CN112023702A - Hydroxylated boron nitride composite film and preparation method and application thereof - Google Patents
Hydroxylated boron nitride composite film and preparation method and application thereof Download PDFInfo
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical class N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 28
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000000084 colloidal system Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000002135 nanosheet Substances 0.000 claims description 19
- 239000000919 ceramic Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 27
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 230000035699 permeability Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 235000014413 iron hydroxide Nutrition 0.000 abstract description 5
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000012528 membrane Substances 0.000 description 31
- 229910052582 BN Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- 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
-
- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/14—Membrane materials having negatively charged functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention discloses a hydroxylated boron nitride composite film. Uniformly mixing the hydroxylated boron nitride, MXene and the metal ferric hydroxide nano colloid in a liquid phase, uniformly dispersing on a support substrate, drying water to form a film, removing the metal ferric hydroxide nano colloid by using dilute acid, and drying in vacuum to obtain the hydroxylated boron nitride composite film with the microporous structure. The introduction of the hydroxylated boron nitride enhances the hydrophilicity of the composite film, and a microporous structure is formed in the composite film through the pore-forming of the iron hydroxide nanoparticles, so that the water permeability of the composite film is good. The interaction of hydrogen bonds exists between the hydroxylated boron nitride and MXene, so that the composite film layer is not easy to fall off, and the mechanical property of the hydroxylated boron nitride composite film is improved. The abundant hydroxyl in the hydroxylated boron nitride composite film enhances the adsorption effect of the composite film on methylene blue.
Description
Technical Field
The method relates to the technical field of materials, in particular to a hydroxylated boron nitride composite film, and a preparation method and application thereof.
Background
With the acceleration of the industrialization process of China, the problem of water pollution is more and more serious. To solve the current water pollution problem, membrane materials related to water treatment have received wide attention. In the field of water treatment, activated carbon is a widely used purification material, and although activated carbon has the advantages of readily available raw materials and low price, the activated carbon has low pollutant adsorption capacity, slow adsorption rate and low recycling rate. In recent years, in order to obtain high-performance water treatment materials, the field of material science is continuously researching and developing new water treatment materials. Boron nitride has a molecular formula of BN, is a crystal composed of nitrogen atoms and boron atoms, has the advantages of strong mechanical properties, high specific surface area, good chemical stability and the like, and has attracted much attention in the field of water treatment. Like the analogues of carbon, boron nitride shows strong hydrophobicity when a pure BN material interacts with water or an aqueous solution, so that the dispersibility of the BN material in an aqueous medium is extremely poor, and the application of the BN material to pollutants in a water treatment process is not facilitated.
The prior art CN 105797596 a discloses a filtration membrane for water purification, which is prepared by repeating the steps of suction filtration, vacuum drying and the like of active boron nitride dispersed in nitric acid solution, and finally forms a 4-layer filtration adsorption membrane supported on the filtration membrane. Although the filtering membrane has excellent water treatment performance, high thermal stability and structural stability, the raw material active boron nitride is not easy to obtain in a large scale, so that the wide use of the filtering membrane is hindered. Meanwhile, the filter membrane prepared by the method is supported on the filter membrane, and in practical application, when hard objects impact the filter membrane at high speed or water flow passes through the filter membrane at high pressure, the risk of breakage or perforation of the filter membrane exists. On the other hand, the active boron nitride film can be stacked and gathered among the active boron nitride sheets in the preparation process, so that the probability of pore formation among the active boron nitride sheets is reduced, the permeability of the active boron nitride film to water is poor, and the filtering speed is low.
Disclosure of Invention
The invention aims to strengthen the application of boron nitride in the field of water treatment, reduce the application cost and solve the problems of weak hydrophilicity and poor dispersibility of boron nitride in water, and provides a hydroxylated boron nitride composite film and a preparation method thereof, wherein the hydroxylated boron nitride is applied to the field of water treatment, so that the hydrophilicity of the boron nitride is enhanced, and the application effect of the boron nitride in the water treatment is enhanced; on the other hand, in order to improve the microporous structure of the membrane material, the invention adds ferric hydroxide nano colloid in the preparation process of the hydroxylated boron nitride composite membrane, and removes the ferric hydroxide nano colloid by using dilute acid solution after membrane formation, so that the prepared membrane has rich microporous structure.
