CN113042077B - Photo-thermal-photochemical synergistic conversion hydrogel material and preparation method and application thereof - Google Patents
Photo-thermal-photochemical synergistic conversion hydrogel material and preparation method and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 97
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 42
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- 229910019606 La0.5Sr0.5CoO3 Inorganic materials 0.000 claims abstract description 9
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 5
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Classifications
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/22—Carbides
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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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
- C02F2101/00—Nature of the contaminant
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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
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
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- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/138—Water desalination using renewable energy
- Y02A20/142—Solar thermal; Photovoltaics
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- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a photo-thermal-photochemical synergistic conversion hydrogel material and a preparation method and application thereof, and belongs to the technical field of photo-thermal and photochemical conversion. Combining a photo-thermal photocatalyst with an interpenetrating polymer of chitosan and polyvinyl alcohol to prepare a hydrogel material with synergistic effect of photo-thermal and photo-catalytic degradation; the photo-thermal photocatalyst is MXene, la 0.5 Sr 0.5 CoO 3 Or La (La) 0.5 Sr 0.5 CoO 3 -MXene. In the hydrogel, the photocatalyst can absorb short-wave photons in the solar spectrum to generate photo-generated carriers, so that photocatalytic degradation reaction occurs, and the photo-thermal material can convert long-wave photons in the solar spectrum into heat energy, so that water evaporation is performed efficiently, photochemical reaction kinetics is accelerated, photocatalytic degradation is promoted, and efficient water production is realized. The hydrogel material has simple preparation process and wide application prospect in the fields of sewage treatment, sea water desalination and the like.
Description
Technical Field
The invention belongs to the technical field of photo-thermal and photochemical conversion, and particularly relates to a photo-thermal-photochemical synergistic conversion hydrogel material, and a preparation method and application thereof.
Background
In recent years, solar energy is sustainable, natural and pollution-free due to abundant resources, and becomes a renewable energy source with great development potential. Fresh water resources are increasingly scarce in the global scope at present, and the technology of utilizing solar energy to drive sea water desalination is widely paid attention to. Therefore, the search for efficient solar energy conversion technologies and materials is critical to the utilization of solar energy. Pathways for solar energy conversion mainly include photochemical conversion and photothermal conversion. The photochemical conversion generates photo-generated carriers through capturing solar energy, and the photo-generated carriers and pollutant molecules undergo migration and degradation reactions, so that the photochemical conversion has great potential in the aspects of environmental pollution treatment, chemical production, fuel development and the like. However, the feasibility of the application of photochemical conversion is severely limited due to the limited absorption of uv-visible light and slow transfer of photo-charges.
Photo-thermal conversion, as a direct conversion pathway for solar energy, represents a significant advantage over photochemical conversion in the full-band utilization of the solar spectrum. The photo-thermal material can absorb infrared region in solar spectrum to perform high-efficiency photo-thermal conversion, and the generated heat energy can be used for evaporating water and promoting photochemical conversion, so that the photo-thermal material has application prospect in sea water desalination, fuel catalytic production, environmental management and the like. Under the background, development of a photo-thermal synergistic photocatalytic material is urgently needed, so that the photo-thermal material can provide kinetic energy for ultraviolet-visible sunlight-driven photo-generated carrier transmission while generating steam by utilizing visible light-near infrared region conversion heat energy, promote photodegradation process and realize full-spectrum efficient utilization of solar spectrum.