CN110937636A - Preparation method and application of black tungsten trioxide nanosheet - Google Patents
Preparation method and application of black tungsten trioxide nanosheet Download PDFInfo
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Abstract
The invention discloses a preparation method of a black tungsten trioxide nanosheet, which comprises the following steps: mixing Na2WO4·2H2Adding O into concentrated nitric acid, and stirring to generate yellow precipitate; washing and drying the yellow precipitate, adding the yellow precipitate into a high-temperature furnace for heating and heat preservation to obtain crystal WO3Powder; crystallizing WO3And mixing the powder with metal reducing agent powder, uniformly grinding, placing in a high-temperature furnace, annealing under the condition of protective atmosphere, washing and drying to obtain the black tungsten trioxide nanosheet. The invention discloses a preparation method and application of a black tungsten trioxide nanosheet. The raw materials used in the synthesis process are cheap and easy to obtain, the preparation process is simple and quick, and the prepared black tungsten trioxide nanosheet is applied to the solar-driven water evaporation technology.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method and application of black tungsten trioxide nano sheets.
Background
Water is one of the most common substances on earth, and without water, there is no life. Nowadays, water is not an inexhaustible natural resource, and fresh water resources available for human life and drinking are reduced year by year. Statistically, 97.6% of the water resources on earth are seawater, and only about 2.4% are fresh water. It is worth noting that a large portion of these few fresh water resources cannot be utilized. For example, in the global fresh water resources, in addition to rivers on the surface, other fresh water resources are mainly distributed in glacier regions, north and south poles, ice layers under frozen soil, deep groundwater, and the like, and are difficult to be utilized. Even in fresh water on the usable ground, agricultural water accounts for 65%, industrial water accounts for 25%, and human life and municipal water accounts for less than 10%. Together with the unreasonable use, many regions in the world face severe shortage crisis of fresh water resources.
In recent years, a technology for obtaining fresh water by using photo-thermal materials for water resource treatment attracts wide attention. For example, Miaoniao Ye et al, Zhejiang university, reduces commercial titanium dioxide P25 using metallic Mg to produce a blue TiO2Photothermal materials (adv. energy mater.2017,7,1601811). Clean water is obtained by evaporation under the irradiation intensity of sunlight, and the photo-thermal conversion efficiency of about 50 percent is obtained; the black mesoporous carbon material for evaporation of light and hot water is obtained by using mushrooms as biomass charcoal materials (adv. mater.2017,29,1606762) by Ning Xu et al of Nanjing university and performing one-step high-temperature carbonization treatment, and the highest efficiency of photothermal conversion can reach 78%. Despite the advances made in this field, it must be acknowledged that the current research has many disadvantages, including insufficient absorption range of materials to sunlight, high preparation cost, low efficiency of photothermal conversion, and many technical obstacles for practical application.
Defective state WO3Has been extensively studied for a long time, and has been expected to exhibit various colors due to its unique crystal structure defect, and the absorption range of which extends from the ultraviolet region to the visible region and even the infrared regionThe material is used for clinical photothermal treatment of tumors and is also a potential material for solar-driven water evaporation technology. Through research and research on literature reports and patent findings of photothermal conversion nano materials for clean water resource regeneration at home and abroad, no black WO exists at present3Preparation of the nano-sheet and application of the nano-sheet in water evaporation under sunlight drive are precedent.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method and application of a black tungsten trioxide nanosheet. Introduction of oxygen defects into WO by means of metal reducing agents at elevated temperatures3In the crystal lattice, the absorption of visible light and infrared light is improved, the non-radiative energy loss process is reduced, the high-efficiency solar-driven water evaporation is finally realized, and the yield of clean water can reach 1.26 kg/h.m2. The raw materials used in the synthesis process are cheap and easily available, and the method is a novel method for preparing the black tungsten trioxide photothermal conversion material simply, quickly and industrially in a large scale.
The invention provides a preparation method of a black tungsten trioxide nanosheet, which comprises the following steps:
s1, mixing Na2WO4·2H2Adding O into concentrated nitric acid, and stirring to generate yellow precipitate;
s2, washing and drying the yellow precipitate, adding the yellow precipitate into a high-temperature furnace, controlling the temperature rising speed, heating to 400-600 ℃, and preserving heat for 2-4 hours to obtain crystal WO3Powder;
s3, crystal WO3The powder and the metal reducing agent powder are mixed and then uniformly ground, the mixture is placed in a high-temperature furnace, under the condition of protective atmosphere, the annealing treatment is carried out, the mixture is cooled to room temperature and then taken out, and then the black tungsten trioxide nano sheet is prepared after washing and drying by ionized water and diluted hydrochloric acid.
