CN112844399A - Preparation method of group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophore - Google Patents
Preparation method of group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophore Download PDFInfo
- Publication number
- CN112844399A CN112844399A CN202011514102.7A CN202011514102A CN112844399A CN 112844399 A CN112844399 A CN 112844399A CN 202011514102 A CN202011514102 A CN 202011514102A CN 112844399 A CN112844399 A CN 112844399A
- Authority
- CN
- China
- Prior art keywords
- toxic
- pharmacophores
- group
- organic layer
- preparation
- 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.)
- Pending
Links
- 231100000331 toxic Toxicity 0.000 title claims abstract description 47
- 230000002588 toxic effect Effects 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012044 organic layer Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 25
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000005516 engineering process Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 8
- 230000003115 biocidal effect Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000011941 photocatalyst Substances 0.000 claims abstract description 7
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 229920006254 polymer film Polymers 0.000 claims abstract description 4
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- -1 aromatic azo Chemical compound 0.000 claims description 10
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 229910002915 BiVO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 2
- 125000004963 sulfonylalkyl group Chemical group 0.000 claims description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000003242 anti bacterial agent Substances 0.000 description 15
- 229940088710 antibiotic agent Drugs 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000005457 ice water Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 125000003368 amide group Chemical group 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 229910008452 SnFe Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 229920000767 polyaniline Polymers 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 2
- 229960000623 carbamazepine Drugs 0.000 description 2
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- 108091005461 Nucleic proteins Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001937 non-anti-biotic effect Effects 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003285 pharmacodynamic effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008684 selective degradation Effects 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophores, which comprises the following steps: (1) adopting a surface molecular imprinting technology of a dummy template, taking a molecule containing the same toxic pharmacophore as a target antibiotic molecule to be degraded as the dummy template molecule, and taking aniline, pyrrole or a mixture of the aniline and the pyrrole as a functional monomer to form a pre-assembly liquid; (2) adding a visible light catalyst, adding an initiator into an acidic medium, and carrying out in-situ polymerization to obtain a conductive polymer film/visible light catalyst composite material combined with toxic pharmacophores; (3) and removing the dummy template molecules in the conductive polymer film by a soxhlet extraction method, and leaving a large number of three-dimensional cavities matched with the size, the shape and the functional groups of the dummy template molecules in the conductive group imprinted polymer film on the surface of the photocatalyst. The method has the outstanding advantages of high yield, good selectivity of the product to toxic pharmacophores and high degradation efficiency.
Description
Technical Field
The invention relates to the technical field of conductive group imprinted layer composite photocatalytic materials, in particular to a method for preparing a conductive group imprinted layer composite photocatalytic material for targeted recognition of toxic pharmacophores by using a dummy template surface molecular imprinting technology.
Background
In recent years, the yield and consumption of antibiotics in China are increasing and account for about 50% of the world, and the method becomes the country with the largest production and consumption of antibiotics. Antibiotics are widely used in human medical treatment, livestock breeding and other industries, bring great convenience to human society, and enter water body environment through human daily life, agricultural production, livestock breeding, pharmaceutical wastewater discharge and other ways. The presence of various antibiotics is detected in rivers and lakes around the world. The surface water of China contains various antibiotics, and the concentration of the antibiotics is far higher than that of developed countries. The antibiotics entering the water body still have biological activity, even trace levels can bring hidden dangers to water environment quality, ecosystem safety and human health, and part of pharmacophores of the antibiotics have toxicity, namely toxic pharmacophores. Toxic pharmacophores are often electron-deficient, have electrophilic properties, and undergo substitution reactions with nucleophilic centers in nucleic acids, proteins or other important components in vivo under physiological conditions, causing irreversible damage to these components in vivo, even with carcinogenic, teratogenic and mutagenic effects. Therefore, how to remove the antibiotics in water, especially to preferentially destroy the toxic pharmacophore of the antibiotics, has become a problem to be solved.
