CN114380349A - S-shaped MoS2Preparation method of-Ti net photo-electric-thermal seawater desalination membrane - Google Patents
S-shaped MoS2Preparation method of-Ti net photo-electric-thermal seawater desalination membrane Download PDFInfo
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- CN114380349A CN114380349A CN202210074356.4A CN202210074356A CN114380349A CN 114380349 A CN114380349 A CN 114380349A CN 202210074356 A CN202210074356 A CN 202210074356A CN 114380349 A CN114380349 A CN 114380349A
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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
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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- C—CHEMISTRY; METALLURGY
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/138—Water desalination using renewable energy
- Y02A20/142—Solar thermal; Photovoltaics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- 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 application discloses S-shaped MoS2The preparation method of the Ti net optical-electric-thermal seawater desalination membrane comprises the following steps of: substrate pretreatment: cleaning a substrate, and then carrying out etching treatment; mixing thiourea and ammonium molybdate tetrahydrate to prepare a light absorption material; reacting the pretreated substrate with a light absorption material to obtain a photothermal film; and cutting the structure of the photo-thermal film to prepare the seawater desalination film. The surface of the seawater desalination membrane is loaded with molybdenum sulfide nanoflowers in a hydro-thermal synthesis mode, wherein a Ti net or a Ti alloy net is used as a substrate material, and MoS is adopted2As a light absorbing material; and by mixing MoS2The cutting of the Ti net into an S-shaped structure can be more favorable for generating Joule heat effect and realizing the photo-electricity-heatAnd (5) seawater desalination.
Description
Technical Field
The application relates to a photothermal conversion material, in particular to an S-shaped MoS2A preparation method of a Ti net light-electricity-heat seawater desalination membrane.
Background
With the continuous improvement of the living standard of human beings, the problems of pollution of rivers and lakes, lack of world clean water and the like appear year by year; solar-driven water evaporation is a green, novel and effective method for solving the problem of the water environment; development of a nontoxic, pollution-free and sustainable effective solution strategy is crucial. In recent years, researchers have developed various novel photothermal conversion materials that can efficiently convert light energy into heat energy, thereby solving problems such as energy and biomedicine; the photothermal conversion material generally has the advantages of higher photothermal conversion efficiency, cheap and easily available raw materials, simple preparation method and the like. However, the currently developed photothermal materials still have many disadvantages, such as poor photothermal stability, narrow optical absorption range and large biological toxicity, and the photothermal film for solar-driven water evaporation has the disadvantages of complex preparation, high cost, low yield and the like; therefore, development of photothermal conversion materials having excellent photothermal stability, broad spectral absorption, and good biosafety is urgently needed.
In addition, in order to better improve the water evaporation performance of the whole system, besides optimizing the light absorption performance of the material and reducing the heat loss efficiency of the device, the whole evaporation rate is improved by introducing an additional energy source. Wind energy is used as inexhaustible clean energy, has unusual performance in reducing carbon dioxide emission, relieving climate change and the like, but is unstable in the natural world and depends on geographical positions and climate conditions to a great extent, and the wind energy is an important factor for limiting the application of the wind energy in the field of photo-thermal water evaporation; although the electric energy cannot be used as inexhaustible as wind energy, the electric energy is the first choice as a second energy source due to the fact that the electric energy can be stably output and is not limited by geographical conditions and the like; heat (Q) generated by an electro-thermal system is related to the resistance (R) and the square of the current (I)2) Proportional ratio (Q ═ I)2R), but the titanium and titanium alloy nets are good conductors, the internal resistance of the titanium and titanium alloy nets is very small, and the internal resistance of the large titanium and titanium alloy nets which are not cut is too small to meet the requirement of high heat productivity of an electro-thermal system. The ratio of R to ρ L/S (ρ is a proportionality coefficient determined by the material of the conductor and the ambient temperature and is called the resistivity, and L is the conductor lengthDegree, S is a conductor cross-sectional area), the conductor internal resistance (R) can be significantly increased by extending the conductor length (L) and reducing the conductor cross-sectional area (S). Therefore, the metal net is cut into specific shapes such as S shape or I shape, etc. to meet the working requirements of the electric heating system.
