CN114307672A - Two-dimensional crystal seed layer mediated covalent organic framework film and preparation and application thereof - Google Patents
Two-dimensional crystal seed layer mediated covalent organic framework film and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a two-dimensional seed crystal layer mediated covalent organic framework film, which comprises a base film, wherein a two-dimensional seed crystal layer is prepared on the base film by adopting a vacuum-assisted self-assembly technology at the interface of the base film, and a covalent organic framework active layer is prepared by the two-dimensional seed crystal layer mediated coupling back diffusion, so that the two-dimensional seed crystal layer mediated covalent organic framework layer is attached to the surface of the base film. The preparation method comprises the steps of preparing covalent organic framework two-dimensional seed crystal dispersion liquid, preparing a covalent organic framework two-dimensional seed crystal layer, preparing a two-dimensional seed crystal layer mediated covalent organic framework film, and cleaning to obtain the film. In the preparation method, the two-dimensional crystal seed layer regulates and controls the diffusion-reaction behavior of the covalent organic framework construction monomer, and induces the limited-area growth of the covalent organic framework, so that the intercrystalline defects of the covalent organic framework membrane can be better eliminated, the charge on the wall surface of the channel inside the membrane can strengthen the electrostatic repulsion mechanism, the high-efficiency desalination is realized, and the technical bottleneck of the macroporous covalent organic framework material for the high-efficiency nanofiltration desalination is broken through.
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 water treatment, and particularly relates to a preparation method of a two-dimensional crystal seed layer mediated 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, 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, electronics, water treatment and the like, and brings great economic and social benefits. The membrane is the core of the membrane separation process, and can be divided into a microfiltration Membrane (MF), an ultrafiltration membrane (UF), a nanofiltration membrane (NF) and a reverse osmosis membrane (RO) according to the pore size in the membrane separation process taking pressure as a driving force.
Nanofiltration is a membrane process with separation properties intermediate between ultrafiltration and reverse osmosis. The aperture of the nanofiltration membrane is between 0.5 and 2nm, the cut-off Molecular Weight (MWCO) is 200-1000Da, organic small molecules and high-valence salt ions with the molecular weight of more than 200Da can be effectively removed, and molecules and monovalent salt ions with the molecular weight of less than 200Da are partially removed. The nanofiltration membrane is produced in the late stage of the 80 s in the 20 th century, fills the gap between ultrafiltration and reverse osmosis membranes, has the advantages of low operating pressure, high efficiency, energy conservation and the like, and is widely applied to brackish water desalination, water advanced treatment, material concentration and purification, wastewater treatment, organic solvent recovery and the like.
According to the introduction of documents, the separation mechanism of the nanofiltration membrane mainly has two points, namely, the size sieving effect is used for passing through small-size molecules and intercepting large-size molecules; the second is electrostatic repulsion effect, the surface of the nanofiltration membrane often has charged groups to make it present certain charge (dissociation of groups), and there is electrostatic interaction with ions or charged small molecules in the object to be separated.
The discovery of nanofiltration membranes began in the 80's of the 20 th century. In 1976, piperazine was used as an aqueous amino monomer by j.e. cadotte et al, and an interfacial polymerization method was used to prepare a piperazine polyamide porous reverse osmosis membrane on a porous polysulfone support, which has higher water permeation flux and lower sodium chloride rejection rate than conventional reverse osmosis membranes. In 1984, the company Filmtec, usa, named this type of membrane a nanofiltration membrane. The company is dedicated to the research and development of nanofiltration membrane components (NF-300, NF-270, NF-290 and the like) and leads the rapid development of the nanofiltration membrane technology. The nanofiltration membrane is researched from the end of 80 years in China, the research on the nanofiltration membrane in China is still in a rapid development stage at present, and although some commercial nanofiltration membranes and components appear, the research still has a larger gap compared with the international advanced commercial nanofiltration membrane. Therefore, the research, development and preparation of the high-performance nanofiltration membrane are the focus of the invention.
Disclosure of Invention
Aiming at the prior art, the invention provides a two-dimensional crystal seed layer mediated covalent organic framework film and a preparation method thereof, the invention designs and prepares a series of two-dimensional crystal seed layer mediated covalent organic framework films, wherein the two-dimensional crystal seed layer regulates and controls the diffusion-reaction behavior of covalent organic framework construction monomers, induces the limited-area growth of the covalent organic framework, is beneficial to better eliminating the intercrystalline defects of the covalent organic framework film, the charge on the wall surface of an internal channel of the film can strengthen the electrostatic repulsion mechanism, realizes high-efficiency desalination, and breaks through the technical bottleneck that a macroporous covalent organic framework material is used for high-efficiency nanofiltration desalination.