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a hydrogel material for photo-thermal-photochemical cooperative conversion. The invention aims to provide a preparation method of the photo-thermal-photochemical synergistic conversion hydrogel material. The invention also aims to provide an application of the photo-thermal-photochemical synergistic conversion hydrogel material in high-efficiency photo-thermal water evaporation synergistic photocatalysis degradation of tetracycline pollutants. The material has outstanding full solar spectrum utilization rate, photo-thermal steam conversion and photodegradation efficiency.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of photo-thermal-photochemical synergistic conversion hydrogel comprises the steps of combining a photo-thermal photocatalyst with an interpenetrating network polymer of chitosan and polyvinyl alcohol to prepare a photo-thermal synergistic photocatalytic degradation hydrogel material; the photo-thermal photocatalyst is a two-dimensional MXene sheet and nano La 0.5 Sr 0.5 CoO 3 Particles and La 0.5 Sr 0.5 CoO 3 -MXene composite. The method comprises the following steps:
(1) Respectively preparing a polyvinyl alcohol aqueous solution, a chitosan aqueous solution, a glutaraldehyde solution and a hydrochloric acid solution;
(2) Mixing the polyvinyl alcohol solution obtained in the step (1) with a chitosan solution to form a precursor solution;
(3) At N 2 Under the protection of atmosphere, adding the photo-thermal photocatalysis mixed powder into the precursor solution, and stirring at a low speed to uniformly mix the powder; then, slowly dripping glutaraldehyde solution and hydrochloric acid solution into the precursor solution, mixing and stirring to perform gel reaction; repeatedly soaking the obtained gel in deionized water to remove hydrochloric acid after the sample is completely gelled;
(4) And sucking the water on the surface of the gel by using filter paper, freezing in a refrigerator, thawing in warm water, and repeating the freezing-tempering operation for a plurality of times to obtain the hydrogel material.
The preparation method of the photo-thermal-photochemical synergistic conversion hydrogel comprises the following steps: adding polyvinyl alcohol with the alcoholysis degree of 87.0-89.0% into hot deionized water according to the mass concentration of 10wt%, heating in a water bath at 100 ℃, and stirring at a high speed until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol solution.
The preparation method of the photo-thermal-photochemical synergistic conversion hydrogel comprises the following steps: and adding polyvinyl alcohol into 2wt% acetic acid solution according to the mass concentration of 5wt%, and stirring at a high speed until the polyvinyl alcohol is completely dissolved to obtain chitosan solution.
The preparation method of the photo-thermal-photochemical synergistic conversion hydrogel comprises the steps of preparing a hydrochloric acid solution, wherein the concentration of the hydrochloric acid solution is 1mol/L, and the mass concentration of glutaraldehyde solution is 4%.
According to the preparation method of the photo-thermal-photochemical synergistic conversion hydrogel, the polyvinyl alcohol solution, the chitosan solution and the photo-thermal photocatalytic powder are mixed according to the weight ratio of 4:1.4:0.018, and then 3.25wt% glutaraldehyde solution and 6.5wt% hydrochloric acid solution are added.
The photo-thermal-photochemical synergistic conversion hydrogel material prepared by the method.
The hydrogel material with the photo-thermal-photochemical synergistic conversion is applied to photo-thermal evaporation purification of seawater, heavy metals, dyes and strong acid and alkali wastewater.
The application of the photo-thermal-photochemical synergistic conversion hydrogel material in water evaporation synergistic photocatalysis degradation of tetracycline pollutants.
The beneficial effects are that: compared with the prior art, the invention has the advantages that:
(1) Under the irradiation of standard sunlight, the photo-thermal-photochemical synergistic conversion hydrogel has a photo-thermal conversion efficiency of 92.3% and an m of 2.24kg -2 h -1 Has 97% high-efficiency photodegradation rate to tetracycline hydrochloride.
(2) The photo-thermal evaporation system formed by the hydrogel can have remarkable photo-thermal purification capability in saline water, heavy metals, dyes and strong acid and alkali wastewater.
(3) The hydrogel material has outstanding light evaporation rate and efficiency and light degradation efficiency, simple preparation process and wide application prospect in the fields of sea water desalination, sewage treatment and the like.
