphene oxide to the layered multi-metal hydroxide is 2: 1-3: 1, a channel with a proper size can be provided for filtering the quantum dot solution, the filtering efficiency of the quantum dot solution can be improved, and the purity of the filtered quantum dot solution is guaranteed.
In the nanofiltration membrane, the mass ratio of the graphene oxide to the layered multi-metal hydroxide can control the electronegativity of the graphene oxide according to the electropositivity of the layered multi-metal hydroxide. In the nanofiltration membrane provided by the embodiment of the invention, the mass ratio of graphene oxide to layered multi-metal hydroxide is 2: 1-3: 1, so that the electronegativity of the layered multi-metal hydroxide in graphene oxide is 50-70%. When the electronegativity of the layered multi-metal hydroxide in graphene oxide is lower than 50%, the layered multi-metal hydroxide cannot be firmly bonded with the graphene oxide layer, and the effect of inserting the layered multi-metal hydroxide between the graphene oxide layers to expand the distance between the graphene oxide layers to accelerate filtration cannot be achieved. When the electronegativity of the layered multi-metal hydroxide on the graphene oxide is higher than 70%, the layered multi-metal hydroxide reacts with a large number of electronegative groups on the surface of the graphene oxide, so that a large number of electronegative groups are consumed, and the effect of removing cationic impurities by means of the electronegative groups on the surface of the graphene oxide is lost. When the electronegativity of the layered multi-metal hydroxide in graphene oxide is 50-70%, the layered multi-metal hydroxide can be firmly combined with the graphene oxide and can be inserted between the graphene oxide layers, the effect of expanding the distance between the graphene oxide layers is achieved, and the residual cation and anion impurities in the quantum dot solution can be removed at the same time.
The invention provides a preparation method of a nanofiltration membrane, which comprises the following steps:
s100, providing a layered multi-metal hydroxide;
s200, dispersing graphene oxide and layered multi-metal hydroxide into a dispersing agent to obtain a mixed solution;
and S300, depositing the mixed solution to obtain the nanofiltration membrane.
The layered multi-metal hydroxide is introduced into the graphene oxide membrane to prepare the nanofiltration membrane. The nanofiltration membrane can remove metal cations and anions and unbound or fallen quantum dot organic ligands in the quantum dot solution, so that the quantum dot solution is effectively separated and filtered, and the effect of purifying the quantum dots is achieved.
The graphene oxide pore channels are gaps among the sheets, and the interlayer spacing of the graphene oxide not only provides a transfer channel of water, but also has steric hindrance effect on some small molecules. According to the invention, the layered multi-metal hydroxide is introduced into the graphene oxide membrane, and the distance between graphene oxide layers is adjusted, so that a two-dimensional nano-channel can be increased, and the filtration rate of a quantum dot solution is increased; electrostatic interaction is generated between the layered multi-metal hydroxide with positive charge and the graphene oxide nanosheet with negative charge, so that the stability of the membrane structure can be enhanced; the graphene oxide and the layered multi-metal hydroxide can remove the residual cationic precursor and anionic precursor in the quantum dot solution in a coordination compound forming manner or in an electrostatic attraction manner.
In addition, the rich oxygen-containing groups on the surface of the graphene oxide have good hydrophilicity, and for oil-soluble quantum dots, micro water molecules in a quantum dot solution can be well removed, so that the luminescence stability of the quantum dot solution is ensured.
The layered multi-metal hydroxide is a two-dimensional cationic material, and can remove anions such as sulfide ions, selenium ions, arsenic ions and the like in various quantum dot solutions in an electrostatic attraction manner due to the existence of a large number of hydroxyl groups and positive charges on the surface, so that the purpose of removing residual anions is achieved.
