CN116396529B - Preparation of porous photo-thermal conversion hydrogel film and application of porous photo-thermal conversion hydrogel film in sewage purification - Google Patents
Preparation of porous photo-thermal conversion hydrogel film and application of porous photo-thermal conversion hydrogel film in sewage purification Download PDFInfo
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- 229940033123 tannic acid Drugs 0.000 claims abstract description 11
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- 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 13
- 241000894006 Bacteria Species 0.000 claims description 13
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 13
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 13
- 229910052724 xenon Inorganic materials 0.000 claims description 12
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- 238000005530 etching Methods 0.000 claims description 6
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- 241000588724 Escherichia coli Species 0.000 claims description 2
- 241000191963 Staphylococcus epidermidis Species 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 239000003504 photosensitizing agent Substances 0.000 abstract description 10
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- 238000011065 in-situ storage Methods 0.000 abstract description 4
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- 238000001704 evaporation Methods 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 12
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 9
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a preparation method of a porous photo-thermal conversion hydrogel film and application thereof in sewage purification, comprising the following steps: adding acrylamide, ammonium persulfate, tannic acid and N, N' -methylene bisacrylamide into water, and stirring to obtain a mixed solution; adding Ti 3C2 MXene suspension into the mixed solution, stirring and uniformly mixing, pouring into a mould, and polymerizing at room temperature to form porous hydrogel; soaking the porous hydrogel in FeCl 3 solution to obtain the porous photo-thermal conversion hydrogel film. The invention enhances the light absorption performance of the hydrogel-based light-heat conversion film by constructing the hydrogel material with a porous structure. TA is uniformly dispersed in the hydrogel by introducing a TA/Fe chelate as a photosensitizer, and the photosensitizer is formed in situ by a soaking mode. Wherein the photosensitizer has good dispersibility, and the hydrogel exhibits excellent light-heat conversion characteristics. The porous hydrogel-based photothermal membranes exhibit good purification characteristics for water contaminated with microorganisms, organics, and ions.
Description
Technical Field
The invention relates to preparation of a porous photo-thermal conversion hydrogel film and application thereof in sewage purification, belonging to the field of environmental remediation.
Background
Water is an important resource for human survival and development, however, it faces the increasingly serious problems of water resource shortage and water pollution. Therefore, the development of efficient, economical and sustainable water purification technology is of great importance. At present, the common water purification technology mainly comprises the traditional technologies such as a chemical precipitation method, an adsorption method, an ion exchange method, an electrochemical treatment method and the like, however, the technologies have the problems of low efficiency, complex operation, high cost and the like, and the problems need to be solved urgently. Therefore, the development of novel and efficient water purification materials and techniques has become a current research hotspot.
The photo-thermal conversion technology is a novel high-efficiency water purification technology, and utilizes the absorption of materials to light energy to generate heat so as to drive water to evaporate from the surface, thereby removing impurities in the water. Compared with the traditional technology, the photo-thermal conversion technology has the advantages of low energy consumption, simple operation, high selectivity to pollutants and the like. As the core of the photothermal conversion technology, a novel photothermal conversion material has received a great deal of attention. A photothermal conversion film refers to a material capable of converting the energy of solar radiation or other light sources into thermal energy and releasing it. Currently, various methods are used to prepare photothermal conversion films, including chemical synthesis, physical vapor deposition, and magnetron sputtering techniques. Although these methods can produce a highly efficient photothermal conversion film, there are problems such as difficulty in processing and insufficient flexibility. Hydrogel-based materials are considered to be good matrices for photothermal conversion materials due to their unique structure and excellent properties. The photo-thermal material is compounded in the hydrogel matrix to obtain the hydrogel material with photo-thermal conversion property. However, the photo-thermal conversion efficiency of hydrogels is limited due to poor light absorption characteristics and poor photosensitizer dispersibility caused by the smooth surface structure. Therefore, development of a hydrogel photo-thermal film having good photo-thermal conversion characteristics is needed to meet the demand.
