CN114669200B - Nanofiltration membrane and preparation method and application thereof - Google Patents
Nanofiltration membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN114669200B CN114669200B CN202011547950.8A CN202011547950A CN114669200B CN 114669200 B CN114669200 B CN 114669200B CN 202011547950 A CN202011547950 A CN 202011547950A CN 114669200 B CN114669200 B CN 114669200B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- metal
- nanofiltration membrane
- metal hydroxide
- layered multi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a nanofiltration membrane and a preparation method and application thereof. Nanofiltration membranes comprising: graphene oxide and a layered multi-metal hydroxide dispersed in the graphene oxide, the graphene oxide and the layered multi-metal hydroxide being bonded together by electrostatic action. 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 Dot) and Quantum Dot related materials and devices have been known as one of the core technological engines in the 4.0 era of industry today. Because each small particle is single crystal particle and has good tunability in size, the material has high color purity, wide color gamut, high crystal stability, narrow and symmetrical fluorescence emission spectrum and wide and continuous ultraviolet absorption spectrum, which makes the material an ideal new material for flexible printing display.
It is well known that in optoelectronic illumination and display devices, the purity requirements for the optoelectronic starting material are very high. The introduction of trace and trace reaction precursor substances not only can influence the optical and electrical characteristics of the photoelectric material, but also can cause irreversible influence on the electroluminescent efficiency, service life and the like in the quantum dot luminescent 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 field of photoelectricity are prepared by hydrothermal synthesis, and the synthesized quantum dots often have cationic precursors and anionic precursors which are remained and can be used only by repeated centrifugation or extraction. Moreover, the two treatment methods are only preliminary separation, and the quantum dot product with higher purity cannot be ensured.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings 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 is obtained.
A nanofiltration membrane comprising: graphene oxide and a layered multi-metal hydroxide dispersed in the graphene oxide, the graphene oxide and the layered multi-metal hydroxide being bonded together by electrostatic action.
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 greater than or equal to 4.
In the nanofiltration membrane, at least two metal elements include: the first metal element, the second metal element and the third metal element, wherein the number of the electronic layers of the first metal element is 4, the number of the electronic layers of the second metal element is 5 and the number of the electronic 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.
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 graphene oxide to layered multi-metal hydroxide is 2:1-3:1.
A method for preparing a nanofiltration membrane, comprising:
providing a layered multi-metal hydroxide;
dispersing graphene oxide and layered multi-metal hydroxide into a dispersing agent to obtain a mixed solution;
and (5) 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 an amide derivative 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 one or more selected from urea, N-dimethylformamide, acrylamide, N-dimethylacetamide, stearic acid amide, erucic acid amide 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 adopting the preparation method of the nanofiltration membrane in the filtration of the quantum dot solution.
The beneficial effects are that: the nanofiltration membrane provided by the invention contains graphene oxide and layered multi-metal hydroxide dispersed in the graphene oxide, and can remove residual cation precursors and anion precursors in the quantum dot solution, so that a quantum dot product with higher 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 purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Graphene is a two-dimensional lamellar material with a honeycomb-like structure, consisting of sp 2 A hybridized carbon atom composition of only one atomic layer thicknessThe strength is very high. Graphene Oxide (GO) is a derivative of graphene, and the surface of graphene oxide is rich in oxygen-containing groups such as hydroxyl groups, carboxyl groups and epoxy groups. The graphene oxide has good hydrophilicity due to rich oxygen-containing functional groups, and the graphene oxide nano sheets can be stacked into a compact lamellar structure due to strong hydrogen bonding. In addition, the graphene oxide has high mechanical strength, good flexibility, acid and alkali resistance and organic solvent resistance and is easy to obtain.
Wherein, the structural formula of single-layer graphene oxide is:
the layered multi-metal hydroxide is a metal hydroxide composed of two or more metal elements, the structure of which is composed of laminate and interlayer anions which are overlapped with each other, in particular, the layered multi-metal hydroxide is composed of positively charged laminate and interlayer exchangeable anions which are orderly assembled.
