CN110813111B - Research on pure two-dimensional covalent organic framework material film for removing liquid-phase antibiotics - Google Patents
Research on pure two-dimensional covalent organic framework material film for removing liquid-phase antibiotics Download PDFInfo
- Publication number
- CN110813111B CN110813111B CN201911229803.3A CN201911229803A CN110813111B CN 110813111 B CN110813111 B CN 110813111B CN 201911229803 A CN201911229803 A CN 201911229803A CN 110813111 B CN110813111 B CN 110813111B
- Authority
- CN
- China
- Prior art keywords
- cof
- film
- pure
- tppa
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 11
- 239000013310 covalent-organic framework Substances 0.000 title claims description 35
- 239000007791 liquid phase Substances 0.000 title claims description 5
- 239000003242 anti bacterial agent Substances 0.000 title abstract description 10
- 229940088710 antibiotic agent Drugs 0.000 title description 9
- 238000011160 research Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002135 nanosheet Substances 0.000 claims abstract description 19
- 230000003115 biocidal effect Effects 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- ZAIPMKNFIOOWCQ-UEKVPHQBSA-N cephalexin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@@H]3N(C2=O)C(=C(CS3)C)C(O)=O)=CC=CC=C1 ZAIPMKNFIOOWCQ-UEKVPHQBSA-N 0.000 claims abstract description 6
- 229940106164 cephalexin Drugs 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- MNBSXKSWDLYJHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3,5-triol Chemical compound CC1=C(O)C(C)=C(O)C(C)=C1O MNBSXKSWDLYJHN-UHFFFAOYSA-N 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 238000001728 nano-filtration Methods 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 10
- 230000004907 flux Effects 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 4
- 238000003828 vacuum filtration Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 abstract description 2
- 229930186147 Cephalosporin Natural products 0.000 abstract 1
- OLVCFLKTBJRLHI-AXAPSJFSSA-N cefamandole Chemical compound CN1N=NN=C1SCC1=C(C(O)=O)N2C(=O)[C@@H](NC(=O)[C@H](O)C=3C=CC=CC=3)[C@H]2SC1 OLVCFLKTBJRLHI-AXAPSJFSSA-N 0.000 abstract 1
- 229960003012 cefamandole Drugs 0.000 abstract 1
- 229940124587 cephalosporin Drugs 0.000 abstract 1
- 150000001780 cephalosporins Chemical class 0.000 abstract 1
- 239000003814 drug Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 230000036541 health Effects 0.000 description 6
- 239000002064 nanoplatelet Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000012984 antibiotic solution Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- MHXLAKJJNRIVDR-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-tricarboxylic acid Chemical compound OC1=C(C(=C(C(=C1C(=O)O)O)C(=O)O)O)C(=O)O MHXLAKJJNRIVDR-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- MQLRYUCJDNBWMV-GHXIOONMSA-N cefetamet Chemical compound N([C@@H]1C(N2C(=C(C)CS[C@@H]21)C(O)=O)=O)C(=O)\C(=N/OC)C1=CSC(N)=N1 MQLRYUCJDNBWMV-GHXIOONMSA-N 0.000 description 1
- 229960004041 cefetamet Drugs 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010889 donnan-equilibrium Methods 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 238000009292 forward osmosis Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A COF-TpPa-SO 3 H membrane with high-efficiency nanofiltration separation on an antibiotic cefamandole acid belongs to the field of novel membrane materials. Firstly, hydrophilic property of sulfonate groups in a molecular structure is used by a simple interfacial polymerization method to obtain more COF nano sheets with high surface-to-thickness ratio, and then the COF-TpPa-SO 3 H film with high mechanical strength and high chemical stability is obtained by vacuum suction filtration in a layer-by-layer stacking mode. The pure COF-TpPa-SO 3 H film prepared under normal temperature vacuum filtration has the removal rate of the cephalosporin cefamain (Cefalexin) up to 95%, the error range is +/-0.6%, the water flux is up to 800L m ‑2·h‑1·MPa‑1, and the water flux of the obtained pure COF film is up to 2500L m ‑2·h‑1·MPa‑1 by changing the deposition quality of the COF. The water flux of the COF film prepared by the work is higher than that of the GO nanofiltration film and other ultrathin two-dimensional material films which are researched at present, and the COF film has better application potential in antibiotic removal.