Drawings
FIG. 1 is a schematic diagram of the MXene/La of the present invention 0.5 Sr 0.5 CoO 3 Schematic diagram of embedded photo-thermal-photochemical cooperative conversion hydrogel material;
FIG. 2 is a schematic diagram of (2 a) MXene/La of the present invention 0.5 Sr 0.5 CoO 3 Transmission electron microscope images of (a); (2b) Scanning electron microscope images of the MLH-2 hydrogel after lyophilization treatment; (2c) La (La) 0.5 Sr 0.5 CoO 3 X-ray diffraction patterns of LM-10, LM-20;
FIG. 3 is a graph showing the measurement of the saturated water content in various hydrogels according to the present invention (3 a); (3 b) measurement of the hydrophilicity of the MLH-2 hydrogel surface; (3c) Dynamic mechanical analysis of storage modulus (G ') and loss modulus (G') of MLH-1 and MLH-2; (3 d) elasticity test of MLH-1 and MLH-2;
FIG. 4 is an absorption spectrum of a different hydrogel according to the invention (4 a) in the solar wavelength range of 250-2500 nm; (4b) The water evaporation weight loss of different hydrogels under one sunlight illumination intensity; (4c) Under the irradiation intensity of sunlight, the water evaporation rates and evaporation efficiencies of different hydrogels are different; (4d) Under the irradiation of sunlight, the circulation stability of the evaporation performance of MLH-2 in seawater is tested;
FIG. 5 is a schematic view showing the photo-thermal evaporation of the hydrogel to purify sewage according to the present invention (5 a); (5b) An MLH-2 hydrogel photo-thermal evaporation dye wastewater (methyl orange MA and methylene blue MB) front and back solution ultraviolet visible absorption spectrum diagram; (5c) Ion concentration changes in seawater and wastewater before and after photo-thermal evaporation of MLH-2 hydrogel; (5d) The pH change of the water measured before and after the photo-thermal evaporation of the MLH-2 hydrogel;
FIG. 6 shows the temperature change during photodegradation under non-circulating water conditions and circulating water conditions according to the present invention (6 a); (6b) Photodegradation rate of the LM photocatalyst to tetracycline hydrochloride under the condition of non-circulating water; (6c) Photodegradation rate of the LM photocatalyst on tetracycline hydrochloride under the circulating water condition; (6d) Light degradation reaction kinetics research of LM photocatalyst on tetracycline hydrochloride under the condition of non-circulating water; (6e) The dynamic research of photodegradation reaction of LM photocatalyst on tetracycline hydrochloride under the condition of circulating water; (6f) And (3) researching the degradation stability of the LM photocatalyst in 10 times of circulation in the photochemical degradation process.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1
The preparation method of the photo-thermal-photochemical synergistic conversion hydrogel comprises the following steps:
(1) Weighing 10g of polyvinyl alcohol (PVA), pouring into a beaker, adding 90mL of hot deionized water, heating in a water bath at 100 ℃, and stirring at a high speed until the polyvinyl alcohol is completely dissolved to obtain 10wt% of polyvinyl alcohol solution;
(2) Adding 2mL of acetic acid to 98mL of deionized water to form an acetic acid solution; 5g of Chitosan (CS) was weighed, poured into a beaker, and 95mL of acetic acid solution was added thereto, and the mixture was stirred at a high speed to dissolve the chitosan, thereby obtaining a 5wt% chitosan solution.
(3) Mixing 4g of polyvinyl alcohol solution with 1.4g of chitosan solution to form a precursor solution;
(4) Glutaraldehyde (195. Mu.L, 4 wt%) and HCl (400. Mu.L, 0.1 wt%) were slowly dropped into the precursor solution in this order, mixed and stirred to undergo a gel reaction, and the sample was completely gelled within 6 hours; repeatedly soaking the obtained gel in deionized water to remove hydrochloric acid; finally, the water on the gel surface was sucked dry with filter paper and frozen in a refrigerator (-24 ℃) and thawed in warm water (40 ℃) and the freeze-thaw operation was repeated 10 times to obtain a hydrogel material (designated as MLH-1).
MLH-1 has better water absorption by saturation moisture content testing (FIG. 3 a). MLH-1 has a certain mechanical strength and elasticity by dynamic mechanical analysis (FIG. 3 c) and elasticity test (FIG. 3 d).