Based on this, the present invention aims to prepare a photothermal conversion film having good photothermal conversion characteristics for purification of sewage by constructing a porous structure and forming a photosensitizer in situ.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
The invention provides a preparation method of a porous photo-thermal conversion hydrogel film, which adopts a porous structure to increase the absorption of hydrogel-based photo-thermal film to light and forms photosensitizer in situ to realize the uniform distribution of the photosensitizer in a hydrogel matrix.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for preparing a porous photothermal conversion hydrogel film, comprising the steps of:
Step one, adding acrylamide, ammonium persulfate, tannic acid and N, N' -methylene bisacrylamide into water, and stirring to obtain a mixed solution;
adding Ti 3C2 MXene suspension into the mixed solution, stirring and uniformly mixing, pouring into a mould, and polymerizing at room temperature to form porous hydrogel;
and thirdly, soaking the porous hydrogel in FeCl 3 solution to obtain the porous hydrogel-based photothermal conversion film.
Preferably, in the first step, the mass ratio of the acrylamide to the ammonium persulfate is 8-12:1; the mass ratio of the acrylamide to the tannic acid is 20-140:1; the mass ratio of the acrylamide to the N, N' -methylene bisacrylamide is 2000-2800:1; the mass ratio of the acrylamide to the water is 0.2-0.3:1.
Preferably, in the second step, the preparation method of the Ti 3C2 MXene suspension comprises the following steps: 1.0g LiF was added to 9.0mol/L HCl solution to obtain an etching solution, 1.0g Ti 3AlC2 was slowly added to the etching solution, stirred at 600rpm and etched at 35℃for 48 hours, then washed with deionized water until the pH was close to 6, and then the mixture was sonicated and centrifuged to obtain a Ti 3C2 MXene suspension; the speed of the centrifugation was 3500rpm and the time was 5 minutes.
Preferably, in the second step, the concentration of the Ti 3C2 MXene suspension is 8-12 mg/mL; the mass volume ratio of the acrylamide to the Ti 3C2 MXene suspension is 2-3 g: 80-120 mu L.
Preferably, in the third step, the concentration of the FeCl 3 solution is 3-8 g/L.
Preferably, in the third step, the soaking time is 10-15 hours.
The invention also provides application of the porous photo-thermal conversion hydrogel film prepared by the preparation method in sewage purification.
The invention also provides an application of the porous photo-thermal conversion hydrogel film prepared by the preparation method in seawater purification, wherein seawater is poured into a container, and then the porous photo-thermal conversion hydrogel film is placed on the seawater surface; and (3) irradiating the surface of the porous photo-thermal conversion hydrogel film by using a 500W xenon lamp to evaporate the seawater, and measuring the cation concentration before and after the seawater is evaporated.
The invention also provides an application of the porous photo-thermal conversion hydrogel film prepared by the preparation method in sewage purification, wherein a water source polluted by methylene blue or eosin Y is poured into a container, and then the porous photo-thermal conversion hydrogel film is placed on the water source polluted by the methylene blue or eosin Y; and (3) irradiating the surface of the porous photo-thermal conversion hydrogel film by using a 500W xenon lamp to purify a water source polluted by methylene blue or eosin Y, so as to obtain a purified water solution.
The invention also provides an application of the porous photo-thermal conversion hydrogel film prepared by the preparation method in sewage purification, wherein a water source polluted by bacteria is poured into a container, and then the porous photo-thermal conversion hydrogel film is placed on the water source polluted by bacteria; adopting a 500W xenon lamp to irradiate the surface of the porous photo-thermal conversion hydrogel film, and purifying a water source polluted by bacteria to obtain a purified water solution; the water source polluted by bacteria is a water source polluted by escherichia coli or a water source polluted by staphylococcus epidermidis.
The invention at least comprises the following beneficial effects:
(1) The absorption performance of the hydrogel-based photothermal conversion film to light is enhanced by constructing the hydrogel material with a porous structure.
(2) By introducing a TA/Fe chelate as a photosensitizer, firstly, uniformly dispersing TA in the hydrogel, and then, forming the photosensitizer in situ by a soaking mode. Wherein the photosensitizer has good dispersibility, and the hydrogel exhibits excellent light-heat conversion characteristics.
(3) The porous photothermal conversion hydrogel film exhibits good purification characteristics for water contaminated with microorganisms, organics and ions.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 (a) is a photograph of a color change of a hydrogel during the manufacturing process, (b) is the workability of the hydrogel, and (c) is the flexibility of the hydrogel; (d) An optical image of a PAM hydrogel, (e) an optical image of a TPAM hydrogel, (f) an optical image of a TA-TPAM hydrogel, (g) an optical image of a 100Fe/TA-TPAM hydrogel, (h) an SEM image of a PAM hydrogel, (i) an SEM image of a 100Fe/TA-PAM hydrogel, and (j) a surface area of a porous hydrogel.