At present, common treatment methods of antibiotics in water bodies mainly comprise advanced oxidation processes such as an adsorption method, a membrane treatment technology, an electrochemical treatment method, an activated sludge method, a chlorination method, an ozone oxidation method, a Fenton method and the like. Although these methods have good results for the removal of antibiotics from water bodies, they still have their own inherent disadvantages. The adsorption and membrane treatment technology is essentially the transfer of pollutants, can not eliminate the antibiotic pollutants fundamentally and still has potential danger to the environment; the flow rate required in the electrochemical treatment process cannot be too high, and the operation cost of the technology is high; the chlorination method can achieve a larger antibiotic removal rate, but the reaction is not thorough, and various byproducts are generated, so that secondary pollution is caused, and the difficulty is increased for subsequent water treatment; the ozone oxidation method has the defects of large equipment investment, high energy consumption, generation of byproducts with stronger toxicity and the like; the conventional activated sludge process has the advantages of large treatment capacity, low cost and the like, but antibiotics can inhibit the activity of microorganisms, and the reaction speed is low and the removal efficiency is low; in the Fenton method, if the pH control is not good, a large amount of hydroxide precipitate is easily generated, and the recovery of the soluble catalyst in the hydroxide precipitate is difficult.
The photocatalytic oxidation technology has the incomparable advantages of high treatment efficiency, simple process equipment, easily controlled operation conditions, no secondary pollution and the like, and is a novel water treatment technology with wide application prospect. However, the process of photocatalytic degradation of organic matters is not selective in principle, and when pollutants are adsorbed on the surface of a catalyst, active species such as hydroxyl radicals cannot selectively and preferentially destroy toxic pharmacophores of antibiotics. Therefore, the improvement of the selectivity of the photocatalytic material is a research work with scientific significance and practical value. The molecular imprinting technology can prepare molecular recognition materials with specific selectivity. The technology uses the interaction of template molecules and functional monomers to form a host-guest compound with multiple action points, the action can be memorized through the polymerization process, then the template molecules are eluted, and cavities which are matched with the spatial configuration of the template molecules and have multiple action points are formed in the polymer, and the cavities have specific selectivity on the template molecules. The molecular imprinting type photocatalytic material prepared by combining the molecular imprinting technology and the photocatalytic technology and taking the target pollutant as the template molecule has excellent photoelectric property and higher selectivity on the template molecule, and can realize the selective conversion and degradation on the target pollutant molecule in a system with various pollutants coexisting. Although the above method has specific recognition ability for target contaminant molecules, it does not selectively preferentially destroy the toxic groups of organic contaminants, so that the degradation products may still be toxic. Therefore, how to design a novel molecular imprinting type photocatalyst with stronger specific binding and selective degradation capability on toxic pharmacophores of antibiotics still remains the key point of whether the photocatalytic water purification technology can be broken through and applied to the practical antibiotic wastewater treatment engineering.
Disclosure of Invention
The invention aims to provide a preparation method of a group imprinting conductive organic layer composite photocatalytic material for target recognition of toxic pharmacophores aiming at the defects of the prior art. The method adopts a false template molecular imprinting technology, takes molecules (non-antibiotic molecules) containing toxic pharmacophores as templates, takes aniline, pyrrole or a mixture of the aniline and the pyrrole as functional monomers, and constructs a layer of group imprinting polymer film capable of identifying the toxic pharmacophores on the surface of a catalyst; the group imprinted polymer membrane contains a large number of imprinted cavities which can be matched with the size, shape and charge of the toxic pharmacophore, and the cavities can be specifically combined with the toxic pharmacophore, so that active species generated by the catalyst can preferentially attack the toxic pharmacophore to degrade the toxic pharmacophore. The composite photocatalyst can target and specifically degrade toxic pharmacophores, and has the characteristics of high selectivity and high efficiency on degradation of the toxic pharmacophores.
The invention is realized by the following technical scheme.