As can be seen by UV-visible near infrared absorption spectroscopy, MLH-1 has a light absorbance of 75.97% for wavelengths of 250-2500nm (FIG. 4 a). Under the irradiation of standard sunlight, the evaporation rate of the photo-thermal evaporation system consisting of MLH-1 can reach 0.96kg m -2 h -1 (FIG. 4 b) the photo-thermal conversion efficiency was 47.4% (FIG. 4 c), which is significantly better than the evaporation performance of pure water.
Example 2
The preparation method of the photo-thermal-photochemical synergistic conversion hydrogel comprises the following steps:
(1) Weigh 0.5g Ti 3 AlC 2 (MAX) powder, soaking in NH 4 F (2.96 g) and HCl (20 mL) in a water bath, heating to 60 ℃, and stirring at a low speed for 48h; after the reaction is finished, centrifuging at 3000rpm, washing with deionized water, and repeating for several times until the pH value of the upper layer solution is 6; taking supernatant liquid, and freeze-drying for 12 hours to obtain MXene nano-sheets;
(2) Weighing 0.220g of MXene nano-sheet, 1.083g of lanthanum nitrate hexahydrate, 0.532g of strontium nitrate hexahydrate, 1.455g of cobalt nitrate hexahydrate and 3.92g of KOH, pouring into a three-port round-bottom flask, adding 80mL of deionized water, and stirring for 2 hours by ultrasonic waves; then, transferring the mixed solution to a hydrothermal reaction kettle (100 mL), and putting the mixture into an oven to perform solvothermal reaction for 48h at 180 ℃; subsequently, the solution was centrifuged at 8000rpm and washed with 75% ethanol and deionized water, and the operation was repeated 3 times, and the precipitate was freeze-dried to obtain La 0.5 Sr 0.5 CoO 3 -MXene complex (denoted LM-10);
(3) Weighing 10g of polyvinyl alcohol (PVA), pouring into a beaker, adding 90mL of hot deionized water, heating in a water bath at 100 ℃, and stirring at a high speed until the polyvinyl alcohol is completely dissolved to obtain 10wt% of polyvinyl alcohol solution;
(4) Adding 2mL of acetic acid to 98mL of deionized water to form an acetic acid solution; weighing 5g of Chitosan (CS), pouring into a beaker, adding 95mL of acetic acid solution, and stirring at a high speed to dissolve the solution to obtain 5wt% chitosan solution;
(5) Mixing 4g of polyvinyl alcohol solution with 1.4g of chitosan solution to form a precursor solution;
(6) At N 2 Under the protection of atmosphere, 18mg of LM-10 is added into the precursor solution, and the precursor solution is stirred at a low speed so as to be uniformly mixed; subsequently, glutaraldehyde (195. Mu.L, 4 wt%) and HCl (400. Mu.L, 1 mol/L) were slowly dropped into the above precursor solution in this order, and mixed and stirred to undergo a gel reaction, and the sample was completely gelled within 6 hours; repeatedly soaking the obtained gel in deionized water to remove hydrochloric acid; finally, the water on the gel surface is sucked by filter paper and is in a refrigerator(-24 ℃) freezing, thawing in warm water (40 ℃) and repeating the freeze-thaw operation 10 times, a hydrogel material (designated MLH-2) was obtained (FIG. 1).
As is evident from the transmission electron microscope image (FIG. 2 a) and the X-ray diffraction pattern of LM-10 (FIG. 2 c), la in LM-10 0.5 Sr 0.5 CoO 3 Nanoparticles were grown successfully on MXene nanoplatelets. The microporous framework of the MLH-2 surface was found by characterization of the hydrogel after lyophilization treatment by scanning electron microscopy (FIG. 2 b).
MLH-2 exhibits excellent hydrophilicity as tested by saturation moisture content (FIG. 3 a) and hydrogel surface contact angle (FIG. 3 b). Through dynamic mechanical analysis and elasticity test, MLH-2 has excellent mechanical strength and elasticity compared with MLH-1.