The embodiment of the invention provides a nanofiltration membrane, which comprises the following components: graphene oxide and a layered multi-metal hydroxide dispersed in the graphene oxide, the graphene oxide and the layered multi-metal hydroxide being bonded together by electrostatic action.
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 cationic precursors and anionic 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 has electronegativity, and residual metal cations in the quantum dot solution can be removed by forming coordination compounds or by electrostatic attraction, for example, the oxygen-containing groups can be hydroxyl groups, carboxyl groups, epoxy groups and the like, the residual metal cations in the quantum dot solution can be zinc ions, cadmium ions, lead ions, indium ions and the like, namely, the oxygen-containing groups of hydroxyl groups, carboxyl groups, epoxy groups and the like can form coordination compounds with the residual metal cations in various quantum dot solutions, such as zinc ions, cadmium ions, lead ions, indium ions and the like, or the residual metal cations can be removed by electrostatic attraction of the metal cations.
Layered multi-metal hydroxides are two-dimensional cationic materials, i.e., the surface of the layered multi-metal hydroxide has a large number of hydroxyl groups and positive charges, which can form a complex with polymers or nanoparticles remaining in the quantum dot solution, for example, the layered multi-metal hydroxide removes the remaining anions in the quantum dot solution, specifically, the remaining ions such as sulfide ions, selenide ions, arsenic ions, etc., in the quantum dot solution by means of electrostatic attraction.
In addition, in the nanofiltration membrane, electrostatic action is generated between the positively charged layered multi-metal hydroxide and the negatively charged graphene oxide nano-sheets, 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 filtration rate can be ensured, 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 layers of graphene oxide is less than 10, the number of layers of graphene oxide is not easy to control, the filtration rate is too fast, and the impurity removal is not good. When the number of layers of the graphene oxide is more than 20, the number of layers of the graphene oxide is excessively complicated, the filtration rate is too slow, and the loss of the quantum dot can be caused. In one embodiment of the invention, the coverage rate of oxygen-containing groups on the surface of graphene oxide is 60-70%, and the graphene oxide has enough negative charges to combine with cationic impurities in the quantum dot solution and enough negative charges to generate electrostatic action with the layered metal hydroxide, so that the intercalation 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 the size 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 between the sheets, and the interlayer spacing of the graphene oxide not only provides a water transmission channel, but also has a steric effect on some small molecules. Although the graphene oxide layer has a certain gap, the graphene oxide layer cannot increase the distance, and the distance of the graphene oxide layer needs to be enlarged by introducing foreign matters so as to improve the filtration speed of the quantum dot solution. The research of the invention also finds that the common metal hydroxide can not or very little be inserted into the graphene oxide sheets, and the layered metal hydroxide can realize effective insertion between the graphene oxide sheets. Based on the above, the embodiment of the invention realizes the regulation and control of the interlayer spacing of the graphene oxide by utilizing the intercalation of the layered multi-metal hydroxide into the graphene oxide. In one embodiment of the present invention, the layered metal hydroxide is capable of increasing the interlayer spacing by 0.5 to 1nm on the basis of graphene protoxide. Alternatively, the interlayer spacing of the 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 realizes the regulation and control of the interlayer spacing of the graphene oxide by utilizing the electrostatic action of the layered multi-metal hydroxide and the graphene oxide. Specifically, when metal atoms with a large number of electron layers (e.g., 4 or more electron layers) are inserted, the layer distance between graphene oxides can be appropriately increased, and the larger the number of electron layers of the metal element is, the larger the increased layer distance is. In one embodiment of the present invention, the layered multi-metal hydroxide includes at least two metal elements, wherein the metal elements are metal elements having 4 or more electron layers. 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 anion binding capacity is, and the residual anion impurities in the quantum dot solution can be removed better. Meanwhile, the metal elements with more electron layers are used, so that the consumption of the metal elements can be reduced, the effect of removing impurities is ensured, and the effect of saving cost is achieved. The invention controls the number of channels and the pore size of the nanofiltration membrane by changing the layered multi-metal hydroxide species in the nanofiltration membrane. In one embodiment of the present invention, the at least two metal elements include: the first metal element, the second metal element and the third metal element, wherein the number of the electronic layers of the first metal element is 4, the number of the electronic layers of the second metal element is 5 and the number of the electronic 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. According to researches, when the mole ratio of the first metal element to the second metal element to the third metal element is smaller 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; and when the mole ratio of the first metal element to the second metal element to the third metal element is greater than 9:2:2, the interlayer distance of the graphene oxide 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 interlayer distance of the graphene oxide 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 pore size of the nanofiltration membrane by changing the content of the layered multi-metal hydroxide in the nanofiltration membrane. In one embodiment of the invention, the mass ratio of graphene oxide to layered multi-metal hydroxide is 2:1 to 3:1. The research shows that the larger the content of the layered multi-metal hydroxide in the nanofiltration membrane is, the larger the distance between the nanofiltration membrane layers is, namely, the larger the aperture of the 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 the filtration of the quantum dot solution, the filtration efficiency of the quantum dot solution can be improved, and the purity of the filtered quantum dot solution is ensured.