Disclosure of Invention
In view of the above, the present application provides an S-shaped MoS2A preparation method of a-Ti net photo-electric-thermal seawater desalination membrane, aiming at providing a light absorption material MoS2Compounding with a stabilized Ti or Ti alloy mesh substrate to form MoS with excellent properties2-Ti mesh membrane and by pairing MoS2The secondary structure of the Ti net is designed to have more initial MoS under the condition of ensuring the original integrity to the maximum extent2The greater internal resistance of the Ti network, providing greater evaporation performance for the subsequent photo-electro-thermal evaporation.
The technical scheme of the application is realized as follows:
s-shaped MoS2The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane specifically comprises the following steps:
(1) substrate pretreatment: cleaning a substrate, and then carrying out etching treatment;
(2) mixing thiourea and ammonium molybdate tetrahydrate to prepare a light absorption material;
(3) reacting the pretreated substrate with a light absorption material to obtain a photothermal film;
(4) and cutting the structure of the photo-thermal film to prepare the seawater desalination film.
The further technical scheme is that the titanium alloy is composed of titanium and one or more elements of transition metals and nonmetal.
Still further technical scheme is that the transition metal comprises one or more elements of vanadium, molybdenum, niobium, chromium, iron, copper, cobalt, nickel, zirconium, zinc, cadmium, manganese, palladium and rhodium.
Still further technical solution is that the nonmetal includes one or more elements of carbon, nitrogen, and oxygen.
The further technical scheme is that the mass fraction of titanium in the titanium alloy is 2-99%.
The further technical scheme is that the substrate is one of a titanium mesh, a titanium alloy mesh or a stainless steel mesh.
The further technical scheme is that the etching treatment specifically comprises the following steps: and putting the cleaned substrate into an oxalic acid solution with the mass fraction of 5% -15%, etching for 35-45min in a boiling state, washing the etched substrate with deionized water, and drying.
The further technical scheme is that in the step (2), thiourea, ammonium molybdate tetrahydrate and deionized water are mixed for 5-15min according to the weight ratio of 1.3-1.8:1:50-60 to prepare the light absorption material.
The further technical scheme is that the specific method of the step (3) is as follows: the pretreated substrate and the light absorption material react for 18-25h at the temperature of 180-230 ℃, and then deionized water is used for cleaning and drying to prepare the photo-thermal film, which is also called as hydro-thermal synthesis. MoS grows on the surface of the etched Ti net in situ in a hydrothermal mode2The particles are in a nanometer flower shape under a scanning electron microscope, have larger specific surface area and surface roughness and are beneficial to the whole light absorption effect.
The further technical proposal is that the mesh number of the substrate is 250-350 meshes, and the thickness is 0.2-0.8 mm; the shape of the structure cut in the step (4) comprises an S shape (as shown in fig. 4), the whole size of the structure cut is 10.5-13.5cm in length and 2.5-3.5cm in width (namely the length and the width shown in fig. 4), and the cross section of one end of the structure after cutting is 0.2-0.8mm x 3-6 mm.
The step (1) of cleaning the cut substrate refers to that the cut substrate is cleaned for multiple times by acetone or ethanol to remove redundant impurities on the surface so as to obtain a clean substrate.
Molybdenum sulfide belongs to semiconductor materials, has excellent near infrared absorption characteristics and characteristics of easy synthesis and the like due to narrow forbidden band width, generally has excellent photo-thermal stability and light absorption rate, and is a very excellent potential solar energy capturing material.
The Ti net has many excellent characteristics of light weight, high strength, strong heat resistance, corrosion resistance and the like, and a compact oxide film with strong adhesive force and large inertia can be generated on the surface of the Ti net in a corrosion-resistant medium environment to generate a passivation phenomenon, so that a Ti net matrix is protected from being corroded, and a strong corrosion resistance effect is achieved; the corrosion resistance is more excellent particularly in the following use environments, such as: seawater, wet chlorine, chlorite and hypochlorite solutions, nitric acid, chromic acid metal chlorides, organic salts, and the like.
Compared with single titanium metal, the titanium alloy contains other miscellaneous elements except titanium, can enrich the electronic structure and energy level transition situation in the material, has promotion effect on light absorption and photo-thermal conversion, and is also beneficial to the adhesion growth of other materials, so that the evaporation performance of the seawater desalination film can be obviously improved. In addition, the titanium alloy has stronger corrosion resistance and is more beneficial to the long-term stability of the film. In a similar way, the stainless steel is not only corrosion resistant, but also contains various miscellaneous elements, and can also obviously improve the evaporation performance of the seawater desalination membrane.
Compared with the prior art, the beneficial effects of this application are:
(1) the surface of the seawater desalination membrane is loaded with molybdenum sulfide nanoflowers in a hydro-thermal synthesis mode, wherein a Ti net or a Ti alloy net is used as a substrate material, and MoS is adopted2As a light absorbing material; and by mixing MoS2The Ti net is cut into an S-shaped structure, so that the Ti net can be more favorable for generating joule heating effect and realizing the light-electricity-heat seawater desalination. (2) In the process of seawater desalination, the seawater desalination membrane can generate water vapor stably and efficiently under the illumination condition, can realize more efficient and universal all-weather photo-electricity-hot water evaporation under the condition of external electric energy input, and produces fresh water at high flux.
Drawings
FIG. 1 is a diagram of a seawater desalination membrane.
Fig. 2 is a microscopic view of the seawater desalination membrane under a Scanning Electron Microscope (SEM).
FIG. 3 shows MoS2Microscopic image of nanoflower under Scanning Electron Microscope (SEM).
Fig. 4 is a three-dimensional schematic diagram of an S-shaped seawater desalination membrane.
FIG. 5 is a graph of the integrated water evaporation rate at different currents and different light conditions.
FIG. 6 is a temperature rise diagram of the S-shaped seawater desalination membrane under different currents.
Detailed Description
In order to better understand the technical content of the application, the following specific embodiments are provided to further explain the application in conjunction with the attached drawings.
Example 1
S-shaped MoS2The preparation method of the-Ti net light-electricity-heat seawater desalination membrane, wherein the seawater desalination membrane takes a titanium net as a substrate and is combined with a light absorption material to prepare the seawater desalination membrane, and the preparation method specifically comprises the following steps:
(1) substrate pretreatment: cutting a substrate, cleaning the substrate with acetone, and then etching;
(2) mixing thiourea and ammonium molybdate tetrahydrate to prepare a light absorption material;
(3) reacting the pretreated substrate with a light absorption material to obtain MoS2Ti membrane for desalination of sea water (see FIGS. 1 and 2).
The mesh number of the substrate is 300 meshes, and the thickness is 0.5 mm.
The structure is cut in an S-shape (see fig. 4) with a length of 12cm and a width of 3 cm.
The etching treatment specifically comprises the following steps: and putting the cleaned substrate into an oxalic acid solution with the mass fraction of 10%, etching for 40min in a boiling state, washing the etched substrate with deionized water, and drying.
In the step (2), thiourea, ammonium molybdate tetrahydrate and deionized water are mixed for 10min according to the weight ratio of 1.8:1:55 to prepare the light absorption material.
The specific method of the step (3) is as follows: and (3) reacting the pretreated substrate with a light absorption material at 200 ℃ for 24 hours, and then washing and drying the substrate by using deionized water to prepare the seawater desalination membrane. In-situ growth of MoS on surface of substrate by light absorption material2The particles, which appeared in the shape of nanoflower under scanning electron microscopy (see fig. 3).
Example 2
S-shaped MoS2Method for preparing-Ti net light-electricity-heat seawater desalination membrane, wherein the seawater desalination membrane takes titanium alloy net as baseThe method is characterized in that the seawater desalination membrane is prepared by combining the light absorption material with the base material, and specifically comprises the following steps:
(1) substrate pretreatment: cutting a substrate, cleaning the substrate with acetone, and then etching;
(2) mixing thiourea and ammonium molybdate tetrahydrate to prepare a light absorption material;
(3) reacting the pretreated substrate with a light absorption material to obtain MoS2-Ti seawater desalination membrane.
The titanium alloy consists of titanium and cobalt elements.
The mass fraction of titanium in the titanium alloy is 2%.
The mesh number of the substrate is 250 meshes, and the thickness is 0.2 mm.
The structure is cut into an S shape, the length of the structure cutting dimension is 10.5cm, and the width of the structure cutting dimension is 2.5 cm.
The etching treatment specifically comprises the following steps: and putting the cleaned substrate into an oxalic acid solution with the mass fraction of 5%, etching for 35min in a boiling state, washing the etched substrate with deionized water, and drying.
In the step (2), thiourea, ammonium molybdate tetrahydrate and deionized water are mixed for 15min according to the weight ratio of 1.3:1:50 to prepare the light absorption material.
The specific method of the step (3) is as follows: and (3) reacting the pretreated substrate with a light absorption material at 180 ℃ for 25h, and then washing and drying the substrate by using deionized water to prepare the seawater desalination membrane.
Example 3
S-shaped MoS2The preparation method of the-Ti net optical-electric-thermal seawater desalination membrane comprises the following steps of:
(1) substrate pretreatment: cutting a substrate, cleaning the substrate with ethanol, and then etching;
(2) mixing thiourea and ammonium molybdate tetrahydrate to prepare a light absorption material;
(3) reacting the pretreated substrate with a light absorption material to obtain MoS2-Ti seawater desalination membrane.
The titanium alloy is composed of titanium and oxygen.
The mass fraction of titanium in the titanium alloy is 60%.
The mesh number of the substrate is 350 meshes, and the thickness is 0.8 mm.
The structure is cut into an S shape, the length of the structure cutting size is 13.5cm, and the width of the structure cutting size is 3.5 cm.
The etching treatment specifically comprises the following steps: and putting the cleaned substrate into an oxalic acid solution with the mass fraction of 15%, etching for 45min in a boiling state, washing the etched substrate with deionized water, and drying.
In the step (2), thiourea, ammonium molybdate tetrahydrate and deionized water are mixed for 5min according to the weight ratio of 1.5:1:60 to prepare the light absorption material.
The specific method of the step (3) is as follows: and (3) reacting the pretreated substrate with a light absorption material at 230 ℃ for 18h, and then washing and drying the substrate by using deionized water to prepare the seawater desalination membrane.
Example 4
The substrate is a stainless steel mesh and the other steps are the same as in example 2.
Comparative example 1
Compared with the embodiment 2, the structure cuts an S shape with the length of 15cm, and other steps are the same as the embodiment 2.
Comparative example 2
The substrate thickness was 0.1mm compared to example 2, and the other steps were the same as in example 2.
Evaporation performance
The seawater desalination membranes prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to an evaporation rate test using an evaporation performance tester to test 1sun (i.e., 1 kW/m)2) The evaporation rate at 1.5A is shown in Table 1.
TABLE 1
As can be seen from example 1 and example 2 in table 1, the evaporation rate of the seawater desalination membrane made of titanium alloy is greater than that of the seawater sensitive membrane made of titanium alone. As can be seen from examples 2 and 4, the titanium alloy has the same evaporation rate as the seawater desalination membrane prepared from stainless steel. It can be seen from the embodiment 2 and the comparative example 1 that the length of the structure cut in the shape of S greatly affects the evaporation rate of the seawater desalination membrane, and the evaporation rate is reduced when the length is too long, mainly because the seawater desalination membrane forms a capillary action at the contact position with the seawater due to its own porous structure during the use process, the seawater is condensed and evaporated under the capillary action of the seawater desalination membrane, and after the seawater is evaporated, the salt in the seawater is easily remained on the seawater desalination membrane, so that a large amount of salt is remained at the membrane, thereby affecting the evaporation rate of the membrane. As can be seen from example 2 and comparative example 2, the thickness of the substrate has an influence on the evaporation rate of the seawater desalination membrane, because the substrate with too small thickness can generate light transmission, and the influence on light absorption further influences the evaporation rate.
In addition, the input of electrical energy can increase the temperature of the surface of the film (see fig. 6), the existence of illumination can reduce the humidity of the surface, the coupling of the two energy sources can realize 1+1 > 2, but it should be noted that the forward coupling can not be realized under all conditions, for example, when the input current on both sides of the S-shaped MoS2-Ti photothermal film is large enough, the electro-thermal evaporation is the main evaporation of the whole evaporation system, namely, the evaporation effect of light-heat on the whole is not obvious, so the 1+1 < 2 condition can occur; this is why the total water evaporation rate is less than the sum of the pure hot water evaporation rate and the pure hot water evaporation rate when the current input is 2A (amperes) in fig. 5.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. S-shaped MoS2The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: the method specifically comprises the following steps:
(1) substrate pretreatment: cleaning a substrate, and then carrying out etching treatment;
(2) mixing thiourea and ammonium molybdate tetrahydrate to prepare a light absorption material;
(3) reacting the pretreated substrate with a light absorption material to obtain a photothermal film;
(4) and cutting the structure of the photo-thermal film to prepare the seawater desalination film.
2. An S-shaped MoS according to claim 12The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: the titanium alloy is composed of titanium and one or more elements of transition metal and nonmetal.
3. An S-shaped MoS according to claim 22The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: the transition metal comprises one or more elements of vanadium, molybdenum, niobium, chromium, iron, copper, cobalt, nickel, zirconium, zinc, cadmium, manganese, palladium and rhodium.
4. An S-shaped MoS according to claim 22The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: the nonmetal comprises one or more elements of carbon, nitrogen and oxygen.
5. An S-shaped MoS according to claim 1 or 22The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: the mass fraction of titanium in the titanium alloy is 2-99%.
6. An S-shaped MoS according to claim 12The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: the substrate is one of a titanium mesh, a titanium alloy mesh or a stainless steel mesh.
7. An S-shaped MoS according to claim 12The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: the etching treatment specifically comprises the following steps: cleaning the substratePlacing the substrate into oxalic acid solution with the mass fraction of 5% -15%, etching for 35-45min under the boiling state, washing the etched substrate with deionized water, and drying.
8. An S-shaped MoS according to claim 12The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: in the step (2), thiourea, ammonium molybdate tetrahydrate and deionized water are mixed for 5-15min according to the weight ratio of 1.3-1.8:1:50-60 to prepare the light absorption material.
9. An S-shaped MoS according to claim 12The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: the specific method of the step (3) is as follows: and (3) reacting the pretreated substrate with a light absorption material at the temperature of 180-230 ℃ for 18-25h, and then cleaning and drying the substrate by using deionized water to obtain the photothermal film.
10. An S-shaped MoS according to claim 12The preparation method of the-Ti net photo-electric-thermal seawater desalination membrane is characterized by comprising the following steps of: the mesh number of the substrate is 250-350 meshes, and the thickness is 0.2-0.8 mm; the shape of the structure cut in the step (4) comprises an S shape, and the cutting size is 10.5-13.5cm in length and 2.5-3.5cm in width.
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