FIG. 2 is an XPS spectrum of hydrogels TA-TPAM and 100 Fe/TA-TPAM);
FIG. 3 (a) is an infrared image of a 100Fe/TA-TPAM hydrogel film under 1 kW.m -2 sun light; (b) Is the temperature change curve of hydrogel (PAM, fe/TA-PAM and 100 Fe/TA-TPAM) under the sun illumination;
FIG. 4 is UV-Vis-NIR spectral absorption of PAM and 100Fe/TA-TPAM hydrogels;
FIG. 5 (a) is the real-time mass change of the hydrogel film as it undergoes solar irradiation with clean water, (b) is the solar efficiency of the hydrogel film; (c) A durability of the 100Fe/TA-TPAM hydrogel film under 1 kW.m -2 sun light; (d) The concentration change of cations in seawater is removed for a 100Fe/TA-TPAM hydrogel film;
FIG. 6 (a) is an optical photograph of the UV-visible spectrum and corresponding physical image of the dyes (eosin-Y and methylene blue) before and after solar thermal purification and (b) is an unpurified and purified bacterial solution after co-culture on agar plates.
The specific embodiment is as follows:
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The preparation of the Ti 3C2 MXene suspension in the following examples was: 1.0g LiF was added to 9.0mol/L HCl solution to obtain an etching solution, 1.0g Ti 3AlC2 was slowly added to the etching solution, stirred at 600rpm and etched at 35℃for 48 hours, then washed with deionized water until the pH was close to 6, and then the mixture was sonicated and centrifuged to obtain a Ti 3C2 MXene suspension; the speed of the centrifugation was 3500rpm and the time was 5 minutes.
Example 1:
A method for preparing a porous photothermal conversion hydrogel film, comprising the steps of:
Step one, adding 2.6g of acrylamide, 0.25 ammonium persulfate, 20mg of tannic acid and 1mg of N, N' -methylenebisacrylamide into 10mL of water, and stirring to obtain a mixed solution;
Step two, adding 100 mu L of Ti 3C2 M Xene suspension (10.0 mg/mL) into the mixed solution, stirring and uniformly mixing, pouring into a mould, and polymerizing at room temperature to form porous hydrogel (20 TA-TPAM);
and thirdly, immersing the porous hydrogel in a 5.0g/L FeCl 3 solution for 12 hours, and then taking out and removing the water on the surface to obtain the porous hydrogel-based photothermal conversion film (20 Fe/TA-TPAM).
Example 2:
A method for preparing a porous photothermal conversion hydrogel film, comprising the steps of:
step one, adding 2.6g of acrylamide, 0.25 ammonium persulfate, 60mg of tannic acid and 1mg of N, N' -methylenebisacrylamide into 10mL of water, and stirring to obtain a mixed solution;
Step two, adding 100 mu L of Ti 3C2 M Xene suspension (10.0 mg/mL) into the mixed solution, stirring and uniformly mixing, pouring into a mould, and polymerizing at room temperature to form porous hydrogel (60 TA-TPAM);
And thirdly, immersing the porous hydrogel in a 5.0g/L FeCl 3 solution for 12 hours, and then taking out and removing the water on the surface to obtain the porous hydrogel-based photothermal conversion film (60 Fe/TA-TPAM).
Example 3:
A method for preparing a porous photothermal conversion hydrogel film, comprising the steps of:
Step one, adding 2.6g of acrylamide, 0.25 ammonium persulfate, 100mg of tannic acid and 1mg of N, N' -methylenebisacrylamide into 10mL of water, and stirring to obtain a mixed solution;
Step two, adding 100 mu L of Ti 3C2 M Xene suspension (10.0 mg/mL) into the mixed solution, stirring and mixing uniformly, pouring into a mould, and polymerizing at room temperature to form porous hydrogel (100 TA-TPAM);
And thirdly, immersing the porous hydrogel in a 5.0g/L FeCl 3 solution for 12 hours, and then taking out and removing the water on the surface to obtain the porous hydrogel-based photothermal conversion film (100 Fe/TA-TPAM).
Comparative example 1:
step one, adding 2.6g of acrylamide, 0.25 g of ammonium persulfate and 1mg of N, N' -methylene bisacrylamide into 10mL of water, and stirring to obtain a mixed solution;
And step two, adding 10 mu L N, N, N ', N' -tetramethyl ethylenediamine into the mixed solution, stirring and mixing uniformly, pouring into a mould, and polymerizing at room temperature to form the hydrogel (PAM).
Comparative example 2:
step one, adding 2.6g of acrylamide, 0.25 g of ammonium persulfate and 1mg of N, N' -methylene bisacrylamide into 10mL of water, and stirring to obtain a mixed solution;
And step two, adding 100 mu L of Ti 3C2 M Xene suspension (10.0 mg/mL) into the mixed solution, stirring and mixing uniformly, pouring into a mould, and polymerizing at room temperature to form the hydrogel (TPAM).
Comparative example 3:
step one, adding 2.6g of acrylamide, 0.25 ammonium persulfate, 60mg of tannic acid and 1mg of N, N' -methylenebisacrylamide into 10mL of water, stirring to obtain a mixed solution, pouring the mixed solution into a mold, and polymerizing at room temperature to form porous hydrogel (100 TA-PAM);
And thirdly, immersing the porous hydrogel in 5.0g/L FeCl 3 solution for 12 hours, and then taking out and removing the water on the surface to obtain a hydrogel film (60 Fe/TA-PAM).
Comparative example 4:
Step one, adding 2.6g of acrylamide, 0.25 ammonium persulfate, 100mg of tannic acid and 1mg of N, N' -methylenebisacrylamide into 10mL of water, stirring to obtain a mixed solution, pouring the mixed solution into a mold, and polymerizing at room temperature to form porous hydrogel (100 TA-PAM);
And thirdly, immersing the porous hydrogel in 5.0g/L FeCl 3 solution for 12 hours, and then taking out and removing the water on the surface to obtain the hydrogel film (100 Fe/TA-PAM).
FIG. 1a shows a digital image of a hydrogel film prepared in accordance with the present invention, wherein TPAM (pure PAM hydrogel polymerized by incorporating Ti 3C2 MXene), 100TA-TPAM and 100Fe/TA-PAM show yellow, brown and black colors, respectively. As shown in FIG. 1b, the 100Fe/TA-TPAM hydrogel film can be easily processed into specific shapes (e.g., rectangular, triangular, star-shaped, circular, etc.), which indicates that the hydrogel has good machinability. In addition, the Fe/TA-TPAM hydrogel films also exhibited good flexibility and could be stretched and twisted without failure (FIG. 1 c). These satisfactory processability and flexibility make hydrogel films a perfect candidate for water-purifying photothermal conversion.
The microstructure of the hydrogel film was analyzed by optical microscopy and scanning electron microscopy. Optical microscopy pictures showed that the pure PAM hydrogel was optically transparent, homogeneous on the surface and inside (fig. 1 d). With the addition of Ti 3C2 MXene, the TPAM, 100TA-TPAM and 100Fe/TA-TPAM hydrogels all showed uniform pore structure with pore size of 800 μm (FIGS. 1e-1 g). After addition of tannic acid TA, 100TA-TPAM exhibited a more uniform pore structure compared to TPAM. Studies have shown that pores are created by the escape of NH 3 (generated during APS decomposition) and H 2 O vapor (caused by exothermic processes). Since the TA molecule is rich in reducing catechol hydroxyl groups, the polymerization reaction of the hydrogel can be regulated by partial consumption of the hydroxyl groups generated by APS decomposition, which ultimately results in a uniform pore structure. In addition, SEM images (FIGS. 1h and 1 i) provide evidence that porous hydrogel films were successfully prepared by incorporating Ti 3C2 MXene into PAM-based hydrogels. Due to the pore structure, 100Fe/TA-TPAM shows a higher specific surface area (28.9 m 2·g-l) than PAM (11.9 m 2·g-1) and TPAM (14.5 m 2·g-2) (FIG. 1 j), which increases the contact area between the hydrogel film and the solution, which will help to purify contaminated water.
The color of the hydrogel changed with the addition of TA and Fe 3+. As shown in FIG. 1e, the addition of Ti 3C2 MXene resulted in a darker color of the TPAM hydrogel. The introduction of TA resulted in the 100TA-TPAM hydrogel turning brown in color. Thanks to the specific chelation of TA and Fe 3+, 100Fe/TA-TPAM hydrogels showed darker colors after soaking 100TA-TPAM hydrogels in Fe 3+ solution.
