CN115197459B - Optomagnetic dual-drive type composite mineralization film and preparation method and application thereof - Google Patents

Optomagnetic dual-drive type composite mineralization film and preparation method and application thereof Download PDF

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CN115197459B
CN115197459B CN202210900642.1A CN202210900642A CN115197459B CN 115197459 B CN115197459 B CN 115197459B CN 202210900642 A CN202210900642 A CN 202210900642A CN 115197459 B CN115197459 B CN 115197459B
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丁春梅
张鸿博
李建树
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Sichuan University
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Abstract

The preparation method and application of the magneto-optical double-drive type composite mineralization membrane comprise the following steps: bi is mixed with 2 S 3 Dispersing the powder in deionized water, adding isopropanol and ammonia water, uniformly mixing, and adding dopamine hydrochloride; dissolving tris (hydroxymethyl) aminomethane, sodium periodate and sodium hydroxide to obtain a first solution, and uniformly mixing the first solution with a dopamine hydrochloride solution to obtain a second solution; the second solution is quickly dripped on the surface of the filter membrane; mixing ferric trichloride hexahydrate, ferrous sulfate heptahydrate and Bi 2 S 3 Obtaining a third solution by the PDA, dripping the third solution on the polytetrafluoroethylene substrate, inverting the composite filter membrane on the polytetrafluoroethylene substrate, and simultaneously applying an upward external magnetic field; ammonia was added dropwise to the confined space around. The magneto-optical double-drive type composite mineralization film has two driving modes of near-infrared light driving and magnetic driving, and can meet the actual complex application requirements by rapidly switching the movement modes in a complex water area environment.

Description

Optomagnetic dual-drive type composite mineralization film and preparation method and application thereof
Technical Field
The invention relates to the field of functional materials, in particular to a magneto-optical double-drive composite mineralization membrane, and a preparation method and application thereof.
Background
Stimulus-responsive drivers that respond to external stimuli and convert their received energy into dynamic locomotor activity show great potential applications in the fields of robotics, biomedical engineering, etc. Numerous propulsion strategies based on steam, catalysis, light sources, sound waves, marangoni effect and magnetic forces have been developed in order to achieve self-driving movement of the driver.
Surface actuation based on the Marangoni effect is considered a potential strategy with the advantages of rapid response, non-contact, inexpensive and environmental protection. This strategy creates a local temperature gradient and thus a surface tension gradient in the liquid surface by converting light energy into heat energy, which causes the liquid to spontaneously flow from the low surface tension region to the high surface tension region, driving the float.
However, conventional photothermal material systems are complex in design. In order to enhance the Marangoni effect, researchers generally select a composite system based on a carbon-based material to obtain better photo-thermal performance, and meanwhile, a layered structure is prepared by laser etching and other technologies to further enhance the photo-response. In addition, the traditional photo-thermal material has a single driving form, and the prepared driver has a Marangoni effect failure in some complex water environments containing high-concentration surfactant for example due to the limitation of the functional properties of the photo-thermal material, and the Marangoni effect is difficult to realize the large-range movement of the driver in a short time.
Disclosure of Invention
The invention aims to provide a preparation method of a photomagnetic double-drive type composite mineralized membrane, which comprises the steps of assembling Bi coated with a polydopamine layer on the surface of a polytetrafluoroethylene-polydopamine composite filter membrane 2 S 3 Nanometer aggregate (Bi) 2 S 3 @ PDA), and Bi 2 S 3 The magnetic ferrite mineral is formed on the surface of the PDA in situ, so that the prepared composite mineralized film has two modes of near infrared light driving and magnetic force driving, and not only can highly controllable fine movement be performed in a tiny range, but also the composite mineralized film can be preparedThe composite mineralized membrane can realize rapid movement in a large range, has excellent photocatalysis characteristics, and can realize high-efficiency degradation of pollutants on the water surface under the irradiation of near infrared light.
The invention is realized by the following technical scheme:
the preparation method of the magneto-optical double-drive type composite mineralized film comprises the following steps:
preparation of Bi 2 S 3 PDA, bi 2 S 3 Dispersing the powder in deionized water, adding isopropanol and ammonia water, mixing, adding dopamine hydrochloride, and stirring to react to obtain Bi coated with polydopamine layer 2 S 3 Nano aggregate Bi 2 S 3 @PDA；
Preparing a composite filter membrane, dissolving tris (hydroxymethyl) aminomethane, sodium periodate and sodium hydroxide to obtain a first solution, and uniformly mixing the first solution with a dopamine hydrochloride solution to obtain a second solution; the second solution is quickly dripped on the surface of the polytetrafluoroethylene filter membrane, the second solution is removed after a period of time is kept, and the composite filter membrane is obtained after cleaning and drying;
preparing composite mineralized film, mixing ferric trichloride hexahydrate, ferrous sulfate heptahydrate and Bi 2 S 3 Obtaining a third solution by @ PDA, dripping the third solution onto a polytetrafluoroethylene substrate, placing one surface of the composite filter membrane, which is provided with a polydopamine layer, on the polytetrafluoroethylene substrate downwards, wherein the third solution is positioned in a limited space between the polytetrafluoroethylene substrate and the composite filter membrane, and simultaneously applying an upward external magnetic field; and (3) dropwise adding ammonia water to the periphery of the limited space, enabling ammonia gas to freely diffuse into the third solution, reacting the reaction system for a period of time under a closed condition, removing the ammonia water, and cleaning and drying to obtain the composite mineralized membrane.
In the technical scheme, bi 2 S 3 The @ PDA is Bi with a polydopamine layer coated on the surface 2 S 3 Nano-aggregates. Bi (Bi) 2 S 3 Bi adopted in PDA preparation 2 S 3 The powder may be Bi 2 S 3 Powder, also bismuth nitrate pentahydrateSynthesis of Bi 2 O 3 Powder, then pass through Bi 2 O 3 Powder synthesis of Bi 2 S 3 And (3) powder.
Bi is mixed with 2 S 3 Dispersing the powder in deionized water, adding isopropanol and ammonia water, stirring and mixing thoroughly, adding dopamine hydrochloride, stirring and reacting at room temperature to obtain Bi finally 2 S 3 @ PDA. In one or more embodiments, the Bi is prepared 2 S 3 Bi used for PDA 2 S 3 The mass ratio of the powder to the dopamine hydrochloride is 0.8-1.4:1, preferably Bi 2 S 3 The mass ratio of the powder to the dopamine hydrochloride is 1:1.
The preparation method of the polytetrafluoroethylene-polydopamine composite filter membrane comprises the steps of dissolving dopamine hydrochloride in water to obtain a dopamine hydrochloride aqueous solution, dissolving tris (hydroxymethyl) aminomethane, sodium periodate and sodium hydroxide in water to obtain a first solution, and then mixing the two solutions preferably in a volume ratio of 1:1, and sufficiently oscillating to form a uniform second solution. Next, the second solution is immediately dropped onto the surface of the polytetrafluoroethylene filter membrane, preferably, the second solution is dropped onto the rougher side of the polytetrafluoroethylene filter membrane, after a period of time, the second solution on the surface is removed, the polytetrafluoroethylene filter membrane is immersed in deionized water for rinsing, and is blown with an inert gas such as nitrogen, and the polytetrafluoroethylene-polydopamine composite filter membrane is obtained after drying in an oven. In one or more embodiments, the second solution may be repeatedly added dropwise to the roughened surface of the composite filter membrane, and after a period of time, the second solution is removed, rinsed, dried, and dried multiple times to obtain the composite filter membrane with the roughened surface having the polydopamine layer formed thereon.
Preparing Bi 2 S 3 After @ PDA and the composite filter membrane, ferric trichloride hexahydrate, ferrous sulfate heptahydrate and Bi are added 2 S 3 Mixing @ PDA according to a certain ratio to obtain a third solution, dripping the third solution onto a polytetrafluoroethylene substrate, then enabling the rough surface of the composite filter membrane to face downwards, and inverting the composite filter membrane on the polytetrafluoroethylene substrate so that the third solution is positioned in a limited space between the composite filter membrane and the substrate, wherein the side surface of the limited space is an opening surface, and the same asWhen an external magnetic field is added to the third solution, in one or more embodiments, the external magnetic field has a magnetic field strength of 0.16 to 0.20T, preferably 0.18T. Subsequently, ammonia was dropped around the confined space, and ammonia gas was freely diffused into the third solution through the opening face of the confined space. Then, the whole reaction system is placed in a closed space, such as a culture dish with a cover for mineralization reaction, the closed space is relieved after a period of reaction, ammonia water solution is removed, the composite mineralization membrane is taken out after natural drying at room temperature, and the composite mineralization membrane is cleaned and dried.
In the technical scheme, the limited reaction space comprises a limited space formed between the composite filter membrane and the substrate and a third solution in the limited space, namely mineralized solution. Mineralizing Bi in solution 2 S 3 PDA can chelate mixed iron ions in the solution, ammonia gas which is freely diffused into the mineralized solution, bi 2 S 3 The mixed iron ions chelated on the surface of PDA can generate the ferrite mineral with magnetism in situ. Under the action of an external magnetic field, the magnetic ferrite minerals can carry Bi 2 S 3 The @ PDA was aggregated and reassembled to the surface of the composite filter. As the surface of the composite filter membrane is also provided with the polydopamine coating, the fiber surface of the whole composite filter membrane can be coated with the doped Bi in situ 2 S 3 The mineralized layer of PDA nanoclusters is strongly adhered and immobilized.
Bi in composite mineralized film 2 S 3 The semiconductor is a narrow band gap semiconductor of an orthorhombic system, has band gap energy of about 1.33eV, high near infrared absorption and good photo-thermal stability. In the formation of nano aggregate Bi 2 S 3 After PDA, the mineralization layer of the composite mineralization film is provided with a layer consisting of Bi 2 S 3 The graded micro-nano structure formed by PDA and ferrite minerals has higher specific surface area, is beneficial to enhancing the capturing capability of near infrared light, and shows more excellent photo-thermal response characteristics, so that the composite mineralized film can perform photo-driving based on Marangoni effect. Meanwhile, the ferrite minerals in the mineralized layer have remarkable magnetism, so that the composite mineralized film can be magnetically driven under the guidance of an external magnet, and further the two kinds of driving are flexibly drivenThe dynamic modes are combined together, so that not only can highly controllable fine movement be performed in a tiny range, but also rapid movement can be realized in a large range, and the actual complex application requirements are met by rapidly switching the movement modes in a complex water area environment.
Furthermore, due to Bi 2 S 3 Is narrow when near infrared laser is irradiated to Bi of mineralized layer 2 S 3 After @ PDA, bi 2 S 3 The absorbed energy is larger than photons in the self energy band gap, electrons in the valence band are excited and transition to the conduction band, holes are formed in the valence band, then electron-hole pairs are separated and react with a substrate to generate free radicals, so that the composite mineralized film has the function of catalytic degradation. In addition, the excellent photo-thermal effect of the composite mineralized filter membrane can further promote Bi 2 S 3 More free radicals are generated, so that the photocatalysis effect is greatly improved, and the high-efficiency degradation of pollutants on the water surface can be realized.
As a preferred embodiment of the present invention, the iron trichloride hexahydrate is mixed with Bi 2 S 3 The mol ratio of @ PDA is 1100:1-16:1, and the ferrous sulfate heptahydrate and Bi are prepared by the following steps 2 S 3 The mol ratio of @ PDA is 550:1-8:1. Ferric trichloride hexahydrate, ferrous sulfate heptahydrate not only used for forming ferrite mineral driven Bi 2 S 3 PDA moves from bottom to top in a limited reaction space and gathers on a composite filter membrane, and the formed ferrite mineral and Bi 2 S 3 The @ PDA together form a hierarchical micro-nano structure of the mineralized layer. Thus, ferric trichloride hexahydrate, ferrous sulfate heptahydrate and Bi 2 S 3 The @ PDA ratio affects the Bi in the mineralized solution 2 S 3 Driving force of PDA finally affects ferrite minerals and Bi in mineralized layer 2 S 3 Content ratio of @ PDA, ferrite minerals of different sizes and Bi 2 S 3 The @ PDA determines the hierarchical micro-nano structure of the mineralization layer, so that the specific surface area, infrared light capturing capability, photo-thermal response capability and photocatalysis characteristics of the mineralization layer are changed.
In the technical proposal, ferric trichloride hexahydrate and Bi are mixed 2 S 3 The molar ratio @ PDA is determined to be from 1100:1 to 16:1, preferably from 132:1 to 16:1. Ferrous sulfate heptahydrate and Bi 2 S 3 The molar ratio @ PDA is determined to be 550:1 to 8:1, preferably 61:1 to 8:1. By mixing ferric trichloride hexahydrate, ferrous sulfate heptahydrate and Bi 2 S 3 The @ PDA is adjusted to the above ratio, bi 2 S 3 The @ PDA can be uniformly and densely distributed in the mineralization layer, and the ratio of the PDA to the ferrite mineral ensures that the mineralization layer has better specific surface area, and the photo-thermal effect and the photo-catalytic property of the composite mineralization film are further improved.
In a partially preferred embodiment, the iron trichloride hexahydrate, ferrous sulfate heptahydrate, bi 2 S 3 The mol ratio of @ PDA is 2:1:0.0152-0.1216.
Further, the height of the limited space is 700-900 μm. The height of the limited space is not too large, otherwise Bi accumulated on the composite filter membrane is obviously reduced 2 S 3 PDA amount, but if the height of the confined space is too low, ammonia is not easily able to diffuse into the third solution by free diffusion. Therefore, in the present solution, the height of the limited space, i.e., the distance between the substrate and the composite filter membrane is determined to be 700 to 900 μm, preferably 800 μm. In one or more embodiments, for 0.6X0.6 cm 2 The volume of the third solution in the limited space is 25-32 mu L.
Further, the Bi is prepared 2 S 3 The @ PDA further comprises the steps of:
dissolving bismuth nitrate pentahydrate in nitric acid, adding urea, glycol and polyvinylpyrrolidone, uniformly mixing to obtain a fourth solution, performing hydrothermal treatment on the fourth solution, centrifuging, collecting, washing and drying to obtain Bi 2 O 3 A powder;
thioacetamide and said Bi 2 O 3 Respectively dissolving the powder, uniformly mixing to obtain a fifth solution, carrying out hydro-thermal treatment on the fifth solution, centrifugally collecting and washing to obtain the Bi 2 S 3 Powder, bi to be produced 2 S 3 The powder is directly dispersed in deionized water for preparingThe Bi is 2 S 3 @PDA。
In the technical scheme, bismuth nitrate pentahydrate is adopted to prepare bismuth oxide, bismuth sulfide powder is prepared by bismuth oxide, and the prepared bismuth sulfide powder is not dried and is directly dispersed in deionized water for subsequent Bi 2 S 3 And (3) preparing the modified bismuth sulfide powder by PDA (personal digital assistant) so as to greatly reduce the aggregation of the bismuth sulfide powder, improve the polydopamine coating effect on the surface of the bismuth sulfide powder and be beneficial to forming a subsequent mineralized layer.
Further, the polydimethylsiloxane and the matched curing agent are dissolved in normal hexane solution to obtain sixth solution, and the sixth solution is sprayed on the composite mineralized film and then cured at high temperature. According to the technical scheme, after Polydimethylsiloxane (PDMS) and a matched curing agent are dissolved in a normal hexane solution to obtain a sixth solution, the composite mineralization film is arranged on a hot table, the prepared sixth solution is sprayed on the surface of the composite mineralization film, the PMDS modified composite mineralization film can be obtained after the composite mineralization film is cured at a high temperature for a period of time, a hydrophobic layer formed by the PDMS endows the composite mineralization film with excellent hydrophobic performance, and when the composite mineralization film is driven on a water surface, the movement resistance can be reduced by utilizing an air layer between liquid/solid interfaces, so that the driving effect of the composite mineralization film is further improved. In one or more embodiments, other existing means of forming a hydrophobic layer on the surface of the composite mineralized film may be used, such as, for example, applying a hydrophobic coating such as beeswax.
The invention also provides the photomagnetic double-drive composite mineralized film prepared based on the preparation method of any one of the composite mineralized films. The composite mineralized film not only can be driven by using two modes of near infrared light and magnetic force, can quickly switch the motion mode in a complex water area environment, can perform highly controllable fine motion in a micro range, can also quickly move in a large range, but also has excellent photocatalysis characteristics, and can realize high-efficiency degradation of water surface pollutants by utilizing the promotion effect of a narrow band gap and photo-thermal under the irradiation of the near infrared light.
The invention also provides application of any composite mineralization film, which is used for moving under the drive of near infrared light or magnetic force and degrading water surface pollutants by utilizing the photocatalysis effect. In practical application, devices for moving on the water surface and degrading water surface pollutants such as a water robot, a water driver, a water cleaner and the like can be prepared based on the composite mineralized film.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the magneto-optical double-drive type composite mineralization film has two driving modes of near infrared light driving and magnetic driving, can perform highly controllable fine movement in a micro range, can realize rapid movement in a large range, and can meet actual complex application requirements by rapidly switching the movement modes in a complex water area environment;
2. the magneto-optical double-drive composite mineralized film can utilize Bi under the irradiation of near infrared light 2 S 3 The narrow band gap and the promotion effect of photo-heat realize the high-efficiency degradation of the water surface pollutants, and have quite excellent photocatalysis characteristics;
3. the invention is characterized in that the ferric trichloride hexahydrate, the ferrous sulfate heptahydrate and the Bi are reasonably arranged 2 S 3 The ratio of @ PDA is such that the composite mineralized film has a mineralized layer with a hierarchical micro-nano structure, and the ferrite minerals and Bi in the mineralized layer are utilized 2 S 3 The photo-thermal effect and the photo-catalytic property of the composite mineralized film are further improved due to the morphological characteristics of the micro-nano structure;
4. the invention uses Bi 2 S 3 The polydopamine layer on the surface of the PDA ensures that the mineral layer of the mineralized filter membrane is aggregated and assembled in situ, has more excellent adhesiveness, and ensures the structural and functional stability of the composite mineralized membrane in the working state and the durability of long-time repeated use;
5. the bismuth sulfide powder prepared by adopting the bismuth nitrate pentahydrate is directly dispersed in deionized water without drying for subsequent Bi 2 S 3 And (3) preparing the modified bismuth sulfide powder by PDA (personal digital assistant) so as to greatly reduce the aggregation of the bismuth sulfide powder, improve the polydopamine coating effect on the surface of the bismuth sulfide powder and be beneficial to forming a subsequent mineralized layer.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention. In the drawings:
FIG. 1 is a block flow diagram of a method of preparation in an embodiment of the invention;
FIG. 2 shows Bi in an embodiment of the present invention 2 S 3 High-power transmission electron microscope image of PDA nano aggregate;
FIG. 3 is a high-power scanning electron microscope image of the surface of the composite mineralized film prepared in the embodiment of the invention;
FIG. 4 shows near infrared photothermal test data of a composite mineralized film prepared in an embodiment of the invention;
FIG. 5 is a graph showing the static water contact angle of a composite mineralized film modified with PDMS according to an embodiment of the present invention;
FIG. 6 is a near infrared light driving process of a water surface robot based on a composite mineralized film in an embodiment of the invention;
FIG. 7 is a magnetic force driving process of a water surface robot based on a composite mineralized film in an embodiment of the invention;
fig. 8 shows catalytic test data of a composite mineralized film based water surface robot in an embodiment of the invention.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
All the raw materials of the present invention are not particularly limited in their sources, and can be commercially available or prepared according to conventional methods well known to those skilled in the art. All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs the purity requirements conventional in the field of analytical or functional materials. All raw materials of the invention, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
1. Preparation of composite mineralized film
[ example 1 ]
(1) 364mg of bismuth nitrate pentahydrate is dissolved in 10mL of nitric acid solution with the concentration of 1M, 160mg of urea, 50mL of ethylene glycol and 600mg of polyvinylpyrrolidone are sequentially added, and the mixture is fully mixed to form a fourth solution which is uniformly mixed;
(2) Transferring the fourth solution into a stainless steel autoclave, performing hydrothermal treatment at 150deg.C for 3 hr, centrifuging, collecting, washing with deionized water for at least 5 times, and drying to obtain Bi 2 O 3 A powder;
(3) 59mg of thioacetamide and 59mg of Bi are reacted 2 O 3 Respectively dissolving the powder in 20mL of deionized water, and fully mixing the two solutions to form a uniformly mixed fifth solution;
(4) Transferring the fifth solution into a stainless steel autoclave, performing hydrothermal treatment at 150deg.C for 12h, cooling to room temperature, centrifuging, collecting, and washing with deionized water for at least 5 times to obtain Bi 2 S 3 A powder;
(5) 20mg of Bi 2 S 3 Dispersing the powder in 40mL deionized water, adding 160mL isopropyl alcohol and 4mL ammonia water (28%), stirring and mixing thoroughly for 1h, adding 20mg dopamine hydrochloride, stirring and reacting at room temperature for 24h to obtain Bi 2 S 3 @PDA；
(6) Dissolving 151.67mg of dopamine hydrochloride in 10mL of deionized water to obtain a dopamine hydrochloride solution, dissolving 242mg of tris (hydroxymethyl) aminomethane, 342mg of sodium periodate and 2.4mg of sodium hydroxide in 10mL of deionized water, and uniformly shaking by ultrasonic waves to obtain a first solution;
(7) Mixing the dopamine hydrochloride solution and the first solution in a small amount according to the volume ratio of 1:1, and sufficiently oscillating to form a uniformly mixed second solution;
(8) At room temperatureNext, a small amount of the second solution was immediately dropped into an area of 0.6X0.6 cm 2 After keeping the rough surface of the polytetrafluoroethylene filter membrane for 2min, removing the solution on the surface, immersing the polytetrafluoroethylene filter membrane in deionized water for rinsing, blowing with nitrogen and drying in a 60 ℃ oven to obtain a composite filter membrane;
(9) Repeating the step (8) for three times;
(10) Preparing 0.16M ferric trichloride hexahydrate, 0.08M ferrous sulfate heptahydrate and 0.000152M Bi in 10mL deionized water 2 S 3 A third solution @ PDA and protected for 5 minutes under a nitrogen atmosphere;
(11) Preparing 25wt.% ammonia water into 2wt.% ammonia water solution;
(12) The third solution obtained in 28.8. Mu.L was dropped onto a polytetrafluoroethylene substrate, and the size was 0.6X0.6 cm 2 The rough surface of the composite filter membrane is inverted, the mixed solution is placed in a limited space with the thickness of 800 mu m, and an external magnetic field with the size of 0.18T upwards is applied;
(13) Dropwise adding 10mL of 2wt.% ammonia water solution to the periphery of the limited space, so that ammonia gas is freely diffused into the mixed solution;
(14) The whole reaction system is placed in a culture dish with a cover for mineralization reaction for 24 hours;
(15) Removing the cover of the culture dish and the ammonia water solution, and naturally drying the reacted filter membrane at room temperature;
(16) Taking out the naturally dried mineralized film, washing with water, and drying in a 60 ℃ oven;
(17) Polydimethylsiloxane PDMS and a matched curing agent are mixed according to the weight ratio of 10:1, dissolving in n-hexane solution, and fully stirring for 2min to obtain a uniform PDMS-n-hexane mixed solution with the concentration of 2%;
(18) Placing the mineralized film obtained in the step (16) on a hot table at 40 ℃, and spraying the mixed solution obtained in the step (17) on the surface of the mineralized film;
(19) And (5) continuously curing at high temperature on a hot table for 5min to finally obtain the composite mineralized membrane M1.
The high-power scanning electron microscope image of the surface of the prepared composite mineralized film M1 is shown in fig. 3 (a).
[ example 2 ]
Steps (1) - (9) are the same as in example 1.
Step (10) preparing 0.16M ferric trichloride hexahydrate, 0.08M ferrous sulfate heptahydrate and 0.001216M Bi in 10mL deionized water 2 S 3 A third solution @ PDA and protected for 5 minutes under a nitrogen atmosphere;
(11) Preparing 25wt.% ammonia water into 2wt.% ammonia water solution;
(12) The third solution obtained in 28.8. Mu.L was dropped onto a polytetrafluoroethylene substrate, and the size was 0.6X0.6 cm 2 The rough surface of the composite filter membrane is inverted, the mixed solution is placed in a limited space with the thickness of 800 mu m, and an external magnetic field with the size of 0.18T upwards is applied;
(13) Dropwise adding 10mL of 2wt.% ammonia water solution to the periphery of the limited space, so that ammonia gas is freely diffused into the mixed solution;
(14) The whole reaction system is placed in a culture dish with a cover for mineralization reaction for 24 hours;
(15) Removing the cover of the culture dish and the ammonia water solution, and naturally drying the reacted filter membrane at room temperature;
(16) Taking out the naturally dried mineralized film, washing with water, and drying in a 60 ℃ oven;
(17) Polydimethylsiloxane PDMS and a matched curing agent are mixed according to the weight ratio of 10:1, dissolving in n-hexane solution, and fully stirring for 2min to obtain a uniform PDMS-n-hexane mixed solution with the concentration of 2%;
(18) Placing the mineralized film obtained in the step (16) on a hot table at 40 ℃, and spraying the mixed solution obtained in the step (17) on the surface of the mineralized film;
(19) And (5) continuously curing at high temperature on a hot table for 5min to finally obtain the composite mineralized membrane M2.
Bi for preparing composite mineralized film M2 2 S 3 A high-power transmission electron microscope image of the @ PDA nano-aggregate is shown in FIG. 2, and as can be seen from the image, bi with layered overlapping is provided 2 S 3 The size of the @ PDA nanoclusters is approximately 300nm. High-power scanning electricity for surface of prepared composite mineralized film M2As shown in FIG. 3 (b), it is clear from a comparison of FIG. 3 (a) and FIG. 3 (b) that M1 is also formed with a mineralized layer having a hierarchical micro-nano structure, but is composed of ferric trichloride hexahydrate, ferrous sulfate heptahydrate, and Bi 2 S 3 The scale of the @ PDA is regulated, the hierarchical micro-nano structure level of the mineralized layer of M2 is clearer, and the situation of appearance collapse and loss is obviously reduced.
[ example 3 ]
Steps (1) - (9) are the same as in example 1.
Step (10) preparing 0.16M ferric trichloride hexahydrate, 0.08M ferrous sulfate heptahydrate and 0.009725M Bi in 10mL deionized water 2 S 3 A third solution @ PDA and protected for 5 minutes under a nitrogen atmosphere;
(11) Preparing 25wt.% ammonia water into 2wt.% ammonia water solution;
(12) The third solution obtained in 28.8. Mu.L was dropped onto a polytetrafluoroethylene substrate, and the size was 0.6X0.6 cm 2 The rough surface of the composite filter membrane is inverted, the mixed solution is placed in a limited space with the thickness of 800 mu m, and an external magnetic field with the size of 0.18T upwards is applied;
(13) Dropwise adding 10mL of 2wt.% ammonia water solution to the periphery of the limited space, so that ammonia gas is freely diffused into the mixed solution;
(14) The whole reaction system is placed in a culture dish with a cover for mineralization reaction for 24 hours;
(15) Removing the cover of the culture dish and the ammonia water solution, and naturally drying the reacted filter membrane at room temperature;
(16) Taking out the naturally dried mineralized film, washing with water, and drying in a 60 ℃ oven;
(17) Polydimethylsiloxane PDMS and a matched curing agent are mixed according to the weight ratio of 10:1, dissolving in n-hexane solution, and fully stirring for 2min to obtain a uniform PDMS-n-hexane mixed solution with the concentration of 2%;
(18) Placing the mineralized film obtained in the step (16) on a hot table at 40 ℃, and spraying the mixed solution obtained in the step (17) on the surface of the mineralized film;
(19) And (5) continuously curing at high temperature on a hot table for 5min to finally obtain the composite mineralized membrane M3.
2. Application test of composite mineralized film
Fig. 4 (a) and 4 (b) show near infrared photothermal test data of the composite mineralized films M1 and M2, respectively. As can be seen by comparing FIG. 4 (a) with FIG. 4 (b), the power is 0.39W/cm 2 After the near infrared laser irradiates the composite mineralized film for 180 seconds, the composite mineralized films M1 and M2 both show good photo-thermal effect, and the near infrared laser irradiates the composite mineralized film through ferric trichloride hexahydrate, ferrous sulfate heptahydrate and Bi 2 S 3 Compared with the composite mineralization film M1, the temperature of the composite mineralization film M2 with the ratio regulated by @ PDA reaches 67.5 ℃, and the photo-thermal effect is improved by 19.89%.
Fig. 5 shows the static water contact angle of the PDMS-modified composite mineralized film M2. From the graph, after PDMS is modified on the surface of the composite mineralization film, the surface of the composite mineralization film reaches a super-hydrophobic state with a contact angle of more than 150 degrees.
Fig. 6 shows two sets of near infrared light driving processes of the water surface robot processed based on the composite mineralized film M2. By irradiating the different positions of the robot, the movement form thereof can be precisely adjusted. As shown in the first row of four figures in fig. 5, the robot may self-rotate in a clockwise direction when irradiating the hypotenuse left side of the triangular water surface robot for 0-2.15 seconds; as shown in the second row of four figures in fig. 5, at 0 to 2.08 seconds, when the end of the right-angle side of the triangular water surface robot is irradiated, the robot can perform revolution in the counterclockwise direction around the vertex pointed at by the right angle. It can be seen that the near infrared light based driving method enables a controllable fine movement in a small range in a short time.
Fig. 7 shows two sets of magnetic driving processes of the water surface robot processed based on the composite mineralized film M2. By utilizing the magnetism of the ferrite minerals in the mineralized layer, the robot can be driven under the guidance of an external magnet to perform a large range of different movements in a short time. As shown in fig. 7, 5 figures of the first row and 5 figures of the second row, the robot performs a circular motion and a motion along a Z-shaped trajectory, respectively, under the guidance of an external magnet.
FIG. 8 shows complex-basedAnd synthesizing catalytic test data of the water surface robot processed by the mineralized film M2. The experiments were divided into four experimental groups: stationary-Bi 2 S 3 For mineralizing only ferrite minerals in the layer, bi is not introduced 2 S 3 Mineralized filter membrane of @ PDA is in static state, stationary+Bi 2 S 3 Is to introduce Bi 2 S 3 Under the static state, the composite mineralized film M2 of the @ PDA is MR, bi is introduced 2 S 3 Composite mineralization membrane M2 of @ PDA MR under the condition of magnetic force rotation&NIR for introducing Bi 2 S 3 Composite mineralized film M2 of @ PDA was magnetically rotated and near infrared radiation (0.39W/cm 2 ) Is the case for (a). Using methyl orange (5 mg L) -1 pH 3.0) as a model for organic pollutants, 0.82. Mu.L of H was added to each of the four experimental groups 2 O 2 (30%) and the degradation rate was measured by carrying out a catalytic reaction for 40 minutes. As shown in fig. 8, the results indicate that: introducing Bi 2 S 3 Composite mineralized film M2 of @ PDA and Bi-free 2 S 3 The group of PDA is compared, can show extra catalytic effect to, with the help of its more excellent photo-thermal effect that brings, can further promote the effect of photocatalysis by a wide margin.
The use of "first," "second," "third," etc. (e.g., first solution, second solution, third solution, etc.) herein is merely for clarity of description to distinguish between corresponding components and is not intended to limit any order or emphasize importance, etc. In addition, the term "coupled" as used herein may be directly coupled or indirectly coupled via other components, unless otherwise indicated.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. The preparation method of the magneto-optical double-drive type composite mineralized film is characterized by comprising the following steps of:
preparation of Bi 2 S 3 PDA, bi 2 S 3 Dispersing the powder in deionized water, adding isopropanol and ammonia water, mixing, adding dopamine hydrochloride, and stirring to react to obtain Bi coated with polydopamine layer 2 S 3 Nano aggregate Bi 2 S 3 @PDA；
Preparing a composite filter membrane, dissolving tris (hydroxymethyl) aminomethane, sodium periodate and sodium hydroxide to obtain a first solution, and uniformly mixing the first solution with a dopamine hydrochloride solution to obtain a second solution; the second solution is quickly dripped on the surface of the polytetrafluoroethylene filter membrane, the second solution is removed after a period of time is kept, and the composite filter membrane is obtained after cleaning and drying;
preparing composite mineralized film, mixing ferric trichloride hexahydrate, ferrous sulfate heptahydrate and Bi 2 S 3 Obtaining a third solution by @ PDA, dripping the third solution onto a polytetrafluoroethylene substrate, placing one surface of the composite filter membrane, which is provided with a polydopamine layer, on the polytetrafluoroethylene substrate downwards, wherein the third solution is positioned in a limited space between the polytetrafluoroethylene substrate and the composite filter membrane, and simultaneously applying an upward external magnetic field; and (3) dropwise adding ammonia water to the periphery of the limited space, enabling ammonia gas to freely diffuse into the third solution, reacting the reaction system for a period of time under a closed condition, removing the ammonia water, and cleaning and drying to obtain the composite mineralized membrane.
2. The method for preparing the photomagnetic dual-drive type composite mineralized film according to claim 1, wherein the ferric trichloride hexahydrate and Bi 2 S 3 The mol ratio of @ PDA is 1100:1-16:1.
3. The method for preparing the magneto-optical dual-drive type composite mineralized film according to claim 1, characterized in that the ferrous sulfate heptahydrate and Bi 2 S 3 The mol ratio of @ PDA is 550:1-8:1.
4. The method for preparing a magneto-optical dual-drive type composite mineralized film according to any one of claims 1 to 3, wherein the iron trichloride hexahydrate, ferrous sulfate heptahydrate and Bi 2 S 3 The mol ratio of @ PDA is 2:1:0.0152-0.1216.
5. The method for preparing a magneto-optical double-drive type composite mineralized film according to claim 4, wherein the height of the limited space is 700-900 μm.
6. The method for preparing a magneto-optical dual-drive type composite mineralized film according to claim 1, wherein the Bi is prepared 2 S 3 The @ PDA further comprises the steps of:
dissolving bismuth nitrate pentahydrate in nitric acid, adding urea, glycol and polyvinylpyrrolidone, uniformly mixing to obtain a fourth solution, performing hydrothermal treatment on the fourth solution, centrifuging, collecting, washing and drying to obtain Bi 2 O 3 A powder;
thioacetamide and said Bi 2 O 3 Respectively dissolving the powder, uniformly mixing to obtain a fifth solution, carrying out hydro-thermal treatment on the fifth solution, centrifugally collecting and washing to obtain the Bi 2 S 3 Powder, bi to be produced 2 S 3 Powder is directly dispersed in deionized water for preparing the Bi 2 S 3 @PDA。
7. The method for preparing a photomagnetic dual-drive type composite mineralized film according to claim 1 or 6, wherein the Bi is prepared by 2 S 3 Bi used for PDA 2 S 3 The mass ratio of the powder to the dopamine hydrochloride is 0.8-1.4:1.
8. The method for preparing the magneto-optical dual-drive type composite mineralized film according to claim 1, wherein polydimethylsiloxane and a matched curing agent are dissolved in a normal hexane solution to obtain a sixth solution, and the sixth solution is sprayed on the composite mineralized film and then cured at a high temperature.
9. A magneto-optical double-drive composite mineralization film, characterized in that the composite mineralization film is prepared by the preparation method of any one of claims 1 to 8.
10. The use of a photomagnetic dual-drive type composite mineralization film according to claim 9, wherein the composite mineralization film is used for moving under the drive of near infrared light or magnetic force and degrading water surface pollutants by utilizing the photocatalysis effect.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106958141A (en) * 2017-04-24 2017-07-18 东华大学 A kind of method for preparing photothermal deformation fabric
CN108525702A (en) * 2018-04-16 2018-09-14 成都新柯力化工科技有限公司 A kind of support type bismuth oxychloride photocatalyst and preparation method for sewage disposal
CN112191107A (en) * 2020-09-29 2021-01-08 秦欢欢 Preparation method of high-flux polytetrafluoroethylene reverse osmosis membrane
CN112354379A (en) * 2020-11-08 2021-02-12 董浩 Preparation method of polytetrafluoroethylene reverse osmosis membrane with lasting and stable filtration and separation performance
WO2021109132A1 (en) * 2019-12-06 2021-06-10 百脉迪生物科技(苏州)有限公司 Composite material and preparation method therefor and application thereof
CN113437277A (en) * 2021-07-20 2021-09-24 广东工业大学 Bi2S3/NiS2@ C negative electrode material, sodium ion battery and preparation method of sodium ion battery
CN113527933A (en) * 2021-07-20 2021-10-22 四川大学 Viroid ferrite super-hydrophobic coating and preparation method thereof
CN114560701A (en) * 2022-03-25 2022-05-31 河北科技大学 Bismuth-based photothermal conversion nanofiber material and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106958141A (en) * 2017-04-24 2017-07-18 东华大学 A kind of method for preparing photothermal deformation fabric
CN108525702A (en) * 2018-04-16 2018-09-14 成都新柯力化工科技有限公司 A kind of support type bismuth oxychloride photocatalyst and preparation method for sewage disposal
WO2021109132A1 (en) * 2019-12-06 2021-06-10 百脉迪生物科技(苏州)有限公司 Composite material and preparation method therefor and application thereof
CN112191107A (en) * 2020-09-29 2021-01-08 秦欢欢 Preparation method of high-flux polytetrafluoroethylene reverse osmosis membrane
CN112354379A (en) * 2020-11-08 2021-02-12 董浩 Preparation method of polytetrafluoroethylene reverse osmosis membrane with lasting and stable filtration and separation performance
CN113437277A (en) * 2021-07-20 2021-09-24 广东工业大学 Bi2S3/NiS2@ C negative electrode material, sodium ion battery and preparation method of sodium ion battery
CN113527933A (en) * 2021-07-20 2021-10-22 四川大学 Viroid ferrite super-hydrophobic coating and preparation method thereof
CN114560701A (en) * 2022-03-25 2022-05-31 河北科技大学 Bismuth-based photothermal conversion nanofiber material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Liquid–solid contact triboelectrification and its use in self-powered nanosensor for detecting organics in water;Xiaolong Zhang等;Nano Energy;第30卷(第2016期);321-329页 *
光催化分离复合膜的制备及其在污水处理中的应用;曾安然;林志杰;吉顺峰;;精细石油化工(第05期);72-77页 *

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