CN114835163A - Novel tungsten sulfide photo-thermal material for water quality purification and preparation and application thereof - Google Patents
Novel tungsten sulfide photo-thermal material for water quality purification and preparation and application thereof Download PDFInfo
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- 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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- 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
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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 photothermal material for water purification and preparation and application thereof. Particularly, ammonium tungstate and thiourea are used as precursors, oleylamine is used as a solvent, and W in the shape of flower-like nanospheres is synthesized in one step by controlling reaction conditions 2 S 3 The particle size of the photo-thermal material is 200-250 nm. W prepared herein 2 S 3 The special metal-like characteristics of the photo-thermal material not only enable the material to have the ultra-wide wavelength absorption characteristic, but also have high photo-thermal conversion performance. Flexible film and gel prepared based on nano materialEven under the environment of high-salinity seawater treatment, the water quality can be controlled to be 1.5 kg.m ‑2 ·h ‑1 The seawater evaporation work is finished at the speed of the evaporator, and the evaporation efficiency is as high as 90 percent; therefore, the tungsten sulfide photothermal material disclosed by the application has a very wide application prospect in the field of seawater 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 purification.
Background
The shortage of water resources is one of the most serious problems facing the society today, water is the source of life, and in order to realize sustainable development, people are trying to find a technical scheme for solving the shortage of water resources. The seawater desalination is a process for producing fresh water by utilizing seawater desalination, is an open source increment technology for realizing water resource utilization, can increase the total amount of fresh water, is not influenced by time, space and climate, has huge seawater reserve, and is one of the most abundant natural resources on the earth. Desalination of seawater has become an ideal strategy to alleviate the severe problem of fresh water shortage.
At present, many technical means such as reverse osmosis, membrane filtration, thermal distillation, etc. are developed for the purpose of seawater desalination. However, technologies such as membrane filtration and thermal distillation need to be realized by intensive energy consumption, and the defects of high equipment maintenance cost and high product price generally exist, and the problems affect the energy sustainability, bring about serious environmental problems and do not meet the development requirements of the current society. The demand for low-energy, low-cost, environmentally friendly seawater desalination technology is increasing day by day. Therefore, the technical personnel in the field explore the solar-driven evaporation technology, the technology only needs to utilize solar energy and seawater to produce fresh water, and can obtain high-quality and low-price fresh water resources, so that the technology has the characteristics of energy conservation and environmental protection, and has wide application prospect in the field of seawater desalination.
The key factor of efficient operation of the solar-driven seawater desalination evaporation technology is whether the photo-thermal conversion material has excellent performance, and the realization of the effect depends on whether the photo-thermal conversion material can efficiently convert light energy into heat energy required by steam production.
The current research on photothermal conversion materials has mainly focused on metal materials, carbon materials, and semiconductor materials. The metal material has many movable electrons for thermal conversion, has a unique plasmon resonance effect, but is high in overall cost and is not suitable for large-scale use. However, 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 emit heat in the process of falling back to the ground state, so that the use scene is limited.
The transition metal sulfide has 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 1T 'phase tungsten sulfide of a high catalytic activity electrocatalyst, which comprises the steps of dissolving ammonium tungstate and thiourea in a high boiling point solvent, heating to 120 ℃ under the protection of inert gas, reacting at 320 ℃ under 280 ℃ and naturally cooling to room temperature, adding ethanol, filtering to obtain a filter cake, washing and drying the filter cake to obtain the 1T' phase WS 2 . Although the material has higher conductivity and excellent hydrogen evolution reactivity, WS 2 The materials generally have the common characteristics of wider energy gap and narrow absorption wavelength range, and can limit the application of the materials as photothermal conversion materials in the field of seawater desalination.
Therefore, if a novel transition metal sulfide photothermal material with metal-like 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 photothermal material for water quality purification and preparation and application thereof.
The technical scheme disclosed by the invention is as follows: a preparation method of a novel tungsten sulfide photothermal material for water 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 to the thiourea is 1: 1.5-1: 2, putting the mixture into a reactor, and carrying out 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 processes for several times;
(3) heating the system to 300-320 ℃, preserving heat for 2-3 h, 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) putting the precipitate obtained in the previous step into a vacuum drying oven for drying treatment to obtain W 2 S 3 And (3) nano materials.
Further, in the step (1), the temperature in the magnetic stirring process is 40-60 ℃.
Further, in the step (2), the times of vacuumizing and blowing the inert gas are 3-5 times, and each time is 5-10 min.
Further, in the step (4), the volume ratio of cyclohexane to absolute ethyl alcohol is 1: 3-1: 4.
Further, in the step (5), the temperature of vacuum drying is 50-60 ℃.
The novel tungsten sulfide photothermal material prepared by the method is uniform in appearance, presents a flower-like nanosphere structure, and has a particle size of 200-250 nm.
Further, the novel tungsten sulfide photothermal material has a metalloid light absorption property and a broad wavelength absorption property in the ultraviolet to near infrared region.
The novel tungsten sulfide photothermal material can be applied to the field of seawater desalination.
A flexible film loaded with a novel tungsten sulfide photothermal material is prepared by using the novel tungsten sulfide photothermal material, and the specific preparation process is as follows:
s1, washing the flexible substrate;
s2, mixing W 2 S 3 The nanometer material is mixed in a mixed solution containing naphthol, deionized water and absolute ethyl alcohol to prepare dispersionLiquid;
s3, carrying out ultrasonic treatment on the dispersion liquid obtained in the S2;
s4, immersing the flexible substrate in the dispersion liquid, drying in a vacuum oven, and repeating the immersion drying process for several times until W 2 S 3 And (3) fully coating the nano material on the surface of the flexible substrate to finish 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 5 wt%, 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 step S3, the ultrasonic power is 200-300W, the temperature is 25-30 ℃, and the time is 40-60 min.
The invention has the beneficial effects that:
1. the novel tungsten sulfide photothermal material prepared by the method shows a special metalloid light absorption characteristic, can realize strong absorption in a wide wavelength range from ultraviolet to near infrared region, can raise the water temperature to a higher level in a short time by using an aqueous solution of the material under NIR irradiation, has higher photothermal conversion performance, and has a better application prospect in the field of seawater desalination;
2. the novel tungsten sulfide photothermal material prepared by the method has a unique micro-nano structure, the surface of the novel tungsten sulfide photothermal material shows a hydrophilic and gas-dispersing characteristic, the seawater can be fully contacted with the photothermal material due to the unique morphological structure, the technical effects of adjustable water content and transmission rate are formed in the seawater desalination process, the water transmission of the whole structure is promoted, the evaporation enthalpy is reduced, and the seawater evaporation conversion efficiency can be effectively improved;
3. the film and the gel material prepared based on the novel tungsten sulfide photothermal material disclosed by the application can treat seawater with high salinity by 1.5 kg.m -2 ·h -1 The seawater evaporation work is finished at the speed, and the solar evaporation efficiency reaches up to 90 percent;
4. the preparation process of the novel tungsten sulfide photothermal material disclosed by the application is simple, the preparation efficiency is high, the selectivity is high, the cost is low, the wide application prospect is achieved, the prepared novel tungsten sulfide nano material is uniform in appearance and is in a flower-shaped nanosphere structure, and the diameter is 200-250 nm.
Drawings
FIG. 1 is the novel W prepared in example 1 2 S 3 SEM images of nanomaterials;
FIG. 2 is the novel W prepared in example 1 2 S 3 TEM images of the nanomaterials;
FIG. 3 is the novel W prepared in example 1 2 S 3 HRTEM picture and atomic structure model picture of the nano material;
FIG. 4 is the novel W prepared in example 1 2 S 3 Experimental XRD and simulated XRD patterns of the nanomaterial;
FIG. 5 is a graph showing the surface properties of the novel tungsten sulfide thin film material prepared in application example 1(a) and in application comparative example 1 (b);
FIG. 6 shows W prepared in example 1 2 S 3 Ultraviolet absorption and photo-thermal conversion performance diagram of the nano material aqueous solution;
FIG. 7 is a topographical view of a flexible hydrogel (b) loaded with a novel tungsten sulfide photothermal material prepared in application example 2 and a pure PVA hydrogel (a);
FIG. 8 is a graph of photothermal performance of the novel tungsten sulfide photothermal material loaded flexible hydrogel prepared in application examples 2 and 3;
FIG. 9 is a drawing of a seawater desalination experiment integration apparatus fabricated using a novel tungsten sulfide flexible thin film material;
FIG. 10 is a performance diagram of seawater desalination using the novel tungsten sulfide flexible thin film material.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1: preparation of novel tungsten sulfide photo-thermal material
(1) 51.007mg of ammonium tungstate, 22.836mg of thiourea (the proportion of W to S is 1: 1.5) 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 blowing inert protective gas N into the system 2 Evacuation and filling with N 2 The steps are circulated for 3 times, and each time lasts for 5 minutes;
(3) quickly heating the system to 300 ℃, preserving heat for 2h, naturally cooling to room temperature, and filtering to obtain W 2 S 3 A nanomaterial;
(4) the mixed solution of cyclohexane and absolute ethyl alcohol with the volume ratio of 1:3 is used for the W obtained in the step (3) 2 S 3 Washing the nano material, centrifuging for 10min at 8500rpm, and collecting the obtained precipitate;
(5) the precipitate was placed in a vacuum oven and dried overnight at 60 c and the dried product was collected.
FIGS. 1 and 2 show the novel W prepared in this example 2 S 3 SEM and TEM photographs of the nanomaterials, from which W can be seen 2 S 3 The shape of the nano material is a flower-shaped nanosphere with uniform height, and the particle size is about 200-250 nm.
FIG. 3 shows the novel W obtained in this example 2 S 3 HRTEM photograph (a small picture and b small picture) and atomic structure model picture (c small picture is W) of nano material 2 S 3 Perspective view of atomic structure, d is W 2 S 3 Side view of atomic structure, e panel is W 2 S 3 Side view of the atomic structure after removal of the S atom).
FIG. 4 shows the novel W obtained in this example 2 S 3 The experimental XRD pattern and the simulated XRD pattern of the nano material are compared, so that the tungsten sulfide material prepared by the embodiment is novel W 2 S 3 And (5) structure.
Example 2: preparation of novel tungsten sulfide photo-thermal material
(1) 51.007mg of ammonium tungstate, 30.448mg of thiourea (the proportion 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 blowing inert protective gas N into the system 2 Evacuation and filling with N 2 The steps are circulated for 3 times, and each time lasts for 5 minutes;
(3) quickly heating the system to 300 ℃, preserving heat for 2h, naturally cooling to room temperature, and filtering to obtain W 2 S 3 A nanomaterial;
(4) the mixed solution of cyclohexane and absolute ethyl alcohol with the volume ratio of 1:3 is used for treating the W obtained in the step (3) 2 S 3 Washing the nano material, centrifuging for 10min at 8500rpm, and collecting the obtained precipitate;
(5) the precipitate was placed in a vacuum oven and dried overnight at 60 c 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 proportion of W to S is 1: 1.5) 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 blowing inert protective gas N into the system 2 Evacuation and filling with N 2 The steps are circulated for 3 times, and each time lasts for 5 minutes;
(3) quickly heating the system to 320 ℃, preserving heat for 2 hours, naturally cooling to room temperature, and filtering to obtain W 2 S 3 A nanomaterial;
(4) the mixed solution of cyclohexane and absolute ethyl alcohol with the volume ratio of 1:3 is used for the W obtained in the step (3) 2 S 3 Washing the nano material, centrifuging for 10min at 8500rpm, and collecting the obtained precipitate;
(5) the precipitate was placed in a vacuum oven and dried overnight at 60 c 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 proportion 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 blowing inert protective gas N into the system 2 Evacuation and filling with N 2 The steps are circulated for 3 times, and each time lasts for 5 minutes;
(3) quickly heating the system to 320 ℃, preserving heat for 2 hours, naturally cooling to room temperature, and filtering to obtain W 2 S 3 A nanomaterial;
(4) the mixed solution of cyclohexane and absolute ethyl alcohol with the volume ratio of 1:3 is used for the W obtained in the step (3) 2 S 3 Washing the nano material, centrifuging for 10min at 8500rpm, and collecting the obtained precipitate;
(5) the precipitate was placed in a vacuum oven and dried overnight at 60 c 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 only that the heating and holding 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 only 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 only 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 the embodiment and the embodiment 4 is only that the heating and heat preservation time in the step (3) is 3h, and the rest processes are the same.
Application example 1: preparation of flexible thin film loaded with novel tungsten sulfide photo-thermal material
The flexible substrate selected when the flexible film is prepared 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 multiple times, wherein ultrasonic treatment is assisted in the washing process;
(2) 5.0mg of W prepared in example 1 were taken 2 S 3 Mixing the nano material in the solutionPreparing a nano material dispersion liquid in a mixed solution of 20 mu L of naphthol (Nafion, 5 wt%), 800 mu L of deionized water and 200 mu L of absolute ethyl alcohol;
(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 45 min;
(4) immersing pure hydrophobic carbon cloth (CFC) into the dispersion liquid treated by the ultrasonic wave in the step (3), drying in a vacuum oven at 60 ℃, and repeating the immersion liquid drying process for a plurality of times until W 2 S 3 The nano material is fully coated on the surface of the carbon cloth.
Application comparative example 1: bulk WS 2 Preparation of-CFC Flexible films
(1) Washing pure hydrophobic carbon cloth (CFC) with absolute ethyl alcohol for multiple times, wherein ultrasonic treatment is assisted in the washing process;
(2) WS in bulk at 190. mu.L concentration of 1mg/mL 2 (Bulk WS 2 ) (purchased from Nanjing Musco nanotechnology Co., Ltd.) Dispersion was mixed with 10. mu.L of Afion (5 wt%) to prepare Bulk WS 2 A dispersion liquid;
(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 45 min;
(4) immersing pure hydrophobic carbon cloth (CFC) into the dispersion liquid treated by the ultrasonic wave in the step (3), drying in a vacuum oven at 60 ℃, and repeating the immersion liquid drying process for a plurality of times until the Bulk WS 2 And fully coating the carbon cloth on the surface.
Application comparative example 2: peeling WS 2 Preparation of-CFC Flexible films
(1) Washing pure hydrophobic carbon cloth (CFC) with absolute ethyl alcohol for multiple times, wherein ultrasonic treatment is assisted in the washing process;
(2) peel WS at 190. mu.L concentration of 1mg/mL 2 (purchased from Nanjing Musco nanotechnology Co., Ltd.) Dispersion was added with 10. mu.L of Nafion (5 wt%) to prepare exfoliated WS 2 A dispersion liquid;
(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 45 min;
(4) immersing pure hydrophobic carbon cloth (CFC) into the dispersion liquid treated by the ultrasonic wave in the step (3), and drying in vacuum at 60 DEG COven drying, repeating the immersion drying process several times until WS is peeled off 2 And fully coating the carbon cloth on the surface.
Application example 2: preparation of flexible hydrogel loaded with novel tungsten sulfide photothermal material
(1) Magnetic stirring was heated at 90 ℃ to dissolve 1.0g of PVA-124 in 8mL of 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 previous step 2 S 3 Aqueous solution of nanomaterial to produce precursor solution, W 2 S 3 The concentration of the nano material water solution is 1 mg/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 this freezing and thawing process was repeated three times to prepare hydrogel W 2 S 3 NPs-PVA-1。
Application example 3: preparation of flexible hydrogel loaded with novel tungsten sulfide photothermal material
This application example differs from application example 2 only in that W used in step (2) 2 S 3 The concentration of the nano material water solution is 2 mg/mL.
The hydrogel obtained was designated as W 2 S 3 NPs-PVA-2。
Application example 4: preparation of flexible hydrogel loaded with novel tungsten sulfide photothermal material
This application example differs from application example 2 only in that W used in step (2) 2 S 3 The concentration of the nano material water solution is 4 mg/mL.
The hydrogel obtained was designated as W 2 S 3 NPs-PVA-3。
Correlation performance testing
1) Surface property test of novel tungsten sulfide photo-thermal film
The mass transfer performance is an important consideration for evaluating the seawater desalination material. Macroscopically, the mass transfer effect is represented by the gas precipitation capacity on the surface of the material and the contact property of the aqueous solution and the surface of the material, and the process mainly occurs in a solid-liquid-gas three-phase interface. The surface wettability of the tungsten sulfide photothermal thin films prepared in the application example 1 and the application comparative example 1 was tested, and the results are shown in fig. 5, wherein a is a small graph of the surface characteristics of the thin film material prepared in the application example 1, and b is a small graph of the surface characteristics of the thin film material prepared in the application comparative example 1; the simplified stress analysis of a single bubble on the surface of the material shows that the adhesion force (Fa) plays a key role in bubble separation, the novel tungsten sulfide photothermal material film is compared with the surface of a Bulk tungsten sulfide photothermal film, the seawater is more fully contacted with the photothermal material due to the unique morphological structure of the novel tungsten sulfide photothermal material film, the characteristics enable adjustable water content and transmission rate to be brought in the seawater desalination process, the water transmission of the whole structure can be promoted, the evaporation enthalpy is reduced, and the seawater evaporation conversion efficiency is remarkably improved.
2) Photo-thermal performance test of novel tungsten sulfide nano material
FIG. 6 shows W prepared in example 1 of the present invention 2 S 3 Ultraviolet absorption and photo-thermal conversion performance diagram of the nano material aqueous solution; wherein, the a panel shows W at different concentrations 2 S 3 The photo-thermal material aqueous solution has strong absorption (C) in the ultraviolet to Near Infrared (NIR) region 1 、C 2 、C 3 W of reference 2 S 3 The concentration of the aqueous solution of the photo-thermal material 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 photothermal conversion has been continuously studied, in which the sample is dispersed in deionized water and irradiated with 808nm laser, and the laser power and the irradiation time are 1W/cm respectively 2 And recording the temperature of the novel tungsten sulfide photothermal material solution under laser irradiation by an infrared camera for 10 minutes, wherein the results are shown in b, c and d minigraphs, and the temperature of the solution can reach 76.9 ℃ in 7 minutes under NIR radiation when the concentration of the sample dispersion liquid is 1.0mg/mL, which indicates the efficient photothermal conversion performance of the novel tungsten sulfide photothermal material. From the d small graph, the temperature change of samples with different concentrations under the same irradiation condition can be seen, and the temperature change is greatly increased along with the increase of the concentration of the samples. When the sample concentration is 4mg/mL, the temperature of the solution can be raised to 98.3 ℃.
3) Photo-thermal performance test of novel tungsten sulfide photo-thermal flexible thin film/hydrogel material
The photo-thermal conversion performance of the flexible hydrogel loaded with the novel tungsten sulfide photo-thermal material prepared in example 2 was tested in a related manner and compared with that of the hydrogel made of pure PVA.
FIG. 7 is a topographical view of a flexible hydrogel (b) loaded with the novel tungsten sulfide photothermal material prepared in application example 2 and a pristine PVA hydrogel (a); as can be seen from fig. 7, the PVA hydrogel was colorless and transparent, while the hydrogel supporting the new tungsten sulfide photothermal material was black.
FIG. 8 shows flexible hydrogel W loaded with novel tungsten sulfide photothermal material prepared in application examples 2 and 3 2 S 3 NPs-PVA-1 and W 2 S 3 The photo-thermal performance graph of NPs-PVA-2; as can be seen from the small graphs a and c in FIG. 8, the simulated solar irradiance (100 mW cm) -2 ) Flexible hydrogel W loaded with novel tungsten sulfide photothermal material 2 S 3 The temperature of the NPs-PVA-2 can rise to 205 ℃ within 4 minutes; from the panel b, it can be seen that the temperature rise of the flexible hydrogel loaded with the tungsten sulfide photothermal material is more significant within 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 the irradiation of simulated sunlight by the change of the concentration of the aqueous solution, and the whole body presents a trend of increasing with the concentration.