In order to solve the technical problems, the invention provides a two-dimensional seed layer mediated covalent organic framework film, which comprises a base film, wherein a two-dimensional seed layer is prepared on the base film by adopting a vacuum-assisted self-assembly technology at the interface of the base film, and a covalent organic framework active layer is prepared by the two-dimensional seed layer mediated coupling back diffusion, so that the two-dimensional seed layer mediated covalent organic framework layer is attached to the surface of the base film. The preparation method comprises the following steps:
step one, preparing a covalent organic framework two-dimensional seed crystal dispersion liquid: weighing 2,4, 6-trihydroxy-1, 3, 5-benzene triformal, dissolving in n-octanoic acid, and performing ultrasonic treatment for half an hour to obtain 1mmol/L oil phase solution A; weighing 2, 5-diaminobenzene sulfonic acid powder, dissolving in deionized water, and performing ultrasonic treatment for half an hour to obtain 1mmol/L aqueous phase solution A; slowly dripping the oil phase solution A to the upper layer of the water phase solution A according to the equal volume, reacting for 72 hours, and removing the oil phase solution on the upper layer to obtain 1.0g/L two-dimensional seed crystal dispersion liquid;
step two, preparation of a covalent organic framework two-dimensional seed crystal layer: placing the base film in a suction filtration device, taking the two-dimensional seed crystal dispersion liquid obtained in the step one, and performing suction filtration to obtain a film loaded with a two-dimensional seed crystal layer;
step three, preparing a two-dimensional crystal seed layer mediated covalent organic framework film: placing the film loaded with the two-dimensional seed crystal layer in the second step in the middle of a diffusion cell, weighing 2,4, 6-trihydroxy-1, 3, 5-benzene triformal powder, dissolving in 1,3, 5-trimethylbenzene, and performing ultrasonic treatment for half an hour to obtain 1-3mmol/L of oil phase solution B; weighing 2, 5-diaminobenzene sulfonic acid powder, dissolving in deionized water, and performing ultrasonic treatment for half an hour to obtain 1-3mmol/L aqueous phase solution B; then, according to the equal volume, respectively adding the oil phase solution B and the water phase solution B to the two sides of the diffusion cell, sealing, and standing for 24-72h at room temperature;
and step four, after the reaction in the step three is finished, taking out the membrane, and respectively washing the membrane by using acetone, ethanol and deionized water to obtain the two-dimensional seed crystal layer mediated covalent organic framework membrane.
Further, the preparation method of the invention comprises the following steps:
in the second step, the ratio of the volume of the two-dimensional seed crystal dispersion to the membrane area is 0.1-3mL/16cm2。
In the first step, the concentrations of the oil phase solution A and the water phase solution A are the same, and in the third step, the concentrations of the oil phase solution B and the water phase solution B are the same, preferably, the concentrations are both 1 mmol/L.
In step three, the diffusion reaction time is preferably 72 h.
Compared with the prior art, the invention has the beneficial effects that:
the two-dimensional seed crystal layer mediated covalent organic framework film is prepared by self-assembling the two-dimensional seed crystal layer on the surface of a base film in a vacuum-assisted manner and then generating a covalent organic framework active layer through back diffusion. In the preparation process, the reaction conditions in the preparation steps, such as the volume of the two-dimensional crystal seed dispersion liquid, the concentration of the back diffusion monomer, the reaction time and the like, are adjusted, so that the obtained two-dimensional crystal seed layer mediated covalent organic framework membrane has excellent nanofiltration and desalination performances, and the pure water flux is 0.4-1.8 Lm-2h-1bar-1，Na2SO4The retention rate is 81.1-97.4%, and the NaCl retention rate is 66.4-80.6%, as shown in Table 1.
Drawings
FIG. 1 is a surface and section electron micrograph of a two-dimensional seed layer in examples 1, 2 and 3, wherein (a) and (b) are surface and section electron micrographs of the two-dimensional seed layer in example 1 and (c) and (d) are surface and section electron micrographs of the two-dimensional seed layer in example 2; (e) and (f) are surface and profile electron micrographs of the two-dimensional seed layer in example 3.
FIG. 2 is a surface and section electron micrograph of a two-dimensional seed layer mediated covalent organic framework film obtained in examples 1, 2, 3, wherein (a) and (b) are surface and section electron micrographs of the film obtained in example 1; (c) and (d) is the surface and section electron micrographs of the film obtained in example 2; (e) and (f) are surface and section electron micrographs of the film obtained in example 3.
Figure 3 is a plot of salt rejection and flux versus examples 1, 2 and 3.
Figure 4 is a plot of salt rejection and flux versus examples 1, 4 and 5.
Figure 5 is a plot of salt rejection and flux versus examples 1, 6 and 7.
Detailed Description
The design concept of the two-dimensional seed crystal layer mediated covalent organic framework film provided by the invention is as follows: mainly adopts a vacuum-assisted self-assembly technology to prepare a two-dimensional crystal seed layer on a basal membrane interface, and uses the crystal seed layer to mediate and prepare a covalent organic framework active layer by a coupling back diffusion technology. The nanofiltration process of the invention is a separation process of selectively permeating a membrane by using pressure as a driving force and micromolecules and ions. However, due to the size sieving effect and the electrostatic repulsion effect, the nanofiltration membrane has different interception to small molecules and ions with different sizes and different electric properties. Moreover, the performance of the membrane can be further optimized by effectively adjusting conditions such as the thickness of the seed layer, the concentration of the back diffusion reactant, the operation time and the like.
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.
Example 1 preparation of a two-dimensional seed layer mediated preparation of a covalent organic framework film, the procedure was as follows:
step one, preparing a covalent organic framework two-dimensional seed crystal dispersion liquid: weighing 21mg of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal, dissolving in 100mL of n-octanoic acid, and performing ultrasonic treatment for half an hour to obtain 1mmol/L of oil phase solution; weighing 18.8mg of 2, 5-diaminobenzene sulfonic acid powder, dissolving in 100mL of deionized water, and carrying out ultrasonic treatment for half an hour to obtain 1mmol/L aqueous phase solution; according to the equal volume, the oil phase solution is slowly dripped into the upper layer of the water phase solution for reaction for 72 hours, and the oil phase solution on the upper layer is removed to obtain 1.0g/L of two-dimensional seed crystal dispersion liquid.
Step two, preparation of a covalent organic framework two-dimensional seed crystal layer: an area of 16cm2The polyacrylonitrile ultrafiltration membrane is used as a base membrane and is placed in a vacuum device filter flask, 1mL of the two-dimensional seed crystal dispersion liquid obtained in the first step is taken and filtered to obtain the membrane loaded with the two-dimensional seed crystal layer, and the surface and the section electron microscope image of the two-dimensional seed crystal layer are shown in (a) and (b) in fig. 1.
Step three, preparing a two-dimensional crystal seed layer mediated covalent organic framework film: placing the membrane loaded with the two-dimensional seed crystal layer in the second step in the middle of a diffusion cell, weighing 21mg of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal powder, dissolving in 100mL of 1,3, 5-trimethylbenzene, and carrying out ultrasonic treatment for half an hour to obtain 1mmol/L oil phase solution; weighing 18.8mg of 2, 5-diaminobenzene sulfonic acid powder, dissolving in 100mL of deionized water, and carrying out ultrasonic treatment for half an hour to obtain 1mmol/L aqueous phase solution; then, according to the equal volume, the two-phase solution is respectively and slowly dripped into two sides of the diffusion cell (namely, one side is oil phase solution, and the other side is water phase solution), and the reaction is carried out for 48 hours at room temperature after sealing.
And step four, after the reaction is finished, taking out the membrane, and respectively washing the membrane by using acetone, ethanol and deionized water to obtain the two-dimensional seed crystal layer mediated covalent organic framework membrane. It is evident from (a) and (b) in fig. 1 and (a) and (b) in fig. 2 that the two-dimensional seed layer mediates the attachment of the covalent organic framework layer to the base film surface.
The membrane obtained in example 1 was subjected to a nanofiltration desalination experiment: experiment for respectively selecting NaCl and Na2SO4And (3) taking a penetrating fluid after prepressing for 0.5h to detect the ion concentration for testing the system, and calculating the flux and the salt rejection rate. Pure water flux of 1.5Lm-2h-1bar-1When the salt concentration is 1000ppm, the membrane is paired with Na2SO4The retention of (A) was 91.9% and the NaCl retention was 76.4%, as shown in FIG. 3.
Example 2, preparation of a two-dimensional seed layer mediated preparation of a covalent organic framework film, the volume of the two-dimensional seed dispersion taken in the second step was changed from 1mL to 0.1mL, which was the same as the step in example 1, and finally the two-dimensional seed layer mediated covalent organic framework film was obtained, wherein (c) and (d) in fig. 1 show the surface and cross-sectional electron micrographs of the two-dimensional seed layer, and (c) and (d) in fig. 2 show the surface and cross-sectional electron micrographs of the film. The membrane obtained in example 2 was subjected to a nanofiltration desalination experiment, as a result of which: pure water flux of 1.7Lm-2h-1bar-1When the salt concentration is 1000ppm, the membrane is paired with Na2SO4The retention of (A) was 81.8% and the NaCl retention was 66.4%, as shown in FIG. 3.
Example 3, preparation of a two-dimensional seed layer mediated preparation of a covalent organic framework film, the volume of the two-dimensional seed dispersion taken in the second step was changed from 1mL to 3mL, which was the same as the step in example 1, and finally the two-dimensional seed layer mediated covalent organic framework film was obtained, wherein (e) and (f) in fig. 1 show the surface and the profile electron microscope image of the two-dimensional seed layer, and (e) and (f) in fig. 2 show the surface and the profile electron microscope image of the film. The membrane obtained in example 3 was subjected to a nanofiltration desalination experiment, as a result of which: pure water flux of 0.5Lm-2h-1bar-1When the salt concentration is 1000ppm, the membrane is paired with Na2SO4The retention of (A) was 87.3% and the NaCl retention was 70.1%, as shown in FIG. 3.
Example 4 preparation of two-dimensional seed layer mediated preparation of covalent organic framework films, the procedure of example 1 above was unchanged, except that the monomer weighing in the third step was changedWeighing the amount of monomer 2, 5-diaminobenzene sulfonic acid powder and deionized water, namely weighing 42mg of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal powder, dissolving in 100mL of 1,3, 5-trimethylbenzene, and carrying out ultrasonic treatment for half an hour to obtain 2mmol/L of oil phase solution; 37.6mg of 2, 5-diaminobenzene sulfonic acid powder is weighed and dissolved in 100mL of deionized water, and ultrasonic treatment is carried out for half an hour to obtain 2mmol/L aqueous phase solution. The membrane finally obtained in example 4 was subjected to a nanofiltration desalination experiment, as a result of which: pure water flux of 0.7Lm-2h-1bar-1When the salt concentration is 1000ppm, the membrane is paired with Na2SO4The retention of (A) was 92.3% and the NaCl retention was 77.4%, as shown in FIG. 4.
Example 5, preparation of two-dimensional seed layer mediated preparation of covalent organic framework membrane, and the same procedure as in example 1 above, except that the amounts of the monomer 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid powder and 1,3, 5-trimethylbenzene in step three and the monomer 2, 5-diaminobenzene sulfonic acid powder and deionized water are changed, that is, 63mg of the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid powder is dissolved in 100mL of 1,3, 5-trimethylbenzene, and ultrasonic treatment is carried out for half an hour to obtain 3mmol/L of oil phase solution; 56.4mg of 2, 5-diaminobenzenesulphonic acid powder is weighed out and dissolved in 100mL of deionized water, and ultrasonic treatment is carried out for half an hour to obtain 3mmol/L aqueous phase solution. The membrane finally obtained in example 5 was subjected to a nanofiltration desalination experiment, as a result of which: pure water flux of 0.4Lm-2h-1bar-1When the salt concentration is 1000ppm, the membrane is paired with Na2SO4The retention of (A) was 93.7% and the NaCl retention was 77.8%, as shown in FIG. 4.
Example 6 preparation of two-dimensional seed layer mediated preparation of covalent organic framework films, the procedure of example 1 above was not changed, but the reaction time in step three was changed from 48h to 24 h. The membrane finally obtained in example 6 was subjected to a nanofiltration desalination experiment, as a result of which: pure water flux of 1.8Lm-2h-1bar-1When the salt concentration is 1000ppm, the membrane is paired with Na2SO4The retention of (A) was 85.6% and the NaCl retention was 68.4%, as shown in FIG. 5.
Example 7 preparation of two-dimensional seed layer mediated preparationCovalent organic framework membranes, the procedure of example 1 above was unchanged, except that the reaction time in step three was changed from 48h to 72 h. The membrane finally obtained in example 6 was subjected to a nanofiltration desalination experiment, as a result of which: pure water flux of 1.4Lm-2h-1bar-1When the salt concentration is 1000ppm, the membrane is paired with Na2SO4The retention of (A) was 97.4% and the NaCl retention was 80.6%, as shown in FIG. 5.
The flux and separation performance of the two-dimensional seed layer mediated covalent organic framework membrane prepared in examples 1 to 7 of the present invention are summarized as shown in table 1:
table 1 two-dimensional seed layer mediated flux and separation performance of covalent organic framework membranes
In summary, according to the preparation method of the two-dimensional seed layer mediated covalent organic framework film provided by the invention, since interlayer dislocation shrinkage cavities are generated between the seed layer mediated covalent organic framework layer and the seed layer, the film size sieving effect plays a dominant role, in addition, the wall surface charge of the inner channel of the film can strengthen the electrostatic repulsion mechanism, and the cooperative strengthening of the size sieving mechanism and the electrostatic repulsion mechanism is realized. As shown in fig. 3, fig. 4, fig. 5 and table 1, the flux of the membrane decreased as the volume of the two-dimensional seed dispersion liquid increased, and decreased as the concentration of the oil-water phase solution and the reaction time in the back diffusion increased. The separation performance increases and then decreases with the increase of the volume of the two-dimensional crystal seed dispersion liquid, and increases with the increase of the concentration of the oil-water phase solution and the reaction time in the back diffusion. When the volume of the two-dimensional seed crystal dispersion is 1mL (i.e., the ratio of the volume of the two-dimensional seed crystal dispersion to the membrane area is 1mL/16 cm)2) When the concentration of the oil-water phase solution in the back diffusion is 1mmol/L and the reaction time is 72, the finally prepared two-dimensional seed crystal layer mediated covalent organic framework film has better 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 (7)
1. A two-dimensional seed crystal layer mediated covalent organic framework film is characterized by comprising a base film and a two-dimensional seed crystal layer prepared on the base film by adopting a vacuum assisted self-assembly technology at the interface of the base film, and a covalent organic framework active layer is prepared by the two-dimensional seed crystal layer mediated coupling back diffusion, so that the two-dimensional seed crystal layer mediated covalent organic framework layer is attached to the surface of the base film.
2. A method of preparing a two-dimensional seed layer-mediated covalent organic framework film according to claim 1, characterized by the steps of:
step one, preparing a covalent organic framework two-dimensional seed crystal dispersion liquid: weighing 2,4, 6-trihydroxy-1, 3, 5-benzene triformal, dissolving in n-octanoic acid, and performing ultrasonic treatment for half an hour to obtain 1mmol/L oil phase solution A; weighing 2, 5-diaminobenzene sulfonic acid powder, dissolving in deionized water, and performing ultrasonic treatment for half an hour to obtain 1mmol/L aqueous phase solution A; slowly dripping the oil phase solution A to the upper layer of the water phase solution A according to the equal volume, reacting for 72 hours, and removing the oil phase solution on the upper layer to obtain 1.0g/L two-dimensional seed crystal dispersion liquid;
step two, preparation of a covalent organic framework two-dimensional seed crystal layer: placing the base film in a suction filtration device, taking the two-dimensional seed crystal dispersion liquid obtained in the step one, and performing suction filtration to obtain a film loaded with a two-dimensional seed crystal layer;
step three, preparing a two-dimensional crystal seed layer mediated covalent organic framework film: placing the film loaded with the two-dimensional seed crystal layer in the second step in the middle of a diffusion cell, weighing 2,4, 6-trihydroxy-1, 3, 5-benzene triformal powder, dissolving in 1,3, 5-trimethylbenzene, and performing ultrasonic treatment for half an hour to obtain 1-3mmol/L of oil phase solution B; weighing 2, 5-diaminobenzene sulfonic acid powder, dissolving in deionized water, and performing ultrasonic treatment for half an hour to obtain 1-3mmol/L aqueous phase solution B; then, according to the equal volume, respectively adding the oil phase solution B and the water phase solution B to the two sides of the diffusion cell, sealing, and standing for 24-72h at room temperature;
and step four, after the reaction in the step three is finished, taking out the membrane, and respectively washing the membrane by using acetone, ethanol and deionized water to obtain the two-dimensional seed crystal layer mediated covalent organic framework membrane.
3. The method of claim 2 wherein in step two, the ratio of the volume of the two-dimensional seed dispersion to the membrane area is 0.1-3mL/16cm2。
4. The method of claim 2 wherein the oil phase solution A and the aqueous phase solution A have the same concentration in step one and the oil phase solution B and the aqueous phase solution B have the same concentration in step three.
5. The method of claim 4 wherein the concentrations of oil phase solution A and aqueous phase solution A and the concentrations of oil phase solution B and aqueous phase solution B are 1 mmol/L.
6. The method for preparing a two-dimensional seed layer-mediated covalent organic framework film according to claim 2, wherein in step three, the diffusion reaction time is 72 h.
7. The two-dimensional seed layer mediated covalent organic framework membrane prepared by the method for preparing the two-dimensional seed layer mediated covalent organic framework membrane according to any one of claims 2 to 6 and used for nanofiltration desalination, wherein the pure water flux is 0.4-1.8 Lm-2h-1bar-1，Na2SO4The retention rate is 81.1-97.4%, and the NaCl retention rate is 66.4-80.6%.
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