The nanofiltration membrane can flexibly control the filtration effect of the quantum dot solution. Specifically, in the first place, the graphene oxide surface contains abundant oxygen-containing groups, so that residual metal cations can be removed by forming a coordination compound or by electrostatic attraction, and therefore, the filtration effect of the nanofiltration membrane is controlled by controlling the coverage rate of the oxygen-containing groups on the graphene oxide surface. Secondly, controlling the filtration effect of the nanofiltration membrane by controlling the number of graphene oxide layers; and thirdly, the layered multi-metal hydroxide can adjust the distance between graphene oxide layers, so that the number and the pore size of the nano-filtration membrane channels are controlled by controlling the content of the layered multi-metal. In an embodiment of the present invention, the controlling of the coverage rate of the oxygen-containing group on the surface of the graphene oxide may be controlling the coverage rate of the oxygen-containing group on the surface of the graphene oxide by regulating and controlling corresponding reaction parameters in the process of preparing the graphene oxide. Alternatively, the coverage of the oxygen-containing groups is controlled by how much amount of strong acid is added. For example, the addition amount of the dilute nitric acid is 10% of the volume of the graphene solution, and then the coverage rate of the oxygen-containing groups is 20-30%; the addition amount of the dilute nitric acid is 20% of the volume of the graphene solution, so that the coverage rate of the oxygen-containing groups is 40-50%; and the addition amount of the dilute nitric acid is 30% of the volume of the graphene solution, so that the coverage rate of the oxygen-containing groups is 60-70%, wherein the mass percentage of the dilute nitric acid can be 15%.
The layers in the nanofiltration membrane have mutual synergistic or auxiliary effects. On one hand, the addition of the layered multi-metal hydroxide can adjust the distance between graphene oxide layers, increase two-dimensional nano-channels and increase the filtration rate; on the other hand, electrostatic interaction is generated between the layered multi-metal hydroxide with positive charge and the graphene oxide nanosheet with negative charge, so that the stability of the graphene oxide film structure can be enhanced.
The layered multimetal hydroxide of the present invention has a layered structure comprising two or more metal hydroxides. Specifically, the layered multimetal hydroxide is a novel inorganic material having a hydrotalcite-like layered structure composed of a plurality of metal ions. The invention provides a preparation method of a layered multi-metal hydroxide. In one embodiment of the present invention, there is provided a method for preparing a layered multimetal hydroxide comprising:
s101, providing a metal salt solution;
s102, adding an amide derivative into a metal salt solution for reaction to obtain a layered multi-metal hydroxide;
the metal salt solution comprises at least two metal elements, wherein the metal elements are metal elements with the number of electron layers being more than or equal to 4.
In S101, the metal salt solution includes at least two metal elements, and thus a layered multi-metal hydroxide including a plurality of metal hydroxides can be formed.
In one embodiment of the invention, the metal salt solution is prepared by dissolving a soluble metal salt composition in water, wherein the soluble metal salt composition comprises at least two soluble metal salts. That is, the metal salt solution is prepared by dissolving at least two soluble metal salts in water. The metal in the soluble metal salt is a metal of a multi-electron layer, specifically a metal of 4 layers or more. After dissolving at least two soluble metal salts in water, a metal salt solution containing at least two metal elements is formed.
Specifically, the metal salt solution is prepared by mixing two or more soluble metal salts in distilled water at a certain molar ratio. Further, the metal in the soluble metal salt is a metal of the multi-electron layer, the metal of the multi-electron layer is specifically a metal element with a thickness of 4 layers or more, and the metal element is required to have good coordination. Thus, the soluble metal salt may be referred to as a soluble metal salt of the multi-electron shell.
In one embodiment of the invention, the soluble metal salt is selected from one or more of soluble potassium salt, soluble calcium salt, soluble scandium salt, soluble vanadium salt, soluble chromium salt, soluble manganese salt, soluble iron salt, soluble cobalt salt, soluble nickel salt, soluble copper salt, soluble yttrium salt, soluble zirconium salt, soluble niobium salt, soluble molybdenum salt, soluble ruthenium salt, soluble lanthanum salt, soluble cerium salt, soluble praseodymium salt, soluble neodymium salt, soluble europium salt, and soluble gadolinium salt. Optionally, the soluble metal salt is selected from one or more of potassium nitrate, potassium sulfate, potassium chloride, calcium nitrate, calcium chloride, scandium nitrate, vanadium nitrate, chromium nitrate, manganese sulfate, manganese chloride, iron nitrate, iron sulfate, iron chloride, cobalt sulfate, cobalt nitrate, nickel nitrate, copper sulfate, copper nitrate, copper chloride, yttrium nitrate, zirconium nitrate, niobium nitrate, molybdenum nitrate, ruthenium nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, europium nitrate, gadolinium nitrate.
In one embodiment of the invention, the soluble metal salt composition comprises: the first soluble metal salt, the second soluble metal salt and the third soluble metal salt, namely at least two soluble metal salts are composed of three soluble metal salts.
The first soluble metal salt has 4 metal electronic layers, such as soluble potassium salt, soluble calcium salt, soluble scandium salt, soluble vanadium salt, soluble chromium salt, soluble manganese salt, soluble iron salt, soluble cobalt salt, soluble nickel salt, soluble copper salt, and the like.
The number of metal electron layers in the second soluble metal salt is 5, such as soluble yttrium salt, soluble zirconium salt, soluble niobium salt, soluble molybdenum salt, soluble ruthenium salt, and the like.
The number of metal electron layers in the third soluble metal salt is 6, such as lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, europium nitrate, gadolinium nitrate, and the like.
The molar ratio of the first soluble metal salt to the second soluble metal salt to the third soluble metal salt is 4:2: 1. For example, the molar ratio of potassium nitrate, molybdenum nitrate, lanthanum nitrate is 4:2: 1.
The water is a solvent capable of dissolving soluble metal salts, and the preparation of the layered multi-metal hydroxide is realized by dissolving a plurality of soluble metal salts in the water and reacting. Optionally, the water is distilled water. In one embodiment of the present invention, the molar amount of water is 2 to 3 times the molar amount of the soluble metal salt composition; wherein the molar amount of the soluble metal salt composition is the sum of the molar amounts of the soluble metal salts in the soluble metal salt composition. That is, the molar amount of water is 2 to 3 times of the total molar amount of all the soluble metal salts in the soluble metal salt composition, so that the soluble metal salts can be completely dissolved, and the subsequent reaction can be completely performed.
In one embodiment of the present invention, the reaction temperature is 130 to 180 ℃. Namely, the layered multi-metal hydroxide is rapidly prepared by a hydrothermal reaction method. Specifically, S102 is to add an amide derivative to the metal salt solution in the step S101, stir at room temperature for 20 minutes, transfer into a hydrothermal reaction kettle, and react at 130-180 ℃ for 12-24 hours to obtain the layered multi-metal hydroxide.
In one embodiment of the present invention, the molar amount of the amide derivative is 1 to 2 times the molar amount of the soluble metal salt composition; wherein the molar amount of the soluble metal salt composition is the sum of the molar amounts of the soluble metal salts in the soluble metal salt composition. That is, the molar weight of the amide derivative is 1-2 times of the total molar weight of all soluble metal salts in the soluble metal salt composition, so that all metal ions in the metal salt solution can react with the amide derivative, and the completeness of the anion impurity removal effect is ensured; on the other hand, the method is convenient for accurately controlling the electronegativity of the layered multi-metal hydroxide to be between 50 and 70 percent of that of the graphene oxide. In one embodiment of the present invention, the amide derivative includes: one or more of urea, N-dimethylformamide, acrylamide, N-dimethylacetamide, stearic acid amide, erucamide and sulfonamide.
In one embodiment of the present invention, the reaction by adding the amide derivative to the metal salt solution further comprises: and removing impurities to obtain the layered multi-metal hydroxide. The impurity removal treatment comprises the following steps: washing with water and ethanol repeatedly, and vacuum drying. And removing impurities on the surface of the product by repeated washing, and removing residual impurities such as water, ethanol and the like by vacuum drying. Specifically, after the hydrothermal reaction is finished, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain brown powder, and finally vacuum drying at 60 ℃ to obtain the layered multi-metal hydroxide.
S200, mixing the graphene oxide and the layered multi-metal hydroxide in a dispersing agent. The dispersing agent is used for dispersing graphene oxide and layered multi-metal hydroxide, and a nanofiltration membrane is formed in the dispersing process. In one embodiment of the invention, the dispersant is water. Optionally, the dispersion is ultrasonic dispersion.
The method can control the number and the aperture size of the nanofiltration membrane channels by controlling the proportion of the layered multi-metal in the nanofiltration membrane. In one embodiment of the invention, the mass ratio of the graphene oxide to the layered multi-metal hydroxide to the water is 2:1: 10-3: 1:10, the number and the pore size of the nanofiltration membrane channels are controlled, and the electronegativity of the layered multi-metal compound is ensured to be between 50-70% of the electronegativity of the graphene oxide. And S300, removing the dispersing agent in the mixed solution to prepare the nanofiltration membrane.
In one embodiment of the present invention, depositing the mixed liquid includes: and depositing to obtain the nanofiltration membrane by vacuum filtration and heat treatment. Wherein most of the dispersant can be removed by vacuum filtration, and then the residual dispersant is removed by heating and evaporation.
Specifically, a certain amount of graphene oxide powder is weighed and put into a certain amount of deionized water, ultrasonic dispersion is carried out for a period of time, then a certain amount of layered multi-metal hydroxide powder is added, and ultrasonic treatment is continued to uniformly disperse the layered multi-metal hydroxide powder; then transferring to a bottom membrane, carrying out vacuum filtration, and finally carrying out heat treatment at 40-70 ℃ (such as 50 ℃) to obtain the composite nanofiltration membrane. The base membrane includes, but is not limited to, polysulfone membrane (PSF), polyethersulfone membrane (PES), sulfonated polysulfone membrane (SPS), and sulfonated polyethersulfone membrane (SPES).
The invention provides a nanofiltration membrane, which comprises: graphene oxide and a layered multimetal hydroxide dispersed in the graphene oxide. It can be understood that the nanofiltration membrane can be prepared by the preparation method of the nanofiltration membrane. Specifically, the layered multi-metal hydroxide can be dispersed among the layers of graphene oxide, so that the purposes of adjusting the distance between graphene oxide layers and increasing two-dimensional nano-channels are achieved.
Optionally, the nanofiltration membrane comprises 2-3 parts by weight of graphene oxide and 1 part by weight of layered multi-metal hydroxide. The nanofiltration membrane comprises graphene oxide and layered multi-metal hydroxide, and can be used for effectively separating and filtering the quantum dot solution.
The invention also provides an application of the nanofiltration membrane or the nanofiltration membrane prepared by the preparation method of the nanofiltration membrane in filtering quantum dot solution. For example, the quantum dot solution is filtered by using the above nanofiltration membrane or the nanofiltration membrane prepared by the above method, so as to obtain a purified quantum dot solution.
In one embodiment of the present invention, the quantum dot solution is a centrifuged quantum dot solution or a non-centrifuged quantum dot solution. That is, the quantum dots may be centrifuged prior to the method of purifying the quantum dot solution.
Methods of purifying quantum dot solutions suitable quantum dot systems include, but are not limited to: II-VI, III-V and IV-VI quantum dots, all-inorganic perovskite quantum dots, organic-inorganic perovskite quantum dots and copper-sulfur-indium ternary quantum dots; quantum dot architectures include, but are not limited to: the structure comprises a quantum dot homogeneous binary component mononuclear structure, a quantum dot homogeneous multi-component alloy component mononuclear structure, a quantum dot multi-component gradual change mononuclear structure, a quantum dot binary component discrete core-shell structure, a quantum dot multi-component alloy component discrete core-shell structure or a quantum dot multi-component alloy component gradual change core-shell structure; when the quantum dot is a core-shell structure quantum dot, the core compound and the shell compound can be selected from CdSe, CdS, ZnSe, ZnS, CdTe, ZnTe, CdZnS, ZnSeS, CdSeSte or CdZnSeTe of II-VI family, InP, InAs or InAsP of III-V family, PbS, PbSe, PbSeS, PbSeTe or PbSTe of IV-VI family.
The technical solution of the present invention will be described below by specific examples.
Example 1:
(1) after 4 mmol of lanthanum nitrate and 1 mmol of potassium chloride were mixed with each other, 10 mmol of distilled water was added to obtain a metal salt solution.
