CN115138220A - Anionic covalent organic framework membrane and preparation and application thereof - Google Patents
Anionic covalent organic framework membrane and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses an anionic covalent organic framework membrane, which consists of two reaction monomers, namely 1,3, 5-trihydroxy mesitylene and 1, 4-diaminobenzoic acid, wherein the two reaction monomers firstly generate anionic covalent organic framework nanosheets through a pH-mediated oil-water-oil interface polymerization method, and then the nanosheets are assembled on a porous substrate through a vacuum-assisted assembly method to prepare the anionic covalent organic framework membrane; the membrane integrally presents an asymmetric structure and comprises a compact skin layer and a porous supporting layer, wherein the porous supporting layer is a fiber staggered stacking structure. The covalent organic framework material has sub-nanometer aperture and easy cutting point, so that a hydration layer can be constructed in the channel, the membrane has the screening function on univalent cations, the high-efficiency separation process is realized, and the technical bottleneck of the microporous framework material for ion separation is broken through. In addition, by adjusting conditions such as the kind of the reactive monomer, the monomer concentration, and the dispersion concentration, the film performance can be further optimized.
Description
Technical Field
The invention belongs to the technical field of novel separation membrane materials, relates to the development of membrane materials applied to the field of ion separation, and particularly relates to a preparation method of an anionic covalent organic framework membrane.
Background
The membrane separation technology is a novel separation technology, can realize selective separation aiming at molecular mixtures with different characteristics on the molecular level, and has the characteristics of high efficiency, energy conservation, greenness, environmental protection, small occupied area and the like. At present, the membrane separation technology is widely applied to the fields of medicine, food, biology, chemical industry, environmental protection, electron, water treatment and the like, and brings great economic and social benefits.
Na widely exists in salt lake, sea water and salt water + 、K + And Li + And the like. With the wide application of monovalent metal ions in the fields of energy storage, metallurgy, agriculture and the like, the efficient separation of monovalent cation mixtures becomes an important requirement. At present, univalent cation separation mainly depends on evaporation-precipitation-adsorption, evaporation-extraction, evaporation-calcination and other comprehensive or combined technologies, and has complex process and higher energy consumption. Due to the characteristics of non-thermal property, low carbon and low environmental footprint, the membrane technology has wide prospect in the aspect of separating monovalent cations. However, sub-nanometer ion size (e.g., bare ions)
Hydrated ion
) Differences in angstrom scale
And the same charge valence state between mixtures, make monovalent cation separation one of the most challenging separation tasks. To date, little research has been done on the separation of monovalent/monovalent cations using membrane technology. Where some studies evaluate membrane performance using permeability ratios of single ions, the calculated ideal selectivity is typically between 1.0 and 10. In addition, the separation by membrane technology using a mixture of monovalent ions of two valencies only works two timesReport on [1-2] And the obtained selectivity is only between 1.0 and 2.0, and the precision of the separation process needs to be improved urgently.
COFs built from rigid covalent bonds, long-range ordered frameworks, are of great interest in the field of separation of liquid mixtures. The selection of COF organic precursors and the directional assembly of the framework endow the COF with pore diameters with controllable atomic scale, so that the COF has high flexibility and precision in separation tasks at atomic/molecular scale. In addition, the rich chemical customization of COFs allows a high degree of freedom, allowing the design of multi-stage chemical functions of the channels to enhance the multiple mechanisms of the separation process, depending on the specific requirements of hydrophilicity, activity or polarity in the separation application.
[ reference documents ]
[1]Z.Jia,W.Shi,Tailoring permeation channels of graphene oxide membranes for precise ion separation.Carbon,2016,101,290-295.
[2]Z.Jia,Y.Wang,W.Shi,J.Wang,Diamines cross-linked graphene oxide free-standing membranes for ion dialysis separation.Journal of Membrane Science,2016,520,139-144.
Disclosure of Invention
Aiming at the prior art, the invention provides an anionic covalent organic framework membrane and a preparation method thereof. The hydration function and the confinement function of the anion group are utilized to control the selective transmission of univalent cations, realize the high-efficiency univalent ion separation and break through the technical bottleneck of the macroporous covalent organic framework material for the high-efficiency ion separation.