As can be seen from the analysis of the ultraviolet-visible-near infrared absorption spectrum, the MLH-1 has better absorption capacity to the spectrum with the wavelength of 250-2500nm, and the absorption rate is 94.13% (figure 4 a). Compared with other hydrogel systems under the irradiation of standard sunlight, the photo-thermal evaporation system composed of MLH-2 has the most excellent photo-thermal evaporation characteristic, and the evaporation rate can reach 2.73kg m - 2 h -1 (FIG. 4 b) and the photo-thermal conversion efficiency was 92.3% (FIG. 4 c).
Under the irradiation of a light source of a solar simulator with an AM1.5 optical filter, using the model shown in FIG. 5a as a photo-thermal purification device and MLH-2 as a photo-thermal material, photo-thermally evaporating seawater and alkaline wastewater containing heavy metals, dyes and strong acids, and collecting condensed water. The concentration, pH value and composition of each ion in the water before and after purification are tested by inductively coupled plasma-mass spectrometry (ICP-MS), pH meter, ultraviolet-visible spectrum and the like, the purification effect is shown in figure 5, the characteristic absorption peak of dye (methyl orange and methylene blue) in the purified water collected after photo-thermal evaporation treatment completely disappears, the pH value of the water is close to neutral, pb 2+ ，Cu 2+ ，Zn 2+ ，Na + The ion concentration meets the drinking water standard regulated by the world health organization.
And carrying out photocatalytic degradation test on the tetracycline by using an XPA system photochemical reactor. 40mg of LM-10 photocatalyst was added to a tetracycline solution (TC, 10mg/L,40 mL) and stirred under dark conditions for 60min to reach adsorption equilibrium, and then the reaction vessel was placed in a water tank surrounded by circulating water. Under the two conditions of circulating water and non-circulating water, the TC concentration was measured at intervals of 30min by using an ultraviolet-visible spectrophotometer, and the photodegradation performance obtained is shown in FIG. 6. Under the condition of non-circulating water, the heat generated by the photo-heat causes the temperature of the photodegradation environment to rise, the photodegradation performance is obviously improved, and the LM-10 has the best photodegradation performance and excellent circulating stability, and the photodegradation rate can reach 97 percent.
Example 3
The preparation method of the photo-thermal-photochemical synergistic conversion hydrogel comprises the following steps:
(1) Weigh 0.5g Ti 3 AlC 2 (MAX) powder, soaking in NH 4 F (2.96 g) and HCl (20 mL) in a water bath, heating to 60 ℃, and stirring at a low speed for 48h; after the reaction is finished, centrifuging at 3000rpm, washing with deionized water, and repeating for several times until the pH value of the upper layer solution is 6; taking supernatant liquid, and freeze-drying for 12 hours to obtain MXene nano-sheets;
(2) Weighing 0.110g of MXene nano-sheet, 1.083g of lanthanum nitrate hexahydrate, 0.532g of strontium nitrate hexahydrate, 1.455g of cobalt nitrate hexahydrate and 3.92g of KOH, pouring into a three-port round-bottom flask, adding 80mL of deionized water, and stirring for 2 hours by ultrasonic waves; then, transferring the mixed solution to a hydrothermal reaction kettle (100 mL), and putting the mixture into an oven to perform solvothermal reaction for 48h at 180 ℃; subsequently, the solution was centrifuged at 8000rpm and washed with 75% ethanol and deionized water, and the operation was repeated 3 times, and the precipitate was freeze-dried to obtain La 0.5 Sr 0.5 CoO 3 -MXene complex (denoted LM-20);
(3) Weighing 10g of polyvinyl alcohol (PVA), pouring into a beaker, adding 90mL of hot deionized water, heating in a water bath at 100 ℃, and stirring at a high speed until the polyvinyl alcohol is completely dissolved to obtain 10wt% of polyvinyl alcohol solution;
(4) Adding 2mL of acetic acid to 98mL of deionized water to form an acetic acid solution; weighing 5g of Chitosan (CS), pouring into a beaker, adding 95mL of acetic acid solution, and stirring at a high speed to dissolve the solution to obtain 5wt% chitosan solution;
(5) Mixing 4g of polyvinyl alcohol solution with 1.4g of chitosan solution to form a precursor solution;
(6) At N 2 Under the protection of atmosphere, 18mg of LM-20 is added into the precursor solution, and the precursor solution is stirred at a low speed so as to be uniformly mixed; subsequently, glutaraldehyde (195. Mu.L, 4 wt%) and HCl (400. Mu.L, 0.1 wt%) were slowly dropped into the above precursor solution in this order, and mixed and stirred to undergo a gel reaction, and the sample was completely gelled within 6 hours; repeatedly soaking the obtained gel in deionized water to remove hydrochloric acid; finally, the water on the gel surface was sucked dry with filter paper and frozen in a refrigerator (-24 ℃) and thawed in warm water (40 ℃) and the freeze-thaw operation was repeated 10 times to obtain a hydrogel material (denoted as MLH-3) (FIG. 1).
As is evident from the transmission electron microscope image (FIG. 2 a) and the X-ray diffraction pattern of LM-20 (FIG. 2 c), la in LM-20 0.5 Sr 0.5 CoO 3 Nanoparticles were grown successfully on MXene nanoplatelets.
MLH-2 exhibits a better hydrophilicity by saturation of the water content (FIG. 3 a).
As can be seen from the analysis of the ultraviolet-visible-near infrared absorption spectrum, the MLH-1 has better absorption capacity to the spectrum with the wavelength of 250-2500nm, and the absorption rate is 94.55 percent (figure 4 a). Under the irradiation of standard sunlight, the photo-thermal evaporation system composed of MLH-3 shows good photo-thermal evaporation characteristics, and the evaporation rate can reach 2.59kg m -2 h -1 (FIG. 4 b) and the light-to-heat conversion efficiency was 88.9% (FIG. 4 c).
And carrying out photocatalytic degradation test on the tetracycline by using an XPA system photochemical reactor. 40mg of LM-20 photocatalyst was added to a tetracycline solution (TC, 10mg/L,40 mL) and stirred under dark conditions for 60min to reach adsorption equilibrium, and then the reaction vessel was placed in a water tank surrounded by circulating water. Under the two conditions of circulating water and non-circulating water, the TC concentration was measured at intervals of 30min by using an ultraviolet-visible spectrophotometer, and the photodegradation performance obtained is shown in FIG. 6. Under the condition of non-circulating water, the heat generated by the photo-heat causes the temperature of the photodegradation environment to rise, the photodegradation performance of LM-20 is obviously improved, and the LM-20 has better photodegradation performance and the photodegradation rate can reach 96 percent.
Example 4
The preparation method of the photo-thermal-photochemical synergistic conversion hydrogel comprises the following steps:
(1) Weigh 0.5g Ti 3 AlC 2 (MAX) powder, soaking in NH 4 F (2.96 g) and HCl (20 mL) in a water bath, heating to 60 ℃, and stirring at a low speed for 48h; after the reaction is finished, centrifuging at 3000rpm, washing with deionized water, and repeating for several times until the pH value of the upper layer solution is 6; taking supernatant liquid, and freeze-drying for 12 hours to obtain MXene nano-sheets;
(2) Weighing 10g of polyvinyl alcohol (PVA), pouring into a beaker, adding 90mL of hot deionized water, heating in a water bath at 100 ℃, and stirring at a high speed until the polyvinyl alcohol is completely dissolved to obtain 10wt% of polyvinyl alcohol solution;
(3) Adding 2mL of acetic acid to 98mL of deionized water to form an acetic acid solution; weighing 5g of Chitosan (CS), pouring into a beaker, adding 95mL of glacial acetic acid solution, and stirring at a high speed to dissolve the solution to obtain 5wt% chitosan solution;
(4) Mixing 4g of polyvinyl alcohol solution with 1.4g of chitosan solution to form a precursor solution;
(5) At N 2 Under the protection of atmosphere, 18mg of MXene is added into the precursor solution, and the mixture is stirred at a low speed so as to be uniformly mixed; subsequently, glutaraldehyde (195. Mu.L, 4 wt%) and HCl (400. Mu.L, 0.1 wt%) were slowly dropped into the above precursor solution in this order, and mixed and stirred to undergo a gel reaction, and the sample was completely gelled within 6 hours; repeatedly soaking the obtained gel in deionized water to remove hydrochloric acid; finally, the water on the gel surface was sucked dry with filter paper and frozen in a refrigerator (-24 ℃) and thawed in warm water (40 ℃) and the freeze-thaw operation was repeated 10 times, to obtain a hydrogel material (denoted as MH-MXene) (fig. 1).
By saturation of the water content (FIG. 3 a), MH-MXene exhibits a better hydrophilicity.
As can be seen from the analysis of the ultraviolet visible near infrared absorption spectrum, the MH-MXene has better absorption capacity to the spectrum with the wavelength of 250-2500nm, and the absorption rate is 93.54 percent (figure 4 a). Under standard sunlight irradiation, consists of MH-MXeneThe photo-thermal evaporation system has good photo-thermal evaporation characteristic, and the evaporation rate can reach 2.26kg m -2 h -1 (FIG. 4 b) and the photo-thermal conversion efficiency was 81.9% (FIG. 4 c).
And carrying out photocatalytic degradation test on the tetracycline by using an XPA system photochemical reactor. 40mg of MXene photocatalyst was added to a tetracycline solution (TC, 10mg/L,40 mL) and stirred under dark-field conditions for 60min to reach adsorption equilibrium, and then the reaction vessel was placed in a water tank surrounded by circulating water. Under the two conditions of circulating water and non-circulating water, the TC concentration was measured at intervals of 30min by using an ultraviolet-visible spectrophotometer, and the photodegradation performance obtained is shown in FIG. 6. Under the condition of non-circulating water, the photo-generated heat enables the temperature of the photodegradation environment to rise, the photodegradation performance of MXene is obviously improved, the LM-20 shows poorer photodegradation performance, and the photodegradation rate can only reach 64%.
Example 5
The preparation method of the photo-thermal-photochemical synergistic conversion hydrogel comprises the following steps:
(1) 1.083g lanthanum nitrate hexahydrate, 0.532g strontium nitrate hexahydrate, 1.455g cobalt nitrate hexahydrate and 3.92g KOH are weighed and poured into a three-neck round bottom flask, 80mL deionized water is added, and ultrasonic stirring is carried out for 2 hours; then, transferring the mixed solution to a hydrothermal reaction kettle (100 mL), and putting the mixture into an oven to perform solvothermal reaction for 48h at 180 ℃; subsequently, the solution was centrifuged at 8000rpm and washed with 75% ethanol and deionized water, and the operation was repeated 3 times, and the precipitate was freeze-dried to obtain La 0.5 Sr 0.5 CoO 3 A nanoparticle;
(2) Weighing 10g of polyvinyl alcohol (PVA), pouring into a beaker, adding 90mL of hot deionized water, heating in a water bath at 100 ℃, and stirring at a high speed until the polyvinyl alcohol is completely dissolved to obtain 10wt% of polyvinyl alcohol solution;
(3) Adding 2mL of acetic acid to 98mL of deionized water to form an acetic acid solution; weighing 5g of Chitosan (CS), pouring into a beaker, adding 95mL of glacial acetic acid solution, and stirring at a high speed to dissolve the solution to obtain 5wt% chitosan solution;
(4) Mixing 4g of polyvinyl alcohol solution with 1.4g of chitosan solution to form a precursorA bulk solution; at N 2 Under the protection of atmosphere, 18mg of La 0.5 Sr 0.5 CoO 3 Adding the mixture into the precursor solution, stirring at a low speed, and uniformly mixing; subsequently, glutaraldehyde (195. Mu.L, 4 wt%) and HCl (400. Mu.L, 0.1 wt%) were slowly dropped into the above solutions in this order, and the mixture was stirred to undergo a gel reaction, and the sample was completely gelled within 6 hours; repeatedly soaking the obtained gel in deionized water to remove hydrochloric acid; finally, the water on the gel surface was sucked dry with filter paper and frozen in a refrigerator (-24 ℃) and thawed in warm water (40 ℃) and the freeze-thaw operation was repeated 10 times, to obtain a hydrogel material (denoted as LH-LSC) (fig. 1).