(2) And (2) adding 5 millimole of urea into the metal salt solution obtained in the step (1), stirring at room temperature for 20 minutes, transferring into a hydrothermal reaction kettle, reacting at 130 ℃ for 12 hours, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain white powder, and performing vacuum drying at 60 ℃ to obtain the layered multi-metal hydroxide.
(3) Weighing 2 g of graphene oxide powder in 10 g of deionized water, carrying out ultrasonic dispersion for 10 minutes, then adding 1 g of layered multi-metal hydroxide powder, continuing to carry out ultrasonic dispersion for 30 minutes to uniformly disperse the graphene oxide powder, then transferring the mixture onto a polysulfone base membrane, carrying out vacuum filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-lanthanum-potassium composite nanofiltration membrane.
(4) And (3) adding the stock solution after the CdSe @ ZnS quantum dots which are centrifuged or not centrifuged react into the graphene oxide-lanthanum-potassium composite nanofiltration membrane prepared in the step (3) for filtering to obtain a pure CdSe @ ZnS quantum dot solution.
Example 2:
(1) after 4 mmol of cerium nitrate and 2 mmol of ruthenium nitrate were mixed with each other, 18 mmol of distilled water was added to obtain a metal salt solution.
(2) And then adding 12 millimoles of N, N-dimethylacetamide into the metal salt solution obtained in the step 1, stirring for 20 minutes at room temperature, transferring into a hydrothermal reaction kettle, reacting at 180 ℃ for 24 hours, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain light yellow powder, and performing vacuum drying at 60 ℃ to obtain the layered multi-metal hydroxide.
(3) Weighing 3 g of graphene oxide powder in 10 g of deionized water, carrying out ultrasonic dispersion for 20 minutes, then adding 1 g of layered multi-metal hydroxide powder, and continuing to carry out ultrasonic dispersion for 30 minutes to uniformly disperse the layered multi-metal hydroxide powder. Then transferring the membrane to a polyether sulfone basement membrane, carrying out vacuum filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-cerium-ruthenium composite nanofiltration membrane.
(4) And (3) adding the stock solution after the InAsP @ ZnSe quantum dots which are centrifuged or not centrifuged react into the graphene oxide-cerium-ruthenium composite nanofiltration membrane prepared in the step (3) for filtering to obtain a pure InAsP @ ZnSe quantum dot solution.
Example 3:
(1) after 2 mmol of yttrium nitrate and 1 mmol of iron sulfate were mixed with each other, 8 mmol of distilled water was added to obtain a metal salt solution.
(2) And (2) adding 5 millimole of stearic acid amide into the metal salt solution obtained in the step (1), stirring at room temperature for 20 minutes, transferring into a hydrothermal reaction kettle, reacting at 160 ℃ for 18 hours, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain brownish red powder, and performing vacuum drying at 60 ℃ to obtain the layered multi-metal hydroxide.
(3) Weighing 2.5 g of graphene oxide powder in 10 g of deionized water, carrying out ultrasonic dispersion for 20 minutes, then adding 1 g of layered multi-metal hydroxide powder, and continuing to carry out ultrasonic dispersion for 30 minutes to uniformly disperse the layered multi-metal hydroxide powder. Then transferring the solution to a sulfonated polysulfone base membrane, carrying out vacuum filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-yttrium-iron composite nanofiltration membrane.
(4) And (3) adding the reaction stock solution of the PbSeTe quantum dots which are centrifuged or not centrifuged into the graphene oxide-yttrium-iron composite nanofiltration membrane prepared in the step (3) for filtering to obtain a pure PbSeTe quantum dot solution.
Example 4:
(1) after 4 mmol of nickel nitrate, 2 mmol of zirconium nitrate and 1 mmol of gadolinium nitrate were mixed with each other, 20 mmol of distilled water was added to obtain a metal salt solution.
(2) And (2) adding 14 millimole of sulfamide into the metal salt solution obtained in the step (1), stirring at room temperature for 20 minutes, transferring into a hydrothermal reaction kettle, reacting at 150 ℃ for 20 hours, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain yellow-green powder, and performing vacuum drying at 60 ℃ to obtain the layered multi-metal hydroxide.
(3) Weighing 3 g of graphene oxide powder in 10 g of deionized water, carrying out ultrasonic dispersion for 20 minutes, then adding 1 g of layered multi-metal hydroxide powder, and continuing to carry out ultrasonic dispersion for 30 minutes to uniformly disperse the layered multi-metal hydroxide powder. Then transferring the solution to a sulfonated polyether sulfone basement membrane, carrying out vacuum filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane.
(4) Subjecting organic-inorganic perovskite quantum dots (CH) which have or have not been subjected to centrifugation treatment3NH3-PbCl3Perovskite quantum dots) are added into the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane prepared in the step 3 for filtration, and then pure organic-inorganic perovskite quantum dots can be obtained.
Example 5:
(1) after mixing 2 mmol of nickel nitrate, 1 mmol of zirconium sulfate and 1 mmol of gadolinium nitrate, 20 mmol of distilled water was added to obtain a metal salt solution.
(2) And (2) adding 4 millimole of stearic acid amide into the metal salt solution obtained in the step (1), stirring at room temperature for 20 minutes, transferring into a hydrothermal reaction kettle, reacting at 130 ℃ for 18 hours, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain brownish red powder, and performing vacuum drying at 60 ℃ to obtain the layered multi-metal hydroxide.
(3) Weighing 2.5 g of graphene oxide powder in 10 g of deionized water, carrying out ultrasonic dispersion for 20 minutes, then adding 1 g of layered multi-metal hydroxide powder, and continuing to carry out ultrasonic dispersion for 30 minutes to uniformly disperse the layered multi-metal hydroxide powder. Then transferring the solution to a sulfonated polysulfone base membrane, carrying out vacuum filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane.
(4) And (3) adding the reaction stock solution of the PbSeTe quantum dots which are centrifuged or not centrifuged into the graphene oxide-yttrium-iron composite nanofiltration membrane prepared in the step (3) for filtering to obtain a pure PbSeTe quantum dot solution.
Example 6:
(1) after mixing 2 mmol of nickel nitrate, 2 mmol of zirconium nitrate and 9 mmol of gadolinium nitrate, 20 mmol of distilled water was added to obtain a metal salt solution.
(2) And (2) adding 25 millimoles of sulfamide into the metal salt solution obtained in the step (1), stirring at room temperature for 20 minutes, transferring into a hydrothermal reaction kettle, reacting at 180 ℃ for 20 hours, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain yellow-green powder, and performing vacuum drying at 60 ℃ to obtain the layered multi-metal hydroxide.
(3) Weighing 3 g of graphene oxide powder in 10 g of deionized water, carrying out ultrasonic dispersion for 20 minutes, then adding 1 g of layered multi-metal hydroxide powder, and continuing to carry out ultrasonic dispersion for 30 minutes to uniformly disperse the powder. Then transferring the solution to a sulfonated polyether sulfone basement membrane, carrying out vacuum filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane.
(4) Subjecting organic-inorganic perovskite quantum dots (CH) which have been centrifuged or not3NH3-PbCl3Perovskite quantum dots) are added into the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane prepared in the step 3 for filtration, and then pure organic-inorganic perovskite quantum dots can be obtained.
Example 7
The purity of the pre-filtered quantum dot solution and the post-filtered quantum dot solution of examples 1-4 were tested by agilent high performance liquid chromatography, and the results are shown in table 1. As can be seen from Table 1, the nanofiltration membrane prepared by the method can remove residual impurities in the quantum dot solution, so that a quantum dot product with high purity can be obtained.
TABLE 1 purity of Quantum solutions tested results
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (13)
1. A nanofiltration membrane, comprising: graphene oxide and a layered multi-metal hydroxide dispersed in the graphene oxide,
the graphene oxide and the layered multimetal hydroxide are bonded together by electrostatic interaction.
2. Nanofiltration membrane according to claim 1, wherein the number of graphene oxide layers is 10-20.
3. Nanofiltration membrane according to claim 2, wherein the graphene oxide has an interlayer spacing of 1 to 3 nm.
4. The nanofiltration membrane according to claim 1, wherein the coverage rate of the oxygen-containing groups on the surface of the graphene oxide is 60-70%.
5. Nanofiltration membrane according to claim 1, wherein the layered multi-metal hydroxide comprises at least two metal elements, and the metal elements comprise 4 or more layers of electrons.
6. Nanofiltration membrane according to claim 5, wherein the at least two metal elements comprise a first metal element, a second metal element, and a third metal element, wherein the number of electron layers of the first metal element is 4, the number of electron layers of the second metal element is 5, and the number of electron layers of the third metal element is 6;
wherein the molar ratio of the first metal element to the second metal element to the third metal element is 2:1: 1-9: 2: 2.
7. Nanofiltration membrane according to claim 5, wherein the metal elements are selected from one or more of potassium, calcium, scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, ruthenium, lanthanum, cerium, praseodymium, neodymium, europium, gadolinium.
8. Nanofiltration membrane according to claim 6, wherein the first metal element is selected from one or more of potassium, calcium, scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper;
the second metal element is selected from one or more of yttrium, zirconium, niobium, molybdenum and ruthenium;
the third metal element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, europium and gadolinium.
9. The nanofiltration membrane according to claim 1, wherein the mass ratio of the graphene oxide to the layered multi-metal hydroxide in the nanofiltration membrane is 2: 1-3: 1.
10. A method for preparing a nanofiltration membrane is characterized by comprising the following steps:
providing a layered multimetal hydroxide;
dispersing graphene oxide and layered multi-metal hydroxide into a dispersing agent to obtain a mixed solution;
and depositing the mixed solution to obtain the nanofiltration membrane.
11. The method for preparing nanofiltration membrane according to claim 10, wherein the method for preparing the layered multi-metal hydroxide comprises the following steps:
providing a metal salt solution;
adding an amide derivative into the metal salt solution for reaction to obtain a layered multi-metal hydroxide;
wherein the molar amount of the amide derivative is 1 to 2 times the molar amount of the metal salt.
12. The nanofiltration membrane preparation method according to claim 11, wherein the amide derivative is selected from one or more of urea, N-dimethylformamide, acrylamide, N-dimethylacetamide, stearic acid amide, erucamide, and sulfonamide.
13. Use of a nanofiltration membrane as defined in any one of claims 1 to 9 or prepared by a method for preparing a nanofiltration membrane as defined in any one of claims 10 to 12 in the filtration of quantum dot solutions.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509634A (en) * | 2011-10-31 | 2012-06-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene-based flexible multilayer composite film and preparing method thereof |
| CN104183830A (en) * | 2014-08-19 | 2014-12-03 | 中南大学 | Preparation method of two-dimensional inorganic layered compound/graphene composite material |
| CN107720886A (en) * | 2017-10-17 | 2018-02-23 | 山东大学 | A kind of nano-particle intercalation graphene oxide film and preparation method and application |
| US20200377388A1 (en) * | 2019-05-29 | 2020-12-03 | Uchicago Argonne, Llc | Layered hydroxides as anion insertion materials |
-
2020
- 2020-12-24 CN CN202011547950.8A patent/CN114669200B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509634A (en) * | 2011-10-31 | 2012-06-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene-based flexible multilayer composite film and preparing method thereof |
| CN104183830A (en) * | 2014-08-19 | 2014-12-03 | 中南大学 | Preparation method of two-dimensional inorganic layered compound/graphene composite material |
| CN107720886A (en) * | 2017-10-17 | 2018-02-23 | 山东大学 | A kind of nano-particle intercalation graphene oxide film and preparation method and application |
| US20200377388A1 (en) * | 2019-05-29 | 2020-12-03 | Uchicago Argonne, Llc | Layered hydroxides as anion insertion materials |
Non-Patent Citations (2)
| Title |
|---|
| 司学见: ""氧化石墨烯复合纳滤膜片层间距调控及其染料分离性能研究", 《中国优秀硕士论文全文数据库(工程科技Ⅰ辑)》 * |
| 周阿武等: "自支撑LDH/rGO复合薄膜的制备及其超电容性能", 《石油化工》 * |
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