Preferably, the molar concentration of the concentrated nitric acid in S1 is not lower than 5 mol/L.
Preferably, the stirring time in S1 is not less than 48 h.
Preferably, the temperature rise speed of the high-temperature furnace in S2 is 5-15 ℃/min.
Preferably, the protective atmosphere in S3 is nitrogen and/or argon.
Preferably, the metal reductant powder in S3 is one or more of aluminum, lithium, magnesium.
Preferably, metal reductant powder and crystalline WO 33The mass ratio of the powder is not less than 1.
Preferably, the annealing treatment in S3 is carried out at a temperature of not less than 700 ℃ for an annealing time of not less than 2 h.
The invention also provides application of the black tungsten trioxide nanosheet prepared by the preparation method in a solar-driven water evaporation technology.
The invention provides a black WO with high light-heat conversion efficiency3A preparation method of the nano-sheet. Mainly adopts wet chemistry to prepare WO3·2H2O precursor is calcined at high temperature in the air to remove crystal water in crystal lattices to prepare crystal WO3. Then, the black WO is prepared by taking metal aluminum as a reducing agent under the condition of high temperature3A photothermal material. The chemical principle is that the strong reducibility of the metal aluminum under the high temperature condition is utilized to capture WO3Oxygen atoms in the crystal lattice, thereby forming oxygen vacancies, so that WO3The energy band is narrowed to enhance the absorbance thereof. The invention has simple preparation process, uniform product appearance and size, no toxic and harmful substances, and can be industrially produced in large scale. Under the irradiation of 1 sunlight intensity, black WO3The surface temperature can reach 63 ℃ at most, and the yield of the evaporated water by photo-thermal conversion can reach 1.26 kg/h.m2。
The invention has the beneficial effects that:
1. toxic and harmful raw materials are not used, and the environment is not polluted;
2. the synthesis process is simple, and industrial equipment can be adopted for mass production;
3. obtained black WO3The nano-sheet has strong absorption to sunlight, and the absorption spectrum covers the whole solar spectrum;
4. has high photo-thermal conversion efficiency, can effectively evaporate and prepare clean water, and has the yield of 1.26 kg/h.m2。
Drawings
FIG. 1 shows the black WO prepared in example 13A sample photograph of the nanoplatelets;
FIG. 2 is the black WO prepared in example 13SEM photograph of nanosheets;
FIG. 3 is the black WO prepared in example 13Absorption spectra of the nanoplatelets;
FIG. 4 shows the black WO prepared in example 13The nanosheet electron paramagnetic resonance spectrum of (a);
FIG. 5 is the black WO prepared in example 13The change curve of the clean water yield of the nanosheets under the irradiation of sunlight along with time;
FIG. 6 is the black WO prepared in example 13And (3) infrared imaging of the nanosheets under sunlight irradiation.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a black tungsten trioxide nanosheet comprises the following steps:
s1, adding 0.5 g of Na2WO4·2H2Adding O into concentrated nitric acid with the molar concentration of 8mol/L, and continuously stirring for 72 hours to generate yellow precipitate;
s2, washing the yellow precipitate with deionized water and ethanol for 3 times respectively, drying in a vacuum oven at 60 ℃, adding into a high-temperature muffle furnace, heating to 400 ℃ at a speed of 5 ℃/min, keeping the temperature for 2 hours, and obtaining crystal WO after the temperature in the furnace is reduced to room temperature3Powder;
s3, 1 g of crystal WO3The powder and 1 g of metallic aluminum reducing agent powder are mixed and then uniformly ground, the mixture is placed in a high-temperature tube furnace, annealing treatment is carried out at 700 ℃ for 4 under the nitrogen atmosphere condition, the mixture is cooled to room temperature and then taken out, and the black tungsten trioxide nano-sheet is obtained after washing for 3 times by ionized water and diluted hydrochloric acid and drying.
Example 2
A preparation method of a black tungsten trioxide nanosheet comprises the following steps:
s1, adding 0.5 g of Na2WO4·2H2Adding O into concentrated nitric acid with the molar concentration of 5mol/L, and continuously stirring for 96 hours to generate yellow precipitate;
s2, washing the yellow precipitate with deionized water and ethanol for 3 times respectively, drying in a vacuum oven at 60 ℃, adding into a high-temperature muffle furnace, heating to 500 ℃ at a speed of 10 ℃/min, keeping the temperature for 4h, and obtaining crystal WO after the temperature in the furnace is reduced to room temperature3Powder;
s3, 1 g of crystal WO3The powder is mixed with 2 g of metallic aluminum reducing agent powder, then the mixture is uniformly ground, the mixture is placed in a high-temperature tube furnace, annealing treatment is carried out at 800 ℃ for 2 times under the nitrogen atmosphere condition, the mixture is cooled to room temperature and then taken out, and the black tungsten trioxide nano-sheet is obtained after washing for 3 times by ionized water and diluted hydrochloric acid and drying.
Example 3
A preparation method of a black tungsten trioxide nanosheet comprises the following steps:
s1, mixing 2 g of Na2WO4·2H2Adding O into concentrated nitric acid with the molar concentration of 6mol/L, and continuously stirring for 72 hours to generate yellow precipitate;
s2, washing the yellow precipitate with deionized water and ethanol for 3 times respectively, drying in a vacuum oven at 60 ℃, adding into a high-temperature muffle furnace, heating to 450 ℃ at the speed of 8 ℃/min, keeping the temperature for 2.5 hours, and obtaining crystal WO after the temperature in the furnace is reduced to room temperature3Powder;
s3, 2 g of crystal WO3The powder is mixed with 3 g of metal lithium reducing agent powder, then the mixture is uniformly ground, the mixture is placed in a high-temperature tube furnace, annealing treatment is carried out for 3.5h at 750 ℃ under the nitrogen atmosphere condition, the mixture is cooled to room temperature and then taken out, and then the black tungsten trioxide nano-sheet is obtained after washing for 3 times by ionized water and diluted hydrochloric acid and drying.
Example 4
A preparation method of a black tungsten trioxide nanosheet comprises the following steps:
s1, mixing 5 g of Na2WO4·2H2Adding O into concentrated nitric acid with the molar concentration of 10mol/L, and continuously stirring for 48 hours to generate yellow precipitate;
s2, de-ionized water and yellow precipitateWashing with ethanol for 3 times, drying in a vacuum oven at 60 deg.C, adding into a high temperature muffle furnace, heating to 550 deg.C at a speed of 12 deg.C/min, maintaining for 2.5 hr, and cooling to room temperature to obtain crystal WO3Powder;
s3, crystallizing 5 g of WO3The powder is mixed with 12.5 g of metal magnesium reducing agent powder, then the mixture is uniformly ground, the mixture is placed in a high-temperature tube furnace, under the condition of nitrogen atmosphere, after annealing treatment is carried out at 850 ℃ for 2.5h, the mixture is cooled to room temperature and then taken out, and then the black tungsten trioxide nano-sheet is obtained after washing for 3 times by ionized water and diluted hydrochloric acid and drying.
FIG. 1 is black WO3A photograph of a sample dispersed in water confirmed its dark black appearance, which also indicates that the sample had good dispersibility. FIG. 2 shows black WO3The scanning electron microscope image of the sample proves the microscopic appearance of the nano-sheet, the length and the width can reach about 1 micron, and the thickness is about 100 nanometers. FIG. 3 is black WO3The absorption spectrum of the sample confirms that it has strong absorption in the ultraviolet, visible and infrared regions. FIG. 4 shows WO black3The electron paramagnetic resonance spectrum of the sample proves that the surface of the sample contains a large amount of W5+Ions. FIG. 5 shows WO black3The sample is used as a photo-thermal conversion agent, and the change curve of the quality of evaporated water along with time is irradiated by 1 sunlight intensity. FIG. 6 shows WO color3Infrared photographs of the samples during photo-thermal evaporation of water show that black WO suspended on the surface of the liquid3The film temperature is far higher than the temperature of the surrounding environment, and can reach about 50 ℃ at most, thereby proving the high-efficiency photothermal conversion capability.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A preparation method of a black tungsten trioxide nanosheet is characterized by comprising the following steps:
s1, mixing Na2WO4·2H2Adding O into concentrated nitric acid, and stirring to generate yellow precipitate;
s2, washing and drying the yellow precipitate, adding the yellow precipitate into a high-temperature furnace, controlling the temperature rising speed, heating to 400-600 ℃, and preserving heat for 2-4 hours to obtain crystal WO3Powder;
s3, crystal WO3The powder and the metal reducing agent powder are mixed and then uniformly ground, the mixture is placed in a high-temperature furnace, under the condition of protective atmosphere, the annealing treatment is carried out, the mixture is cooled to room temperature and then taken out, and then the black tungsten trioxide nano sheet is prepared after washing and drying by ionized water and diluted hydrochloric acid.