4) Seawater desalination test by using novel tungsten sulfide photo-thermal flexible thin film material
Fig. 9 shows an integrated device for outdoor seawater desalination experiments under real sunlight.
The water purification production performance of the novel tungsten sulfide flexible photo-thermal film is evaluated by utilizing real Weihai seawater. And collecting system quality change data once per hour. As a result, as shown in FIG. 10, in the seawater purification system, the novel tungsten sulfide flexible photo-thermal film material evaporates seawater at a high and stable speed, and the actual evaporation rate is 1.5kg m -2 ·h -1 The solar evaporation efficiency is up to 90%, and the excellent solar seawater evaporation performance is shown.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a novel tungsten sulfide photothermal material for water purification is characterized by comprising the following steps:
(1) adding ammonium tungstate and thiourea into oleylamine, wherein the molar ratio of W to S in the ammonium tungstate to the thiourea is 1: 1.5-1: 2, putting the mixture into a reactor, and carrying out 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 processes for several times;
(3) heating the system to 300-320 ℃, preserving heat for 2-3 h, 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) putting the precipitate obtained in the previous step into a vacuum drying oven for drying treatment to obtain W 2 S 3 A nano-material.
2. The preparation method of the novel tungsten sulfide photothermal material for water purification as claimed in 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 photothermal material for water purification as claimed in claim 1, wherein in step (2), the number of times of vacuuming and inert gas blowing is 3-5 times, and each time is 5-10 min.
4. The preparation method of the novel tungsten sulfide photothermal material for water purification as claimed in claim 1, wherein in the step (4), the volume ratio of cyclohexane to absolute ethyl alcohol is 1:3 to 1: 4.
5. The method for preparing the novel tungsten sulfide photothermal material for water purification as claimed in claim 1, wherein in the step (5), the temperature for vacuum drying is 50-60 ℃.
6. A novel tungsten sulfide photothermal material is characterized by being prepared by the preparation method of the novel tungsten sulfide photothermal material for water purification according to any one of claims 1-5, wherein the photothermal material is uniform in appearance, has a flower-like nanosphere structure, and has a particle size of 200-250 nm; the material has the metal-like light absorption characteristic and can realize the absorption of light with wide wavelength from ultraviolet to near infrared.
7. The application of the novel tungsten sulfide photothermal material as claimed in claim 6 in the field of seawater desalination.
8. A flexible film loaded with a novel tungsten sulfide photothermal material, which is prepared from the novel tungsten sulfide photothermal material according to claim 6, and the specific preparation process is as follows:
s1, washing the flexible substrate;
s2, mixing W 2 S 3 Mixing the nano material 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 S2;
s4, immersing the flexible substrate in the dispersion liquid, drying in a vacuum oven, repeating the immersion and drying process for several times until W 2 S 3 And (3) fully coating the nano material on the surface of the flexible substrate to finish the preparation of the film material.
9. The flexible film supporting a tungsten sulfide photothermal material as claimed in claim 8, wherein in step S2, W is 2 S 3 The dosage of the nano material is 5-20 mg, and the weight percentage of naphthol is5 wt%, 20-80 mu L, 0.8-3.2 mL of deionized water, and 0.2-0.8 mL of absolute ethyl alcohol.
10. The novel tungsten sulfide-loaded flexible film as claimed in claim 8, wherein in step S3, the ultrasonic power is 200-300W, the temperature is 25-30 ℃, and the time is 40-60 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115725112A (en) * | 2022-11-09 | 2023-03-03 | 山东科技大学 | Janus double-layer aerogel and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014076940A (en) * | 2012-09-21 | 2014-05-01 | Sekisui Chem Co Ltd | Method for producing sulfide semiconductor fine particle |
| WO2016065253A1 (en) * | 2014-10-23 | 2016-04-28 | Leal Juan | Synthesis of molybdenum sulfide (mos2) and tungsten sulfide (ws2) catalyst |
| CN106075439A (en) * | 2016-06-17 | 2016-11-09 | 上海理工大学 | A kind of WS2pVP nanometer sheet and its preparation method and application |
| WO2016190818A1 (en) * | 2015-05-26 | 2016-12-01 | Nanyang Technological University | Synthesis and application of tungsten chalcogenide hetero-structured nanomaterials |
| CN107188232A (en) * | 2017-05-11 | 2017-09-22 | 苏州大学 | A kind of petal-shaped tungsten sulfide nanosphere, preparation method and applications |
| US20170275180A1 (en) * | 2016-03-28 | 2017-09-28 | Shenzhen University | Tungsten Sulfide Thin Film and Preparation Method Therefor |
| CN107416905A (en) * | 2017-06-22 | 2017-12-01 | 河南大学 | A kind of preparation method of oil-soluble tungsten disulfide nano slices |
| CN107625744A (en) * | 2017-09-05 | 2018-01-26 | 上海理工大学 | A kind of nuclear shell structure nano capsule and its preparation method and application |
| CN108080005A (en) * | 2017-11-13 | 2018-05-29 | 西安交通大学 | A kind of preparation method of high catalytic activity elctro-catalyst 1T ' phase tungsten sulfides |
-
2022
- 2022-05-24 CN CN202210567597.2A patent/CN114835163B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014076940A (en) * | 2012-09-21 | 2014-05-01 | Sekisui Chem Co Ltd | Method for producing sulfide semiconductor fine particle |
| WO2016065253A1 (en) * | 2014-10-23 | 2016-04-28 | Leal Juan | Synthesis of molybdenum sulfide (mos2) and tungsten sulfide (ws2) catalyst |
| WO2016190818A1 (en) * | 2015-05-26 | 2016-12-01 | Nanyang Technological University | Synthesis and application of tungsten chalcogenide hetero-structured nanomaterials |
| US20170275180A1 (en) * | 2016-03-28 | 2017-09-28 | Shenzhen University | Tungsten Sulfide Thin Film and Preparation Method Therefor |
| CN106075439A (en) * | 2016-06-17 | 2016-11-09 | 上海理工大学 | A kind of WS2pVP nanometer sheet and its preparation method and application |
| CN107188232A (en) * | 2017-05-11 | 2017-09-22 | 苏州大学 | A kind of petal-shaped tungsten sulfide nanosphere, preparation method and applications |
| CN107416905A (en) * | 2017-06-22 | 2017-12-01 | 河南大学 | A kind of preparation method of oil-soluble tungsten disulfide nano slices |
| WO2018233371A1 (en) * | 2017-06-22 | 2018-12-27 | 河南大学 | Method for preparing oil-soluble tungsten disulfide nanosheet |
| CN107625744A (en) * | 2017-09-05 | 2018-01-26 | 上海理工大学 | A kind of nuclear shell structure nano capsule and its preparation method and application |
| CN108080005A (en) * | 2017-11-13 | 2018-05-29 | 西安交通大学 | A kind of preparation method of high catalytic activity elctro-catalyst 1T ' phase tungsten sulfides |
Non-Patent Citations (4)
| Title |
|---|
| XIE LINGBIN: "WS2 moire superlattices derived from mechanical flexibility for hydrogen evolution reaction", 《NATURE COMMUNICATIONS》, vol. 12, pages 1 - 9 * |
| 刘兆肃;张仕源;刘国濠;郑晓婷;叶晓宜;徐海涛;劳媚媚;: "二硫化钨二维材料的制备与应用研究进展", 广东化工, no. 18 * |
| 王龙禄: "二硫化钼结构调控及光/电催化制氢性能研究", 《中国优秀硕士学位论文全文数据库》 * |
| 艾汉华, 黄新堂: "硫化钨花形二维纳米晶的控制生长研究", 材料科学与工程学报, no. 05 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115725112A (en) * | 2022-11-09 | 2023-03-03 | 山东科技大学 | Janus double-layer aerogel and preparation method and application thereof |
| CN115725112B (en) * | 2022-11-09 | 2023-09-19 | 山东科技大学 | Janus double-layer aerogel and preparation method and application thereof |
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