Description
Technical Field
The invention belongs to the technical field of new material films, and provides a preparation method of a pure COF-TpPa-SO 3 H film which is prepared by stacking nano sheets layer by layer and is applied to liquid-phase antibiotic removal nanofiltration.
Background
With the improvement of the life quality of people, the consumption and production of health care medicines are continuously increasing worldwide, and the scientific research on the health care medicines in recent years has a trend of increasing year by year. At the same time, drugs released into water from domestic sewage and factory discharge sources can also affect the entire ecosystem and human health. Drugs are potentially bioactive chemicals specifically designed for production and use, aimed at affecting the activity of human cells and thereby improving the physical functioning of humans. But they have an unpredictable adverse effect on ecological species if their release into the environment is not controlled. At present, no drug concentration index is specified in many drinking water indexes worldwide, so that the existing or new water treatment technology is urgently needed to remove the drug concentration in the environmental water source to the maximum extent. The World Health Organization (WHO) suggests a sustainable solution to prevent drugs from entering an aqueous environment by employing a more efficient wastewater treatment system. Existing water treatment methods include coagulation-flocculation, adsorption, oxidation and advanced oxidation (i.e., ozone, ultraviolet light), biological treatment and membrane separation. Among these techniques, pressure driven membrane processes such as Reverse Osmosis (RO) and Nanofiltration (NF) are promising alternatives to drug removal. They are also suitable for recovering and reprocessing antibiotics or other valuable pharmaceutical compounds from waste.
Antibiotics have been widely used for human health, veterinary medicine, and to promote cell growth. However, recently, there has been much attention paid to the adverse effect of antibiotics on the environment. For example, they may enhance antibiotic resistance in a microbial population; potential risks are presented to the balance of the aquatic ecosystem and ultimately human health. It is therefore important to remove these compounds from the waste stream before they are discharged into the aquatic environment. However, conventional wastewater treatment plants (WWTP) do not adequately eliminate trace amounts of organic contaminants. Emerging membrane technologies such as Ultrafiltration (UF), nanofiltration (NF), reverse Osmosis (RO), and Forward Osmosis (FO) have shown promise for the removal of microcontaminants such as antibiotics. Nanofiltration (NF) is an attractive pressure driven membrane separation technique. Due to their high retention of multivalent ions and organic compounds, which can have a molecular weight of several hundred, at relatively low operating pressures, they have been widely used in potable water quality control, wastewater treatment and industrial applications. The separation mechanisms of NF mainly include size exclusion and Donnan effect (electrostatic interactions). Although size exclusion is the primary mechanism of neutral molecular retention, both are important for the separation of ionic species. Antibiotics generally have both positive and negative functional groups. When a charged NF membrane is used, both size exclusion and charge interactions between the antibiotic molecules and the membrane surface can significantly affect antibiotic retention. The invention provides a method for preparing a pure COF film by stacking vacuum filtration layers, wherein the COF contains special sulfonate groups, so that the pore size of a film material is obviously reduced, the addition of hydrophilic groups is more beneficial to the permeation of water molecules, and the permeability of the water molecules is obviously improved. The preparation of a large number of high-quality COF nano-sheets is realized by an interfacial polymerization method, the nano-sheets are controlled to be thinner by the existence of sulfonate, and the provided hydrophilicity enables the nano-sheets to be uniformly dispersed in an aqueous solvent. The pure COF film is gradually paid attention to because of the controllability of the pore size and the easiness in preparing the film material, and the designable pore size provided by the pure COF film has a huge application prospect for the regulation and separation of antibiotics.