2. A method for preparing black tungsten trioxide nanoplates as described in claim 1, wherein the molar concentration of concentrated nitric acid in S1 is not less than 5 mol/L.
3. A method for producing black tungsten trioxide nanoplates as described in claim 1, wherein the stirring time in S1 is not less than 48 hours.
4. The method for producing black tungsten trioxide nanosheets according to claim 1, wherein the temperature rise rate of the high-temperature furnace in S2 is 5 to 15 ℃/min.
5. The method for preparing black tungsten trioxide nanoplates as described in claim 1, wherein the protective atmosphere in S3 is nitrogen and/or argon.
6. The method for preparing black tungsten trioxide nanoplates according to claim 1, wherein the metal reducing agent powder in S3 is one or more of aluminum, lithium and magnesium, preferably aluminum powder.
7. The method for producing black tungsten trioxide nanosheets according to claim 1, wherein the metal reducing agent powder and crystalline WO 3 are3The mass ratio of the powder is not less than 1.
8. The method for preparing black tungsten trioxide nanosheets according to claim 1, wherein the temperature of the annealing treatment in S3 is not lower than 700 ℃ and the annealing time is not lower than 2 hours.
9. An application of the black tungsten trioxide nanosheet prepared by the preparation method of claim 1 in a solar-driven water evaporation technology.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816417A (en) * | 2021-10-20 | 2021-12-21 | 西北大学 | Black gallium oxide nano-particles and preparation method thereof |
| CN114229897A (en) * | 2021-09-14 | 2022-03-25 | 中国科学技术大学 | Preparation method of metal phase tungsten oxide and application of metal phase tungsten oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006743A (en) * | 2016-05-31 | 2016-10-12 | 上海应用技术学院 | Preparation method of orthorhombic black WO3 |
| CN107597098A (en) * | 2017-09-27 | 2018-01-19 | 大连民族大学 | A kind of one pot process has visible light-responded photochemical catalyst LaVO4/WO3The preparation method of nanometer sheet |
| CN108607539A (en) * | 2018-04-23 | 2018-10-02 | 南京信息工程大学 | A kind of sheet tungstic acid and preparation method thereof and purposes with photocatalyst |
-
2019
- 2019-11-29 CN CN201911205186.3A patent/CN110937636A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006743A (en) * | 2016-05-31 | 2016-10-12 | 上海应用技术学院 | Preparation method of orthorhombic black WO3 |
| CN107597098A (en) * | 2017-09-27 | 2018-01-19 | 大连民族大学 | A kind of one pot process has visible light-responded photochemical catalyst LaVO4/WO3The preparation method of nanometer sheet |
| CN108607539A (en) * | 2018-04-23 | 2018-10-02 | 南京信息工程大学 | A kind of sheet tungstic acid and preparation method thereof and purposes with photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| ZHENKUI LI等: ""Broadband-absorbing WO3-x nanorod-decorated wood evaporator for highly efficient solar-driven interfacial steam generation"", 《SOLAR ENERGY MATERIALS AND SOLAR CELLS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114229897A (en) * | 2021-09-14 | 2022-03-25 | 中国科学技术大学 | Preparation method of metal phase tungsten oxide and application of metal phase tungsten oxide |
| CN114229897B (en) * | 2021-09-14 | 2022-09-30 | 中国科学技术大学 | Preparation method of metal phase tungsten oxide and application of metal phase tungsten oxide |
| CN113816417A (en) * | 2021-10-20 | 2021-12-21 | 西北大学 | Black gallium oxide nano-particles and preparation method thereof |
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