The chemical structure of the hydrogels was evaluated by XPS spectroscopy. Three peaks at 284eV, 401eV and 533eV (FIG. 2) were observed on the measured spectrum of 100TA-TPAM, corresponding to the C1s, N1s and O1s spectra. As for 100Fe/TA-TPAM, only the Fe2p peak (710 eV) was observed in the total spectrum, and no Cl2p peak was observed, indicating that Fe 3+ chelated with the molecules in the hydrogel.
FIG. 3a is an infrared image of a 100Fe/TA-TPAM hydrogel film under 1 kW.m -2 sun light. FIG. 3b is a graph showing the temperature change of hydrogels (PAM, 100Fe/TA-PAM and 100 Fe/TA-TPAM) under solar irradiation.
FIG. 4 is the UV-Vis-NIR spectral absorption of PAM and 100Fe/TA-TPAM hydrogels.
A 500W xenon arc lamp (CEL-S500W) was chosen as the simulated solar light source and an infrared camera was used to record the temperature change of the hydrogel film during illumination. The mass loss of the solution was tested in a steady state by an electronic balance connected to a computer. The water evaporation experiment was continued at room temperature (25 ℃) with a humidity of 45%.
In general, light absorption and light-to-heat conversion efficiency are two key parameters of light-to-heat conversion capability. For a 100Fe/TA-TPAM hydrogel, the porous structure and the introduction of Fe/TA are the main reasons for the photothermal conversion performance. The porous structure forms a natural light trap structure, and light is scattered multiple times through the pore structure inside the hydrogel to reduce light reflection. Furthermore, since the Fe/TA chelate has a good absorption capacity in the UV-Vis spectrum, the captured light can be absorbed during multiple scattering. As expected, UV-Vis-NIR spectral absorption results also confirm this result, wherein the porous Fe/TA-TPAM hydrogel showed higher light absorption properties than the original PAM hydrogel (fig. 4), all of which confirm that the inclusion of the porous structure and Fe/TA chelate enhances the photothermal conversion of the hydrogel.
The Fe/TA-TPAM hydrogel has good photo-thermal conversion function, so that the Fe/TA-TPAM hydrogel is expected to be used as a photo-thermal conversion film for water evaporation. The evaporation performance of water was evaluated by evaporating seawater from Bohai sea in China.
Firstly, taking a 10mL beaker, then pouring seawater into the beaker, and then intercepting a hydrogel film with a large beaker opening to be placed on the water surface; the evaporation system is placed on a balance, finally, a xenon lamp (1 standard solar light intensity, 500W xenon arc lamp (CEL-S500W)) is adopted for irradiation, the light water evaporation efficiency of the evaporation system is obtained by recording the mass change process, and the cation concentration before and after the evaporation of the seawater is measured.
As expected, the 100Fe/TA-TPAM hydrogel film exhibited a much higher evaporation rate than pure water (FIG. 5 a). Notably, the porous structure of the hydrogel film has a higher water evaporation efficiency. Among them, the water evaporation rate of the normal hydrogel (no porous structure) was 0.9 kg.m -2·h-1 (60 Fe/TA-PAM) and 1.0 kg.m -2·h-1 (100 Fe/TA-PAM), and the solar energy efficiency of the porous hydrogel was 1.2 kg.m -2·h-2 (60 Fe/TA-TPAM) and 1.4 kg.m -2·h-1 (100 Fe/TA-TPAM), respectively. The calculated solar energy efficiency also provides evidence that porous hydrogels also exhibit higher solar energy efficiency than conventional hydrogels (fig. 5 b). The high solar efficiency is mainly due to the unique structure of hydrogel-based photo-thermal films. The porous structure not only enhances the conversion of light to heat, but also promotes the transport of water vapor. Furthermore, as shown in FIG. 5c, the water evaporation efficiency remained stable after 10 cycles, which also demonstrates the good durability of the 100Fe/TA-TPAM hydrogel.
The results in FIG. 5d also demonstrate that the 100Fe/TA-TPAM hydrogel film reduces the ion concentration in seawater. All these results indicate that the 100Fe/TA-TPAM hydrogel film is a good photothermal conversion film for water evaporation.
The Fe/TA-TPAM porous hydrogel film also has good function of purifying organic wastewater.
Firstly, a 10mL beaker is taken, then 10mg/L Methylene Blue (MB) solution or eosin Y (E-Y) solution is poured into the beaker, then a hydrogel film with a large beaker opening is cut off and placed on the water surface, a xenon lamp (1 standard solar light intensity, 500W xenon arc lamp (CEL-S500W)) is adopted for irradiation, and the color of the solution before and after purification is observed.
FIG. 6a shows the purification behavior of a 100Fe/TA-TPAM porous hydrogel film on Methylene Blue (MB) and eosin Y (E-Y) solutions. The original MB and E-Y solutions showed blue and orange colors. After purification by a photothermal gel membrane, a colorless solution (i.e., a purified aqueous solution) was obtained. The UV-Vis absorption spectra of the purified aqueous solutions also demonstrated the purification effect of the hydrogel films, wherein the original MB and E-Y solutions showed distinct absorption peaks at 514nm and 613nm, respectively, and the purified aqueous solutions were consistent with the baseline of water (calculated removal of dye was about 99%).
In addition, the 100Fe/TA-TPAM hydrogel film also shows good purification ability for biologically contaminated water. Pouring the water source polluted by bacteria into a 10mL beaker, and then placing the porous hydrogel-based photothermal conversion film on the water source polluted by bacteria; and (3) irradiating the surface of the porous hydrogel-based photothermal conversion film by using a 500W xenon lamp, so as to purify a water source polluted by bacteria and obtain a purified water solution.
The water source polluted by bacteria adopted in the invention is the original bacterial liquid after the original bacterial colony is cultured for 12 hours; the culture mode adopted by the original colony is as follows:
Liquid medium: water (30 mL) NaCl (0.9 g) Na 2HPO4 (1.51 g) peptone (3 g) yeast (1.5 g);
Solid medium: water (30 mL) NaCl (0.9 g) Na 2HPO4 (1.51 g) peptone (3 g) yeast (1.5 g) agar powder (4.5 g);
After the preparation of the culture medium (solid/liquid), high temperature sterilization (121 ℃ C., 30 min);
Streaking the frozen bacteria on a solid medium and culturing for 24 hours; individual colonies were picked and placed in liquid medium (10 mL) for cultivation, and bacterial stock (original colonies) were obtained after 24 hours.
Figure 6b shows a digital image of the solid medium after cultivation of purified and unpurified biologically contaminated water. In the unpurified group, a clear bacterial film was observed, but the original solid medium showed cleanliness. After purification with 100Fe/TA-TPAM hydrogel, the bacterial film disappeared and only a few colonies were observed in the purified group.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (8)
1. A method for preparing a porous photothermal conversion hydrogel film, comprising the steps of: step one, adding acrylamide, ammonium persulfate, tannic acid and N, N' -methylene bisacrylamide into water, and stirring to obtain a mixed solution; adding Ti 3C2 MXene suspension into the mixed solution, stirring and uniformly mixing, pouring into a mould, and polymerizing at room temperature to form porous hydrogel; step three, soaking the porous hydrogel in FeCl 3 solution to obtain a porous photothermal conversion hydrogel film;
the mass ratio of the acrylamide to the tannic acid is 20-140:1;
In the second step, the concentration of the Ti 3C2 MXene suspension is 8-12 mg/mL; the mass volume ratio of the acrylamide to the Ti 3C2 MXene suspension is 2-3 g: 80-120 mu L;
in the third step, the concentration of the FeCl 3 solution is 3-8 g/L.
2. The method for preparing a porous photothermal conversion hydrogel film according to claim 1, wherein in the first step, the mass ratio of acrylamide to ammonium persulfate is 8-12:1; the mass ratio of the acrylamide to the N, N' -methylene bisacrylamide is 2000-2800:1; the mass ratio of the acrylamide to the water is 0.2-0.3:1.
3. The method for preparing a porous photothermal conversion hydrogel film according to claim 1, wherein in the second step, the method for preparing the Ti 3C2 MXene suspension comprises: 1.0g LiF was added to 9.0mol/L HCl solution to obtain an etching solution, 1.0g Ti 3AlC2 was slowly added to the etching solution, stirred at 600rpm and etched at 35℃for 48 hours, then washed with deionized water until the pH was close to 6, and then the mixture was sonicated and centrifuged to obtain a Ti 3C2 MXene suspension; the speed of the centrifugation was 3500rpm and the time was 5 minutes.