Disclosure of Invention
The invention aims to provide a pure COF-TpPa-SO 3 H membrane for nanofiltration of antibiotic cefamain (Cefalexin). The COF nanosheets with high aspect ratio are obtained by an interfacial polymerization method, and the pure COF film prepared by stacking layers has high acid and alkali resistance, chemical stability and mechanical stability. The method is simple to operate, and the prepared pure COF film is compact and continuous. The pure COF-TpPa-SO 3 H film prepared by vacuum filtration at normal temperature has a removal rate of 95% for the antibiotic cefamane (Cefalexin), the water flux is up to 800L m -2·h-1·MPa-1, and the water flux of the pure COF film obtained by changing the quality of COF deposition can be up to 2500L m -2·h-1·MPa-1.
1. The specific preparation method of the novel nano material film provided by the invention comprises the following steps:
(1) Synthesis of COF-TpPa-SO 3 H nanosheets 15.7 mg (0.075 mmol) Tp (2, 4, 6-tricarboxyl phloroglucinol) ultrasonic 10 min was dissolved in 100 ml dichloromethane, noted as solution 1, and placed in a large beaker. 21.0 mg (0.112 mmol) Pa-SO 3 H (2, 5-diaminobenzenesulfonic acid) and 38.5 mg (0.224 mmol) PTSA (para-toluenesulfonic acid monohydrate) mixed ultrasound 10 min were dissolved in 100 ml deionized water, designated solution 2. Solution 2 was added dropwise to the upper layer 30min of solution 1, delamination was observed, the beaker was sealed with a film, and left to stand for 3 days.
(2) After the finishing reaction time of the COF-TpPa-SO 3 H nanoplatelets was terminated, the upper aqueous solution was taken out and placed in a 250 ml volumetric flask, and the aqueous solution was observed to appear dark red. The aqueous solution contains unreacted Pa-SO 3 H (2, 5-diaminobenzenesulfonic acid) ligand and regulator PTSA (p-toluenesulfonic acid monohydrate), the solution is placed in a dialysis zone with molecular weight cut-off of 10000, soaked for 3 days, the pure water is changed for 3 times a day, and after 3 days, the COF-TpPa-SO 3 H nano-sheet is obtained. COF concentration was estimated by dry weighing it.
(3) Pure COF-TpPa-SO 3 H film preparation COF nanoplatelets of different masses (mass of COF calculated from COF concentration already estimated and volume of solution taken) were dispersed in 100ml pure deionized water and sonicated 10 min in a sonicator (250 w,20 KHz) to make nanoplatelets dispersed uniformly. The dispersion was suction-filtered onto a nylon substrate (200 nm pore size) of 50mm by a vacuum suction-filtration device at normal temperature, and the prepared COF film was dried 24h at room temperature, and then placed in a vacuum drying oven at 40 ℃ for vacuum drying 24 h.
2. The deposition quality of the COF nano-sheets is changed, and a series of pure COF-TpPa-SO 3 H films are prepared by the same preparation method as that described in 1
3. The quality of the nanoplatelets was observed by characterization methods of AFM, and the effect of the modulator PTSA was studied.
The pure COF nanofiltration membrane is applied to nanofiltration separation of the antibiotic cefamane (Cefalexin), and the removal of the liquid phase is performed through a self-made device, and the concentration change of the antibiotic is obtained through an ultraviolet spectrophotometer of a solution at the permeation side, so that the removal rate of the antibiotic is obtained.
(1) An aqueous solution of cefetamet at a concentration of 400 ppm was prepared as a solution on the feed side.
(2) The pure COF-TpPa-SO 3 H film is placed in a self-made O-shaped sealing gasket, a continuous feeding device is adopted on the feeding side to prevent concentration change on the feeding side, a solution collecting device is arranged on the discharging side, a vacuum pump provides pressure difference, and the pressure difference on the feeding side and the discharging side is read through a pressure difference meter.