LH-LSC exhibits a better hydrophilicity by saturation of the water content (FIG. 3 a).
As can be seen from the UV-visible near-infrared absorption spectroscopy analysis, LH-LSC has excellent absorption capacity for the spectrum with the wavelength of 250-2500nm and the absorption rate is 94.70% (FIG. 4 a). Under the irradiation of standard sunlight, a photo-thermal evaporation system consisting of LH-LSC shows good photo-thermal evaporation characteristics, and the evaporation rate can reach 2.24kg m -2 h -1 (FIG. 4 b) and the photo-thermal conversion efficiency was 81.2% (FIG. 4 c).
And carrying out photocatalytic degradation test on the tetracycline by using an XPA system photochemical reactor. 40mg of LSC photocatalyst was added to a tetracycline solution (TC, 10mg/L,40 mL) and stirred under dark conditions for 60min to reach adsorption equilibrium, and the reaction vessel was placed in a water tank surrounded by circulating water. Under the two conditions of circulating water and non-circulating water, the TC concentration was measured at intervals of 30min by using an ultraviolet-visible spectrophotometer, and the photodegradation performance obtained is shown in FIG. 6. Under the condition of non-circulating water, the heat generated by the photo-heat enables the temperature of the photodegradation environment to rise, the photodegradation performance of the LSC is obviously improved, the LSC has better photodegradation performance, and the photodegradation rate can reach 91%.
Claims (5)
1. The application of the photo-thermal-photochemical synergistic conversion hydrogel material in the photocatalytic degradation of tetracycline pollutants is characterized in that the hydrogel material is prepared by combining a photo-thermal photocatalyst with an interpenetrating network polymer of chitosan and polyvinyl alcoholA photo-thermal synergistic photocatalytic degradable hydrogel material; the photo-thermal photocatalyst is a two-dimensional MXene sheet and nano La 0.5 Sr 0.5 CoO 3 Particles or La 0.5 Sr 0.5 CoO 3 -an MXene composite; the method comprises the following steps:
(1) Respectively preparing a polyvinyl alcohol aqueous solution, a chitosan aqueous solution, a glutaraldehyde solution and a hydrochloric acid solution;
(2) Mixing the polyvinyl alcohol aqueous solution obtained in the step (1) with chitosan aqueous solution to form a precursor solution;
(3) At N 2 Under the protection of atmosphere, adding the photo-thermal photocatalyst into the precursor solution, and stirring at a low speed to uniformly mix the precursor solution; then, slowly dripping glutaraldehyde solution and hydrochloric acid solution into the precursor solution, mixing and stirring to perform gel reaction; repeatedly soaking the obtained gel in deionized water to remove hydrochloric acid after the sample is completely gelled;
(4) And sucking the water on the surface of the gel by using filter paper, freezing in a refrigerator, thawing in warm water, and repeating the freezing-tempering operation for a plurality of times to obtain the hydrogel material.
2. The use according to claim 1, wherein the aqueous polyvinyl alcohol solution is: adding polyvinyl alcohol with the alcoholysis degree of 87.0-89.0% into hot deionized water according to the mass concentration of 10wt%, heating in a water bath at 100 ℃, and stirring at a high speed until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution.
3. The use according to claim 1, wherein chitosan is added to 2wt% acetic acid solution at a mass concentration of 5% wt%, and the mixture is stirred at high speed until the chitosan is completely dissolved, to obtain an aqueous chitosan solution.
4. The use according to claim 1, wherein the concentration of the hydrochloric acid solution is 1mol/L and the mass concentration of the glutaraldehyde solution is 4%.
5. The use according to claim 1, wherein the aqueous polyvinyl alcohol solution, the aqueous chitosan solution and the photo-thermal photocatalyst are mixed in a weight ratio of 4:1.4:0.018, and 3.25wt% glutaraldehyde solution and 6.5wt% hydrochloric acid solution are added.
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