A preparation method of a group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophores is characterized by comprising the following preparation steps: (1) a molecular imprinting technology on the surface of a false template is adopted, molecules (non-target antibiotic molecules) containing the same toxic pharmacophore as degraded target antibiotic molecules are used as the false template molecules, aniline, pyrrole or a mixture of the aniline and the pyrrole are used as functional monomers, and the functional monomers and the toxic pharmacophore interact with each other in a solvent to form pre-assembled liquid, wherein the pi-pi, electrostatic attraction, hydrogen bonds and the like are generated between the functional monomers and the toxic pharmacophore. (2) Adding a proper visible light catalyst, adding an initiator into an acid medium, and carrying out in-situ polymerization to obtain the conductive polymer film/visible light catalyst composite material combined with the toxic pharmacophore. (3) Removing the false template molecules containing toxic pharmacophores in the conductive polymer film by a soxhlet extraction method, and leaving a large number of three-dimensional cavities which can be matched with the sizes, shapes and functional groups of the false template molecules in the conductive group imprinted polymer film on the surface of the photocatalyst to obtain the group imprinted conductive organic layer composite photocatalytic material for targeted recognition of the toxic pharmacophores. The cavities can be specifically combined with toxic pharmacophores, so that active species generated by the catalyst can preferentially attack the toxic pharmacophores to degrade and detoxify the toxic pharmacophores.
Furthermore, the dummy template molecule is a molecule containing aromatic nitro, aromatic nitrogen oxide, aromatic azo, alkyl hydrazine, aromatic primary amine or secondary amine, sulfonyl alkyl ester and other groups.
Further, the visible light catalyst is SnFe2O4/ZnFe2O4Heterojunction, BiVO4、Bi2WO6And the like.
Furthermore, the molar ratio of the dummy template molecules to the functional monomers is 1: 2-1: 10.
Further, the solvent is one of methanol-water solution, ethanol-water solution, methanol-ethanol mixed solution and the like.
Further, the acidic medium is one of hydrochloric acid, phosphoric acid, 2-acrylamido-2-methylpropanesulfonic acid and the like.
Further, the initiator is FeCl3、(NH4)2SO8、KIO3、H2O2And the like.
The beneficial effects of the invention are that the technical scheme of the invention has the following advantages:
(1) the preparation method is an in-situ polymerization method, and is simple and economical.
(2) The photocatalyst prepared by the invention can specifically identify toxic pharmacodynamic factors, and has higher efficiency and selectivity for degrading toxic pharmacophore compared with the traditional photocatalyst.
Drawings
FIG. 1 shows a group-imprinted polyaniline-SnFe prepared in example 12O4/ZnFe2O4XRD pattern of catalyst.
FIG. 2 is a diagram of the group-imprinted polyaniline-SnFe prepared in example 12O4/ZnFe2O4UV-Vis spectra of the catalyst.
FIG. 3 is the group imprinted polyaniline-SnFe prepared in example 12O4/ZnFe2O4Nitrogen adsorption-desorption curve of catalyst.
Detailed Description
The following examples are intended to illustrate the invention without further limiting it.
Example 1
Dissolving 0.004 mol of aniline and 0.001mol of 3- (dimethylamino) -2-hydroxy-6-oxocyclohex-1-enecarboxamide in 5.0 mL of ethanol aqueous solution (1:1, v/v), and continuously stirring for 25min to form a pre-polymerization solution; 0.75 g of SnFe2O4/ZnFe2O4Dispersed ultrasonically in 100mL HCl solution (pH =2), stirred in an ice-water bath for 25min, and then the pre-polymerization solution was added. 5 mL of FeCl with a concentration of 50 g/L is slowly added dropwise under stirring3The solution was reacted in an ice-water bath for 5 hours. Performing suction filtration, washing with deionized water and ethanol for multiple times respectively, and removing 3- (dimethylamino) -2-hydroxy-6-oxocyclohex-1-enecarboxamide template molecules by Soxhlet extraction with methanol and hydrochloric acid mixed solution with volume ratio of 1:1 as eluent to obtain conductive polyaniline group imprinted layer-SnFe capable of identifying amide groups in a targeted manner2O4/ZnFe2O4The composite photocatalytic material can efficiently degrade the amide group of tetracycline. FIG. 1, FIG. 2 and FIG. 3 are respectively SnFe with polyaniline/polypyrrole film prepared by the present invention2O4/ZnFe2O4XRD spectrum, UV-Vis spectrum and nitrogen adsorption-desorption curve of the catalyst.