(3) The antibiotic solution with a certain concentration is placed in the device on the feeding side, the concentration of the antibiotic solution on the feeding side is kept unchanged along with the time, the antibiotic solution passes through the pure COF film, and the permeated solution is collected on the discharging side through the pressure difference provided by the vacuum pump.
(4) To ensure accuracy of the data, each set of experiments was repeated 3 times under the same conditions to exclude occasional errors. The suction filtration time was recorded, the pressure difference between the feed side and the discharge side and the volume of the collected solution were counted after the device had stabilized.
(5) The collected solution was diluted 100 times, and at the same time, the antibiotic solution at the feed side was diluted 100 times as well, and the concentration change was measured using an ultraviolet spectrophotometer. Before measurement, a series of cefamane solutions with concentration are prepared, and a linear relation diagram of the concentration and peak height is obtained through an ultraviolet spectrophotometer. Then, the antibiotic removal rate is obtained after the concentration of the two sides of the feeding side and the discharging side is measured.
Compared with the existing film material, the invention has the advantages that:
(1) The preparation method of the COF film is simple, has few steps and high repeatability.
(2) The COF film has good chemical stability and keeps stable under the acid-base condition.
(3) The membrane has high removal rate of the antibiotic cefamain (Cefalexin) and higher water flux.
(4) The pure COF film prepared by the method is continuous and compact, and the regulation and control of water flux and antibiotic removal rate are realized by changing the deposition amount of the COF.
(5) The film has high mechanical strength, and folding and unfolding do not damage the separation performance.
Drawings
FIG. 1 is an AFM and SEM characterization of COF-TpPa-SO 3 H nanoplatelets of example 1.
FIG. 2 is a schematic representation of the preparation of COF-TpPa-SO 3 H film in example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) characterization of the COF-TpPa-SO 3 H film of example 2.
FIG. 4 is a graph of the antibiotic separation performance of COF-TpPa-SO 3 H film in example 2.
FIG. 5 is a graph of the chemical stability test of COF-TpPa-SO 3 H film in example 2.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the present invention is not limited thereto.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1
The COF-TpPa-SO 3 H nanosheets synthesized by the interfacial polymerization method are washed and collected. Uniformly dispersing the silicon wafer into the solution, uniformly dripping one drop of the dispersion liquid onto the silicon wafer, and drying the silicon wafer at 40 ℃ under vacuum condition for 24 h.
Respectively ultrasonically dissolving Tp and Pa-SO 3 H monomers into dichloromethane and an aqueous solvent, adding a regulator (p-toluenesulfonic acid monohydrate) into the aqueous solvent, and slowly and dropwise adding an aqueous solution containing Pa-SO 3 H into a dichloromethane solution of Tp. Standing for 3 days, collecting the upper layer aqueous solution, dialyzing and cleaning to obtain COF-TpPa-SO 3 H nanosheet aqueous solution, and dispersing the aqueous solution into deionized water to obtain the COF nanosheet solution with a certain concentration. A drop of COF aqueous solution was dropped onto a clean silicon wafer and SEM characterization of the nanoplatelets was tested.
Example 2
The prepared COF film was placed in a separation layer, sealed with an O-ring, and then the prepared feed liquid was placed on the feed side, and the antibiotic removal performance and water flux of the film were tested by a homemade device.
And respectively placing the COF-TpPa-SO 3 H films in a die, sealing by using an O-shaped gasket, placing the prepared cefamain solution with the concentration of 400 ppm on the feeding side, and collecting the solution on the discharging side. After the vacuum pump was turned on, the suction filtration time and the pressure difference on the feed side and the discharge side were recorded. After the permeation was completed, the permeation side solution volume was recorded. The concentration of the solution at the feeding side and the solution at the discharging side is measured by an ultraviolet spectrophotometer, then the removal rate of antibiotics is calculated, and then the flux of water is calculated by the volume of the solution at the discharging side, the suction filtration time and the pressure difference at the two sides. The test of the COF film prepared by changing the deposition amount of other COFs was the same as the test method described above.