In order to achieve the above object, the present invention provides a hydroxylated boron nitride composite film, the composition of which comprises hydroxylated boron nitride, MXene and a supporting substrate.
The invention also provides a preparation method of the hydroxylated boron nitride composite film, which is characterized by comprising the following steps of:
(1) mixing a hydroxylated boron nitride nanosheet, an MXene nanosheet and a metal hydroxide nanocolloid in deionized water to obtain a mixed solution;
(2) uniformly dispersing the mixed solution in the step (1), and performing suction filtration on a substrate to form a film;
(3) and (3) repeatedly washing the film layer in the step (2) by using deionized water and a dilute acid solution, and finally performing vacuum drying to obtain the hydroxylated boron nitride composite film.
The invention has the following excellent technical scheme: the feeding process of the mixed material in the step (1) is to add MXene nanosheets and ferric hydroxide nano colloids into deionized water, and disperse the mixture uniformly to obtain a mixed solution; and then adding the hydroxylated boron nitride nanosheet into the mixed solution, and uniformly mixing. The mixed materials are put into the deionized water step by step, which is beneficial to the dispersion of the materials.
The invention has the following excellent technical scheme: the metal hydroxide nano colloid in the step (1) is ferric hydroxide nano colloid, and the size of the ferric hydroxide nano colloid is 3-8 nm.
The invention has the following excellent technical scheme: the adding amount mass ratio of the hydroxylated boron nitride nanosheet to MXene in the step 1 is 0.5-2: 1, preferably 0.75 to 1.4: 1.
the invention has the following excellent technical scheme: the weight ratio of MXene nanosheets to ferric hydroxide nanocolloids in the step (1) is 1: 0.2-1.
The invention has the following excellent technical scheme: the added mass of the ionic water in the step (1) is 20-100 times of the mass of MXene.
The invention has the following excellent technical scheme: the added mass of the hydroxylated boron nitride nanosheet in the step (1) is 0.7-1.6 times of that of MXene
The invention has the following excellent technical scheme: the support substrate in the step (2) is a ceramic substrate or a polyvinylidene fluoride substrate.
The invention has the following excellent technical scheme: the dilute acid solution in the step (3) is dilute hydrochloric acid, and the concentration is 0.5-1.0 mol/L.
The invention has the following excellent technical scheme: and (4) washing each of the deionized water and the dilute acid solution in the step (3) for 3-4 times.
The invention has the following excellent technical scheme: the drying temperature and the drying time of the vacuum drying in the step (3) are respectively 100 ℃ and 200 ℃ and 1-3 h.
The invention also provides application of the hydroxylated boron nitride composite film, and the hydroxylated boron nitride composite film is used for removing methylene blue in aqueous solution.
The invention provides a hydroxylated boron nitride composite film, and the hydroxylated boron nitride has rich hydroxyl functional groups, so that the hydrophilicity of the hydroxylated boron nitride in an aqueous solution is increased, and the dispersing capacity of the boron nitride in an aqueous phase is improved. MXene is doped in the hydroxylated boron nitride composite film, the MXene contains hydroxyl, and hydrogen bond interaction is formed between the MXene and the hydroxylated boron nitride, so that the composite film with good mechanical property can be obtained. The method overcomes the problems of compact aggregation and poor water permeability of the film in the process of forming the film by using the boron nitride alone through the pore-forming of the ferric hydroxide nano particles, increases the microporous structure of the composite film, and is beneficial to rapidly filtering water from the film. The invention provides application of a hydroxylated boron nitride/MXene composite membrane, wherein the hydroxylated boron nitride is added, so that the composite membrane of the hydroxylated boron nitride and the MXene has abundant hydroxyl functional groups on the whole, the hydroxyl functional groups are negatively charged in an aqueous solution, the interaction attraction of the hydroxyl functional groups and pollutants with positive charge in sewage is facilitated, and the adsorption capacity of the composite membrane of the hydroxylated boron nitride and the MXene to the pollutants with positive charge is improved.
The invention has the beneficial effects that:
1. the hydroxylated boron nitride composite film provided by the scheme has good permeability to water, and the prepared composite film has good hydrophilicity through hydroxylation of the hydroxylated boron nitride; and a microporous structure is formed in the composite film by pore-forming the ferric hydroxide nano particles, so that the composite film has good water permeability.
2. The interaction of hydrogen bonds exists between the hydroxylated boron nitride and MXene containing hydroxyl, so that the composite film layer is not easy to fall off, and the mechanical property of the hydroxylated boron nitride composite film is improved.
3. The hydroxylated boron nitride composite membrane provided by the scheme improves the adsorption and removal capacity of methylene blue with positive electricity in sewage.
Drawings
FIG. 1 is a scanning electron microscope image of the prepared hydroxylated boron nitride composite film.
Detailed Description
The present invention will be described in further detail with reference to examples, which are not intended to limit the technical scope of the present invention. The invention can be used for other purposes by anyone skilled in the art within the technical scope of the invention disclosure, and the relevant changes of raw materials, process conditions and the like can be properly realized by taking the technical content into consideration, and the invention can not depart from the technical content, and all similar substitutes and modifications which are obvious to those skilled in the art are deemed to be included in the technical scope of the invention.
In order to better explain the invention, the following text further illustrates the main content of the invention in connection with specific laboratory examples, but the content of the invention is not limited to the following examples only.
The invention provides a hydroxylated boron nitride composite film which comprises 0.5-2 parts by mass of hydroxylated boron nitride and 1 part by mass of MXene, wherein the composite film formed by the hydroxylated boron nitride and the MXene is distributed on a supporting substrate.
The invention is further illustrated by the following examples:
example 1
The embodiment 1 of the invention provides a preparation method of a hydroxylated boron nitride composite film, which comprises the following specific steps:
step 1: firstly, referring to the literature (Kai Wu, Ping Liao, Rongni Du, Qin Zhang, Feng Chen and Qiang Fu. Preparation of a thermally controlled biodegradable cellulose nanofiber/hydroxylated boron nitride nanosheet film, the critical roll of edge-hydrogenation J. mater. chem. A, 2018, 6, 11863-11873), preparing hydroxylated boron nitride nanosheets, then adding commercial MXene nanosheets and iron hydroxide nanocolloids into deionized water, and uniformly dispersing to obtain a mixed solution; adding a hydroxylated boron nitride nanosheet into the mixed solution, and uniformly mixing to obtain a mixed solution, wherein the adding amount of the hydroxylated boron nitride and MXene is 0.5:1 by mass, the mass ratio of the MXene to the ferric hydroxide nano colloid is 1:0.2, the mass of deionized water is 20-100 times that of the MXene, and the size of the ferric hydroxide nano colloid is 3-8 nm;
step 2: uniformly dispersing the mixed solution obtained in the step 1 on a ceramic substrate with the diameter of 2cm, carrying out suction filtration on the solution on the ceramic substrate, and forming a film layer after moisture is drained;
and step 3: and (3) washing the film layer in the step (2) by using deionized water and 0.5mol/L diluted hydrochloric acid solution for 3-4 times, and finally carrying out vacuum drying for 1 hour at 100 ℃ to obtain the hydroxylated boron nitride composite film.
Example 2
The embodiment 2 of the invention provides a preparation method of a hydroxylated boron nitride composite film, which comprises the following specific steps:
step 1: the difference between the embodiment 2 and the embodiment 1 lies in that the addition amount of each raw material is different, commercial MXene nanosheets and iron hydroxide nanocolloids are added into deionized water and uniformly dispersed to obtain a mixed solution; adding a hydroxylated boron nitride nanosheet into the mixed solution, and uniformly mixing to obtain a mixed solution, wherein the adding amount of the hydroxylated boron nitride and MXene is 1.25:1 by mass, the mass ratio of the MXene to the ferric hydroxide nano colloid is 1:0.6, the mass of deionized water is 20-100 times that of the MXene, and the size of the ferric hydroxide nano colloid is 3-8 nm;
step 2: uniformly dispersing the mixed solution obtained in the step 1 on a 2cm ceramic substrate, carrying out suction filtration on the solution on the ceramic substrate, and forming a film layer after moisture is drained;
and step 3: and (3) washing the film layer in the step (2) by using deionized water and 0.75mol/L diluted hydrochloric acid solution for 3-4 times, and finally carrying out vacuum drying for 2 hours at 150 ℃ to obtain the hydroxylated boron nitride composite film.
Example 3
Embodiment 3 of the invention provides a preparation method of a hydroxylated boron nitride composite film, which comprises the following specific steps:
step 1: the difference between the embodiment 3 and the embodiment 1 lies in that the addition amount of each raw material is different, commercial MXene nanosheets and iron hydroxide nanocolloids are added into deionized water and uniformly dispersed to obtain a mixed solution; adding a hydroxylated boron nitride nanosheet into the mixed solution, and uniformly mixing to obtain a mixed solution, wherein the adding amount of the hydroxylated boron nitride and MXene is 2:1 by mass, the mass ratio of the MXene to the ferric hydroxide nano colloid is 1:1 by mass, the mass of deionized water is 20-100 times of that of the MXene, and the size of the ferric hydroxide nano colloid is 3-8 nm;
step 2: uniformly dispersing the mixed solution obtained in the step 1 on a 2cm ceramic substrate, carrying out suction filtration on the solution on the ceramic substrate, and forming a film layer after moisture is drained;
and step 3: and (3) washing the film layer in the step (2) by using deionized water and 1.0mol/L diluted hydrochloric acid solution for 3-4 times, and finally carrying out vacuum drying for 3 hours at 200 ℃ to obtain the hydroxylated boron nitride composite film.
Example 4
The embodiment 4 of the invention provides an application of a hydroxylated boron nitride composite film in removing methylene blue, which comprises the following specific processes:
preparing 100mL of methylene blue solution with the concentration of 20mg/mL, using the hydroxylated boron nitride composite membrane prepared in the example 1, the example 2 or the example 3 for filtering the methylene blue solution, and taking the methylene blue solution before and after filtering to perform ultraviolet-visible spectrophotometer test, wherein the removal rate is calculated to be 99.1%.
Comparative example 1
The invention provides a preparation method of a single-component hydroxylated boron nitride film, which comprises the following specific steps:
the difference from example 1 is that only the hydroxylated boron nitride is added to the starting material of comparative example 1, and the specific steps are as follows:
step 1: adding a hydroxylated boron nitride nanosheet into deionized water, and uniformly dispersing to obtain a hydroxylated boron nitride nanosheet solution, wherein the use amount of the hydroxylated boron nitride is the same as that in example 1;
step 2: uniformly dispersing the hydroxylated boron nitride nanosheet solution obtained in the step 1 on a 2cm ceramic substrate, carrying out suction filtration on the solution on the ceramic substrate, and forming a film layer after moisture is drained;
and step 3: and (3) cleaning the film layer in the step (2) by using deionized water for 3-4 times, and finally carrying out vacuum drying for 2 hours at the temperature of 150 ℃ to obtain the hydroxylated boron nitride film with a single component. The single-component hydroxylated boron nitride film prepared in comparative example 1 was used for the removal of methylene blue, and the removal rate of 100mL of methylene blue solution having a concentration of 20mg/mL was 93.6%.
Comparative example 2
The invention provides a preparation method of a single-component MXene film, which comprises the following specific steps:
the difference from comparative example 1 is that only MXene was added to the starting material in comparative example 2, and the other steps were the same. The MXene film of a single component obtained in comparative example 2 was used for the removal of methylene blue, and the removal rate of 100mL of methylene blue solution having a concentration of 20mg/mL was 94.7%.
Comparative example 3
The invention provides a preparation method of a hydroxylated boron nitride composite film, which comprises the following specific steps:
the difference from example 1 is that the mass ratio of MXene and ferric hydroxide nanocolloid in comparative example 3 is 1:2, and other steps are the same. The hydroxylated boron nitride composite film prepared in comparative example 3 was used for removing methylene blue, and the removal rate of 100mL of methylene blue solution with the concentration of 20mg/mL was 93.1%.
Comparative example 4
The invention provides a preparation method of a hydroxylated boron nitride composite film, which comprises the following specific steps:
the difference from example 1 is that the mass ratio of MXene and ferric hydroxide nanocolloid in comparative example 4 is 1:0.05, and other steps are the same. The hydroxylated boron nitride composite film prepared in comparative example 4 was used for removing methylene blue, and the removal rate of 100mL of methylene blue solution with the concentration of 20mg/mL was 92.8%.
Table 1 list of the removal effect of different films on methylene blue
TABLE 2 List of the mass ratio of MXene and ferric hydroxide nanocolloid versus the removal of methylene blue
It can be seen from table 1 that the removal rate of the filtering membrane prepared from a single raw material to methylene blue is lower than that of the composite membrane to methylene blue, and through the doping of hydroxylated boron nitride and MXene and the pore-forming of iron hydroxide nanoparticles, a microporous structure is formed inside the composite membrane, and a large number of microporous structures enable the contact area of the composite membrane and the methylene blue to be larger in the process of filtering the methylene blue, so that the adsorption and interception of the membrane to the methylene blue are facilitated, and the removal effect of the composite membrane to the methylene blue is better. The water permeability of the composite membrane is good, meanwhile, the hydroxylated boron nitride composite membrane provided by the scheme has good water permeability in the filtering process, and the prepared composite membrane has good hydrophilicity through hydroxylation of the hydroxylated boron nitride; and (4) passing.
As can be seen from table 2, the mass ratio range of MXene and ferric hydroxide nanocolloid exceeds the mass ratio range given by the method, so that the removal rate of the composite membrane to methylene blue is reduced, which indicates that the amount of ferric hydroxide nanocolloid has an important influence on the formation of the microporous structure, and the possible reason is that too low amount of ferric hydroxide nanocolloid causes too few microporous structures, too high amount of ferric hydroxide nanocolloid causes too large microporous structures, the fewer microporous structures have less contact area with methylene blue, the larger microporous structure causes methylene blue to be directly filtered out from micropores during the filtration process, and effective interception cannot be achieved, which indicates that the composite membrane prepared within the range selected by the scheme has the best removal effect on methylene blue.
The embodiments of the present invention have been described above by way of example, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the application of the present invention shall fall within the scope of the patent of the present invention.
Claims (10)
1. A hydroxylated boron nitride composite film is characterized in that: the composite film comprises 0.5-2 parts of hydroxylated boron nitride and 1 part of MXene in parts by mass, and the composite film formed by the hydroxylated boron nitride and the MXene is distributed on a supporting substrate.
2. The hydroxylated boron nitride composite film of claim 1, wherein: the hydroxylated boron nitride and the MXene are both nanosheets, and the supporting substrate is a ceramic substrate or a polyvinylidene fluoride substrate.
3. A method for preparing a hydroxylated boron nitride composite film according to claim 1 or 2, characterized by comprising the following steps:
step 1: mixing the hydroxylated boron nitride, MXene and metal hydroxide nano colloid in a liquid phase to obtain a uniformly mixed solution;
step 2: uniformly dispersing the mixed solution obtained in the step 1 on a support substrate, carrying out suction filtration on the solution on the support substrate, and forming a film layer after moisture is drained;
and step 3: and (3) repeatedly washing the film layer in the step (2) by using deionized water and a dilute acid solution, and finally carrying out vacuum drying to obtain the hydroxylated boron nitride composite film.
4. The method for preparing a hydroxylated boron nitride composite film according to claim 3, characterized in that: the metal hydroxide nano colloid is ferric hydroxide nano colloid, and the size of the ferric hydroxide nano colloid is 3-8 nm.
5. The method for preparing a hydroxylated boron nitride composite film according to claim 4, characterized in that: the addition amount mass ratio of the hydroxylated boron nitride to the MXene is 0.5-2: 1.
6. the method for preparing a hydroxylated boron nitride composite film according to claim 5, characterized in that: the mixing sequence of the hydroxylated boron nitride, MXene and metal hydroxide nano colloid in the step (1) is as follows: adding MXene and ferric hydroxide nano colloid into deionized water to obtain a mixed solution, and adding hydroxylated boron nitride into the mixed solution of MXene and ferric hydroxide nano colloid to obtain a uniformly mixed solution.
7. The method for preparing a hydroxylated boron nitride composite film according to claim 6, wherein: the mass ratio of the MXene to the ferric hydroxide nano colloid is 1: 0.2-1, wherein the mass of the deionized water is 20-100 times of that of the MXene.
8. The method for preparing a hydroxylated boron nitride composite film according to claim 7, characterized in that: the dilute acid solution is 0.5-1.0 mol/L dilute hydrochloric acid.
9. The method for preparing a hydroxylated boron nitride composite film according to claim 8, characterized in that: the times of repeatedly washing the deionized water and the dilute hydrochloric acid solution are 3-4 times respectively.
10. The method for preparing a hydroxylated boron nitride composite film according to claim 3, characterized in that: the drying temperature of the vacuum drying in the step 3 is 100-200 ℃, and the drying time is 1-3 h.
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