CN111249931A - Preparation method of metalloporphyrin covalent grafting photocatalytic membrane - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 82
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 19
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000011968 lewis acid catalyst Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 238000005345 coagulation Methods 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 29
- 239000011941 photocatalyst Substances 0.000 abstract description 18
- 239000004065 semiconductor Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000004071 biological effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
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- 238000012986 modification Methods 0.000 abstract description 2
- 238000006303 photolysis reaction Methods 0.000 abstract description 2
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- 230000003595 spectral effect Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 11
- 230000004907 flux Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 150000004032 porphyrins Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- -1 porphyrin compound Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
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- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical class N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B01D71/06—Organic material
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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Abstract
The invention relates to a preparation method of a metalloporphyrin covalent grafting photocatalytic membrane, belonging to the technical field of membrane separation and water treatment. According to the invention, chloroacetyl chloride is used for performing chloroacetylation modification on a membrane material, and then amino metalloporphyrin reacts with the membrane material subjected to chloroacetylation, so that metalloporphyrin is covalently grafted on the surface of the membrane material. The photocatalyst in the obtained photocatalytic film is connected with the base film by a covalent bond, and the defects that the traditional inorganic semiconductor photocatalyst is poor in stability and easy to run off in the base film and blocks the pore channels of the separation film are overcome. The photocatalytic film has the advantages of abundant and easily-obtained raw materials, good biological property and simple preparation method. The obtained photocatalyst film has higher photolysis activity in the ultraviolet light and visible light spectral ranges, can obviously improve the pollution resistance of the separation film and the treatment capacity of organic wastewater, and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method of a metalloporphyrin covalent grafting photocatalytic membrane, belonging to the technical field of membrane separation and water treatment.
Background
The membrane separation technology is a process for separating, purifying and concentrating different components of a liquid material by taking external energy or chemical potential difference as a driving force through the selective osmosis of a membrane. The membrane separation technology has been widely researched and explored in the field of industrial wastewater treatment as a high and new technology, and has great technical advantages in the field of water treatment due to the characteristics of high separation efficiency, no phase change, energy conservation, environmental protection, simple equipment, simple and convenient operation and the like, so that the membrane separation technology becomes one of indispensable technologies in the field of water treatment. However, with the continuous advance of industrial process, the membrane separation technology with single function has been difficult to meet the increasing technical requirements of social industrial production and environmental pollution prevention, especially in the field of water treatment application. Therefore, the development, application and popularization of the multifunctional novel membrane separation technology are the leading directions of the membrane industry development which are not negligible.
The photocatalytic degradation technology of organic pollutants is a technology of exciting electron transition in a photocatalyst by illumination to generate hydroxyl radicals and completely converting the organic pollutants into water and carbon dioxide under the aerobic condition. The photocatalysis technology and the membrane separation technology are coupled, so that the technical defects of a single treatment process can be effectively overcome, and the wastewater treatment efficiency is improved. The photocatalytic film can realize a plurality of functions of film filtration physical separation, photocatalytic degradation of organic matters and the like in one unit. Meanwhile, photocatalytic membranes are generally superior to conventional membranes in reducing membrane fouling and improving permeability. The cake layer of conventional separation membranes due to membrane fouling often results in pore blockage, resulting in a significant drop in water flux. Moreover, membrane filtration is focused only on physical concentration of contaminants, which require further treatment before discharge. On the contrary, the photocatalytic film can degrade pollutants in water through oxygen-containing active free radicals under the illumination condition, thereby preventing the formation of a filter cake layer on the surface of the film, reducing the blockage of film pores and improving the permeation quality. The existing photocatalytic film is mainly formed by compounding inorganic semiconductor on a separation film, such as TiO2、ZnO、WO3And so on. The inorganic semiconductor is difficult to form a stable composite structure with the base film due to the property difference between the inorganic semiconductor and the organic base film, so that the inorganic semiconductor is unevenly distributed on the surface of the base film, is easy to fall off and run off in the using process, is easy to block a pore channel of a separation film, and seriously restricts the application of the inorganic semiconductor.
Porphyrin is a general name of homologues and derivatives of porphin with substituent at outer ring, and has functions of electron transfer, oxygen transfer, charge separation and the like in organisms. The porphyrin compound has better absorption in a visible light region and a near infrared region, and has a Soret band with strong absorption, wherein the absorption spectrum range is generally 400-450 nm; the Q band of weak absorption, the absorption spectrum range is generally 500-750 nm. In addition, the porphyrin compound also has excellent carrier transport performance. The porphyrin has stable property, the melting point is generally more than 300 ℃, so the porphyrin can be used as a visible light photocatalyst with stable performance, and the performance of the visible light photocatalyst can be modulated through reactions such as ion coordination and the like.
Based on the photocatalysis performance of the porphyrin, the invention develops a preparation method of a metalloporphyrin covalent grafting photocatalysis membrane. The photocatalyst in the obtained photocatalytic film is connected with the base film by a covalent bond, and the defects that the traditional inorganic semiconductor photocatalyst is poor in stability and easy to run off in the base film and blocks the pore channels of the separation film are overcome. The photocatalytic film has the advantages of abundant and easily-obtained raw materials, good biological property and simple preparation method. The obtained photocatalyst film has higher photolysis activity in the ultraviolet light and visible light spectral ranges, can obviously improve the pollution resistance of the separation film and the treatment capacity of organic wastewater, and has wide application prospect.
Disclosure of Invention
The invention aims to provide a preparation method of a metalloporphyrin covalent grafting photocatalytic membrane, which comprises the following preparation steps:
(1) dissolving a membrane material in a solvent N, N-Dimethylformamide (DMF), adding a small amount of Lewis acid catalyst, magnetically stirring to fully dissolve the membrane material, adding chloroacetyl chloride, heating to 50-70 ℃, carrying out reflux reaction for 10-18h, introducing nitrogen for protection of a reaction system, washing and removing excess solvent and unreacted chloroacetyl chloride by using ethanol after the reaction is finished, and drying to obtain a chloroacetylated membrane material;
(2) dissolving the product obtained in the step (1) in N, N-Dimethylacetamide (DMAC) solution, magnetically stirring to fully dissolve the product, adding amino metalloporphyrin, controlling the reaction temperature of the system at 100-150 ℃, reacting for 24-48h, introducing nitrogen for protection, and taking the obtained system as a casting solution after the reaction is finished;
(3) and (3) defoaming the casting solution in vacuum, coating the casting solution on a glass plate, scraping the glass plate to form a film, and immersing the glass plate into a coagulating bath at the temperature of 10-40 ℃ for coagulation to form the film, thereby obtaining the metalloporphyrin covalent grafting photocatalytic film.
Further, the membrane material in the step (1) is selected from polysulfone, polyether ketone and polyvinylidene fluoride.
Further, the Lewis acid catalyst in the step (1) is AlCl3、SnCl4。
Further, the mass ratio of the membrane material to the chloroacetyl chloride in the step (1) is 10: 0.5-5.
Further, the structural formula of the amino metalloporphyrin in the step (2) is as follows:
Further, the molar ratio of the chloracetyl chloride to the amino metalloporphyrin is 1: 1.
In the invention, chloroacetyl chloride is used for performing chloroacetylation modification on a membrane material in the presence of a Lewis acid catalyst, so that exchangeable chlorine is introduced to a macromolecular chain of the membrane material, and then nucleophilic substitution reaction is performed on the exchangeable chlorine and amino metalloporphyrin, so that the metalloporphyrin is grafted on the membrane material in a covalent bond form.
In metalloporphyrins, the metal center acts as an electron acceptor. Under the condition of illumination, porphyrin ligand is taken as an electron donor, and after being excited by light, generated photoelectrons can be transferred to an electron acceptor, so that charge separation is carried out, and an electron-hole pair which is similar to a semiconductor and has oxidizability and reducibility is generated, thereby endowing the metalloporphyrin with photocatalysis performance.
The metalloporphyrin covalent grafting photocatalytic membrane can synergistically play a role in intercepting pollutants of the separation membrane and the photocatalytic degradation performance of the photocatalyst. In the membrane separation unit, the separation membrane continuously intercepts organic pollutants, and intercepted organic matter molecules can be degraded into small molecules under the photocatalysis of metalloporphyrin, so that the pollution resistance of the separation membrane is obviously improved, and the treatment efficiency of the membrane separation unit is improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the organic photocatalyst is adopted to replace an inorganic semiconductor photocatalyst, so that the organic photocatalyst is grafted on a macromolecular chain of a membrane material through a covalent bond, the binding force of the photocatalyst and the membrane material is obviously improved, the dispersibility of the photocatalyst on the surface of the membrane material is improved, and the loss of the photocatalyst in the use process and the blockage of a pore channel caused by the photocatalyst on a separation membrane are avoided;
(2) the metalloporphyrin covalent grafting photocatalytic membrane can synergistically exert the pollutant interception performance of the separation membrane and the photocatalytic degradation performance of the photocatalyst, and the pollution resistance of the separation membrane is obviously improved, so that the treatment efficiency of a membrane separation unit is improved;
(3) the raw materials for preparing the separation membrane have wide sources, are environment-friendly, have low cost, have simple and easily-operated preparation process, are suitable for large-scale production, and have wide industrial application prospects.
Drawings
Fig. 1 is a graph showing the change in membrane flux of a photocatalytic membrane for organic wastewater treatment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Dissolving 1g polysulfone in N, N-Dimethylformamide (DMF), adding small amount of AlCl3Magnetically stirring to fully dissolve the chloracetyl chloride, adding 0.1g of chloracetyl chloride, heating to 50 ℃, carrying out reflux reaction for 10 hours, introducing nitrogen into a reaction system for protection, washing and removing redundant solvent and unreacted chloracetyl chloride by using ethanol after the reaction is finished, and drying to obtain chloracetyl polysulfone;
(2) dissolving the product obtained in the step (1) in N, N-Dimethylacetamide (DMAC) solution, magnetically stirring to fully dissolve the product, adding amino Cu-porphyrin with the molar weight equal to that of chloroacetyl chloride, controlling the reaction temperature of the system at 120 ℃, reacting for 24 hours, introducing nitrogen into the reaction system for protection, and taking the obtained system as a casting solution after the reaction is finished;
(3) and (3) defoaming the membrane casting solution in vacuum, coating the membrane casting solution on a glass plate, scraping the membrane casting solution to form a membrane, and immersing the membrane into a coagulating bath at the temperature of 30 ℃ for coagulating the membrane to form the membrane, so as to obtain the Cu-porphyrin covalent grafting polysulfone membrane which is marked as the number S-1.
Example 2
(1) Dissolving 1g polysulfone in N, N-Dimethylformamide (DMF), adding small amount of AlCl3Magnetically stirring to fully dissolve the chloracetyl chloride, adding 0.2g of chloracetyl chloride, heating to 50 ℃, carrying out reflux reaction for 10 hours, introducing nitrogen into a reaction system for protection, washing and removing redundant solvent and unreacted chloracetyl chloride by using ethanol after the reaction is finished, and drying to obtain chloracetyl polysulfone;
(2) dissolving the product obtained in the step (1) in N, N-Dimethylacetamide (DMAC) solution, magnetically stirring to fully dissolve the product, adding amino Zn-porphyrin with the molar weight equal to that of chloroacetyl chloride, controlling the reaction temperature of the system at 130 ℃, reacting for 36 hours, introducing nitrogen into the reaction system for protection, and taking the obtained system as a casting solution after the reaction is finished;
(3) and (3) defoaming the membrane casting solution in vacuum, coating the membrane casting solution on a glass plate, scraping the glass plate to form a membrane, and immersing the glass plate into a coagulating bath at the temperature of 30 ℃ for coagulating the membrane to form the membrane, so as to obtain the Zn-porphyrin covalent grafted polysulfone membrane which is marked as the number S-2.
Example 3
Organic wastewater is used as membrane test sewage, the membrane test sewage is filtered by a photocatalytic membrane, a xenon lamp is used for irradiating the photocatalytic membrane at the same time, the operation is carried out for 5 hours, and the change of membrane flux along with time is measured, as shown in figure 1. For comparison, a blending method was usedPreparation of inorganic semiconductor TiO2The conventional photocatalytic film compounded with the base film, denoted as D-1, was also subjected to the above organic wastewater treatment, and the change of the film flux with time was also shown in FIG. 1.
As can be seen from FIG. 1, the membrane flux of both the metalloporphyrin-covalently grafted photocatalytic membrane prepared by the present invention and the conventional inorganic semiconductor photocatalytic membrane decreases with the increase of the filtration time, because some contaminants accumulate in the membrane pores and on the membrane surface, forming membrane pore plugging and cake layer contamination. However, with the further advance of the filtration time, the membrane flux attenuation of the metalloporphyrin covalent grafted photocatalytic membrane obtained by the invention is obviously slowed down, which shows that the degradation efficiency of the photocatalytic membrane obtained by the invention is obviously superior to that of the traditional inorganic semiconductor photocatalytic membrane.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. A preparation method of a metalloporphyrin covalent grafting photocatalytic membrane is characterized by comprising the following preparation steps:
(1) dissolving a membrane material in a solvent N, N-Dimethylformamide (DMF), adding a small amount of Lewis acid catalyst, magnetically stirring to fully dissolve the membrane material, adding chloroacetyl chloride, heating to 50-70 ℃, carrying out reflux reaction for 10-18h, introducing nitrogen for protection of a reaction system, washing and removing excess solvent and unreacted chloroacetyl chloride by using ethanol after the reaction is finished, and drying to obtain a chloroacetylated membrane material;
(2) dissolving the product obtained in the step (1) in N, N-Dimethylacetamide (DMAC) solution, magnetically stirring to fully dissolve the product, adding amino metalloporphyrin, controlling the reaction temperature of the system at 100-150 ℃, reacting for 24-48h, introducing nitrogen for protection, and taking the obtained system as a casting solution after the reaction is finished;
(3) and (3) defoaming the casting solution in vacuum, coating the casting solution on a glass plate, scraping the glass plate to form a film, and immersing the glass plate into a coagulating bath at the temperature of 10-40 ℃ for coagulation to form the film, thereby obtaining the metalloporphyrin covalent grafting photocatalytic film.
2. The method for preparing a photocatalytic membrane according to claim 1, wherein the membrane material in step (1) is selected from polysulfone, polyether ketone, polyvinylidene fluoride.
3. The method for producing a photocatalytic film according to claim 1, wherein the Lewis acid catalyst in the step (1) is AlCl3、SnCl4。
4. The method for producing a photocatalytic film according to claim 1, wherein the mass ratio of the film material to chloroacetyl chloride in step (1) is 10: 0.5-5.
5. The method for producing a photocatalytic film according to claim 1, wherein the structural formula of the amino metalloporphyrin in the step (2) is:
6. The method for producing a photocatalytic film according to claim 1, wherein the molar ratio of chloroacetyl chloride to amino metalloporphyrin is 1: 1.
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