Claims (4)
1. A preparation method of a pure two-dimensional covalent organic framework material film comprises the following steps:
(1) Synthesis of COF-TpPa-SO 3 H nanosheets, 2, 4, 6-trimethylphloroglucinol ultrasound 10 min of 15.7 mg was dissolved in 100 ml dichloromethane, noted as solution 1, and placed in a large beaker; 21.0 mg of 2, 5-diaminobenzenesulfonic acid and 38.5 mg of p-toluenesulfonic acid monohydrate mixed ultrasonic 10 min were dissolved in 100 ml deionized water, designated solution 2; dropwise adding the solution 2 into the upper layer 30 min of the solution 1, observing layering phenomenon, sealing a beaker mouth with a film, and standing for 3 days;
(2) After finishing the COF-TpPa-SO 3 H nanosheets, taking out the upper aqueous solution after the reaction time is over, placing the upper aqueous solution into a 250 ml volumetric flask, observing that the aqueous solution is dark red, placing the aqueous solution containing unreacted complete 2, 5-diaminobenzenesulfonic acid ligand and a regulator p-toluenesulfonic acid monohydrate into a dialysis belt with the molecular weight cutoff of 10000 Da, soaking for 3 days, changing pure water for 3 times a day, and obtaining the COF-TpPa-SO 3 H nanosheets after 3 days;
(3) Preparing a pure COF-TpPa-SO 3 H film, dispersing COF nano-sheets with different qualities into 100ml pure deionized water, and carrying out ultrasonic treatment on the nano-sheets in an ultrasonic box with the power of 250W and the ultrasonic frequency of 20KHz for 10min to uniformly disperse the nano-sheets; the dispersion was suction-filtered onto a nylon substrate having a pore size of 200nm by a vacuum suction-filtration device at normal temperature, and the prepared COF film was dried 24 h at room temperature, and then vacuum-dried 24 h at 40 ℃ in a vacuum drying oven.
2. The method for preparing the pure two-dimensional covalent organic framework material film according to claim 1, which is characterized in that: in the step (3), the prepared COF film is formed by stacking COF nano-sheets layer by layer.
3. Use of a membrane prepared by the preparation method according to any one of claims 1-2 in liquid phase antibiotic removal.
4. A use according to claim 3, characterized in that: the antibiotic is cefalexin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911229803.3A CN110813111B (en) | 2019-12-05 | 2019-12-05 | Research on pure two-dimensional covalent organic framework material film for removing liquid-phase antibiotics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911229803.3A CN110813111B (en) | 2019-12-05 | 2019-12-05 | Research on pure two-dimensional covalent organic framework material film for removing liquid-phase antibiotics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110813111A CN110813111A (en) | 2020-02-21 |
| CN110813111B true CN110813111B (en) | 2024-06-25 |
Family
ID=69543997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911229803.3A Active CN110813111B (en) | 2019-12-05 | 2019-12-05 | Research on pure two-dimensional covalent organic framework material film for removing liquid-phase antibiotics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110813111B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113976049B (en) * | 2021-10-12 | 2022-11-04 | 中国地质大学（武汉） | COF/CS aerogel and preparation method and application thereof |
| CN114618331B (en) * | 2022-04-20 | 2023-07-25 | 中科南京绿色制造产业创新研究院 | Covalent organic framework doped polyamide reverse osmosis membrane and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252153A (en) * | 2019-07-09 | 2019-09-20 | 北京化工大学 | A kind of preparation method and application of the ultra-thin COF/GO film of controllable separating property |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11512099B2 (en) * | 2016-07-12 | 2022-11-29 | University Of Central Florida Research Foundation, Inc. | Mechanically shaped 2-dimensional covalent organic frameworks |
| CN109012243A (en) * | 2018-08-22 | 2018-12-18 | 南开大学 | The preparation and Separate Efficiency Study of macromolecule-covalent organic frame material (polyCOF) composite membrane |
| CN110305347B (en) * | 2019-06-06 | 2020-10-16 | 中国石油大学(北京) | Modified chitosan-based proton exchange membrane and preparation method thereof |
-
2019
- 2019-12-05 CN CN201911229803.3A patent/CN110813111B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252153A (en) * | 2019-07-09 | 2019-09-20 | 北京化工大学 | A kind of preparation method and application of the ultra-thin COF/GO film of controllable separating property |
Non-Patent Citations (1)
| Title |
|---|
| "Interplaying Intrinsic and Extrinsic Proton Conductivities in Covalent Organic Frameworks";Suman Chandra et al.;《Chemistry of materials》;20160216;第28卷(第5期);1489-1494 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110813111A (en) | 2020-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Long et al. | Fabrication of chitosan nanofiltration membranes by the film casting strategy for effective removal of dyes/salts in textile wastewater | |
| Hau et al. | Exploration of EDTA sodium salt as novel draw solution in forward osmosis process for dewatering of high nutrient sludge | |
| Xu et al. | Recent advances in forward osmosis (FO) membrane: Chemical modifications on membranes for FO processes | |
| Hu et al. | Application of nano TiO2 modified hollow fiber membranes in algal membrane bioreactors for high-density algae cultivation and wastewater polishing | |
| Bojnourd et al. | Preparation and characterization of a nanoclay/PVA/PSf nanocomposite membrane for removal of pharmaceuticals from water | |
| Choi et al. | A study on the removal of organic acids from wastewaters using nanofiltration membranes | |
| CN107469633B (en) | Method for preparing membrane with enhanced water flux | |
| Yu et al. | Photoinduced graft polymerization of acrylamide on polypropylene microporous membranes for the improvement of antifouling characteristics in a submerged membrane-bioreactor | |
| CN110813111B (en) | Research on pure two-dimensional covalent organic framework material film for removing liquid-phase antibiotics | |
| Yu et al. | Surface modification of polypropylene microporous membrane to improve its antifouling characteristics in an SMBR: N2 plasma treatment | |
| Zhang et al. | Treatment of municipal wastewater with aerobic granular sludge membrane bioreactor (AGMBR): Performance and membrane fouling | |
| EP2366449A2 (en) | Membrane with a patterned surface, method for manufacturing same, and water treatment process using same | |
| Xing et al. | MOFs self-assembled molecularly imprinted membranes with photoinduced regeneration ability for long-lasting selective separation | |
| Li et al. | Ultra-smooth and ultra-thin polyamide thin film nanocomposite membranes incorporated with functionalized MoS2 nanosheets for high performance organic solvent nanofiltration | |
| CN108993165B (en) | Layered inorganic material organic solvent nanofiltration composite membrane and preparation method thereof | |
| Wang et al. | Host-guest nanofiltration membranes having amino-complexed cucurbituril supramolecular channel for monovalent/divalent salts separation | |
| Zhang et al. | Facile fabrication of covalent organic framework composite membranes via interfacial polymerization for enhanced separation and anti-fouling performance | |
| Zhang et al. | Deprotonated tannic acid regulating pyrrole polymerization to enhance nanofiltration performance for molecular separations under both aqueous and organic solvent environments | |
| Zhang et al. | Covalent organic framework-immobilized wood membrane for efficient, durable, and high-flux nanofiltration | |
| Osman et al. | Membrane technology for energy saving: principles, techniques, applications, challenges, and prospects | |
| CN113019137B (en) | Preparation and application of MXene @ COF composite film | |
| Hameed et al. | A review on recent advances in covalent organic frameworks-based membranes: synthesis, modification, and applications in liquid phase separation | |
| CN111944177B (en) | Polymer ultrathin film forming system and polymer ultrathin film | |
| Visakh et al. | Nanostructured Polymer Membranes, Volume 2: Applications | |
| CN109081430A (en) | It can accelerate the preparation method of the reproducibility graphene oxide Modified Membrane of water treatment procedure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |