CN114835163B - Novel tungsten sulfide photo-thermal material for water purification and preparation and application thereof - Google Patents
Novel tungsten sulfide photo-thermal material for water purification and preparation and application thereof Download PDFInfo
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
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- C01P2004/32—Spheres
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- 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
- Y02A20/124—Water desalination
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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
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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
Abstract
The invention discloses a novel tungsten sulfide photo-thermal material for water quality purification, and preparation and application thereof. Specifically, the method takes ammonium tungstate and thiourea as precursors, takes oleylamine as a solvent, and synthesizes W in the shape of flower-like nanospheres in one step by controlling reaction conditions 2 S 3 The particle size of the photo-thermal material is 200-250 nm. W prepared by the application 2 S 3 The self-specific metalloid characteristic of the photo-thermal material not only ensures that the material has ultra-wide wavelength absorption characteristic, but also has higher photo-thermal conversion performance. The flexible film and gel prepared based on the nano material can be 1.5 kg.m even under the high salinity seawater treatment environment ‑2 ·h ‑1 The evaporation work of seawater is completed at the speed, and the evaporation efficiency is up to 90%; therefore, the tungsten sulfide photo-thermal material disclosed by the application has extremely wide application prospect in the field of sea water desalination.
Description
Technical Field
The invention relates to the technical field of nano materials and catalysis, in particular to preparation and application of a novel tungsten sulfide photo-thermal material for water quality purification.
Background
The lack of water resources is one of the most serious problems facing the society today, water is a life source, and in order to realize the sustainable development, people are striving to find a technical solution for solving the shortage of water resources. The sea water desalination is a process for producing fresh water by utilizing sea water desalination, is an open source increment technology for realizing water resource utilization, can increase the total amount of fresh water, is not influenced by space time and climate, has huge sea water reserves, and is one of the most abundant natural resources on the earth. Thus, desalination of sea water has become an ideal strategy for alleviating the severe problem of shortage of fresh water.
Currently, in order to achieve sea water desalination, many technical means such as reverse osmosis, membrane filtration, thermal distillation, etc. have been developed. However, technologies such as membrane filtration and thermal distillation are realized by relying on intensive energy consumption, and the defects of high equipment maintenance cost and high product price generally exist, and the problems affect the energy sustainability and bring about serious environmental problems, so that the development requirements of the current society are not met. The demand for low energy, low cost, environmentally friendly sea water desalination technology is increasing. Therefore, the technology of solar energy driven evaporation is explored by the skilled person, the technology only needs to use solar light energy and seawater to produce fresh water, and fresh water resources with high quality and low price can be obtained, so the technology has the characteristics of energy conservation and environmental protection, and has wide application prospect in the field of seawater desalination.
One key factor in the efficient operation of solar-driven desalination and evaporation technology is whether the photo-thermal conversion material has excellent performance, and the effect depends on whether the photo-thermal conversion material can convert light energy into heat energy required for producing steam.
At present, researches on photothermal conversion materials are mainly focused on metal materials, carbon materials and semiconductor materials. The metal material has many movable electrons for heat conversion and unique plasma resonance effect, but has high overall cost and is not suitable for large-scale use. The conventional semiconductor material has a wide energy gap, and needs to absorb incident light (such as ultraviolet light) with high energy to excite electrons and release heat in the process of falling back to the ground state, so that the use field is limited.
The transition metal sulfide has been widely focused on the advantages of simple preparation process, low cost, strong chemical stability, adjustable band gap and the like, and Chinese patent CN 108080005B discloses a preparation method of high catalytic activity electrocatalyst 1T 'phase tungsten sulfide, which comprises the steps of dissolving ammonium tungstate and thiourea in a high boiling point solvent, heating to 100-120 ℃ under the protection of inert gas, reacting at 280-320 ℃ and naturally cooling to room temperature, adding ethanol, filtering to obtain a filter cake, washing and drying the filter cake to obtain 1T' phase WS 2 . Although the material has higher conductivity and better hydrogen evolution reaction activity, WS 2 The similar materials generally have the commonality of wider energy gaps and narrow absorption wavelength range, and can limit the application of the similar materials as photothermal conversion materials in the field of sea water desalination.
Therefore, if a novel transition metal sulfide photo-thermal material with metalloid characteristics and wide spectrum absorption can be designed, beneficial assistance can be provided for efficient solar seawater desalination.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a novel tungsten sulfide photo-thermal material for water quality purification, and preparation and application thereof.
The technical scheme disclosed by the invention is as follows: the preparation method of the novel tungsten sulfide photo-thermal material for water quality purification specifically comprises the following steps:
(1) Adding ammonium tungstate and thiourea into oleylamine, wherein the molar ratio of W to S in the ammonium tungstate and the thiourea is 1:1.5-1:2, and adding the mixture into a reactor for constant-temperature magnetic stirring;
(2) Heating the system to 100-120 ℃, vacuumizing, blowing inert protective gas into the system, and circulating the vacuumizing and inflating process for several times;
(3) Heating the system to 300-320 ℃, preserving heat for 2-3 hours, cooling to room temperature, and filtering;
(4) Washing the filter material obtained in the previous step with cyclohexane and absolute ethyl alcohol, centrifuging, and collecting precipitate;
(5) Placing the precipitate in a vacuum drying oven for drying to obtain W 2 S 3 A nanomaterial.
Further, in the step (1), the temperature of the magnetic stirring process is 40-60 ℃.
Further, in the step (2), the times of vacuumizing and blowing in the inert gas are 3-5 times, and each time is 5-10 minutes.
Further, in the step (4), the volume ratio of the cyclohexane to the absolute ethyl alcohol is 1:3-1:4.
Further, in the step (5), the temperature of the vacuum drying is 50-60 ℃.
The novel tungsten sulfide photo-thermal material prepared by the method has uniform appearance, presents a flower-like nanosphere structure and has the particle size of 200-250 nm.
Furthermore, the novel tungsten sulfide photo-thermal material has metal-like light absorption characteristics and wide-wavelength absorption characteristics from ultraviolet to near infrared.
The novel tungsten sulfide photo-thermal material can be applied to the field of sea water desalination.
A flexible film loaded with novel tungsten sulfide photo-thermal material is prepared by the novel tungsten sulfide photo-thermal material, and the specific preparation process is as follows:
s1, washing a flexible substrate;
s2, W is taken as 2 S 3 Mixing the nano materials in a mixed solution containing naphthol, deionized water and absolute ethyl alcohol to prepare a dispersion liquid;
s3, carrying out ultrasonic treatment on the dispersion liquid obtained in the step S2;
s4, immersing the flexible substrate into the dispersion liquid, drying in a vacuum oven, and repeating the immersion liquid drying process for a plurality of timesUp to W 2 S 3 The nano material is fully coated on the surface of the flexible substrate, thus finishing the preparation of the film material.
Further, in step S2, W 2 S 3 The dosage of the nano material is 5-20 mg, the weight percentage of naphthol is 5wt%, the dosage is 20-80 mu L, the dosage of deionized water is 0.8-3.2 mL, and the dosage of absolute ethyl alcohol is 0.2-0.8 mL.
Further, in the step S3, the ultrasonic power is 200-300W, the temperature is 25-30 ℃ and the time is 40-60 min.
The beneficial effects of the invention are as follows:
1. the novel tungsten sulfide photo-thermal material prepared by the method has the characteristic of metal-like light absorption, can realize strong absorption of wide wavelength from ultraviolet to near infrared, can raise the water temperature to a higher level in a short time under NIR irradiation, has higher photo-thermal conversion performance, and has better application prospect in the field of sea water desalination;
2. the novel tungsten sulfide photo-thermal material prepared by the method has a unique micro-nano structure, the surface of the novel tungsten sulfide photo-thermal material shows the characteristics of hydrophilicity and hydrophobicity, the unique morphology structure can enable seawater to be fully contacted with the photo-thermal material, the technical effect of adjustable water content and transmission rate is achieved in the seawater desalination process, the water transmission of the whole structure is promoted, the evaporation enthalpy is reduced, and the evaporation conversion efficiency of the seawater can be effectively improved;
3. film and gel materials prepared based on the novel tungsten sulfide photothermal materials disclosed herein can be used at 1.5 kg.m even though high salinity seawater is treated -2 ·h -1 The seawater evaporation work is completed at the speed, and the solar evaporation efficiency is up to 90%;
4. the novel tungsten sulfide photo-thermal material disclosed by the application is simple in preparation process, high in preparation efficiency, high in selectivity, low in cost and wide in application prospect, and the prepared novel tungsten sulfide nano material is uniform in appearance, is of a flower-shaped nano sphere structure and has a diameter of 200-250 nm.
Drawings
FIG. 1 is a novel W prepared in example 1 2 S 3 SEM images of nanomaterials;
FIG. 2 is a novel W prepared in example 1 2 S 3 TEM image of nanomaterial;
FIG. 3 is a novel W prepared in example 1 2 S 3 HRTEM picture and atomic structure model picture of the nanometer material;
FIG. 4 is a novel W prepared in example 1 2 S 3 Experimental XRD and simulated XRD patterns of the nanomaterial;
FIG. 5 is a surface property graph of the novel tungsten sulfide thin film material prepared in application example 1 (a) and application comparative example 1 (b);
FIG. 6 is a W prepared in example 1 2 S 3 Ultraviolet absorption and photo-thermal conversion performance of the aqueous solution of the nano material;
FIG. 7 is a morphology graph of the flexible hydrogel (b) loaded with the novel tungsten sulfide photo-thermal material and the pure PVA hydrogel (a) prepared in application example 2;
FIG. 8 is a photo-thermal property diagram of the flexible hydrogel loaded with the novel tungsten sulfide photo-thermal material prepared in application examples 2 and 3;
FIG. 9 is a photograph of an integrated seawater desalination plant made of a novel tungsten sulfide flexible film material;
FIG. 10 is a graph showing the performance of sea water desalination using a novel tungsten sulfide flexible film material.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit of the invention are intended to be within the scope of the present invention.
Example 1: preparation of novel tungsten sulfide photo-thermal material
(1) 51.007mg of ammonium tungstate, 22.836mg of thiourea (the ratio of W to S is 1:1.5) and 7mL of oleylamine are mixed and put into a reactor, and magnetic stirring is carried out uniformly at a constant temperature of 60 ℃;
(2) Heating the system to 120 ℃, vacuumizing, and then blowing inert protective gas N into the system 2 Vacuumizing and filling N 2 The steps are circulated for 3 times, each time for 5 minutes;
(3) Heating the system to 300 deg.C, maintaining for 2 hr, naturally cooling to room temperature, and filtering to obtain W 2 S 3 A nanomaterial;
(4) And (3) mixing the W obtained in the step (3) with a mixed solution of cyclohexane and absolute ethyl alcohol in a volume ratio of 1:3 2 S 3 Washing the nano material, centrifuging for 10min under the condition of 8500rpm, and collecting the obtained precipitate;
(5) The precipitate was placed in a vacuum oven and dried overnight at 60 ℃ and the dried product was collected.
FIGS. 1 and 2 show novel W's obtained in this example 2 S 3 SEM and TEM photographs of nanomaterials, from which it can be seen that W 2 S 3 The shape of the nano material is a highly uniform flower-shaped nano sphere, and the particle size is about 200-250 nm.
FIG. 3 shows a novel W produced in this example 2 S 3 HRTEM photograph (a small image and b small image) and atomic structure model image (c small image is W) of nano material 2 S 3 Atomic structure perspective view, d small drawing is W 2 S 3 Atomic structure side view, e panel W 2 S 3 Side view of atomic structure after removal of S atoms).
FIG. 4 shows a novel W produced in this example 2 S 3 Experimental XRD patterns and simulated XRD patterns of the nanomaterial, from which it can be seen by comparison that the tungsten sulfide material prepared in the present example is a novel W 2 S 3 Structure is as follows.
Example 2: preparation of novel tungsten sulfide photo-thermal material
(1) 51.007mg of ammonium tungstate, 30.448mg of thiourea (the ratio of W to S is 1:2) and 7mL of oleylamine are mixed and put into a reactor, and the mixture is stirred uniformly by magnetic force at a constant temperature of 60 ℃;
(2) Heating the system to 120 ℃, vacuumizing, and then blowing inert protective gas N into the system 2 Vacuumizing and filling N 2 The steps are circulated for 3 times, each time for 5 minutes;
(3) Heating the system to 300 deg.C, maintaining for 2 hr, naturally cooling to room temperature, and filtering to obtain W 2 S 3 A nanomaterial;
(4) And (3) mixing the W obtained in the step (3) with a mixed solution of cyclohexane and absolute ethyl alcohol in a volume ratio of 1:3 2 S 3 Washing the nano material, centrifuging for 10min under the condition of 8500rpm, and collecting the obtained precipitate;
(5) The precipitate was placed in a vacuum oven and dried overnight at 60 ℃ and the dried product was collected.
Example 3: preparation of novel tungsten sulfide photo-thermal material
(1) 51.007mg of ammonium tungstate, 22.836mg of thiourea (the ratio of W to S is 1:1.5) and 7mL of oleylamine are mixed and put into a reactor, and magnetic stirring is carried out uniformly at a constant temperature of 60 ℃;
(2) Heating the system to 120 ℃, vacuumizing, and then blowing inert protective gas N into the system 2 Vacuumizing and filling N 2 The steps are circulated for 3 times, each time for 5 minutes;
(3) Heating the system to 320 deg.c, maintaining for 2 hr, cooling to room temperature, and filtering to obtain W 2 S 3 A nanomaterial;
(4) And (3) mixing the W obtained in the step (3) with a mixed solution of cyclohexane and absolute ethyl alcohol in a volume ratio of 1:3 2 S 3 Washing the nano material, centrifuging for 10min under the condition of 8500rpm, and collecting the obtained precipitate;
(5) The precipitate was placed in a vacuum oven and dried overnight at 60 ℃ and the dried product was collected.
Example 4: preparation of novel tungsten sulfide photo-thermal material
(1) 51.007mg of ammonium tungstate, 30.448mg of thiourea (the ratio of W to S is 1:2) and 7mL of oleylamine are mixed and put into a reactor, and the mixture is stirred uniformly by magnetic force at a constant temperature of 60 ℃;
(2) Heating the system to 120 ℃, vacuumizing, and then blowing inert protective gas N into the system 2 Vacuumizing and filling N 2 The steps are circulated for 3 times, each time for 5 minutes;
(3) Heating the system to 320 deg.c, maintaining for 2 hr, cooling to room temperature, and filtering to obtain W 2 S 3 A nanomaterial;
(4) With cyclohexane in a volume ratio of 1:3Mixing the solution of alkane and absolute ethyl alcohol to obtain W in the step (3) 2 S 3 Washing the nano material, centrifuging for 10min under the condition of 8500rpm, and collecting the obtained precipitate;
(5) The precipitate was placed in a vacuum oven and dried overnight at 60 ℃ and the dried product was collected.
Example 5: preparation of novel tungsten sulfide photo-thermal material
The difference between this example and example 1 is that the heating and heat-preserving time in step (3) is 3h, and the rest of the process is the same.
Example 6: preparation of novel tungsten sulfide photo-thermal material
The difference between this example and example 2 is that the heating and holding time in step (3) is 3h, and the rest of the process is the same.
Example 7: preparation of novel tungsten sulfide photo-thermal material
The difference between this example and example 3 is that the heating and holding time in step (3) is 3h, and the rest of the process is the same.
Example 8: preparation of novel tungsten sulfide photo-thermal material
The difference between this example and example 4 is that the heating and heat-preserving time in step (3) is 3 hours, and the rest of the process is the same.
Application example 1: preparation of flexible film loaded with novel tungsten sulfide photo-thermal material
The flexible substrate selected in the preparation of the flexible film can be carbon cloth, carbon paper, foam nickel and the like, the specific types are not limited, and pure hydrophobic carbon cloth (CFC) is selected as the flexible substrate in the application example; the preparation process comprises the following steps:
(1) Washing pure hydrophobic carbon cloth (CFC) with absolute ethyl alcohol for a plurality of times, and carrying out ultrasonic treatment in the washing process;
(2) 5.0mg of W prepared in example 1 was taken 2 S 3 Nanomaterial mix in a mixed solution containing 20 μl naphthol (Nafion, 5 wt%), 800 μl deionized water and 200 μl absolute ethanol to prepare nanomaterial dispersion;
(3) Carrying out ultrasonic treatment on the dispersion liquid obtained in the previous step, wherein the ultrasonic power is 200W, the temperature is 25 ℃, and the time is 45min;
(4) Immersing pure hydrophobic carbon cloth (CFC) in the dispersion liquid treated by ultrasonic treatment in the step (3), drying in a vacuum oven at 60 ℃, repeating the immersion drying process for several times until W 2 S 3 The nano material is fully coated on the surface of the carbon cloth.