Example 2
Dissolving 0.003 mol of aniline and 0.001mol of 3- (dimethylamino) -2-hydroxy-6-oxocyclohex-1-enecarboxamide in 5.0 mL of methanol-ethanol mixture (1:1, v/v), and stirring for 25min to form a pre-polymerization solution; 0.6 g of Bi2WO6Dispersed ultrasonically in 100mL HCl solution (pH =2), stirred in an ice-water bath for 25min, and then the pre-polymerization solution was added. Slowly under the condition of stirring5 mL of 50 g/L FeCl is added dropwise3The solution was reacted in an ice-water bath for 5 hours. Performing suction filtration, washing with deionized water and ethanol for multiple times respectively, and removing 3- (dimethylamino) -2-hydroxy-6-oxocyclohex-1-enecarboxamide template molecules by Soxhlet extraction with methanol and hydrochloric acid mixed solution with volume ratio of 1:1 as eluent to obtain conductive polyaniline group imprinted layer-Bi capable of identifying amide groups in a targeted manner2WO6The composite photocatalytic material can efficiently degrade the amide group of tetracycline.
Example 3
Dissolving 0.003 mol of pyrrole and 0.001mol of (z) -2, 3, 6, 7-tetrahydro-a-heptine-1-carboxamide in 5.0 mL of methanol-ethanol mixture (1:1, v/v) and stirring continuously for 25min to form a pre-polymerization solution; 0.6 g of Bi2WO6Dispersed ultrasonically in 100mL HCl solution (pH =2), stirred in an ice-water bath for 25min, and then the pre-polymerization solution was added. 5 mL of FeCl with a concentration of 50 g/L is slowly added dropwise under stirring3The solution was reacted in an ice-water bath for 5 hours. Performing suction filtration, washing with deionized water and ethanol for multiple times respectively, removing template molecules by Soxhlet extraction with mixed solution of methanol and hydrochloric acid with the volume ratio of 1:1 as eluent to obtain conductive polypyrrole group imprinted layer-Bi capable of identifying amide groups in a targeted manner2WO6The composite photocatalytic material can efficiently degrade the carboxamide group of carbamazepine.
Example 4
Dissolving 0.002 mol of aniline/pyrrole mixture (molar ratio 1: 1) and 0.001mol of (z) -2, 3, 6, 7-tetrahydro-a-heptine-1-carboxamide in 5.0 mL of ethanol aqueous solution (1:1, v/v) and continuously stirring for 25min to form a pre-polymerization solution; 0.5 g of BiVO4Dispersed ultrasonically in 100mL HCl solution (pH =2), stirred in an ice-water bath for 25min, and then the pre-polymerization solution was added. 5 mL of 40 g/L ammonium persulfate solution is slowly dropped into the solution under the stirring condition, and the reaction is carried out for 5 hours in an ice water bath. Performing suction filtration, washing with deionized water and ethanol for multiple times respectively, and removing (z) -2, 3, 6, 7-tetrahydro-a-heptein-1-carboxamide template molecules by using a methanol and hydrochloric acid mixed solution with a volume ratio of 1:1 as an eluent through a Soxhlet extraction method to obtain a conductive polyaniline/pyrrole group imprinted layer-BiVO capable of identifying amide groups in a targeted manner4Composite lightThe catalytic material can efficiently degrade the carboxamide group of carbamazepine.
Example 5
Dissolving 0.002 mol of aniline and 0.001mol of (z) -2, 3, 6, 7-tetrahydro-a-heptine-1-carboxamide in 5.0 mL of ethanol aqueous solution (1:1, v/v) and stirring continuously for 25min to form a pre-polymerization solution; 0.5 g of BiVO4Dispersed ultrasonically in 100mL HCl solution (pH =2), stirred in an ice-water bath for 25min, and then the pre-polymerization solution was added. 5 mL of 40 g/L ammonium persulfate solution is slowly dropped into the solution under the stirring condition, and the reaction is carried out for 5 hours in an ice water bath. Performing suction filtration, washing with deionized water and ethanol for multiple times respectively, and removing (z) -2, 3, 6, 7-tetrahydro-a-heptine-1-carboxamide template molecules by Soxhlet extraction with methanol and hydrochloric acid mixed solution with the volume ratio of 1:1 as eluent to obtain a conductive polyaniline group imprinted layer-BiVO capable of identifying amide groups in a targeted manner4A composite photocatalytic material.
The above embodiments are merely preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and any changes, substitutions, combinations, simplifications, modifications, etc. made by those skilled in the art without departing from the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (7)
1. A preparation method of a group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophores is characterized by comprising the following preparation steps: (1) adopting a surface molecular imprinting technology of a dummy template, taking a molecule containing the same toxic pharmacophore as a degraded target antibiotic molecule as the dummy template molecule, taking aniline, pyrrole or a mixture of the aniline and the pyrrole as a functional monomer, and carrying out pi-pi, electrostatic attraction and hydrogen bond interaction on the functional monomer and the toxic pharmacophore in a solvent to form a pre-assembly liquid; (2) adding a proper visible light catalyst, adding an initiator into an acidic medium, and carrying out in-situ polymerization to obtain a conductive polymer film/visible light catalyst composite material combined with toxic pharmacophores; (3) removing the false template molecules containing toxic pharmacophores in the conductive polymer film by a soxhlet extraction method, and leaving a large number of three-dimensional cavities which can be matched with the sizes, shapes and functional groups of the false template molecules in the conductive group imprinted polymer film on the surface of the photocatalyst to obtain the group imprinted conductive organic layer composite photocatalytic material for targeted recognition of the toxic pharmacophores.
2. The preparation method of the group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophores, according to claim 1, is characterized in that: the dummy template molecule is a molecule containing aromatic nitro, aromatic nitrogen oxide, aromatic azo, alkyl hydrazine, aromatic primary amine or secondary amine and sulfonyl alkyl group.
3. The preparation method of the group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophores, according to claim 1, is characterized in that: the visible light catalyst is SnFe2O4/ZnFe2O4Heterojunction, BiVO4、Bi2WO6One of them.
4. The preparation method of the group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophores, according to claim 1, is characterized in that: the molar ratio of the dummy template molecules to the functional monomers is 1: 2-1: 10.
5. The preparation method of the group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophores, according to claim 1, is characterized in that: the solvent is one of methanol-water solution, ethanol-water solution and methanol-ethanol mixed solution.
6. The preparation method of the group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophores, according to claim 1, is characterized in that: the acidic medium is one of hydrochloric acid, phosphoric acid and 2-acrylamide-2-methylpropanesulfonic acid.
7. The preparation method of the group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophores, according to claim 1, is characterized in that: the initiator is FeCl3、(NH4)2SO8、KIO3、H2O2One of them.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011514102.7A CN112844399A (en) | 2020-12-21 | 2020-12-21 | Preparation method of group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011514102.7A CN112844399A (en) | 2020-12-21 | 2020-12-21 | Preparation method of group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112844399A true CN112844399A (en) | 2021-05-28 |
Family
ID=75997680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011514102.7A Pending CN112844399A (en) | 2020-12-21 | 2020-12-21 | Preparation method of group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112844399A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125877A (en) * | 2011-01-05 | 2011-07-20 | 江苏大学 | Method for preparing selectively degraded ciprofloxacin photocatalyst |
| CN102319591A (en) * | 2011-07-15 | 2012-01-18 | 江苏大学 | Preparation method of molecular imprinting modification composite photocatalyst with selective degradation |
| CN102600906A (en) * | 2012-02-28 | 2012-07-25 | 江苏大学 | Preparation method of molecular imprinting type photocatalyst |
| CN103285892A (en) * | 2013-06-07 | 2013-09-11 | 南昌航空大学 | Method for preparing Lewis acidic molecular imprinting type BiOI photo-catalyst with visible-light response and high selectivity by hydrothermal method |
| CN103418363A (en) * | 2013-08-22 | 2013-12-04 | 南昌航空大学 | Method for preparing high-selectivity inorganic skeleton molecularly-imprinted grapheme-TiO2 composite photocatalyst at low temperature by sol-hydrothermal method |
| WO2014005320A1 (en) * | 2012-07-06 | 2014-01-09 | Empire Technology Development Llc | Molecularly imprinted catalysts and methods of making and using the same |
| CN103586088A (en) * | 2013-11-20 | 2014-02-19 | 宿州学院 | Preparation method for selective degradation of hydroquinone composite photocatalyst |
| CN105562112A (en) * | 2015-12-28 | 2016-05-11 | 陕西科技大学 | Magnetic titanate / graphene oxide molecularly imprinted photocatalytic composite material and preparation method thereof |
| CN105728041A (en) * | 2016-03-16 | 2016-07-06 | 江苏大学 | Selective specific recognition PPy@ZnFe2O4 magnetic imprinted composite photocatalyst preparation method |
| CN107649101A (en) * | 2017-09-29 | 2018-02-02 | 湖南大学 | Mercapto-functionalized titania molecule trace composite and its aqueous phase preparation method and application |
-
2020
- 2020-12-21 CN CN202011514102.7A patent/CN112844399A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125877A (en) * | 2011-01-05 | 2011-07-20 | 江苏大学 | Method for preparing selectively degraded ciprofloxacin photocatalyst |
| CN102319591A (en) * | 2011-07-15 | 2012-01-18 | 江苏大学 | Preparation method of molecular imprinting modification composite photocatalyst with selective degradation |
| CN102600906A (en) * | 2012-02-28 | 2012-07-25 | 江苏大学 | Preparation method of molecular imprinting type photocatalyst |
| WO2014005320A1 (en) * | 2012-07-06 | 2014-01-09 | Empire Technology Development Llc | Molecularly imprinted catalysts and methods of making and using the same |
| CN103285892A (en) * | 2013-06-07 | 2013-09-11 | 南昌航空大学 | Method for preparing Lewis acidic molecular imprinting type BiOI photo-catalyst with visible-light response and high selectivity by hydrothermal method |
| CN103418363A (en) * | 2013-08-22 | 2013-12-04 | 南昌航空大学 | Method for preparing high-selectivity inorganic skeleton molecularly-imprinted grapheme-TiO2 composite photocatalyst at low temperature by sol-hydrothermal method |
| CN103586088A (en) * | 2013-11-20 | 2014-02-19 | 宿州学院 | Preparation method for selective degradation of hydroquinone composite photocatalyst |
| CN105562112A (en) * | 2015-12-28 | 2016-05-11 | 陕西科技大学 | Magnetic titanate / graphene oxide molecularly imprinted photocatalytic composite material and preparation method thereof |
| CN105728041A (en) * | 2016-03-16 | 2016-07-06 | 江苏大学 | Selective specific recognition PPy@ZnFe2O4 magnetic imprinted composite photocatalyst preparation method |
| CN107649101A (en) * | 2017-09-29 | 2018-02-02 | 湖南大学 | Mercapto-functionalized titania molecule trace composite and its aqueous phase preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| JIE WANG ET AL.: "Rapid toxicity elimination of organic pollutants by the photocatalysis of environment-friendly and magnetically recoverable step-scheme SnFe2O4/ZnFe2O4 nano-heterojunctions", 《CHEMICAL ENGINEERING JOURNAL》 * |
| QINGBIN YUAN ET AL.: "Selective Adsorption and Photocatalytic Degradation of Extracellular Antibiotic Resistance Genes by Molecularly-Imprinted Graphitic Carbon Nitride", 《ENVIRONMENTAL SCIENCE AND TECHNOLOGY》 * |
| SHOUTAI WEI ET AL.: "Rapid degradation of Congo red by molercularly imprinted polypyrrole-coated magnetic TiO2 nanoparticles in dark at ambient conditions", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 沈先涛: "分子印迹型系列TiO2光催化剂的制备及其选择性降解有机污染物的研究", 《万方数据（学位论文）》 * |
| 邓芳等: "光催化降解有机污染物的微结构调控机制", 《中国知网（科技成果）》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Karimi-Maleh et al. | Recent advances in removal techniques of Cr (VI) toxic ion from aqueous solution: A comprehensive review | |
| Ceretta et al. | Biological degradation coupled to photocatalysis by ZnO/polypyrrole composite for the treatment of real textile wastewater | |
| Phoon et al. | Conventional and emerging technologies for removal of antibiotics from wastewater | |
| Dung et al. | A comprehensive study on the heterogeneous electro-Fenton degradation of tartrazine in water using CoFe2O4/carbon felt cathode | |
| Zhao et al. | Construction of three-dimensional hemin-functionalized graphene hydrogel with high mechanical stability and adsorption capacity for enhancing photodegradation of methylene blue | |
| Cheng et al. | Visible-light-assisted degradation of dye pollutants over Fe (III)-loaded resin in the presence of H2O2 at neutral pH values | |
| Yin et al. | Preparation and characteristics of novel dialdehyde aminothiazole starch and its adsorption properties for Cu (II) ions from aqueous solution | |
| Ali et al. | Characterization and deployment of surface-engineered chitosan-triethylenetetramine nanocomposite hybrid nano-adsorbent for divalent cations decontamination | |
| CN112607843B (en) | Reagent for accelerating Fenton reaction and preparation method and application thereof | |
| Mostafa et al. | Preparation of poly (DMAEM)-cross linked pregelled starch graft copolymer and its application in waste water treatments | |
| Kang et al. | Starch-derived flocculant with hyperbranched brush architecture for effectively flocculating organic dyes, heavy metals and antibiotics | |
| CN110665486A (en) | Magnetic ferroferric oxide-PAMAM-antibody complex and preparation method and application thereof | |
| Bai et al. | Conversion of aniline contaminant to valuable polyaniline polymers from wastewater under alkaline conditions | |
| CN108569754B (en) | Environment-friendly sewage treatment agent and use method and application thereof | |
| Liu et al. | Novel immobilized polyoxometalate heterogeneous catalyst for the efficient and durable removal of tetracycline in a Fenton-like system | |
| CN112844399A (en) | Preparation method of group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophore | |
| Gahrouei et al. | From wastewater to clean water: Recent advances on the removal of metronidazole, ciprofloxacin, and sulfamethoxazole antibiotics from water through adsorption and advanced oxidation processes (AOPs) | |
| Azqandi et al. | Intensified photo-decontamination of tetracycline antibiotic by S-scheme spinel manganese ferrite-grafted ZIF-8 heterojunction photocatalyst: Mechanism conception, degradation pathway and DFT studies | |
| CN107188265B (en) | Method for treating heavy metal complex wastewater based on UV/chlorine advanced oxidation technology | |
| Wu et al. | Simultaneously photocatalytic removal of Cr (VI) and metronidazole by asynchronous cross-linked modified sodium alginate | |
| CN109734840B (en) | Preparation method of natural graft flocculant based on beta-CD | |
| Wang et al. | Simultaneous removal of organic micropollutants and metals from water by a multifunctional β-cyclodextrin polymer-supported-polyaniline composite | |
| CN107626325B (en) | Nickel-doped manganese ferrite-coated magnesium silicate composite catalyst and preparation method and application thereof | |
| Cai et al. | Selective reduction of NO3− to N2 using a highly stable Cu0/Cu2O-PANI-CNTs as a photocatalyst at neutral pH | |
| CN115025773A (en) | Method for preparing carbon/palladium composite material for efficiently degrading p-nitrophenol by using carbon dots as reducing agent |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210528 |