In addition, in the nanofiltration membrane, the mass ratio of graphene oxide to layered multi-metal hydroxide can control the electronegativity of the layered multi-metal hydroxide in graphene oxide. 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 is between 50 and 70% of that of the graphene oxide. Wherein, when the electronegativity of the layered multi-metal hydroxide is lower than 50% in the graphene oxide, the layered multi-metal hydroxide cannot be combined with the graphene oxide layer firmly enough, and the effect of enlarging the interlayer spacing of the graphene oxide layer by inserting the graphene oxide layer is not achieved so as to accelerate filtration. When the electronegativity of the layered multi-metal hydroxide is higher than 70% in the graphene oxide, the layered multi-metal hydroxide can react with a large amount of negative groups on the surface of the graphene oxide, and consume a large amount of negative groups, so that the effect of removing cationic impurities by means of the negative groups on the surface of the graphene oxide is lost. When the electronegativity of the layered multi-metal hydroxide is between 50 and 70 percent of that of the graphene oxide, the layered multi-metal hydroxide can be firmly combined with the graphene oxide and can be inserted between graphene oxide layers to play a role in expanding the interlayer distance of the graphene oxide and simultaneously remove residual cations and anion impurities in the quantum dot solution.
The invention provides a preparation method of a nanofiltration membrane, which comprises the following steps:
s100, providing layered multi-metal hydroxide;
s200, dispersing graphene oxide and layered multi-metal hydroxide into a dispersing agent to obtain a mixed solution;
s300, depositing the mixed solution to obtain the nanofiltration membrane.
According to the invention, layered multi-metal hydroxide is introduced into a graphene oxide membrane to prepare the nanofiltration membrane. The nanofiltration membrane can remove metal cations and anions in the quantum dot solution and quantum dot organic ligands which are not combined or fall off, 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 between the sheets, and the interlayer spacing of the graphene oxide not only provides a water transmission channel, but also has a steric effect on some small molecules. According to the invention, the layered multi-metal hydroxide is introduced into the graphene oxide film, the interlayer spacing of the graphene oxide film is adjusted, a two-dimensional nano channel can be increased, and the filtration rate of the quantum dot solution is increased; the electrostatic effect is generated between the positively charged layered multi-metal hydroxide and the negatively charged graphene oxide nano-sheets, so that the stability of the film structure can be enhanced; graphene oxide and layered multi-metal hydroxides are capable of removing residual cationic and anionic precursors in the quantum dot solution either in a manner that forms a complex or in a manner that is electrostatically attracted.
In addition, the oxygen-containing groups rich in the surface of the graphene oxide have good hydrophilicity, so that trace water molecules in the quantum dot solution can be well removed for the oil-soluble quantum dots, and the luminescence stability of the quantum dot solution is ensured.
The layered multi-metal hydroxide is a two-dimensional cationic material, and because a large number of hydroxyl groups and positive charges exist on the surface, anions such as sulfide ions, selenium ions, arsenic ions and the like in various quantum dot solutions can be removed in an electrostatic attraction mode, so that the aim of removing residual anions is fulfilled.
The nanofiltration membrane can flexibly control the filtration effect on the quantum dot solution. Specifically, the first graphene oxide surface contains rich oxygen-containing groups, and residual metal cations can be removed through a coordination compound forming mode or an electrostatic attraction mode, so that 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; thirdly, as the layered multi-metal hydroxide can adjust the interlayer spacing of the graphene oxide, the number and the pore size of the nanofiltration membrane channels are controlled by controlling the content of the layered multi-metal. In one embodiment of the invention, the coverage rate of the oxygen-containing groups on the surface of the graphene oxide can be controlled by regulating corresponding reaction parameters in the process of preparing the graphene oxide and controlling the coverage rate of the oxygen-containing groups on the surface of the graphene oxide. Alternatively, the coverage of the oxygen-containing groups is controlled by how much strong acid is added. For example, the dilute nitric acid is added in an amount of 10% of the volume of the graphene solution, so that 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%; 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. Specifically, on one hand, the addition of the layered multi-metal hydroxide can play a role in adjusting the interlayer spacing of the graphene oxide, increasing the two-dimensional nano channel and increasing the filtration rate; on the other hand, electrostatic action is generated between the positively charged layered multi-metal hydroxide and the negatively charged graphene oxide nano-sheets, so that the stability of the graphene oxide film structure can be enhanced.
The layered multi-metal hydroxide of the present invention has a layered structure and contains two or more metal hydroxides. In particular, layered multi-metal hydroxides are novel inorganic materials with hydrotalcite-like layered structures composed of various metal ions. The invention provides a preparation method of layered multi-metal hydroxide. In one embodiment of the present invention, there is provided a method for producing a layered multi-metal hydroxide comprising:
s101, providing a metal salt solution;
s102, adding an amide derivative into a metal salt solution for reaction to obtain 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 multiple electron layers, 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 a multi-electron layer, and the metal of the multi-electron layer is specifically a metal element 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 layer.
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, 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 present invention, a soluble metal salt composition includes: 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 number of metal electron layers in the first soluble metal salt is 4, such as soluble potassium salt, soluble calcium salt, soluble scandium salt, soluble vanadium salt, soluble chromium salt, soluble manganese salt, soluble ferric salt, soluble cobalt salt, soluble nickel salt, soluble copper salt, etc.
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, etc.
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, etc.
The molar ratio of the first soluble metal salt, the second soluble metal salt and the third soluble metal salt is 4:2:1. For example, the molar ratio of potassium nitrate, molybdenum nitrate and lanthanum nitrate is 4:2:1.
The water of the present invention is a solvent capable of dissolving soluble metal salts, and the preparation of layered multi-metal hydroxide is achieved by dissolving a plurality of soluble metal salts in water, and by reacting. Alternatively, the water is distilled water. In one embodiment of the 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 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 completed.
In one embodiment of the invention, the temperature of the reaction is 130 to 180 ℃. That is, the layered multi-metal hydroxide is rapidly prepared by a hydrothermal reaction method. Specifically, S102 is to add an amide derivative into the metal salt solution in the step S101, stir the mixture at room temperature for 20 minutes, transfer the mixture into a hydrothermal reaction kettle, and then react for 12-24 hours at 130-180 ℃ to obtain the layered multi-metal hydroxide.
In one embodiment of the 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 amount of the amide derivative is 1 to 2 times the total molar amount of all the soluble metal salts in the soluble metal salt composition, so that all the metal ions in the metal salt solution can react with the amide derivative, and on one hand, the completeness of the effect of removing the anionic impurities is ensured; on the other hand, the electronegativity of the layered multi-metal hydroxide is convenient to accurately control to be 50-70% of that of the graphene oxide. In one embodiment of the present invention, the amide derivative comprises: urea, N-dimethylformamide, acrylamide, N-dimethylacetamide, stearic acid amide, erucic acid amide, sulfonamide.
In one embodiment of the present invention, the method further comprises the steps of: and (3) performing impurity removal treatment to obtain the layered multi-metal hydroxide. The impurity removal treatment comprises the following steps: repeatedly washing with water and ethanol, and vacuum drying. The impurities on the surface of the product are removed by repeated washing, and the impurities such as residual water, ethanol and the like are removed by vacuum drying. Specifically, after the hydrothermal reaction is completed, 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 is to mix graphene oxide and layered multi-metal hydroxide in a dispersant. 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. Alternatively, dispersion is ultrasonic dispersion.
The invention can control the number and the pore size of the nanofiltration membrane channels by controlling the proportion of layered polymetallic in the nanofiltration membrane. In one embodiment of the invention, the mass ratio of graphene oxide, layered multi-metal hydroxide to water is 2:1:10 to 3:1:10, the number and pore size of nanofiltration membrane channels are controlled, and the electropositivity of the layered multi-metal compound is ensured to be between 50 and 70% of the electronegativity of the graphene oxide. S300, removing the dispersing agent in the mixed solution to prepare the nanofiltration membrane.
In one embodiment of the present invention, the deposition mixture includes: and depositing by vacuum filtration and heat treatment to obtain the nanofiltration membrane. Wherein, the vacuum filtration can remove most of the dispersing agent, and the residual dispersing agent is removed by heating and evaporating.
Specifically, a certain amount of graphene oxide powder is weighed and placed in 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 is continued to be carried out to enable the layered multi-metal hydroxide powder to be uniformly dispersed; then transferring to a basement membrane, vacuum filtering, and finally carrying out heat treatment at 40-70 ℃ (such as 50 ℃), thus obtaining the composite nanofiltration membrane. Among them, the base membrane includes, but is not limited to, polysulfone membrane (PSF), polyethersulfone membrane (PES), sulfonated polysulfone membrane (SPS), sulfonated polyethersulfone membrane (SPES), and the like.
The invention provides a nanofiltration membrane, which comprises the following components: graphene oxide and layered multi-metal hydroxide dispersed in graphene oxide. It is understood that the nanofiltration membrane can be prepared by the above nanofiltration membrane preparation method. Specifically, the layered multi-metal hydroxide can be dispersed among graphene oxide layers, so that the purposes of adjusting the interlayer spacing of the graphene oxide and increasing the two-dimensional nano channel are achieved.
Optionally, the nanofiltration membrane comprises 2-3 parts of graphene oxide and 1 part of layered multi-metal hydroxide in parts by weight. The nanofiltration membrane comprises graphene oxide and layered multi-metal hydroxide, so that effective separation and filtration of the quantum dot solution can be realized.
The invention also provides an application of the nanofiltration membrane or the nanofiltration membrane prepared by the preparation method of the nanofiltration membrane in the filtration of the quantum dot solution. For example, the quantum dot solution is filtered by using the nanofiltration membrane or the nanofiltration membrane prepared by the method, so as to obtain the purified quantum dot solution.
In one embodiment of the invention, the quantum dot solution is a centrifuged quantum dot solution or a quantum dot solution without centrifugation. That is, the quantum dots may be subjected to centrifugation 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, IV-VI quantum dots, all-inorganic perovskite quantum dots, organic-inorganic perovskite quantum dots, copper-sulfur-indium ternary quantum dots; quantum dot architectures include, but are not limited to: the quantum dot homogeneous binary component mononuclear structure, the quantum dot homogeneous multi-element alloy component mononuclear structure, the quantum dot multi-element alloy component gradual change mononuclear structure, the quantum dot binary component discrete core-shell structure, the quantum dot multi-element alloy component discrete core-shell structure or the quantum dot multi-element 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, cdSeS, cdSeSTe of II-VI groups or CdZnSeSTe and the like, inP of III-V groups, inAs or InAsP and the like, pbS, pbSe, pbSeS, pbSeTe of IV-VI groups or PbSTe and the like.
The technical scheme of the invention is described below through 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) Then adding 5 millimoles of urea into the metal salt solution in the step 1, stirring for 20 minutes at room temperature, transferring into a hydrothermal reaction kettle, reacting for 12 hours at 130 ℃, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain white powder, and drying in vacuum at 60 ℃ to obtain layered multi-metal hydroxide.