Comparative example 1 was applied: bulk WS 2 Preparation of CFC flexible films
(1) Washing pure hydrophobic carbon cloth (CFC) with absolute ethyl alcohol for a plurality of times, and carrying out ultrasonic treatment in the washing process;
(2) Block WS at a concentration of 1mg/mL at 190. Mu.L 2 (Bulk WS 2 ) Preparation of Bulk WS by adding 10. Mu.L NAFATION (5 wt%) to a dispersion purchased from Nanjing pasturaceae, nanotechnology Co., ltd 2 A dispersion;
(3) Carrying out ultrasonic treatment on the dispersion liquid obtained in the previous step, wherein the ultrasonic power is 200W, the temperature is 25 ℃, and the time is 45min;
(4) Immersing pure hydrophobic carbon cloth (CFC) in the dispersion liquid treated by ultrasonic treatment in the step (3), drying in a vacuum oven at 60 ℃, and repeating the immersion drying process for several times until Bulk WS 2 Fully coating the carbon cloth surface.
Comparative example 2 was applied: stripping WS 2 Preparation of CFC flexible films
(1) Washing pure hydrophobic carbon cloth (CFC) with absolute ethyl alcohol for a plurality of times, and carrying out ultrasonic treatment in the washing process;
(2) Stripping WS at a concentration of 1mg/mL at 190. Mu.L 2 Preparation of peeled WS by adding 10. Mu.L Nafion (5 wt%) to the dispersion purchased from Nanjing, nanjiake, nanotechnology Co., ltd 2 A dispersion;
(3) Carrying out ultrasonic treatment on the dispersion liquid obtained in the previous step, wherein the ultrasonic power is 200W, the temperature is 25 ℃, and the time is 45min;
(4) Immersing pure hydrophobic carbon cloth (CFC) in the dispersion liquid treated by ultrasonic treatment in the step (3), drying in a vacuum oven at 60 ℃, repeating the immersion drying process for several times until WS is stripped 2 Fully coating the carbon cloth surface.
Application example 2: preparation of flexible hydrogel loaded with novel tungsten sulfide photo-thermal material
(1) Magnetic stirring was heated at 90 ℃ to dissolve 1.0g PVA-124 in 8mL deionized water;
(2) After cooling to room temperature, 2mL of W prepared in example 1 was added dropwise to the PVA solution prepared in the above step 2 S 3 Aqueous solutions of nanomaterials to produce precursor solutions, W 2 S 3 The concentration of the aqueous solution of the nano material is 1mg/mL;
(3) After stirring, the precursor solution was transferred to a mold, frozen at-20℃for 23 hours, and thawed at 25℃for 1 hour, and the freeze-thawing process was repeated three times to obtain a hydrogel W 2 S 3 NPs-PVA-1。
Application example 3: preparation of flexible hydrogel loaded with novel tungsten sulfide photo-thermal material
The application example differs from application example 2 only in that W used in step (2) 2 S 3 The concentration of the aqueous nanomaterial solution was 2mg/mL.
The hydrogel obtained is denoted as W 2 S 3 NPs-PVA-2。
Application example 4: preparation of flexible hydrogel loaded with novel tungsten sulfide photo-thermal material
The application example differs from application example 2 only in that W used in step (2) 2 S 3 The concentration of the aqueous nanomaterial solution was 4mg/mL.
The hydrogel obtained is denoted as W 2 S 3 NPs-PVA-3。
Correlation performance test
1) Surface property test of novel tungsten sulfide photo-thermal film
Mass transfer performance is an important consideration in evaluating sea water desalination materials. Macroscopically, the mass transfer effect is characterized by the gas precipitation capability of the surface of the material and the contact property of the aqueous solution and the surface of the material, and the process mainly occurs at a solid-liquid-gas three-phase interface. The surface wettability of the different tungsten sulfide photo-thermal films prepared in application example 1 and application comparative example 1 was tested, and the results are shown in fig. 5, wherein a plot is a surface characteristic diagram of the film material prepared in application example 1, and b plot is a surface characteristic diagram of the film material prepared in application comparative example 1; simplified stress analysis of single bubbles on the surface of the material shows that the adhesion force (Fa) plays a key role in bubble separation, compared with the surface of the Bulk tungsten sulfide photo-thermal film, the novel tungsten sulfide photo-thermal material film has the unique morphology structure that the seawater is in full contact with the photo-thermal material, and the characteristic that the seawater can be brought with adjustable water content and transmission rate in the seawater desalination process can promote the water transmission of the integral structure, reduce evaporation enthalpy and contribute to remarkably improving the seawater evaporation conversion efficiency.
2) Novel light and heat performance test of tungsten sulfide nano material
FIG. 6 is a drawing of W prepared in example 1 of the present invention 2 S 3 Ultraviolet absorption and photo-thermal conversion performance of the aqueous solution of the nano material; wherein the a panels show W at different concentrations 2 S 3 The aqueous solutions of photothermal materials have strong absorption in the ultraviolet to Near Infrared (NIR) region (C 1 、C 2 、C 3 W is denoted by 2 S 3 The concentration of the photo-thermal material aqueous solution is 0.05mg/mL, 0.1mg/mL and 0.2mg/mL respectively), and the material has the absorption characteristic of ultra-wide wavelength;
accordingly, the application of the sample in the aspect of photo-thermal conversion is continuously studied, in particular, the sample is dispersed in deionized water and irradiated by a 808nm laser, and the laser power and the irradiation time are respectively 1W/cm 2 And 10 minutes, the temperature of the novel tungsten sulfide photo-thermal material solution under the irradiation of a laser is recorded through an infrared camera, and the results are shown in b, c and d panels, and as can be seen from the b panel, when the concentration of the sample dispersion liquid is 1.0mg/mL, the temperature of the solution under the NIR radiation within 7 minutes can reach 76.9 ℃, so that the high-efficiency photo-thermal conversion performance of the novel tungsten sulfide photo-thermal material is shown. From the d plot, it can be seen that the temperature change of samples with different concentrations under the same irradiation conditions, and the temperature change also greatly increases with the increase of the sample concentration. When the sample concentration is 4mg/mL, the temperature of the solution may be raised to 98.3 ℃.
3) Photothermal performance test of novel tungsten sulfide photothermal flexible film/hydrogel material
The photo-thermal conversion performance of the flexible hydrogel loaded with the novel tungsten sulfide photo-thermal material prepared in application example 2 was tested in relation to the hydrogel made of pure PVA.
FIG. 7 is a morphology graph of the flexible hydrogel (b) loaded with the novel tungsten sulfide photo-thermal material and the pure PVA hydrogel (a) prepared in application example 2; as can be seen from fig. 7, the pure PVA hydrogel is colorless and transparent, while the hydrogel loaded with the novel tungsten sulfide photo-thermal material is black.
FIG. 8 shows a flexible hydrogel W loaded with a novel tungsten sulfide photo-thermal material prepared in application examples 2 and 3 2 S 3 NPs-PVA-1 and W 2 S 3 Photo-thermal performance map of NPs-PVA-2; as can be seen from the panels a and c in FIG. 8, the solar irradiance (100 mW cm -2 ) Under the condition, flexible hydrogel W loaded with novel tungsten sulfide photo-thermal material 2 S 3 NPs-PVA-2 can be heated to 205 ℃ within 4 minutes; as can be seen from panel b, the temperature rise of the flexible hydrogel loaded with tungsten sulfide photo-thermal material was more pronounced over 4 minutes compared to the pure PVA hydrogel, and with the W used 2 S 3 The hydrogel composite material can reach different equilibrium temperatures under simulated sunlight irradiation, and the overall trend of the hydrogel composite material is gradually increased along with the concentration.
4) Sea water desalination test by using novel tungsten sulfide photo-thermal flexible film material
Fig. 9 shows an integrated device for performing outdoor seawater desalination experiments under real sunlight.
The actual Wiggaisea water is utilized to evaluate the water purification production performance of the novel tungsten sulfide flexible photo-thermal film. System quality change data are collected, once an hour. As a result, as shown in FIG. 10, in the seawater purification system, the novel tungsten sulfide flexible photo-thermal film material evaporated seawater at a high and stable rate, the actual evaporation rate was 1.5 kg.m -2 ·h -1 The solar evaporation efficiency is as high as 90%, and the solar seawater evaporation performance is excellent.
The foregoing has outlined and described the basic principles, features, and advantages of the present invention. However, the foregoing is merely specific examples of the present invention, and the technical features of the present invention are not limited thereto, and any other embodiments that are derived by those skilled in the art without departing from the technical solution of the present invention are included in the scope of the present invention.
Claims (10)
1. The preparation method of the novel tungsten sulfide photo-thermal material for water quality purification is characterized by comprising the following steps of:
(1) Adding ammonium tungstate and thiourea into oleylamine, wherein the molar ratio of W to S in the ammonium tungstate and the thiourea is 1:1.5-1:2, and adding the mixture into a reactor for constant-temperature magnetic stirring;
(2) Heating the system to 100-120 ℃, vacuumizing, blowing inert protective gas into the system, and circulating the vacuumizing and inflating process for several times;
(3) Heating the system to 300-320 ℃, preserving heat for 2-3 hours, cooling to room temperature, and filtering;
(4) Washing the filter material obtained in the previous step with cyclohexane and absolute ethyl alcohol, centrifuging, and collecting precipitate;
(5) Placing the precipitate in a vacuum drying oven for drying to obtain W 2 S 3 A nanomaterial.
2. The method for preparing a novel tungsten sulfide photo-thermal material for water purification according to claim 1, wherein in the step (1), the temperature of the magnetic stirring process is 40-60 ℃.
3. The method for preparing a novel tungsten sulfide photo-thermal material for water purification according to claim 1, wherein in the step (2), the times of vacuumizing and blowing inert gas are 3-5 times, and each time is 5-10 min.
4. The method for preparing a novel tungsten sulfide photo-thermal material for water purification according to claim 1, wherein in the step (4), the volume ratio of cyclohexane to absolute ethyl alcohol is 1:3-1:4.
5. The method for preparing a novel tungsten sulfide photo-thermal material for water purification according to claim 1, wherein in the step (5), the temperature of vacuum drying is 50-60 ℃.
6. The novel tungsten sulfide photo-thermal material is characterized in that the novel tungsten sulfide photo-thermal material is prepared by the preparation method of the novel tungsten sulfide photo-thermal material for water purification according to any one of claims 1-5, the photo-thermal material is uniform in appearance, presents a flower-like nanosphere structure and has a particle size of 200-250 nm; the material has the characteristic of metal-like light absorption, and can realize wide-wavelength light absorption from ultraviolet to near infrared.
7. The application of the novel tungsten sulfide photo-thermal material in the field of sea water desalination as claimed in claim 6.
8. The flexible film loaded with the novel tungsten sulfide photo-thermal material is characterized in that the flexible film is prepared from the novel tungsten sulfide photo-thermal material according to claim 6, and the specific preparation process is as follows:
s1, washing a flexible substrate;
s2, W is taken as 2 S 3 Mixing the nano materials in a mixed solution containing naphthol, deionized water and absolute ethyl alcohol to prepare a dispersion liquid;
s3, carrying out ultrasonic treatment on the dispersion liquid obtained in the step S2;
s4, immersing the flexible substrate into the dispersion liquid, drying in a vacuum oven, and repeating the immersion liquid and drying process for several times until W 2 S 3 The nano material is fully coated on the surface of the flexible substrate, thus finishing the preparation of the film material.
9. The flexible film carrying a novel tungsten sulfide photo-thermal material according to claim 8, wherein in step S2, W 2 S 3 The dosage of the nano material is 5-20 mg, the weight percentage of naphthol is 5wt%, the dosage is 20-80 mu L, the dosage of deionized water is 0.8-3.2 mL, and the dosage of absolute ethyl alcohol is 0.2-0.8 mL.
10. The flexible film carrying a novel tungsten sulfide photo-thermal material according to claim 8, wherein in the step S3, the ultrasonic power is 200-300W, the temperature is 25-30 ℃ and the time is 40-60 min.
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