4. The method for preparing a porous photothermal conversion hydrogel film according to claim 1, wherein in the third step, the soaking time is 10-15 hours.
5. Use of a porous photothermal conversion hydrogel membrane prepared by the preparation method of any one of claims 1 to 4 in sewage purification.
6. Use of the porous photothermal conversion hydrogel film prepared by the preparation method of any one of claims 1 to 4 in seawater purification, wherein seawater is poured into a container, and then the porous photothermal conversion hydrogel film is placed on the seawater surface; and (3) irradiating the surface of the porous photo-thermal conversion hydrogel film by using a 500W xenon lamp to evaporate seawater, and measuring the cation concentration before and after the seawater is evaporated.
7. Use of the porous photothermal conversion hydrogel film prepared by the method of any one of claims 1 to 4 in sewage purification, wherein a water source contaminated with methylene blue or eosin Y is poured into a container, and then the porous photothermal conversion hydrogel film is placed on the water source contaminated with methylene blue or eosin Y; and (3) irradiating the surface of the porous photo-thermal conversion hydrogel film by using a 500W xenon lamp to purify a water source polluted by methylene blue or eosin Y, so as to obtain a purified water solution.
8. Use of the porous photothermal conversion hydrogel film prepared by the preparation method of any one of claims 1 to 4 in sewage purification, wherein a water source contaminated with bacteria is poured into a container, and then the porous photothermal conversion hydrogel film is placed on the water source contaminated with bacteria; adopting a 500W xenon lamp to irradiate the surface of the porous photo-thermal conversion hydrogel film, and purifying a water source polluted by bacteria to obtain a purified water solution; the water source polluted by bacteria is a water source polluted by escherichia coli or a water source polluted by staphylococcus epidermidis.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112808253A (en) * | 2020-12-30 | 2021-05-18 | 合肥学院 | Electric field sensitive polyacrylamide/MXene hydrogel and preparation method and application thereof |
| CN113583193A (en) * | 2021-08-16 | 2021-11-02 | 南京工业大学 | Photo-thermal ion gel film and preparation method and application thereof |
| WO2022121777A1 (en) * | 2020-12-11 | 2022-06-16 | 东莞理工学院 | Preparation method for floating mxene assembly solar-thermal conversion material, and application thereof |
| CN114805848A (en) * | 2022-03-25 | 2022-07-29 | 太原理工大学 | Preparation method of MXene-based conductive hydrogel with repairability and oxidation resistance |
| CN114874479A (en) * | 2022-06-07 | 2022-08-09 | 成都大学 | Preparation method of spongy macroporous hydrogel and application of spongy macroporous hydrogel in antibiosis |
| CN115491020A (en) * | 2022-09-21 | 2022-12-20 | 青岛科技大学 | Janus type composite foam photo-thermal functional material and preparation method and application thereof |
-
2023
- 2023-04-14 CN CN202310400133.7A patent/CN116396529B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022121777A1 (en) * | 2020-12-11 | 2022-06-16 | 东莞理工学院 | Preparation method for floating mxene assembly solar-thermal conversion material, and application thereof |
| CN112808253A (en) * | 2020-12-30 | 2021-05-18 | 合肥学院 | Electric field sensitive polyacrylamide/MXene hydrogel and preparation method and application thereof |
| CN113583193A (en) * | 2021-08-16 | 2021-11-02 | 南京工业大学 | Photo-thermal ion gel film and preparation method and application thereof |
| CN114805848A (en) * | 2022-03-25 | 2022-07-29 | 太原理工大学 | Preparation method of MXene-based conductive hydrogel with repairability and oxidation resistance |
| CN114874479A (en) * | 2022-06-07 | 2022-08-09 | 成都大学 | Preparation method of spongy macroporous hydrogel and application of spongy macroporous hydrogel in antibiosis |
| CN115491020A (en) * | 2022-09-21 | 2022-12-20 | 青岛科技大学 | Janus type composite foam photo-thermal functional material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Porous Hydrogel Photothermal Conversion Membrane to Facilitate Water Purification";Hongping Zhang et al.;《Langmuir》;20230519;第7345−7352页 * |
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