(3) 2 g of graphene oxide powder is weighed into 10 g of deionized water, ultrasonic dispersion is carried out for 10 minutes, then 1 g of layered multi-metal hydroxide powder is added, ultrasonic dispersion is continued for 30 minutes to enable the layered multi-metal hydroxide powder to be uniformly dispersed, then the layered multi-metal hydroxide powder is transferred onto a polysulfone basement membrane and subjected to vacuum suction filtration, and finally heat treatment is carried out at 50 ℃ to obtain the graphene oxide-lanthanum-potassium composite nanofiltration membrane.
(4) And (3) adding the raw liquid after the reaction of the centrifuged or non-centrifuged CdSe@ZnS quantum dots into the graphene oxide-lanthanum-potassium composite nanofiltration membrane prepared in the step (3) for filtration, thus obtaining the 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) Then adding 12 millimoles of N, N-dimethylacetamide into the metal salt solution in the step 1, stirring for 20 minutes at room temperature, transferring into a hydrothermal reaction kettle, reacting for 24 hours at 180 ℃, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain pale yellow powder, and vacuum drying at 60 ℃ to obtain layered multi-metal hydroxide.
(3) 3 g of graphene oxide powder is weighed into 10 g of deionized water, dispersed for 20 minutes by ultrasonic, then 1 g of layered multi-metal hydroxide powder is added, and ultrasonic is continued for 30 minutes to enable the layered multi-metal hydroxide powder to be dispersed uniformly. And then transferring the membrane onto a polyethersulfone basement membrane, carrying out vacuum suction filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-cerium-ruthenium composite nanofiltration membrane.
(4) And (3) adding the raw liquid after the InAsP@ZnSe quantum dots are reacted, which are subjected to centrifugation or are not subjected to centrifugation, into the graphene oxide-cerium-ruthenium composite nanofiltration membrane prepared in the step (3) for filtration, so that a pure InAsP@ZnSe quantum dot solution can be obtained.
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) Then adding 5 millimoles of stearic acid amide into the metal salt solution in the step 1, stirring for 20 minutes at room temperature, transferring into a hydrothermal reaction kettle, reacting for 18 hours at 160 ℃, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain brownish red powder, and vacuum drying at 60 ℃ to obtain layered multi-metal hydroxide.
(3) 2.5 g of graphene oxide powder is weighed into 10 g of deionized water, dispersed for 20 minutes by ultrasonic, then 1 g of layered multi-metal hydroxide powder is added, and ultrasonic treatment is continued for 30 minutes to enable the layered multi-metal hydroxide powder to be dispersed uniformly. And then transferring the mixture to a sulfonated polysulfone basement membrane, carrying out vacuum suction filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-yttrium-iron composite nanofiltration membrane.
(4) And (3) adding the raw solution after the centrifugal or non-centrifugal PbSeTe quantum dot reaction into the graphene oxide-yttrium-iron composite nanofiltration membrane prepared in the step (3) for filtration, thus obtaining the 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) Then adding 14 millimoles of sulfonamide into the metal salt solution in the step 1, stirring for 20 minutes at room temperature, transferring into a hydrothermal reaction kettle, reacting for 20 hours at 150 ℃, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain yellowish green powder, and vacuum drying at 60 ℃ to obtain layered multi-metal hydroxide.
(3) 3 g of graphene oxide powder is weighed into 10 g of deionized water, dispersed for 20 minutes by ultrasonic, then 1 g of layered multi-metal hydroxide powder is added, and ultrasonic is continued for 30 minutes to enable the layered multi-metal hydroxide powder to be dispersed uniformly. And then transferring the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane onto a sulfonated polyether sulfone basement membrane, carrying out vacuum suction filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane.
(4) Organic-inorganic perovskite quantum dots (CH) 3 NH 3 -PbCl 3 Perovskite quantum dots) and adding the stock solution into the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane prepared in the step 3 for filtration, thus obtaining the pure organic-inorganic perovskite quantum dots.
Example 5:
(1) After 2 mmol of nickel nitrate, 1 mmol of zirconium sulfate 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) Then adding 4 millimoles of stearic acid amide into the metal salt solution in the step 1, stirring for 20 minutes at room temperature, transferring into a hydrothermal reaction kettle, reacting for 18 hours at 130 ℃, cooling to room temperature, repeatedly washing with deionized water and ethanol, filtering to obtain brownish red powder, and vacuum drying at 60 ℃ to obtain layered multi-metal hydroxide.
(3) 2.5 g of graphene oxide powder is weighed into 10 g of deionized water, dispersed for 20 minutes by ultrasonic, then 1 g of layered multi-metal hydroxide powder is added, and ultrasonic treatment is continued for 30 minutes to enable the layered multi-metal hydroxide powder to be dispersed uniformly. And then transferring the mixture to a sulfonated polysulfone basement membrane, carrying out vacuum suction 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 raw solution after the centrifugal or non-centrifugal PbSeTe quantum dot reaction into the graphene oxide-yttrium-iron composite nanofiltration membrane prepared in the step (3) for filtration, thus obtaining the pure PbSeTe quantum dot solution.
Example 6:
(1) After 2 mmol of nickel nitrate, 2 mmol of zirconium nitrate and 9 mmol of gadolinium nitrate were mixed with each other, 20 mmol of distilled water was added to obtain a metal salt solution.
(2) Then 25 millimoles of sulfonamide is added into the metal salt solution in the step 1, stirring is carried out for 20 minutes at room temperature, the mixture is transferred into a hydrothermal reaction kettle, the mixture is cooled to room temperature after reacting for 20 hours at 180 ℃, deionized water and ethanol are used for repeated washing, yellow-green powder is obtained after filtration, and layered multi-metal hydroxide is obtained after vacuum drying at 60 ℃.
(3) 3 g of graphene oxide powder is weighed into 10 g of deionized water, dispersed for 20 minutes by ultrasonic, then 1 g of layered multi-metal hydroxide powder is added, and ultrasonic is continued for 30 minutes to enable the layered multi-metal hydroxide powder to be dispersed uniformly. And then transferring the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane onto a sulfonated polyether sulfone basement membrane, carrying out vacuum suction filtration, and finally carrying out heat treatment at 50 ℃ to obtain the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane.
(4) Organic-inorganic perovskite quantum dots (CH) 3 NH 3 -PbCl 3 Perovskite quantum dots) and adding the stock solution into the graphene oxide-gadolinium-zirconium-nickel composite nanofiltration membrane prepared in the step 3 for filtration, thus obtaining the pure organic-inorganic perovskite quantum dots.
Example 7
The purity of the pre-and post-filtration quantum dot solutions of examples 1 to 4 were tested using 1260 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 invention can remove the residual impurities in the quantum dot solution, thereby obtaining the quantum dot product with higher purity.
TABLE 1 purity of Quantum solutions results of tests
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (7)
1. A nanofiltration membrane, comprising: graphene oxide and layered multi-metal hydroxide dispersed in the graphene oxide,
the graphene oxide and the layered multi-metal hydroxide are bonded together by electrostatic action;
the number of the layers of the graphene oxide is 10-20;
the layered multi-metal hydroxide comprises a first metal element, a second metal element and a third metal element;
the first metal element is selected from one or more of potassium, nickel and iron;
the second metal element is selected from one or more of yttrium, zirconium and ruthenium;
the third metal element is selected from one or more of lanthanum, cerium and gadolinium;
the interlayer spacing of the graphene oxide is 1-3 nm.
2. The nanofiltration membrane according to claim 1, wherein the coverage of oxygen-containing groups on the graphene oxide surface is 60-70%.
3. The nanofiltration membrane according to claim 1, wherein the mass ratio of graphene oxide to layered multi-metal hydroxide in the nanofiltration membrane is 2:1-3:1.
4. A method of preparing a nanofiltration membrane as claimed in any one of claims 1 to 3, comprising:
providing a layered multi-metal 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.
5. The method for preparing a nanofiltration membrane according to claim 4, wherein the method for preparing a layered multi-metal hydroxide comprises:
providing a metal salt solution;
adding an amide derivative 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.
6. The method for preparing nanofiltration membrane according to claim 5, wherein the amide derivative is one or more selected from urea, N-dimethylformamide, acrylamide, N-dimethylacetamide, stearic acid amide, erucic acid amide, and sulfonamide.