In order to solve the technical problems, the anionic covalent organic framework membrane provided by the invention is composed of two reaction monomers, namely 1,3, 5-trihydroxy benzenetricarboxylic acid and 1, 4-diaminobenzoic acid, wherein the two reaction monomers are firstly used for generating anionic covalent organic framework nanosheets through a pH-mediated oil-water-oil interfacial polymerization method, and then the nanosheets are prepared into the anionic covalent organic framework membrane through a vacuum-assisted assembly method; the membrane integrally presents an asymmetric structure and comprises an compact skin layer and a porous supporting layer, wherein the average pore diameter of the compact skin layer is 1.3-1.5nm, and the thickness of the compact skin layer is 0.1-5.0 mu m; the porous supporting layer is of a fiber staggered stacking structure, and the average pore diameter is 2.0 mu m. The preparation steps of the membrane are as follows:
step one, preparing an anionic covalent organic framework nanosheet by adopting an oil-water-oil interface polymerization method:
dissolving 1,3, 5-trihydroxy mesitylene in dichloromethane according to the concentration of 0.5-3mol/L, and carrying out ultrasonic treatment for 15 minutes to obtain a solution which is marked as an oil phase solution A; dissolving 1, 4-diaminobenzoic acid in N, N-dimethylformamide according to the concentration of 0.75-4.5mol/L, and carrying out ultrasonic treatment for 15 minutes to obtain a solution, namely an oil phase solution B; adding acetic acid or sodium bicarbonate into deionized water, adjusting pH to 4-12, and performing ultrasonic treatment for 15 min to obtain water phase solution; slowly assembling the oil phase solution A, the water phase solution and the oil phase solution B in a sequence from bottom to top according to the volume ratio of (4-8) to 1:2, reacting for 72 hours, extracting, separating liquid, and collecting the water phase solution to obtain the anionic covalent organic framework nanosheet dispersion liquid;
step two, preparing the anionic covalent organic framework membrane by a vacuum-assisted assembly method:
adjusting the concentration of the anionic covalent organic framework nanosheet dispersion prepared in the first step to 0.1-0.5g/L, and performing suction filtration and assembly on a porous substrate of a solvent filter device under the vacuum condition of 0.05-0.1MPa to obtain an anionic covalent organic framework membrane; the porous substrate is polytetrafluoroethylene with the average pore diameter of 0.2 mu m, and the effective interception radius of the anionic covalent organic framework membrane is 0.6-1.0 cm.
Further, in the preparation method of the present invention, the 1, 4-diaminobenzene acid is one of 1, 4-diaminobenzene phosphonic acid, 1, 4-diaminobenzene sulfonic acid and 1, 4-diaminobenzene carboxylic acid.
The 1, 4-diaminobenzene acid is 1, 4-diaminobenzene phosphonic acid, and the pH value is 11.
The 1, 4-diaminobenzene acid is 1, 4-diaminobenzene sulfonic acid, and the pH value is 4.
The 1, 4-diaminobenzene acid is 1, 4-diaminobenzene carboxylic acid, and the pH value is 7.
The concentration of the oil phase solution A is 0.5mol/L, and the concentration of the oil phase solution B is 0.75mol/L.
In the second step, the concentration of the anionic covalent organic framework nanosheet dispersion is 0.1g/L.
The anion covalent organic framework membrane prepared by the invention is used for the separation process of univalent cations, and the permeation rate of potassium ions is 0.010-0.016mol h -1 m -2 The selectivity of the binary mixture of potassium ions/lithium ions is 1.0-4.2, and the selectivity of the binary mixture of potassium ions/sodium ions is 0.8-2.5.
Compared with the prior art, the invention has the beneficial effects that:
the anionic covalent organic framework film disclosed by the invention is prepared by strengthening the interlayer electrostatic interaction of the anionic covalent organic framework and promoting the in-plane growth of the covalent organic framework to obtain a nanosheet through a pH-mediated oil-water-oil interface polymerization method so as to solve the film forming problem of the anionic covalent organic framework. And then, a film is processed by using a vacuum-assisted assembly method, and the film preparation method is convenient, simple, controllable and convenient to operate. In the preparation process, the anionic covalent organic framework membrane structure is optimized by adjusting the reaction conditions in the preparation steps, such as monomer types, monomer concentration, dispersion solution concentration and the like. Abundant groups in the prepared anionic covalent organic framework membrane endow a stable limited domain hydration structure for a membrane channel, and the selectivity of the membrane to univalent cations is enhanced, so that the membrane has excellent univalent cation separation performance.
Drawings
FIG. 1 is a surface and section electron micrograph and pore size distribution plot of the anionic covalent organic framework films of examples 1, 2 and 3, wherein:
(a), (b), and (c) are the surface, sem and pore size distributions, respectively, of the anionic covalent organic framework film of example 1;
(d) (e) and (f) are respectively the surface, sem image and pore size distribution plots for the anionic covalent organic framework film of example 1;
(g) (h) and (i) are the surface, sem image and pore size distribution plots, respectively, for the anionic covalent organic framework film of example 1;
FIG. 2 is the ion permeation rate and binary ion mixture selectivity of the anionic covalent organic framework membranes of examples 1, 2 and 3.
FIG. 3 is the ion permeation rate and binary ion mixture selectivity of the anionic covalent organic framework membranes of examples 1,4 and 5.
FIG. 4 is the ion permeation rate and binary ion mixture selectivity of the anionic covalent organic framework membranes of examples 1, 6 and 7.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
The design concept of the anionic covalent organic framework membrane provided by the invention is as follows: the membrane is composed of two reaction monomers of 1,3, 5-trihydroxy mesitylene and 1, 4-diaminobenzoic acid, wherein the two reaction monomers firstly generate anionic covalent organic framework nano sheets by a pH-mediated oil-water-oil interface polymerization method, and then the nano sheets are assembled on a porous substrate by a vacuum-assisted assembly method to prepare the anionic covalent organic framework membrane; the membrane integrally presents an asymmetric structure and comprises an compact skin layer and a porous supporting layer, wherein the average pore diameter of the compact skin layer is 1.3-1.5nm, and the thickness of the compact skin layer is 0.1-5.0 mu m; the porous supporting layer is of a fiber staggered stacking structure, and the average pore diameter is 2.0 mu m. The anion covalent organic framework nanosheet has high aspect ratio and good ductility, and is beneficial to preparing and obtaining the anion covalent organic framework film which is continuous, free of defects and controllable in thickness. The pore diameter of less than 2 nanometers in the membrane and the acid groups which are easy to control are beneficial to designing a hydration structure in the membrane, endowing the membrane with a screening function for different univalent cations, and realizing an efficient univalent cation separation process, thereby breaking through the technical bottleneck of using microporous frame materials for ion separation. In addition, the properties of the film can be further optimized by adjusting the conditions of the kind of the monomer, the concentration of the dispersion, and the like.
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings and specific embodiments, which are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
Preparing an anionic covalent organic framework film, comprising the following steps:
step one, preparing an anionic covalent organic framework nanosheet by adopting an oil-water-oil interfacial polymerization method:
weighing 8.4g of 1,3, 5-trihydroxy mesitylene and dissolving in 80mL of dichloromethane, and performing ultrasonic treatment for 15 minutes to obtain a solution with the concentration of 0.5mol/L, which is marked as an oil phase solution A; weighing 7.1g of 1, 4-diaminobenzoic acid, dissolving in 50mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 15 minutes to obtain a solution with the concentration of 0.75mol/L, wherein the solution is marked as an oil phase solution B; dissolving 0.8mg of acetic acid in 20mL of deionized water, and carrying out ultrasonic treatment for 15 minutes to obtain an aqueous phase solution with the pH value of 4;
slowly assembling the oil phase solution A, the water phase solution and the oil phase solution B in a sequence from bottom to top at a speed of 0.5mL/s according to a volume ratio of 4;
step two, preparing the anionic covalent organic framework membrane by a vacuum-assisted assembly method:
adjusting the concentration of the anionic covalent organic framework nanosheet dispersion prepared in the first step to 0.1g/L, taking 60mL of the anionic covalent organic framework nanosheet dispersion, and performing suction filtration and assembly on a porous substrate of a solvent filter device under the vacuum condition of 0.075MPa to obtain an anionic covalent organic framework membrane, which is marked as membrane 1. The porous substrate is polytetrafluoroethylene with an average pore diameter of 0.2 mu m, and the effective interception radius of the membrane is 0.7 cm.
In fig. 1 (a) and (b), it can be observed that the membrane 1 has a continuous defect-free surface and dense cross-sectional morphology, and the membrane as a whole exhibits an asymmetric structure including a dense skin layer having a thickness of about 2.0nm and a porous support layer having a fiber staggered stack structure with an average pore size of 2.0 μm. In FIG. 1 (c), it can be found that the dense skin layer of the membrane 1 has an average pore diameter of 1.4nm.
Membrane 1 was subjected to monovalent cation separation experiments: the experiment adopts a concentration diffusion device, and 200mL of the concentration is selectedThe mixed solution of potassium chloride with the degree of 0.1mol/L and lithium chloride with the degree of 0.1mol/L is placed on the raw material side, 200mL of deionized water is selected to be placed on the permeation side, and the cation permeation rate and the ion selectivity of the membrane are evaluated. The potassium ion permeation rate of the membrane is 0.013mol h -1 m -2 The selectivity of the binary potassium/lithium ion mixture was 2.5 and the selectivity of the binary potassium/sodium ion mixture was 1.2, as shown in FIG. 2.
Example 2
An anionic covalent organic framework membrane was prepared, which was identical to the procedure described in example 1 above, except that the monomer used in one of the procedures was changed from 1, 4-diaminobenzenesulphonic acid to 1, 4-diaminobenzenephosphonic acid, and sodium bicarbonate was added to change the pH of the aqueous phase from 4 to 8, to finally obtain an anionic covalent organic framework membrane, denoted as membrane 2. Fig. 1 (d) and (e) show surface and cross-sectional electron micrographs of the film. The membrane as a whole exhibited an asymmetric structure comprising a dense skin layer having a thickness of about 2.0nm and a porous support layer having a fiber staggered stack structure with an average pore size of 2.0 μm. In FIG. 1 (f) the dense skin of membrane 2 can be found to have an average pore size of 1.3nm. The membrane 2 was subjected to a monovalent cation separation experiment, which resulted in: the potassium ion permeation rate is 0.016mol h -1 m -2 The selectivity of the binary potassium/lithium ion mixture was 4.2, and the selectivity of the binary potassium/sodium ion mixture was 2.5, as shown in FIG. 2.
Example 3
An anionic covalent organic framework membrane was prepared, which was designated as membrane 3 by changing the C monomer used in one of the steps from 1, 4-diaminobenzenesulphonic acid to 1, 4-diaminobenzenecarboxylic acid and adding sodium bicarbonate to change the pH of the aqueous solution from 4 to 12, without changing the steps from example 1. Fig. 1 (g) and (h) show surface and cross-sectional electron micrographs of the film 3. The membrane as a whole exhibited an asymmetric structure comprising a dense skin layer having a thickness of about 2.0nm and a porous support layer having a fiber staggered stack structure with an average pore size of 2.0 μm. The dense skin layer of membrane 3 can be found in fig. 1 (i) to have an average pore size of 1.4nm. The membrane prepared in example 3 was subjected to a monovalent cation separation experiment, as a result of which: the potassium ion permeation rate is 0.015mol h - 1 m -2 Potassium ion/lithium ion twoThe selectivity of the mixture is 1.0, and the selectivity of the potassium ion/sodium ion binary mixture is 0.8, as shown in figure 2.
Example 4
The anionic covalent organic framework membrane was prepared by changing the oil phase solution concentration in the first step from 0.5mol/L to 1.0mol/L and the oil phase solution B concentration from 1.5mol/L to 4.5mol/L, without changing the steps from example 1, and was designated as membrane 4. The membrane 4 was subjected to a monovalent cation separation experiment, which resulted in: the potassium ion permeation rate is 0.012mol h -1 m -2 The selectivity of the binary potassium/lithium ion mixture was 2.1, and the selectivity of the binary potassium/sodium ion mixture was 1.1, as shown in FIG. 3.
Example 5
The anionic covalent organic framework membrane was prepared by changing the oil phase solution concentration in the first step from 0.5mol/L to 3mol/L and the oil phase solution B from 0.75mol/L to 4.5mol/L, without changing the steps from example 1 above, to obtain anionic covalent organic framework membrane, denoted as membrane 5. The membrane 5 was subjected to a monovalent cation separation experiment, which resulted in: the potassium ion permeation rate is 0.010mol h -1 m -2 The selectivity of the binary potassium/lithium ion mixture was 1.8, and the selectivity of the binary potassium/sodium ion mixture was 1.0, as shown in FIG. 3.
Example 6
And (3) preparing an anionic covalent organic framework membrane, wherein the concentration of the nanosheet dispersion in the second step is changed from 0.1g/L to 0.3g/L without changing the steps in the above example 1, and the anionic covalent organic framework membrane is marked as membrane 6. The membrane 6 was subjected to a monovalent cation separation experiment, which resulted in: the potassium ion permeation rate is 0.011mol h -1 m -2 The selectivity of the binary potassium/lithium ion mixture was 2.6, and the selectivity of the binary potassium/sodium ion mixture was 1.4, as shown in FIG. 4.
Example 7
Preparing an anionic covalent organic framework membrane, and only changing the concentration of the nanosheet dispersion in the second step from 0.1g/L without changing the steps in the above example 1At 0.5g/L, an anionic covalent organic framework membrane was obtained, designated as membrane 7. The membrane 7 was subjected to a monovalent cation separation experiment, which resulted in: the potassium ion permeation rate is 0.010mol h -1 m -2 The selectivity of the binary potassium/lithium ion mixture was 2.8 and the selectivity of the binary potassium/sodium ion mixture was 1.5, as shown in FIG. 4.
The monovalent cation permeation rates and the monovalent cation binary mixture selectivities of the membranes 1 to 7 are summarized in Table 1, wherein in Table 1, A represents 1, 4-diaminobenzene sulfonic acid, B represents 1, 4-diaminobenzene phosphonic acid, and C represents 1, 4-diaminobenzene carboxylic acid.
TABLE 1
In summary, according to the preparation method of the anionic covalent organic framework film provided by the invention, the interlayer electrostatic interaction of the anionic covalent organic framework is strengthened by using a pH-mediated oil-water-oil interfacial polymerization method, and the in-plane growth of the covalent organic framework is promoted to obtain the nanosheet, so that the film forming problem of the anionic covalent organic framework is solved. The anion covalent organic framework membrane prepared from the nanosheets has a pore diameter smaller than 2 nanometers and an acid group which is easy to modulate, a hydration structure can be created in the membrane, a screening function for different monovalent cations is obtained, and an efficient monovalent cation separation process is realized, as shown in fig. 2, fig. 3, fig. 4 and table 1, the potassium ion permeation rate and the ion selectivity of the membrane are both reduced along with the increase of the concentration of an oil phase solution, the potassium ion permeation rate of the membrane is reduced along with the increase of the dispersion concentration of the nanosheets, and the ion selectivity of the membrane is improved along with the increase of the concentration of a nanosheet dispersion solution. When 1, 4-diaminobenzene phosphonic acid is selected as a monomer, the concentration of the oil phase solution A is 0.5mol/L, the concentration of the oil phase solution B is 0.75mol/L, and the concentration of the nanosheet dispersion liquid is 0.1g/L, the finally prepared anionic covalent organic framework membrane has good separation performance.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (9)
1. An anionic covalent organic framework membrane is characterized by comprising two reaction monomers of 1,3, 5-trihydroxy benzenetricarboxylic acid and 1, 4-diaminobenzoic acid, wherein the two reaction monomers firstly generate anionic covalent organic framework nano sheets through a pH-mediated oil-water-oil interfacial polymerization method, and then the nano sheets are assembled on a porous substrate through a vacuum-assisted assembly method to prepare the anionic covalent organic framework membrane; the membrane integrally presents an asymmetric structure and comprises an compact skin layer and a porous supporting layer, wherein the average pore diameter of the compact skin layer is 1.3-1.5nm, and the thickness of the compact skin layer is 0.1-5.0 mu m; the porous supporting layer is a fiber staggered stacking structure, and the average pore diameter is 2.0 mu m.
2. The method of claim 1, comprising the steps of:
step one, preparing an anionic covalent organic framework nanosheet by adopting an oil-water-oil interface polymerization method:
dissolving 1,3, 5-trihydroxy mesitylene in dichloromethane according to the concentration of 0.5-3mol/L, and carrying out ultrasonic treatment for 15 minutes to obtain a solution which is marked as an oil phase solution A;
dissolving 1, 4-diaminobenzoic acid in N, N-dimethylformamide according to the concentration of 0.75-4.5mol/L, and carrying out ultrasonic treatment for 15 minutes to obtain a solution, namely an oil phase solution B;
adding acetic acid or sodium bicarbonate into deionized water, adjusting pH to 4-12, and performing ultrasonic treatment for 15 min to obtain water phase solution;
slowly assembling the oil phase solution A, the water phase solution and the oil phase solution B in a sequence from bottom to top according to the volume ratio of (4-8) to 1:2, reacting for 72 hours, extracting, separating liquid, and collecting the water phase solution to obtain the anionic covalent organic framework nanosheet dispersion liquid;
step two, preparing the anionic covalent organic framework membrane by a vacuum-assisted assembly method:
adjusting the concentration of the anionic covalent organic framework nanosheet dispersion prepared in the first step to 0.1-0.5g/L, and performing suction filtration and assembly on a porous substrate of a solvent filter device under the vacuum condition of 0.05-0.1MPa to obtain an anionic covalent organic framework membrane; the porous substrate is polytetrafluoroethylene with the average pore diameter of 0.2 mu m, and the effective interception radius of the anionic covalent organic framework membrane is 0.6-1.0 cm.
3. The method of claim 2, wherein the 1, 4-diaminobenzenecarboxylic acid is one of 1, 4-diaminobenzenephosphonic acid, 1, 4-diaminobenzenesulphonic acid and 1, 4-diaminobenzenecarboxylic acid.
4. The method according to claim 3, wherein the 1, 4-diaminobenzenecarboxylic acid is 1, 4-diaminobenzenephosphonic acid and has a pH of 11.
5. The method according to claim 3, wherein the 1, 4-diaminobenzenecarboxylic acid is 1, 4-diaminobenzenesulphonic acid and has a pH of 4.
6. The method according to claim 3, wherein the 1, 4-diaminobenzenecarboxylic acid is 1, 4-diaminobenzenecarboxylic acid and has a pH of 7.
7. The method according to claim 2, wherein the concentration of the oil phase solution a is 0.5mol/L, and the concentration of the oil phase solution B is 0.75mol/L.
8. The method of claim 2, wherein in step two, the concentration of the dispersion of anionic covalent organic framework nanosheets is 0.1g/L.
9. An anionic covalent organic framework membraneUse of the anionic covalent organic framework membrane according to claim 1 prepared by the preparation method according to any one of claims 2 to 8 in monovalent cation separation processes, wherein the potassium ion permeation rate is 0.010-0.016mol h -1 m -2 The selectivity of the potassium ion/lithium ion binary mixture is 1.0-4.2, and the selectivity of the potassium ion/sodium ion binary mixture is 0.8-2.5.
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| CN116926718A (en) * | 2023-08-07 | 2023-10-24 | 有研资源环境技术研究院(北京)有限公司 | Covalent organic framework hollow fiber membrane, preparation method and application thereof |
| CN116926718B (en) * | 2023-08-07 | 2024-02-27 | 有研资源环境技术研究院(北京)有限公司 | Covalent organic framework hollow fiber membrane, preparation method and application thereof |
| CN117638130A (en) * | 2024-01-26 | 2024-03-01 | 杭州德海艾科能源科技有限公司 | Porous diaphragm for high-resistance vanadium all-vanadium redox flow battery and preparation method thereof |
| CN117638130B (en) * | 2024-01-26 | 2024-04-30 | 杭州德海艾科能源科技有限公司 | Porous diaphragm for high-resistance vanadium all-vanadium redox flow battery and preparation method thereof |
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