CN115518692B - Porphyrin-titanium dioxide-based molecularly imprinted polymer for photo-depositing metallic silver, and preparation method and application thereof - Google Patents
Porphyrin-titanium dioxide-based molecularly imprinted polymer for photo-depositing metallic silver, and preparation method and application thereof Download PDFInfo
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- CN115518692B CN115518692B CN202211350235.4A CN202211350235A CN115518692B CN 115518692 B CN115518692 B CN 115518692B CN 202211350235 A CN202211350235 A CN 202211350235A CN 115518692 B CN115518692 B CN 115518692B
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- porphyrin
- titanium dioxide
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- metallic silver
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 41
- 239000004332 silver Substances 0.000 title claims abstract description 41
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000151 deposition Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 38
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 38
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 37
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 36
- 239000012265 solid product Substances 0.000 claims description 36
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 21
- 239000012498 ultrapure water Substances 0.000 claims description 21
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- 238000005286 illumination Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000011282 treatment Methods 0.000 claims description 15
- 239000011668 ascorbic acid Substances 0.000 claims description 12
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 12
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- HJCNSOVRAZFJLK-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 HJCNSOVRAZFJLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 2
- 238000006303 photolysis reaction Methods 0.000 claims 6
- FXXMDJFRMDVSCF-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrate Chemical compound O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O FXXMDJFRMDVSCF-RXSVEWSESA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
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- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
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- 238000001782 photodegradation Methods 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 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
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- B01J23/48—Silver or gold
- B01J23/50—Silver
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
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Abstract
The invention discloses a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver, and a preparation method and application thereof, and belongs to the technical field of nano material preparation. The invention adopts porphyrin-metal complex functionalized carbon nanotube composite material as a substrate material, tetrabutyl titanate as a functional monomer and a cross-linking agent, adopts a fixed template method surface molecular imprinting technology, and prepares porphyrin-titanium dioxide molecular imprinting polymer MPT@TiO with photocatalysis response characteristics to ultraviolet light and visible light simultaneously 2 . Then, the mixture is deposited on MPT@TiO by a photo-deposition technology 2 The surface is loaded with metallic silver. The preparation method is simple, the conditions are mild, the thickness of the imprinting layer is adjustable, and the metal silver is uniformly loaded. In addition, the molecularly imprinted polymer prepared by the method has higher selectivity, larger adsorption capacity, stronger performance of removing template molecules by solar catalysis, excellent stability and recycling property, and can be used in the fields of photoelectric conversion, photocatalysis, electrocatalysis, adsorption, separation and the like.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a porphyrin-titanium dioxide-based molecularly imprinted polymer for photo-depositing metallic silver, and a preparation method and application thereof.
Background
The molecular imprinting technique is a method for constructing a molecular imprinted polymer with specific recognition sites. In the preparation process of the molecularly imprinted polymer, the removal of the template molecules has important significance for obtaining the molecularly imprinted polymer with specific recognition performance and recycling thereof. At present, the template molecules are mostly removed by a solvent elution method based on organic reagents, strong acid/alkali solution and the like, but the solvent elution method inevitably brings the problems of consumption of a large amount of organic reagents, time consumption, low regeneration efficiency of imprinting sites, destruction of a molecular imprinting cavity structure and the like. In addition, most of the template molecules are toxic or harmful substances, so that secondary pollution is caused after the solvent is eluted.
Photocatalytic degradation is a way to degrade pollutants by photochemical reaction, and is a strong photochemical oxidation process, and active oxygen species formed by conversion after light energy absorption can fully or nearly fully mineralize organic targets to generate harmless water, carbon dioxide and other inorganic ions. Therefore, the photocatalytic degradation technology is introduced into molecular imprinting, so that the consumption of harmful reagents can be greatly reduced or even eliminated, and the green and efficient regeneration of imprinting sites is realized.
Currently, porphyrin and TiO loaded with metal promoters 2 The molecular imprinting polymer of the material and the removal of template molecules by sunlight photocatalysis have not been reported yet.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a porphyrin-titanium dioxide-based molecularly imprinted polymer for photo-depositing metallic silver, a preparation method and application thereof, wherein the preparation method is simple, the efficiency of catalyzing and degrading template molecules is high, and the molecularly imprinted material prepared by the method is high in stability, wide in photoresponse range, high in selectivity and excellent in photocatalytic performance, so that the molecularly imprinted polymer can be applied to selective separation, enrichment and photocatalytic removal of organic pollutants in environment, particularly in water.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a porphyrin-titanium dioxide-based molecularly imprinted polymer for photo-depositing metallic silver, which comprises the following steps:
1) Adding an ethanol solution of Methylene Blue (MB) into the porphyrin-metal complex functionalized carbon nano tube composite material, carrying out ultrasonic mixing to obtain a mixed system, and carrying out pre-adsorption treatment;
2) Adding tetrabutyl titanate into the mixed system prepared in the step 1), then adding ultrapure water, and stirring to obtain uniform dispersion;
3) Carrying out magnetic stirring reaction on the dispersion liquid prepared in the step 2), centrifuging after the reaction is finished, washing and drying to obtain a solid product;
4) Dispersing the solid product obtained in the step 3) by using ultrapure water, then adding a silver nitrate aqueous solution and an ascorbic acid aqueous solution, carrying out ultrasonic treatment to uniformly disperse the solid product, and then radiating the solid product by using simulated solar light to obtain a solid product after illumination;
5) Washing and drying the solid product after illumination to prepare the porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver.
Preferably, in step 1), the MB ethanol solution has a concentration of 0.001 to 1 mg.mL -1 And the dosage ratio of MB ethanol solution to porphyrin-metal complex functionalized carbon nano tube composite material is 15mL: (10-100) mg.
Preferably, in step 1), the pre-adsorption treatment time is 0.5 to 1.5 hours.
Preferably, in step 2), tetrabutyl titanate is added in an amount of 1.0 to 10.0. Mu.L per mL of MB of ethanol solution.
Preferably, in step 2), the volume of ultrapure water is 25 times the volume of tetrabutyl titanate added.
Preferably, in the steps 1) and 4), the ultrasonic power is 100-150W, the ultrasonic temperature is 16-28 ℃, and the ultrasonic time is 10-60 min.
Preferably, in the steps 2) and 3), the rotation speed of the magnetic stirring is 200-600 rpm, and the stirring time is 0.5-6 h.
Preferably, in step 4), the concentration of the silver nitrate aqueous solution added is 10 mmol.L -1 The concentration of the ascorbic acid aqueous solution is 10 mmol.L -1 And the added silver nitrate aqueous solution and ascorbic acid aqueous solution have the same volume, and the dosage ratio of the solid product to the ultrapure water and the silver nitrate aqueous solution is 10mg:30mL: (0.3-3) mL.
Preferably, in step 4), the light source wavelength ranges from 200 to 780nm.
Preferably, in step 4), the illumination time is 1-3 hours.
The invention also discloses a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver, which is prepared by the preparation method.
The invention also discloses the application of the porphyrin-titanium dioxide based molecularly imprinted polymer loaded with the metal silver as a photocatalysis adsorbent, wherein the adsorption capacity of the porphyrin-titanium dioxide composite material based molecularly imprinted polymer loaded with the metal silver to MB is 38-121 mg.g -1 。
Preferably, the method can be expanded to applications in aspects of MB detection, enrichment, separation and removal, photoelectric conversion, photocatalysis and the like in sewage.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver, which is characterized in that porphyrin-titanium dioxide molecularly imprinted polymer (MPT@TiO) imprinted with MB is formed on the surface of porphyrin-metal complex functionalized carbon nanotube composite material (MWCNTs@TCPP-Sn, MPT) through hydrolysis self-polymerization reaction of titanium dioxide precursor at room temperature 2 ). Then under the irradiation of simulated sunlight, silver nitrate is reduced through photocatalysis, and template molecules MB are removed through photodegradation, so that the porphyrin-titanium dioxide-based molecularly imprinted polymer (MPT@TA) loaded with metallic silver is obtained. MPT is used as a substrate material, so that the template molecular imprinting with larger specific surface area and higher quantity is facilitatedThe high-performance visible light photocatalytic performance is beneficial to the response to visible light and the rapid removal of template molecules. In addition, the invention uses tetrabutyl titanate as functional monomer and cross-linking agent, which can have stronger non-covalent interaction with the template and the substrate surface, good water dispersibility and ultraviolet response characteristic. In addition, the photo-deposition technology is adopted to prepare the high-density polyethylene (MPT@TiO) 2 The surface is loaded with the metal silver, so that the template molecule MB can be removed by the same photodegradation, and the efficiency of removing the template molecule by photocatalysis can be improved by the loaded metal silver. The preparation method is simple to operate, and the raw materials are cheap and easy to obtain.
Further, the photodegradation removal rate of the template molecules can be controlled by adjusting the proportion of TCPP and MWCNTs, the feeding amount of tetrabutyl titanate, the feeding amount of silver nitrate and the like.
The porphyrin-titanium dioxide-based molecularly imprinted polymer (MPT@TA) loaded with metallic silver prepared by the method has good sunlight response characteristics, high specific selectivity and high recycling property, and experiments prove that the polymer still has high stability and selectivity after being recycled for ten times under simulated sunlight irradiation.
From the application point of view, the MPT@TA has a large number of holes which are completely matched with MB in terms of size, shape, space chemistry and the like, so that the MPT@TA can be specifically combined with MB in the environment and solution, thereby achieving the purposes of separation, purification and removal, and the adsorption quantity of the MPT@TA to MB is 38-121 mg.g -1 . In addition, MPT@TA has ultraviolet light and visible light photocatalysis response characteristics, so that the MPT@TA has wide application in the aspects of detection, enrichment, separation and removal of MB in water, photoelectric conversion, photocatalysis and the like.
Drawings
FIG. 1 is a transmission electron micrograph of MPT@TA;
fig. 2 shows Zeta potential data of mpt@ta.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
the invention provides a preparation method of a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver. MPT (porphyrin-metal complex functionalized carbon nanotube composite) is adopted as a substrate material, tetrabutyl titanate is adopted as a functional monomer and a cross-linking agent, and a fixed template method surface molecular imprinting technology is adopted to prepare a porphyrin-titanium dioxide molecularly imprinted polymer MPT@TiO with photocatalysis response characteristics to ultraviolet light and visible light simultaneously 2 . Then, the mixture is deposited on MPT@TiO by a photo-deposition technology 2 The surface is loaded with metallic silver. The molecular engram polymer with high-efficiency light removal of template molecules and sunlight response characteristics can be prepared by adjusting the proportion of the carbon nano tube to porphyrin, the feeding amount of tetrabutyl titanate, the feeding amount of silver nitrate and the like.
Specifically, the preparation method of the porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver comprises the following steps:
1) Adding the ethanol solution of MB into MPT, carrying out ultrasonic mixing to obtain a mixed solution, and carrying out pre-adsorption;
2) Adding tetrabutyl titanate into the mixture prepared in the step 1), then adding ultrapure water, and stirring to obtain a uniform dispersion;
3) Magnetically stirring the dispersion liquid in the step 2) at room temperature, centrifuging after the reaction is finished, washing, and drying to obtain a solid product;
4) Dispersing the solid product obtained in the step 3) by using ultrapure water, then adding a silver nitrate aqueous solution and an ascorbic acid aqueous solution, carrying out ultrasonic treatment to uniformly disperse the solid product, and then irradiating the solid product by using simulated solar light to obtain an irradiated solid product;
5) And (3) after illumination, washing and drying the solid product after illumination in the step (4) to obtain the porphyrin-titanium dioxide-based molecularly imprinted polymer (MPT@TA) loaded with metallic silver.
The preparation method of the porphyrin-metal complex functionalized carbon nanotube composite material (MWCNTs@TCPP-Sn, MPT) is described in the patent with the application number of 201910328908.8. Namely: 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin (TCPP) is reacted with Sn by one-step solvothermal reaction 2+ And performing coordination self-assembly on the surface of the multi-wall carbon nano tube (MWCNTs) to obtain the porphyrin-metal complex (MWCNTs@TCPP-Sn) functionalized carbon nano tube composite material with uniformly distributed active sites.
The preparation method specifically comprises the following steps:
1) Anhydrous SnCl 2 And 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin is dissolved in a mixed solvent of absolute ethyl alcohol and N, N-dimethylformamide to obtain a mixed solution;
2) Adding the carbon nano tube into the mixed solution prepared in the step 1), and carrying out ultrasonic treatment to obtain uniform dispersion;
3) Carrying out solvothermal reaction on the dispersion liquid, wherein the reaction temperature is 80-150 ℃, the reaction time is 20-48 h, naturally cooling to room temperature after the reaction is finished, and carrying out centrifugal separation to obtain a solid product;
4) Washing and drying the solid product to obtain the porphyrin-metal complex functionalized carbon nanotube composite material with controllable layer thickness.
Wherein, the controllable layer thickness refers to the controllable thickness of the porphyrin-metal complex shell layer on the surface of the carbon nano tube.
Example 1
A preparation method of a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver, which comprises the following steps:
1) MB in ethanol (0.001 mg.mL) -1 15 mL) is added into MPT (10 mg), and the mixture is uniformly mixed by ultrasonic, the ultrasonic power is 100W, the ultrasonic temperature is 16 ℃, the ultrasonic time is 10min, and the pre-adsorption is carried out for 0.5h;
2) Tetrabutyl titanate (15 mu L) is added into the mixture prepared in the step 1), then 0.375mL of ultrapure water is added, and stirring treatment is carried out, so as to obtain a uniform dispersion liquid;
3) Magnetically stirring the dispersion liquid obtained in the step 2) (200 r/min) at room temperature, reacting for 0.5h, centrifuging after the reaction is finished, washing, and drying to obtain a solid product;
4) The solid product (10 mg) was dispersed with ultrapure water (30 mL), and then an aqueous silver nitrate solution (10 mmol.L) -1 0.3 mL), and aqueous ascorbic acid (10 mmol.L) -1 0.3 mL), uniformly dispersing the materials by ultrasonic waves, wherein the ultrasonic power is 100W, the ultrasonic temperature is 16 ℃, the ultrasonic time is 10min, and then simulating sunlight irradiation (200-780 nm) by using a xenon lamp light source for 1h;
5) And (3) after illumination is finished, washing and drying the solid product after illumination in the step (4) to obtain the MPT@TA.
Example 2
A preparation method of a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver, which comprises the following steps:
1) MB in ethanol (0.01 mg.mL) -1 15 mL) is added into MPT (20 mg), and the mixture is uniformly mixed by ultrasonic, the ultrasonic power is 120W, the ultrasonic temperature is 25 ℃, the ultrasonic time is 20min, and the pre-adsorption is carried out for 1.0h;
2) Tetrabutyl titanate (20 mu L) is added into the mixture prepared in the step 1), then 0.5mL of ultrapure water is added, and stirring treatment is carried out, so as to obtain a uniform dispersion liquid;
3) Magnetically stirring the dispersion liquid obtained in the step 2) (300 r/min) at room temperature, reacting for 0.5h, centrifuging after the reaction is finished, washing, and drying to obtain a solid product;
4) The solid product (10 mg) was dispersed with ultrapure water (30 mL), and then an aqueous silver nitrate solution (10 mmol.L) -1 0.5 mL), and aqueous ascorbic acid (10 mmol.L) -1 0.5 mL), uniformly dispersing the materials by ultrasonic waves, wherein the ultrasonic power is 120W, the ultrasonic temperature is 25 ℃, the ultrasonic time is 20min, and then simulating sunlight irradiation (200-780 nm) by using a xenon lamp light source for 2h;
5) And (3) after illumination is finished, washing and drying the solid product after illumination in the step (4) to obtain the MPT@TA.
Example 3
A preparation method of a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver, which comprises the following steps:
1) MB in ethanol (0.1 mg.mL) -1 15 mL) is added into MPT (30 mg), and the mixture is uniformly mixed by ultrasonic, the ultrasonic power is 120W, the ultrasonic temperature is 25 ℃, the ultrasonic time is 20min, and the pre-adsorption is carried out for 1.0h;
2) Tetrabutyl titanate (30 mu L) is added into the mixture prepared in the step 1), then 0.75mL of ultrapure water is added, and stirring treatment is carried out, so as to obtain a uniform dispersion liquid;
3) Magnetically stirring the dispersion liquid obtained in the step 2) (500 r/min) at room temperature, reacting for 3h, centrifuging after the reaction is finished, washing, and drying to obtain a solid product;
4) The solid product (10 mg) was dispersed with ultrapure water (30 mL), and then an aqueous silver nitrate solution (10 mmol.L) -1 2 mL), and aqueous ascorbic acid (10 mmol.L) -1 2 mL), uniformly dispersing the materials by ultrasonic waves, wherein the ultrasonic power is 120W, the ultrasonic temperature is 25 ℃, the ultrasonic time is 20min, and then simulating sunlight irradiation (200-780 nm) by using a xenon lamp light source for 2h;
5) And (3) after illumination is finished, washing and drying the solid product after illumination in the step (4) to obtain the MPT@TA.
Example 4
A preparation method of a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver, which comprises the following steps:
1) Ethanol of MB solution (0.001 mg.mL) -1 15 mL) is added into MPT (100 mg), the mixture is mixed evenly by ultrasonic, the ultrasonic power is 150W, ultrasonic temperature is 25 ℃, ultrasonic time is 30min, and pre-adsorption is carried out for 1.5h;
2) Tetrabutyl titanate (100 mu L) is added into the mixture prepared in the step 1), then 2.5mL of ultrapure water is added, and stirring treatment is carried out, so as to obtain a uniform dispersion liquid;
3) Magnetically stirring the dispersion liquid obtained in the step 2) (600 r/min) at room temperature, reacting for 4.0h, centrifuging after the reaction is finished, washing, and drying to obtain a solid product;
4) The solid product (10 mg) was dispersed with ultrapure water (30 mL), and then an aqueous silver nitrate solution (10 mmol.L) -1 2.5 mL), and aqueous ascorbic acid (10 mmol.L) -1 2.5 mL), uniformly dispersing the materials by ultrasonic waves, wherein the ultrasonic power is 150W, the ultrasonic temperature is 25 ℃, the ultrasonic time is 30min, and then simulating sunlight irradiation (200-780 nm) by using a xenon lamp light source for 2.5h;
5) And (3) after illumination is finished, washing and drying the solid product after illumination in the step (4) to obtain the MPT@TA.
Example 5
A preparation method of a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver, which comprises the following steps:
1) MB in ethanol (0.1 mg.mL) -1 15 mL) is added into MPT (10 mg), and the mixture is uniformly mixed by ultrasonic, the ultrasonic power is 120W, the ultrasonic temperature is 25 ℃, the ultrasonic time is 20min, and the pre-adsorption is carried out for 1.0h;
2) Tetrabutyl titanate (40 mu L) is added into the mixture prepared in the step 1), then 1.0mL of ultrapure water is added, and stirring treatment is carried out, so as to obtain a uniform dispersion liquid;
3) Magnetically stirring the dispersion liquid obtained in the step 2) (400 rpm) at room temperature, reacting for 2.0h, centrifuging after the reaction is finished, washing, and drying to obtain a solid product;
4) Dispersing the solid product (10 mg) with ultra pure water (30 mL)Then, an aqueous silver nitrate solution (10 mmol.L) -1 1.5 mL), and aqueous ascorbic acid (10 mmol.L) -1 1.5 mL), uniformly dispersing the materials by ultrasonic waves, wherein the ultrasonic power is 120W, the ultrasonic temperature is 25 ℃, the ultrasonic time is 20min, and then simulating sunlight irradiation (200-780 nm) by using a xenon lamp light source for 2h;
5) And (3) after illumination is finished, washing and drying the solid product after illumination in the step (4) to obtain the MPT@TA.
Example 6
A preparation method of a porphyrin-titanium dioxide-based molecularly imprinted polymer loaded with metallic silver, which comprises the following steps:
1) MB in ethanol (1 mg mL) -1 15 mL) is added into MPT (100 mg), and the mixture is uniformly mixed by ultrasonic, the ultrasonic power is 150W, the ultrasonic temperature is 28 ℃, the ultrasonic time is 60min, and the pre-adsorption is carried out for 1.5h;
2) Tetrabutyl titanate (150 mu L) is added into the mixture prepared in the step 1), 3.75mL of ultrapure water is added, and stirring treatment is carried out, so as to obtain a uniform dispersion liquid;
3) Magnetically stirring the dispersion liquid obtained in the step 2) (600 r/min) at room temperature, reacting for 6h, centrifuging after the reaction is finished, washing, and drying to obtain a solid product;
4) The solid product (10 mg) was dispersed with ultrapure water (30 mL), and then an aqueous silver nitrate solution (10 mmol.L) -1 3 mL), and aqueous ascorbic acid (10 mmol.L) -1 3 mL), uniformly dispersing the materials by ultrasonic waves, wherein the ultrasonic power is 150W, the ultrasonic temperature is 28 ℃, the ultrasonic time is 60min, and then simulating sunlight irradiation (200-780 nm) by using a xenon lamp light source for 3h;
5) And (3) after illumination is finished, washing and drying the solid product after illumination in the step (4) to obtain the MPT@TA.
Taking MPT@TA prepared in example 5 as an experimental example, the invention adopts a Transmission Electron Microscope (TEM) and Zeta potential to characterize the MPT@TA as follows:
(1) Characterization of topography
The morphology of the prepared MPT@TA was observed by using a JEM-F200 (HR) transmission electron microscope, and the results are shown in FIG. 1. As can be seen from fig. 1, the prepared mpt@ta imprinting layer is uniform, and the coating of the carbon nanotube shell layer is uniform and obvious.
(2) Surface potential characterization
The surface potential of the prepared molecularly imprinted polymer nanomaterial is characterized by a Malvern Nano-ZS90 Zeta potential analyzer, and the result is shown in FIG. 2. As can be seen from the figure, compared with carbon nanotubes (MWCNTs), the electrical properties of MPT are significantly reversed due to the four electronegative carboxyl groups per TCPP molecule. While TiO 2 Has weak electronegativity, and is imprinted with TiO on MPT surface 2 Then, the prepared molecular imprinting material MPT@TiO 2 The electronegativity of the MIP will decrease and the electronegativity of the material after surface deposition of silver will decrease further, indicating a successful preparation of mpt@ta.
As the MPT@TA prepared by the method has a large number of holes which are completely matched with the template molecule MB in the aspects of size, shape, space chemistry and the like, and the substrate material has larger specific surface area, the MB can be selectively adsorbed and separated. In addition, the base material MPT and the imprinting layer TiO 2 The photocatalyst has the photocatalytic response characteristics of visible light and ultraviolet light, and the supported metal silver can promote the separation of photo-generated electrons and holes, so that high-activity active oxygen species can be generated under simulated sunlight illumination, and the photocatalyst has high-efficiency photocatalytic performance. Therefore, after MPT@TA adsorbs/blots MB, template molecules MB can be catalyzed to decompose under the irradiation of simulated sunlight, and MPT@TA is regenerated, so that the aim of recycling can be fulfilled.
Hereinafter, the adsorption, photocatalytic removal and recycling properties of MPT@TA obtained in examples 1 to 6 to MB were examined specifically.
5.0mg of MPT@TA obtained in examples 1 to 6 was weighed out and dispersed in 20mL of MB in water (0.05 mmol.L) -1 ) After shaking for 60min at room temperature, the mixture was filtered and separated. And detecting the absorbance of the MB aqueous solution before and after adsorption by using an ultraviolet-visible spectrophotometer, and calculating the adsorption quantity.
The adsorption amounts of MPT@TA obtained in examples 1 to 6 to MB aqueous solutions were 49.52 mg.g, respectively, by calculation -1 、58.75mg·g -1 、70.25mg·g -1 、40.16mg·g -1 、80.10mg·g -1 、102.22mg·g -1 Thus, it was demonstrated that the adsorbent had good adsorption performance for MB.
Then, the separated MPT@TA with the MB specifically adsorbed is redispersed in 40mL of deionized water, and the MB molecules adsorbed by photocatalytic decomposition are removed. Repeating the adsorption-photocatalytic removal process, the adsorption quantity of MPT@TA to MB is still kept above 96% after ten cycles, which proves that the MPT@TA prepared by the method has excellent stability and reusability.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing a porphyrin-titanium dioxide-based molecularly imprinted polymer for photodecomposition of metallic silver, which is characterized by comprising the following steps:
1) Adding methylene blue ethanol solution into the porphyrin-metal complex functionalized carbon nanotube composite material, carrying out ultrasonic mixing uniformly, and then carrying out pre-adsorption treatment to obtain a mixed system;
2) Adding tetrabutyl titanate into the mixed system, and then adding ultrapure water for stirring treatment to obtain uniform dispersion;
3) Stirring the dispersion liquid for reaction, centrifugally separating, washing and drying to obtain a solid product;
4) Dispersing the solid product with water, adding silver nitrate water solution and ascorbic acid water solution, uniformly dispersing by ultrasonic, performing light treatment, washing and drying to obtain the porphyrin-titanium dioxide-based molecularly imprinted polymer for electrodepositing metallic silver.
2. The method for preparing a porphyrin-titanium dioxide based molecularly imprinted polymer with metallic silver photo-deposited according to claim 1, wherein in the step 1), the concentration of methylene blue in the ethanol solution of methylene blue is 0.001-1 mg.ml -1 The method comprises the steps of carrying out a first treatment on the surface of the Methylene (S)The dosage ratio of the ethanol solution of the base blue to the porphyrin-metal complex functionalized carbon nano tube composite material is 15mL: (10-100) mg.
3. The method for preparing a molecular engram polymer based on porphyrin-titanium dioxide for photo-depositing metallic silver as claimed in claim 1, wherein in step 1), the porphyrin-metallic complex functionalized carbon nanotube composite material is MWCNTs@TCPP-Sn, 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin and Sn are reacted by one-step solvothermal reaction 2+ And (3) carrying out coordination self-assembly on the surface of the multiwall carbon nanotube.
4. The method for preparing a porphyrin-titanium dioxide based molecularly imprinted polymer for photodecomposition of metallic silver according to claim 1, wherein the pre-adsorption treatment time is 0.5 to 1.5 hours in step 1).
5. The method for preparing a porphyrin-titanium dioxide-based molecularly imprinted polymer with metallic silver photo-deposited according to claim 1, wherein in the step 2), the ratio of the amount of tetrabutyl titanate to the amount of the methylene blue ethanol solution added is (10.0-100.0) μl:1mL; the volume of the ultra-pure water added is 20-30 times of the volume of the tetrabutyl titanate added.
6. The method for preparing a porphyrin-titanium dioxide-based molecularly imprinted polymer for photodecomposition of metallic silver according to claim 1, wherein in the steps 1) and 4), the ultrasonic power is 100-150W, the ultrasonic temperature is 16-28 ℃, and the ultrasonic time is 10-60 min.
7. The method for preparing a porphyrin-titanium dioxide-based molecularly imprinted polymer for photodecomposition of metallic silver according to claim 1, wherein in the steps 2) and 3), magnetic stirring is adopted for the stirring treatment, the stirring speed is 200-600 rpm, and the stirring time is 0.5-6 h.
8. The photodeposited gold of claim 1A process for preparing molecular engram polymer based on porphyrin-titanium dioxide as silver features that in step 4), the concentration of silver nitrate aqueous solution added is 10 mmol.L -1 The concentration of the ascorbic acid aqueous solution is 10 mmol.L -1 And the added silver nitrate aqueous solution and ascorbic acid aqueous solution have the same volume, and the dosage ratio of the solid product to the ultrapure water and the silver nitrate aqueous solution is 10mg:30mL: (0.3-3) mL; the wavelength range of the light source used for the illumination treatment is 200-780nm, and the illumination time is 1-3 h.
9. Porphyrin-titanium dioxide-based molecularly imprinted polymer of photo-deposited metallic silver prepared by the preparation method of any one of claims 1 to 8.
10. The use of a porphyrin-titania-based molecularly imprinted polymer of a photodecomposition of metallic silver as defined in claim 9 as a photocatalytic adsorbent, characterized in that the molecular imprinted polymer of a photodecomposition of metallic silver has an adsorption amount of 38 to 121mg·g to methylene blue -1 。
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