7. Use of a nanofiltration membrane according to any one of claims 1 to 3 or a nanofiltration membrane prepared by a method for preparing a nanofiltration membrane according to any one of claims 4 to 6 in filtration of a quantum dot solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011547950.8A CN114669200B (en) | 2020-12-24 | 2020-12-24 | Nanofiltration membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011547950.8A CN114669200B (en) | 2020-12-24 | 2020-12-24 | Nanofiltration membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114669200A CN114669200A (en) | 2022-06-28 |
| CN114669200B true CN114669200B (en) | 2023-08-01 |
Family
ID=82069723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011547950.8A Active CN114669200B (en) | 2020-12-24 | 2020-12-24 | Nanofiltration membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114669200B (en) |
Citations (3)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11858826B2 (en) * | 2019-05-29 | 2024-01-02 | Uchicago Argonne, Llc | Layered hydroxides as anion insertion materials |
-
2020
- 2020-12-24 CN CN202011547950.8A patent/CN114669200B/en active Active
Patent Citations (3)
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| "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;司学见;《中国优秀硕士论文全文数据库(工程科技Ⅰ辑)》;20191215(第12期);39-49 * |
| 自支撑LDH/rGO复合薄膜的制备及其超电容性能;周阿武等;《石油化工》;20161231;第45卷(第12期);1420-1425 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114669200A (en) | 2022-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111081816B (en) | Perovskite nanocrystalline with alkali metal ion passivated surface defect and preparation and application thereof | |
| JP2020045491A (en) | Luminescent crystals and manufacturing thereof | |
| JP7286069B2 (en) | Composite light-emitting material, its production method and its use | |
| KR101619933B1 (en) | Three-Layer Core-Shell Nano Particle for Manufacturing Light Absorbing Layer of Solar Cell and Manufacturing Method thereof | |
| KR101037825B1 (en) | Lithium phosphate aggregates, a process for preparing thereof and a process for preparing lithium iron phosphor system complex oxides | |
| US11193060B2 (en) | Method for synthesizing perovskite quantum dot film | |
| KR20140097981A (en) | Method for Manufacturing Metal Nano Particle for Solar Cell, Ink Composition Comprising the Metal Nano Particle and Method for Manufacturing Thin Film Solar Cell Using the Same | |
| JP2018140934A (en) | Sodium- or antimony-doped nanoparticles | |
| CN109585844B (en) | Sodium-supplementing positive electrode active material, positive electrode material, sodium ion battery, and preparation and application thereof | |
| CN111676010B (en) | Preparation method of perovskite quantum dot/Eu-MOF composite luminescent material | |
| CN114669200B (en) | Nanofiltration membrane and preparation method and application thereof | |
| KR101606420B1 (en) | Ink Composition for Preparation of Light Absorbing Layer of Solar Cell and Manufacturing Method of Solar Cell Thin Film Using the Same | |
| US20170301807A1 (en) | Precursor for preparing light absorption layer of solar cells and method of preparing the same | |
| US10797316B2 (en) | Coated nickel hydroxide powder for alkali secondary battery positive electrode active material and method of producing same | |
| CN111490171A (en) | Zinc oxide nano material, preparation method thereof and luminescent device comprising zinc oxide nano material | |
| KR101660268B1 (en) | Metal Calcogenide Nano Particle for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same | |
| KR101643579B1 (en) | Aggregate Phase Precursor for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same | |
| CN116002773A (en) | Preparation method for preparing modified sodium ion battery precursor by regenerating copper-manganese liquid | |
| CN116199270A (en) | Treatment process for reducing wastewater in cobalt oxide production process | |
| CN110759383B (en) | Heteropolyacid crystal, preparation method thereof, secondary battery negative electrode material, secondary battery and electric device | |
| KR20160133672A (en) | Precursor for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same | |
| CN101664686B (en) | Preparation method of nano metal sulphide compound semiconductor photocatalytic material | |
| TWI735722B (en) | Composition | |
| CN116410749A (en) | Quantum dot purification method and quantum dot | |
| KR101723033B1 (en) | Precursor for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |