CN113816455B - Two-dimensional tricotitanium carbide/titanium dioxide heterojunction-based film and preparation method and application thereof - Google Patents
Two-dimensional tricotitanium carbide/titanium dioxide heterojunction-based film and preparation method and application thereof Download PDFInfo
- Publication number
- CN113816455B CN113816455B CN202111214192.2A CN202111214192A CN113816455B CN 113816455 B CN113816455 B CN 113816455B CN 202111214192 A CN202111214192 A CN 202111214192A CN 113816455 B CN113816455 B CN 113816455B
- Authority
- CN
- China
- Prior art keywords
- dimensional
- film
- carbide
- trititanium
- heterojunction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- 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
- C02F1/08—Thin film evaporation
-
- 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
- C02F1/10—Treatment of water, waste water, or sewage by heating by distillation or evaporation by direct contact with a particulate solid or with a fluid, as a heat transfer medium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a two-dimensional titanium carbide/titanium dioxide heterojunction-based film and a preparation method and application thereof, belonging to the technical field of photo-thermal conversion materials. According to the invention, the two-dimensional trititanium carbide suspension is subjected to suction filtration, so that the trititanium carbide film with micron-sized thickness is formed to ensure sufficient light absorption; then annealing the titanium carbide two-dimensional film under vacuum to form a film consisting of a two-dimensional titanium carbide two-dimensional/titanium dioxide heterojunction. The heterojunction effectively promotes the transfer kinetics of the heat charge generated by the two-dimensional titanium carbide under the illumination condition, and finally greatly improves the photo-thermal conversion property of the film. When the two-dimensional trititanium dicarbonate/titanium dioxide heterojunction-based film prepared by the invention is used for photo-thermal seawater desalination, on one hand, the composite film can efficiently convert solar energy into heat energy; on the other hand, the composite film prepared by the invention has excellent salt resistance.
Description
Technical Field
The invention relates to the technical field of photo-thermal conversion materials, in particular to a two-dimensional trititanium carbide/titanium dioxide heterojunction-based film and a preparation method and application thereof.
Background
With the continuous decrease of fossil fuels, solar energy has become an important component in energy utilization of people. The photothermal conversion can directly convert solar energy into heat energy and utilize the heat energy, and is one of the main ways to realize the utilization of solar energy. However, since the solar energy has a small and discontinuous energy density after reaching the earth, it is difficult to develop and utilize the solar energy on a large scale. The photothermal conversion functional material is a material that can effectively utilize solar energy by means of photothermal conversion, and allows conversion of light energy into heat energy, thereby enabling the photothermal conversion functional material to be applied to various fields.
The ideal photothermal material should have extremely high photothermal conversion capability, and various kinds of nanostructured photothermal materials have been widely explored, such as metal nanoparticles, semiconductors, nanocarbon materials, two-dimensional transition metal carbides and nitrides (MXenes), and even some organic polymers. In recent years, two-dimensional MXene having metal-like properties exhibits an attractive photothermal conversion capability due to its LSPR effect and absorption capability covering almost the entire solar spectrum. However, the lateral dimension of the two-dimensional MXene sheets is generally less than 5 μm, so that the two-dimensional MXene sheets generally have to be assembled into a stacked two-dimensional MXene form (such as a filtering film and a porous foam film) in application to absorb sufficient light energy to meet the requirements of practical application scenarios; moreover, internal thermal resistance caused by the stacking form of the two-dimensional MXene enables photo-thermal conversion of the composite material to be remarkably reduced compared with that of a two-dimensional MXene nanosheet; in addition, the two-dimensional MXene is restricted by the preparation method thereof, and mass production is difficult. The further application of the two-dimensional MXene material in the field of photo-thermal is severely limited by the factors. Therefore, there is a need to develop a new material or structure based on two-dimensional MXene to overcome the internal thermal resistance caused by the two-dimensional sheet stacking, so as to significantly enhance the light-to-heat conversion performance thereof and reduce the material amount requirement, thereby further promoting the practical application thereof.
Disclosure of Invention
The invention aims to provide a two-dimensional trititanium carbide/titanium dioxide heterojunction-based thin film and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method based on a two-dimensional titanium carbide/titanium dioxide heterojunction film, which comprises the following steps:
providing a two-dimensional titanium dicarbonic nano-sheet suspension;
carrying out suction filtration on the two-dimensional trititanium carbide nanosheet suspension to obtain a trititanium carbide thin film;
and annealing the trititanium dicarbonide film in vacuum to obtain the two-dimensional trititanium dicarbonide/titanium dioxide heterojunction-based film.
Preferably, the concentration of the two-dimensional trititanium carbide suspension is 0.1-10 mg/mL.
Preferably, the annealing atmosphere comprises nitrogen, argon or vacuum.
Preferably, the degree of vacuum in the apparatus during annealing is-0.07 to-0.1 MPa.
Preferably, the temperature of the annealing is 350 to 650 ℃.
Preferably, the heating rate of heating to the annealing temperature is 2-15 ℃/min.
Preferably, the duration of the heat preservation stage in the annealing process is 0.5-2 h.
The invention also provides a film based on the two-dimensional tricotitanium carbide/titanium dioxide heterojunction, which is prepared by the preparation method in the technical scheme and comprises a composite film consisting of the two-dimensional tricotitanium carbide and the titanium dioxide heterojunction.
The invention also provides the application of the two-dimensional titanium carbide/titanium dioxide heterojunction-based film in seawater desalination, which is characterized in that the two-dimensional titanium carbide/titanium dioxide heterojunction-based film is provided with holes for water evaporation.
Preferably, the density of the holes is 90/cm 2 The diameter of the hole is 0.23mm.
The invention provides a preparation method based on a two-dimensional titanium carbide/titanium dioxide heterojunction film, which comprises the following steps: providing a two-dimensional titanium dicarbonic nano-sheet suspension; carrying out suction filtration on the two-dimensional trititanium carbide nanosheet suspension to obtain a trititanium carbide thin film; annealing the film consisting of the two-dimensional titanium carbide nano-sheets in vacuum to obtain two-dimensional titanium carbide/titanium dioxide (hereinafter referred to as Ti for short) 3 C 2 /TiO 2 ) The heterojunction forms a composite film with high-efficiency photothermal conversion performance. The invention is realized by mixing two-dimensional Ti 3 C 2 The nano-sheet suspension is filtered to form Ti with micron-sized thickness 3 C 2 Thin films to ensure sufficient light absorption; then adding Ti 3 C 2 Annealing the film under vacuum to make the two-dimensional Ti 3 C 2 The oxygen-containing functional groups on the surface are broken to generate surface hydrophobicity, and meanwhile, the oxygen element and the Ti element are combined in the lamella to form rich two-dimensional Ti 3 C 2 /TiO 2 A heterojunction; and the heterojunction is distributed in two-dimensional Ti 3 C 2 Due to two-dimensional Ti 3 C 2 Has a large specific surface area, so that the two-dimensional Ti 3 C 2 /TiO 2 The heterojunction compound film can effectively promote the transfer kinetics of the thermal charge generated by MXene under the illumination condition, and finally the photo-thermal conversion performance of the film is greatly improved. When the film prepared by the invention is used for seawater desalination, on one hand, the film has excellent photo-thermal conversion performance and is based on two-dimensional Ti 3 C 2 /TiO 2 The heterojunction film can convert sunlight into heat energy to the maximum extent, and is favorable for application of seawater desalination. In another aspect, the invention provides two-dimensional Ti-based articles prepared by the method of the invention 3 C 2 /TiO 2 The heterojunction film has excellent salt resistance, so that salt in seawater cannot permeate into the material, and the photo-thermal conversion capability of the material cannot be influenced. The results of the examples show that the Ti-based material prepared by the preparation method provided by the invention is based on two-dimensional Ti 3 C 2 /TiO 2 The heterojunction film has 1.52 Kg.m under 1 sun illumination -2 ·h -1 The water evaporation rate of (2). Meanwhile, the surface of the film is not adhered with salt within 12h of illumination, and the film has good salt resistance.
Drawings
FIG. 1 is a schematic diagram of a seawater desalination apparatus provided by the present invention;
FIG. 2 is a photograph of a trititanium carbide thin film prepared in example 1 of the present invention;
FIG. 3 is a TEM (transmission electron microscope) image of two-dimensional trititanium carbide in a trititanium carbide thin film prepared in example 1 of the present invention;
FIG. 4 shows a three-titanium-carbide thin film prepared in example 1, and two-dimensional Ti-based thin films prepared in examples 1 and 2 according to the present invention 3 C 2 /TiO 2 XRD (X-ray diffraction) pattern of the heterojunction thin film;
FIG. 5 shows two-dimensional Ti-based alloy prepared in example 1 of the present invention 3 C 2 /TiO 2 SEM (scanning electron microscope) images of the heterojunction thin film cross-section;
FIG. 6 shows two-dimensional Ti-based alloy prepared in example 1 of the present invention 3 C 2 /TiO 2 In the heterojunction thin film is composed ofTwo-dimensional Ti 3 C 2 /TiO 2 A TEM image of the constructed two-dimensional heterojunction;
FIG. 7 is a diagram showing the mass change of the seawater desalination plant assembled in the application examples 1 to 3 of the present invention under 1 sun illumination for 30 minutes;
Detailed Description
The invention provides a two-dimensional Ti-based material 3 C 2 /TiO 2 The preparation method of the heterojunction thin film comprises the following steps:
providing a two-dimensional titanium dicarbonic nano-sheet suspension;
carrying out suction filtration on the two-dimensional trititanium carbide nanosheet suspension to obtain a trititanium carbide film;
annealing the titanium carbide nitride film under vacuum to obtain the titanium nitride film based on two-dimensional Ti 3 C 2 /TiO 2 A heterojunction thin film.
The invention provides a two-dimensional trititanium dicarbocarbide nanosheet suspension. In the present invention, the number of layers of the two-dimensional trititanium carbide nanosheet is preferably a small number of layers, more preferably 1 to 3 layers, and still more preferably a single layer. In the present invention, the concentration of the two-dimensional trititanium carbide suspension is preferably 0.1 to 10mg/mL, and more preferably 4 to 8mg/mL. In the invention, when the concentration of the single-layer two-dimensional trititanium dicarbonate suspension is in the range, the two-dimensional trititanium dicarbonate nanosheet suspension which is uniformly dispersed can be obtained more favorably, and the titanium tricatanium dicarbonate thin film with uniform thickness can be obtained favorably during suction filtration. In the invention, the solvent of the two-dimensional trititanium carbide suspension is preferably deionized water.
The preparation method of the two-dimensional titanium carbide nanosheet suspension is not particularly limited, and the two-dimensional titanium carbide nanosheet suspension can be uniformly mixed with a solvent. In the invention, the preparation method of the two-dimensional titanium dicarbonide suspension is preferably to mix the two-dimensional titanium dicarbonide and the solvent uniformly under ultrasound.
The source of the two-dimensional trititanium carbide is not particularly limited in the present invention, and commercially available products known to those skilled in the art or two-dimensional trititanium carbide prepared by a conventional preparation method may be used. In the present invention, the two dimensions areThe titanocene carbo-diimide is preferably commercially available Ti well known to those skilled in the art 3 C 2 T x 。
After the two-dimensional titanium carbide nano-sheet suspension is obtained, the two-dimensional titanium carbide nano-sheet suspension is subjected to suction filtration to obtain the titanium carbide thin film.
The method of suction filtration is not particularly limited in the present invention, and a suction filtration method known to those skilled in the art may be used. In the invention, the solvent in the two-dimensional trititanium carbide suspension can be removed by suction filtration, so that the two-dimensional trititanium carbide is stacked to form the trititanium carbide film. In the present invention, the filter paper subjected to suction filtration is preferably a mixed cellulose film.
After the suction filtration is finished, the filter paper obtained after the suction filtration and the tricotitanium dicarbonide film are preferably dried and separated to obtain the tricotitanium dicarbonide film. In the present invention, the drying temperature is preferably 60 ℃, and the drying time is preferably 12 hours. In the present invention, when the drying temperature and time are within the above ranges, the filter paper and the trititanium carbide thin film obtained after the suction filtration can be sufficiently dried.
The method for separating is not particularly limited, and the separation of the trititanium carbide film and the filter paper can be realized without damaging the trititanium carbide film. In the present invention, the method of separating the trititanium carbide thin film from the filter paper is preferably repeated kneading. In the present invention, the repeated kneading enables the separation of the two without damaging the trititanium carbide film.
After the trititanium dicarbonide film is obtained, the trititanium dicarbonide film is annealed in vacuum to obtain two-dimensional Ti 3 C 2 /TiO 2 A heterojunction thin film. In the invention, the annealing can break the oxygen-containing functional groups on the surface of the titanium carbide triticum film to change the titanium carbide triticum film from hydrophilic to hydrophobic Ti 3 C 2 A thin film having excellent photothermal conversion properties; meanwhile, oxygen element and Ti element are combined in the lamella to form rich two-dimensional Ti 3 C 2 /TiO 2 A heterojunction. The heterojunction effectively promotes MX under illumination conditionThe transfer kinetics of the charges generated by ene finally lead to the great improvement of the photothermal conversion property of the film.
In the present invention, the annealing is performed under vacuum. In the present invention, the degree of vacuum in the apparatus at the time of annealing when the annealing is maintained in a vacuum state is preferably-0.07 to-0.1 MPa, more preferably-0.1 MPa. In the present invention, the atmosphere for the annealing is preferably nitrogen, argon, or vacuum. In the present invention, the vacuum can prevent the trititanium carbide thin film from being excessively oxidized during annealing.
The method and apparatus for the annealing operation of the present invention are not particularly limited, and annealing methods and apparatuses known to those skilled in the art may be used. In the present invention, the annealing apparatus is preferably a tube furnace.
In the present invention, the temperature of the annealing is preferably 350 to 650 ℃, more preferably 500 ℃. In the present invention, when the annealing temperature is in the above range, the trititanium carbide thin film can have excellent hydrophobic photothermal conversion performance; furthermore, oxygen and Ti combine to form more two-dimensional Ti in the sheet layer 3 C 2 /TiO 2 And the heterojunction improves the photo-thermal conversion performance of the composite film.
In the present invention, the rate of temperature rise until the annealing is performed is preferably 2 to 15 ℃/min, more preferably 5 to 10 ℃/min. In the invention, when the temperature rise rate is in the above range, annealing can be performed sufficiently, and the titanium tricarboxide film can be prevented from being damaged in the annealing process due to the excessively high temperature rise rate.
In the present invention, the duration of the heat-preserving stage in the annealing process is preferably 0.5 to 2 hours, and more preferably 1 to 2 hours. In the present invention, when the annealing is carried out for a holding time within the above range, the oxygen-containing functional groups on the surface of the trititanium carbide thin film can be sufficiently cleaved to change the hydrophilicity of the trititanium carbide thin film into a trititanium carbide thin film having excellent hydrophobicity; furthermore, oxygen and Ti combine to form more two-dimensional Ti in the sheet layer 3 C 2 /TiO 2 The heterojunction improves the photo-thermal conversion performance of the photo-thermal film.
In the invention, the cooling mode is that the tricotanium carbide film is still in a vacuum state during furnace cooling, so that the material can be prevented from being excessively oxidized in the cooling process to influence the photo-thermal conversion performance of the tricotanium carbide film.
The preparation method provided by the invention is simple to operate, and can be based on two-dimensional Ti by only annealing the trititanium carbide film 3 C 2 /TiO 2 A heterojunction film, and the film has super-strong photo-thermal conversion performance.
The invention also provides two-dimensional Ti-based material prepared by the preparation method of the technical scheme 3 C 2 /TiO 2 A heterojunction film comprises a composite film consisting of a two-dimensional trititanium carbide and titanium dioxide heterojunction. The invention provides two-dimensional Ti 3 C 2 /TiO 2 The heterojunction film is characterized in that the annealing treatment is carried out on the tricontanium carbide film in the preparation process, so that the two-dimensional tricontanium carbide in the composite film formed by the two-dimensional tricontanium carbide and the titanium dioxide heterojunction still keeps a single-layer or few-layer state.
The invention also provides the technical scheme based on the two-dimensional Ti 3 C 2 /TiO 2 The heterojunction film is applied to seawater desalination.
In the present invention, the two-dimensional Ti-based 3 C 2 /TiO 2 When the heterojunction film is applied to seawater desalination, the two-dimensional Ti-based film 3 C 2 /TiO 2 The heterojunction film is provided with holes for water evaporation. In the present invention, the two-dimensional Ti-based 3 C 2 /TiO 2 The surface of the heterojunction film is provided with holes, so that water vapor is discharged during seawater desalination. In the present invention, the number of the holes is preferably two or more. The invention is about the two-dimensional Ti 3 C 2 /TiO 2 The number of the holes in the heterojunction thin film is not particularly limited and can be adjusted as required. In the present invention, the density of the holes is 90 per square centimeter; the pore diameter of the pores is preferably 0.23 μm. In the present invention, when the number and diameter of the holes are in the above ranges, the water vapor can be discharged more easily.
In the present invention, the base is twoVitamin Ti 3 C 2 /TiO 2 When the heterojunction film is used for seawater desalination, the preparation method is preferably based on two-dimensional Ti 3 C 2 /TiO 2 The heterojunction film is perforated, more preferably before annealing the trititanium carbide film. In the invention, the titanium tricarboxide thin film is punched before annealing, so that the hole interface has more excellent hydrophobicity during annealing, and further, the water vapor is discharged.
The invention is about the two-dimensional Ti 3 C 2 /TiO 2 The application device of the heterojunction film in seawater desalination is not particularly limited, and a seawater desalination device well known to those skilled in the art can be adopted.
In the invention, the seawater desalination device preferably consists of an evaporation layer, a transportation layer and a support layer which are arranged from top to bottom in sequence. In the present invention, the schematic diagram of the seawater desalination apparatus is preferably as shown in fig. 1. In fig. 1, the seawater to be treated is placed in a container on the underside of the support layer; the support layer of the device is made of polystyrene with low density and good heat preservation; the transport layer is preferably polyurethane sponge, and the polyurethane sponge as the transport layer can transport the lower seawater to the evaporation layer through the surface tension of water; the evaporation layer (photothermal film) is the two-dimensional Ti-based film prepared by the invention 3 C 2 /TiO 2 The heterojunction film utilizes the superstrong light and heat conversion performance of this membrane can be with solar energy conversion heat energy to the realization is to the evaporation of sea water.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Based on two-dimensional Ti 3 C 2 /TiO 2 The preparation method of the heterojunction film comprises the following steps:
300mg of a single layer of two-dimensional titanocene-dicarbonide powder (Ti) 3 C 2 T x ) Dissolving the mixture in 50mL of deionized water, and stirring to obtain a single-layer two-dimensional titanium dicarbonide suspension;
using a water system mixed cellulose membrane with the aperture of 0.23 mu m and the diameter of 5cm as filter paper, adopting a glass filter flask with the mouth diameter of 4cm to perform vacuum filtration to deposit monolayer two-dimensional tricot carbide in the obtained monolayer two-dimensional tricot carbide suspension on the surface of the filter paper, putting the obtained tricot carbide membrane containing the filter paper into a vacuum drying oven, and drying for 12 hours in an environment with the vacuum degree of-0.1 MPa and the temperature of 60 ℃; repeatedly bending the dried tricontanium carbide film containing the filter paper to separate the tricontanium carbide film from the filter paper to obtain a tricontanium carbide film with the diameter of 4 cm;
annealing the trititanium carbide film, wherein the annealing step comprises the following steps: the membrane, having a diameter of 4cm, was placed in an alumina crucible having dimensions of 100X 50X 30mm and placed in a tube annealing furnace. The temperature is raised to 500 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 1h under the environment of the vacuum degree of minus 0.1MPa and the temperature of 500 ℃, and then the temperature is slowly cooled to the room temperature along with the furnace.
Example 2
The difference from example 1 was that the annealing temperature was 650 deg.C, and the remaining steps were the same as in example 1.
Test example 1
A photograph of the trititanium carbide thin film prepared in example 1 is shown in FIG. 2. As can be seen from FIG. 2, the trititanium carbide film prepared by the present invention is a black film in appearance, and is not broken.
The trititanium carbide thin film prepared in example 1 was tested by a transmission electron microscope, and a TEM image and an electron diffraction photograph were obtained as shown in fig. 3. As can be seen from FIG. 3, the two-dimensional trititanium carbide in the trititanium carbide thin film prepared by the invention is a single layer of trititanium carbide.
Tri-titanium carbide thin film prepared in example 1, two-dimensional Ti-based thin film prepared in examples 1 and 2, and a method of manufacturing the same 3 C 2 /TiO 2 The heterojunction film was tested and the XRD pattern was obtained as shown in FIG. 4Shown in the figure. As can be seen from FIG. 4, the two-dimensional Ti-based material prepared by the preparation method provided by the invention 3 C 2 /TiO 2 The heterojunction film has a characteristic peak at about 5-10 degrees, which shows that the two-dimensional sheet layers forming the film are still in an independent form and are not fused at high temperature; a new peak in the titanium dioxide between 20 and 25 ℃ appears, indicating that the oxidation of the lamella leads to the formation of titanium dioxide. Therefore, the composite film obtained by the preparation method provided by the application can simultaneously generate the characteristic peaks of titanium dioxide and trititanium carbide. This indicates that annealing can change the arrangement of the two-dimensional trititanium carbide MXene composite film comprising TiO 2 And Ti 3 C 2 And forming a heterojunction. This modification allows the two-dimensional Ti-based materials prepared according to the present invention 3 C 2 /TiO 2 The heterojunction thin film has excellent photo-thermal conversion performance.
Two-dimensional Ti-based films prepared in example 1 by scanning Electron microscopy 3 C 2 /TiO 2 The cross section of the heterojunction film was scanned and SEM images were obtained as shown in fig. 5. As can be seen from FIG. 5, the two-dimensional Ti-based alloy prepared by the present invention 3 C 2 /TiO 2 The heterojunction film is formed by stacking single-layer two-dimensional titanium carbide.
Two-dimensional Ti-based material prepared in example 1 of the present invention by transmission electron microscopy 3 C 2 /TiO 2 The heterojunction film is tested to obtain the two-dimensional Ti 3 C 2 /TiO 2 Two-dimensional Ti in the heterojunction film 3 C 2 /TiO 2 A TEM image of the constructed two-dimensional heterojunction is shown in fig. 6. As can be seen from FIG. 6, ti in the thin film prepared by the present invention 3 C 2 /TiO 2 The two-dimensional heterojunction is of a two-dimensional structure.
Tri-titanium carbide thin films prepared in example 1, two-dimensional Ti-based films prepared in examples 1 and 2, and a UV-visible spectrophotometer 3 C 2 /TiO 2 The heterojunction film is tested, and the two-dimensional Ti-based film prepared by the invention 3 C 2 /TiO 2 The heterojunction film has light absorption performance in the wavelength range of 200-1050 nm, which shows that the preparation method of the invention has the advantages of simple process, low cost and high efficiencyBased on two-dimensional Ti 3 C 2 /TiO 2 The heterojunction film has excellent light absorption.
Three-titanium carbide thin films prepared in example 1, two-dimensional Ti-based thin films prepared in examples 1 and 2, and a manufacturing method thereof 3 C 2 /TiO 2 The heterojunction film is tested, and the two-dimensional Ti-based film prepared by the invention 3 C 2 /TiO 2 The power density of the heterojunction film is 1.5w/cm 2 The local highest temperature of the 808nm infrared light irradiation can reach 170 ℃, which is far higher than the local highest temperature of the titanium carbide three film under the infrared light irradiation without annealing, thereby showing that the photothermal conversion film prepared by the invention has excellent photothermal conversion performance.
Application example 1
The preparation method of the embodiment 1 is adopted, and the difference from the embodiment 1 is that before annealing, a needle head with the outer diameter of 0.18mm is adopted to uniformly perforate a trititanium dicarboxide film with the diameter of 4cm to obtain a porous trititanium dicarboxide film, and then annealing is carried out to obtain the titanium dicarboxide film based on two-dimensional Ti 3 C 2 /TiO 2 A heterojunction thin film.
Prepared based on two-dimensional Ti 3 C 2 /TiO 2 The heterojunction film is assembled into a seawater desalination plant according to figure 1.
Comparative application example 1
Except that the evaporation layer was the trititanium carbide thin film prepared in example 1 in application example 1.
Comparative application example 2
The difference from application example 1 is that no evaporation layer was provided and no film was covered.
Test example 2
The sea water desalination devices assembled in application examples 1 to 3 were respectively exposed to 1 sun for 30min, and the mass change of the devices was recorded, and the mass change chart was obtained as shown in fig. 7. As can be seen from FIG. 7, the two-dimensional Ti-based alloy prepared by the present invention 3 C 2 /TiO 2 When the heterojunction film is used as a photothermal film, the photothermal film has a concentration of 1.52 Kg.m under 1 sun illumination -2 ·h -1 The evaporation rate of water is far higher than that of the dicarbonizationThe evaporation rate of the trititanium film as an evaporation film is also far higher than that of water when the evaporation film is not used. Thus, the Ti based on two-dimension prepared by the invention 3 C 2 /TiO 2 When the heterojunction film is used as a photo-thermal film, the evaporation rate and the evaporation efficiency of the seawater are higher than those of the titanium tricarboxide film.
Further, the device of application example 1 was free from salt adhesion on the inner surface within 12h of light irradiation, exhibiting good salt resistance.
As can be seen from the above experimental process, the two-dimensional Ti-based alloy prepared by the invention 3 C 2 /TiO 2 The heterojunction film has excellent photo-thermal conversion performance when being used for seawater desalination. This is probably because the hydroxyl functional groups on the surface of the trititanium carbide film are broken after annealing, so that the trititanium carbide film is changed from hydrophilic to hydrophobic and has excellent photothermal conversion performance. Based on two-dimensional Ti prepared by the invention 3 C 2 /TiO 2 The heterojunction film has excellent photo-thermal conversion performance and hydrophobicity, so that when the heterojunction film is used for seawater desalination, on one hand, the heterojunction film prepared by the method is based on two-dimensional Ti 3 C 2 /TiO 2 The heterojunction film has excellent hydrophobicity, so that seawater cannot enter the film, the salt resistance is excellent, salt in the seawater cannot permeate into the material, and the salt resistance is excellent, so that the photo-thermal capability of the material cannot be influenced; in another aspect, the invention provides two-dimensional Ti-based articles 3 C 2 /TiO 2 The heterojunction film has excellent photo-thermal conversion performance, can convert sunlight into heat energy to the maximum extent, and is favorable for evaporation of seawater.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (5)
1. The application of the two-dimensional trititanium dicarbonate/titanium dioxide-based heterojunction film in seawater desalination is characterized in that holes for water evaporation are formed in the two-dimensional trititanium dicarbonate/titanium dioxide-based heterojunction film; the preparation method based on the two-dimensional titanium carbide/titanium dioxide heterojunction film comprises the following steps:
providing a two-dimensional titanium dicarbonic nano-sheet suspension;
carrying out suction filtration on the two-dimensional trititanium carbide nanosheet suspension to obtain a trititanium carbide thin film;
annealing the titanium carbide nitride film under vacuum to obtain a two-dimensional titanium carbide nitride/titanium dioxide heterojunction-based film; the vacuum degree in the device during annealing is-0.07 to-0.1 MPa; the annealing temperature is 650 ℃; the heating rate of heating to the annealing temperature is 2-15 ℃/min.
2. Use according to claim 1, wherein the density of the holes is 90/cm 2 The diameter of the hole is 0.23mm.
3. Use according to claim 1, wherein the concentration of the two-dimensional trititanium carbide suspension is between 0.1 and 10mg/mL.
4. Use according to claim 1, wherein the annealing atmosphere comprises nitrogen, argon or vacuum.
5. Use according to claim 1, wherein the duration of the holding phase in the annealing process is between 0.5 and 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111214192.2A CN113816455B (en) | 2021-10-19 | 2021-10-19 | Two-dimensional tricotitanium carbide/titanium dioxide heterojunction-based film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111214192.2A CN113816455B (en) | 2021-10-19 | 2021-10-19 | Two-dimensional tricotitanium carbide/titanium dioxide heterojunction-based film and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113816455A CN113816455A (en) | 2021-12-21 |
| CN113816455B true CN113816455B (en) | 2022-12-20 |
Family
ID=78916974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111214192.2A Active CN113816455B (en) | 2021-10-19 | 2021-10-19 | Two-dimensional tricotitanium carbide/titanium dioxide heterojunction-based film and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113816455B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879405B (en) * | 2017-10-26 | 2021-06-11 | 西安交通大学 | Solar water evaporation purification and decomposition device |
| US10960347B1 (en) * | 2018-05-17 | 2021-03-30 | King Abdullah University Of Science And Technology | Water vapor harvesting materials and devices |
| CN109530688B (en) * | 2018-11-05 | 2020-10-20 | 山东科技大学 | Porous ceramic membrane material for photo-thermal seawater desalination and preparation method and application thereof |
| CN109569319B (en) * | 2018-12-14 | 2021-12-21 | 华南理工大学 | Application of two-dimensional self-crosslinking MXene membrane in ion separation |
| CN110152699A (en) * | 2019-05-19 | 2019-08-23 | 北京化工大学 | A kind of application of the preparation method and its photocatalytic reduction of carbon oxide of cuprous oxide and two carbonization Tritanium/Trititanium heterojunction composites |
| CN111122534B (en) * | 2019-10-28 | 2022-08-16 | 苏州大学 | Raman test method of compound based on two-dimensional titanium carbide nanosheet |
| CN113060734B (en) * | 2021-04-06 | 2023-04-28 | 郑州大学 | Infrared low-emissivity MXene film and preparation method thereof |
| CN113023809B (en) * | 2021-05-07 | 2022-08-05 | 南京林业大学 | Preparation method of membrane material for solar interface evaporation seawater desalination |
-
2021
- 2021-10-19 CN CN202111214192.2A patent/CN113816455B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113816455A (en) | 2021-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zheng et al. | Post-annealing reinforced hollow carbon nitride nanospheres for hydrogen photosynthesis | |
| Li et al. | Interfacial charge modulation: carbon quantum dot implanted carbon nitride double-deck nanoframes for robust visible-light photocatalytic tetracycline degradation | |
| RU2003117114A (en) | ELECTRODE-ELECTROLYTE VAPOR BASED ON ZIRCONIUM DIOXIDE (OPTIONS), METHOD FOR ITS PRODUCTION (OPTIONS) AND ORGANOGEL | |
| Qian et al. | China rose petal as biotemplate to produce two-dimensional ceria nanosheets | |
| JP2009221050A (en) | Self-standing mesoporous carbon thin film | |
| US11739985B2 (en) | Boron carbide bilayer foam solar evaporator and method for preparing thereof | |
| JP2008207152A (en) | Porous metal body with reaction efficiency enhanced and its production method | |
| Jiang et al. | Titania nanowires coated PEI/P25 membranes for photocatalytic and ultrafiltration applications | |
| KR100752954B1 (en) | Method for preparing nano porous powders by ultrasonic pyrolysis and its nano powders | |
| CN113816455B (en) | Two-dimensional tricotitanium carbide/titanium dioxide heterojunction-based film and preparation method and application thereof | |
| US20230361315A1 (en) | Method for producing catalyst-coated membranes | |
| US20200355403A1 (en) | Porphyrin covalent organic framework (pof)-based interface | |
| KR20200062049A (en) | Hollow fiber type photocatalyst and manufacturing method thereof | |
| JP4464670B2 (en) | Manufacturing method of composite material | |
| CN114408904B (en) | 3D printing preparation method of graphene macroscopic body with high crystal quality | |
| JP5214907B2 (en) | Solid electrolyte membrane and method for producing the same | |
| CN113130930B (en) | Gas diffusion layer material, electrode comprising same, preparation and application | |
| JP4904481B2 (en) | Gas separation membrane and method for producing the same | |
| CN114405530A (en) | Method for preparing composite photocatalyst | |
| CN113353912A (en) | Preparation method and application of porous carbon material with high light-heat conversion efficiency | |
| Hyodo et al. | Three dimensional arrays of hollow gadolinia-doped ceria microspheres prepared by rf magnetron sputtering employing PMMA microsphere templates | |
| JP4577159B2 (en) | Porous material and method for producing the same | |
| Wijaya et al. | Crystal structure and optical properties of oxygen-deficiency of barium titanate (BaTiO3-x) prepared by sol-gel method | |
| CN115646530B (en) | Double-promotion boron-doped accordion-shaped graphite carbon nitride photocatalyst and preparation method and application thereof | |
| KR102549079B1 (en) | Organic photocatalyst and Method for preparing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |