CN111790424A - Photocatalyst with efficient absorption of visible light and preparation method and application thereof - Google Patents

Photocatalyst with efficient absorption of visible light and preparation method and application thereof Download PDF

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CN111790424A
CN111790424A CN202010641624.7A CN202010641624A CN111790424A CN 111790424 A CN111790424 A CN 111790424A CN 202010641624 A CN202010641624 A CN 202010641624A CN 111790424 A CN111790424 A CN 111790424A
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photocatalyst
preparation
ammoniation
natao
visible light
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韦之栋
上官文峰
江治
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Shanghai Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

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Abstract

The invention discloses a preparation method of a photocatalyst capable of efficiently absorbing visible light, wherein the photocatalyst comprises Ta3N5The preparation method comprises the following steps: ta is prepared by adopting an ammoniation-calcination two-step method3N5. In addition, the invention also discloses a photocatalyst capable of efficiently absorbing visible light, and the photocatalyst is prepared by adopting the preparation method. In addition, the invention also discloses application of the photocatalyst with efficient absorption on visible light, and the photocatalyst is used for solar hydrogen production. The photocatalyst has simple preparation process, low manufacturing cost and simple required preparation conditions, thereby being easy to industrialize.

Description

Photocatalyst with efficient absorption of visible light and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a photocatalyst and a preparation method and application thereof. In particular to a Ta with visible light absorption capability3N5The preparation method of (1).
Background
Among many technical methods for producing hydrogen by solar energy, the suspension system solar photocatalytic hydrogen production method has received extensive attention from the scientific community because it can convert solar energy into hydrogen energy in one step. Meanwhile, the suspension system solar photocatalytic hydrogen production has the characteristics of low manufacturing cost, simple reaction system and easy scale production, thereby also arousing some attention in the industry.
However, the suspension system solar photocatalytic hydrogen production is in industrialization due to the conversion efficiency, which is closely related to many factors such as light absorption efficiency, and further industrialization development is restricted.
Therefore, development of a catalyst having a broad spectral response is one of important means for improving photocatalytic efficiency. Wherein, Ta3N5Has the capability of absorbing visible light, is a photocatalyst with great potential, and is widely applied to photocatalysis. However, Ta3N5The synthesis method is single, and at present, only a high-temperature ammoniation method is adopted, namely, Ta is subjected to a long-time high-temperature calcination process in a pure ammonia atmosphere2O5Or nitriding of metallic tantalum powder to Ta3N5。
However, it should be noted that the above preparation method has many disadvantages, such as: the reaction conditions are harsh, the reaction conditions are difficult to control, or the calcination time is too long, which easily causes the problems of serious sintering of the catalyst and the like.
Through the search of documents and patents, the patents and documents related to the photocatalyst are as follows: the publication number is CN110963471A, the publication number is 2020, 4 and 7 days, and the name is' one molten salt ion exchange type one-step method for synthesizing Ta3N5The Chinese patent document of (1) discloses a fused salt ion exchange type one-step method for synthesizing Ta3N5The method of (1). In the technical scheme disclosed in the patent document, a novel preparation method is provided for overcoming the defects of the traditional method, but the preparation method needs a vacuum tube sealing process, has higher requirements on equipment and experimental operation, and introduces magnesium nitride into the adopted raw materials, thereby increasing the synthesis of Ta3N5The cost of (a).
Another example is: chinese patent publication No. CN104815655A, published as 2015, 8, and 5, entitled "visible-light-responsive plasma photocatalyst and preparation method thereof", discloses a visible-light-responsive plasma photocatalyst. In the technical scheme disclosed in the patent document, the obtained photocatalyst is a nano-gold embedded tantalum nitride plasma photocatalyst.
In view of this, it is desirable to obtain a photocatalyst that is easy to industrialize because of its simple preparation process, low manufacturing cost, and simple preparation conditions required.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a photocatalyst with efficient absorption on visible light, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a method for preparing a photocatalyst having high absorption of visible light, the photocatalyst comprising Ta3N5The preparation method comprises the following steps: ta is prepared by adopting an ammoniation-calcination two-step method3N5。
Preferably, in the preparation method of the invention, the ammoniation-calcination two-step method comprises the following steps:
an ammoniation step: uniformly mixing a nitrogen source and a tantalum source, sealing and carrying out ammoniation treatment to obtain a composite product;
and (3) calcining: the composite product is calcined for the second time in vacuum or inert atmosphere to obtain Ta3N5。
In the above process, the ammoniation step may be performed as follows: for example, the nitrogen source and the tantalum source may be uniformly ground, and then the uniformly ground nitrogen source and tantalum source may be transferred to a crucible, which may be sealed with a double layer of aluminum foil, and then the crucible may be placed in a muffle furnace for elevated temperature and ammoniation treatment.
In the scheme, in the ammoniation step, a large amount of ammonia gas is released during heating, so that the tantalum source is favorably nitrided, and the molten state of the nitrogen source is also favorable for reducing the ammoniation temperature of the tantalum source. Preferably, in some embodiments, less expensive urea may be used for cost control reasons. Furthermore, in some embodiments, considering that gas such as ammonia gas is released during the ammonification process, and in order that the released gas does not react with the inner wall of the sealed container, it can be considered to use aluminum foil at the sealing portion to ensure that the ammonification process is performed smoothly in a sealed environment, and the released gas does not further react with the sealed container.
Preferably, in the preparation method of the present invention, the preparation method further comprises a washing step of: ta prepared by adopting an ammoniation-calcination two-step method3N5Washing with ultrapure water until neutral.
Preferably, in the preparation method of the present invention, in the ammoniation step, the nitrogen source is at least one of urea, cyanamide, dicyandiamide and melamine, and the tantalum source includes NaTaO3、KTaO3、LiTaO3At least one of (a).
In the above scheme, the method is considered to be compared with the metal tantalum simple substance and Ta2O5Having ABO3The perovskite-structured tantalum source is more easily aminated, and therefore, NaTaO may be preferably used3、KTaO3、LiTaO3At least one of (a).
More preferably, urea is chosen as nitrogen source, NaTaO3As a tantalum source.
Preferably, in the preparation method of the invention, in the ammoniation step, the mass ratio of the nitrogen source to the tantalum source is 1: 5-1000: 1, the ammoniation time is 1-24 hours, and the temperature is 500-. When the temperature is too low, the ammonia in the nitrogen source can not be released completely, and when the temperature is too high, the aluminum foil for sealing is easy to melt.
In the scheme, when the mass ratio of the nitrogen source to the tantalum source is lower than 1:5, the theoretical metering tantalum source cannot completely form Ta through the nitridation process3N5And when the mass ratio of the nitrogen source to the tantalum source is more than 1000:1, the cost of the nitrogen source is greatly increased, and the preparation process is not favorably realized in an economic aspect, so that the mass ratio of the nitrogen source to the tantalum source is controlled to be 1: 5-1000: 1 in the preparation method, and in some preferred embodiments, the mass ratio of the nitrogen source to the tantalum source is 10: 1-50: 1.
In addition, if the ammoniation time is less than 1 hour, the tantalum source cannot be completely ammoniated, and in a preferred embodiment, the ammoniation time can be controlled to be 4 to 8 hours.
In an embodiment, the temperature increase rate may be set to be 1 to 50 ℃/min in the ammoniation step, and in a more preferred embodiment, the temperature increase rate is 1 to 5 ℃/min.
In the calcining step of the preparation method, the heat preservation time is 2-12 hours, and the calcining temperature is 600-1200 ℃.
In the above scheme, it is considered that the obtained photocatalyst is easily sintered due to an excessively long calcination time, and the performance is reduced. In view of the above, in the preparation method of the present invention, the calcination time is controlled to be 2 to 12 hours, and in some preferred embodiments, the holding time may be further controlled to be 3 to 5 hours.
Preferably, in the preparation method according to the present invention, in the calcining step, the inert gas is at least one of argon, helium and nitrogen. This is because: ta cannot be obtained by calcination in air or an oxygen-containing atmosphere3N5The product thereof is Ta2O5。
Preferably, in the photocatalyst of the present invention, Ta3N5With NaTaO3Is obtained by synthesizing a solid template agent.
In particular, NaTaO3Ta can be hydrothermally alkalized by NaOH2O5And (4) preparation and obtaining. For example, 0.1 to 48g of NaOH is weighed, dissolved in water, stirred and dissolved uniformly, and then 0.1 to 100g of Ta is added to the NaOH solution2O5And stirring was continued. And then transferring the uniformly stirred solution to a reaction kettle, particularly to a polytetrafluoroethylene lining of the reaction kettle, placing the reaction kettle in an air-blast drying oven for hydrothermal reaction for 0.1-100 hours, centrifuging and washing a product obtained after the hydrothermal reaction to be neutral, and drying to obtain NaTaO3。
Note that, in the photocatalyst of the present invention, Ta is obtained3N5The forbidden band width of the film is 2.1eV, and the wavelength of the visible light capable of being absorbed is more than 600nm, namely the absorption band edge of the film is formed by the original NaTaO3300nm broadening ofTo Ta3N5600 nm.
The invention provides a simple and cheap preparation method of a photocatalyst capable of efficiently absorbing visible light. Compared with the prior art, the photocatalyst with efficient absorption of visible light and the preparation method thereof have the following effects:
1. the preparation method of the photocatalyst with efficient absorption of visible light has simple preparation process and low cost of the adopted raw materials, and particularly can adopt urea to replace pure ammonia, thereby simplifying the process and equipment and being easy to industrialize.
2. The preparation method of the photocatalyst capable of efficiently absorbing visible light is simple in preparation process, low in sintering temperature, energy-saving and environment-friendly.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows Ta prepared by the method of example 1 using a photocatalyst having high absorption of visible light3N5X-ray diffraction patterns of (a);
FIG. 2 shows Ta prepared by the method of example 2 using a photocatalyst having high absorption of visible light3N5Transmission electron microscopy images of (a);
FIG. 3 shows Ta prepared by the method of example 2 using a photocatalyst having high absorption of visible light3N5Transmission electron microscopy at another magnification;
FIG. 4 is a partial enlargement of the structure at A in FIG. 3;
FIG. 5 is a partial enlargement of the structure at B in FIG. 3;
FIG. 6 shows Ta prepared by the method of example 2 using a photocatalyst having high absorption of visible light3N5A scanning electron micrograph of a portion;
FIG. 7 shows Ta prepared by the method of example 2 using a photocatalyst having high absorption of visible light3N5A scanning electron micrograph of another portion;
FIG. 8 shows Ta prepared by the method of example 5 with high visible light absorption in the presence of a photocatalyst3N5Ultraviolet-visible absorption diagram of (a).
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The photocatalyst having high absorption of visible light of example 1 comprises Ta3N5The preparation method comprises the following steps:
preparation of NaTaO3: 48g NaOH was dissolved in 100mL water, followed by the addition of 8.3075g Ta2O5Stirring for 3 hours, transferring the mixture into a polytetrafluoroethylene lining of a 200mL hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, washing the product after reaction to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 0.1g of NaTaO3Mixing with 20g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia gas released in the urea polycondensation process3Ammoniation treatment is carried out, the temperature is raised to 550 ℃ and kept for 4 hours, and the temperature raising rate is 2.3 ℃/min.
And (3) calcining: placing the obtained composite product in a tubular atmosphere furnace filled with high-purity argon for protection, heating to 700 ℃ at the speed of 10 ℃/min, further calcining for 4 hours to remove polymer carbon nitride formed in the urea polycondensation process, washing the product to be neutral to obtain Ta3N5。
Subjecting the sample to X-ray diffraction analysis, wherein the diffraction peak is associated with Ta3N5The standard cards are in one-to-one correspondence. The experimental results are shown in FIG. 1. FIG. 1 is a drawing ofTa prepared by the method for preparing photocatalyst with high visible light absorption of example 13N5X-ray diffraction pattern of (a). In FIG. 1, reference numeral I denotes a template NaTaO3Curve II is a representation of NaTaO3The curve III is the curve representing the standard card PDF #74-2480, and the curve IV is the curve representing Ta3N5The curve V is a curve representing the standard card PDF # 74-1533.
Example 2
Preparation of NaTaO3: 48g NaOH was dissolved in 100mL water, followed by the addition of 8.3075g Ta2O5Stirring for 3 hours, transferring the mixture into a polytetrafluoroethylene lining of a 200mL hydrothermal reaction kettle, washing a product obtained after 8-hour reaction at 160 ℃ to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 0.2g of NaTaO3Mixing with 20g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia gas released in the urea polycondensation process3Ammoniation treatment is carried out, the temperature is raised to 550 ℃ and kept for 4 hours, and the temperature raising rate is 2.3 ℃/min.
And (3) calcining: placing the obtained composite product in a tubular atmosphere furnace filled with high-purity argon for protection, heating to 700 ℃ at the speed of 10 ℃/min, further calcining for 4 hours to remove polymer carbon nitride formed in the urea polycondensation process, washing the product to be neutral to obtain Ta3N5。
The samples showed morphology of both bulk and rod-like solids, and the results can be seen in fig. 2 to 7. Wherein, FIG. 2 shows Ta prepared by the method of example 2 with high visible light absorption for photocatalyst preparation3N5Transmission electron microscopy images of (a). FIG. 3 shows Ta prepared by the method of example 2 using a photocatalyst having high absorption of visible light3N5Transmission electron microscopy at another magnification. Fig. 4 partially enlarges the structure at a in fig. 3. Fig. 5 partially enlarges the structure at B in fig. 3. FIG. 6 shows Ta prepared by the method of example 2 using a photocatalyst having high absorption of visible light3N5A scanning electron microscopy image of a part. FIG. 7 shows Ta prepared by the method of example 2 using a photocatalyst having high absorption of visible light3N5Scanning electron microscopy of another section.
Example 3
Preparation of NaTaO3: 24g NaOH was dissolved in 50mL water, followed by the addition of 4.1538g Ta2O5Stirring for 4 hours, transferring the mixture into a polytetrafluoroethylene lining of a 100mL hydrothermal reaction kettle, reacting for 12 hours at 160 ℃, washing the product after reaction to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 0.5g of NaTaO3Mixing with 20g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia gas released in the urea polycondensation process3Ammoniation treatment is carried out, the temperature is raised to 540 ℃ and kept for 3 hours, and the temperature raising rate is 1 ℃/min.
And (3) calcining: placing the obtained composite product in a protected tubular atmosphere furnace filled with high-purity helium, heating to 1000 ℃ at the speed of 5 ℃/min, further calcining for 2 hours to remove polymer carbon nitride formed in the urea polycondensation process, washing the product to be neutral to obtain Ta3N5。
Example 4
Preparation of NaTaO3: 12g NaOH was dissolved in 25mL water, followed by the addition of 2.0769g Ta2O5Stirring for 1 hour, transferring into a polytetrafluoroethylene lining of a 100mL hydrothermal reaction kettle, reacting for 5 hours at 160 ℃, washing the product after reaction to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 1g of NaTaO3Mixing with 20g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia gas released in the urea polycondensation process3Ammoniation treatment is carried out, the temperature is raised to 550 ℃ and kept for 3.5 hours, and the temperature raising rate is 1.5 ℃/min.
And (3) calcining: placing the obtained composite product in a tubular atmosphere furnace filled with high-purity argon protection, and heating to 700 ℃ at the speed of 7 ℃/minFurther calcining for 4 hours to remove polymer carbon nitride formed in the urea polycondensation process, washing the product to be neutral to obtain Ta3N5. The resulting sample exhibited a brick-red color.
Example 5
Preparation of NaTaO3: 16g NaOH was dissolved in 35mL water, followed by the addition of 2.7692g Ta2O5Stirring for 3.5 hours, transferring into a polytetrafluoroethylene lining of a 100mL hydrothermal reaction kettle, reacting for 9 hours at 180 ℃, washing the product to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 2g of NaTaO3Mixing with 20g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia gas released in the urea polycondensation process3Ammoniation treatment is carried out, the temperature is raised to 550 ℃ and kept for 4.5 hours, and the temperature raising rate is 1.5 ℃/min.
And (3) calcining: placing the obtained composite product in a tubular atmosphere furnace filled with high-purity argon for protection, heating to 750 ℃ at the speed of 15 ℃/min, further calcining for 3 hours to remove polymer carbon nitride formed in the urea polycondensation process, washing the product to be neutral to obtain Ta3N5。
Synthesized Ta3N5Has an absorption edge of 600nm and has strong capability of absorbing visible light. The relevant experimental results can be referred to fig. 8.
FIG. 8 shows Ta prepared by the method of example 5 with high visible light absorption in the presence of a photocatalyst3N5Ultraviolet-visible absorption diagram of (a). Wherein, curve VII is characteristic of NaTaO3Curve VI represents Ta3N5Curve (c) of (d). As shown in FIG. 8, Ta obtained in example 53N5The band gap of the film is 2.1eV, and the wavelength of the visible light capable of being absorbed is more than 600nm, that is, the absorption band edge of the embodiment 5 of the scheme is formed by the original NaTaO3300nm to Ta3N5600 nm.
Example 6
Preparation of NaTaO3: 12g NaOH was dissolved in 25mL water, followed by the addition of 2.0768g Ta2O5Stirring for 3 hours, transferring the mixture into a polytetrafluoroethylene lining of a 50mL hydrothermal reaction kettle, reacting for 6 hours at 170 ℃, washing the product to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 2g of NaTaO3Mixing with 20g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia gas released in the urea polycondensation process3Ammoniation treatment is carried out, the temperature is raised to 580 ℃ and kept for 1 hour, and the temperature raising rate is 2.0 ℃/min.
And (3) calcining: placing the obtained composite product in a tubular atmosphere furnace filled with high-purity nitrogen protection, heating to 600 ℃ at the speed of 5 ℃/min, further calcining for 20 hours to remove polymer carbon nitride formed in the urea polycondensation process, washing the product to be neutral to obtain Ta3N5。
Example 7
Preparation of NaTaO3: 24g NaOH was dissolved in 75mL water, followed by the addition of 6.2306g Ta2O5Stirring for 2 hours, transferring the mixture into a polytetrafluoroethylene lining of a 200mL hydrothermal reaction kettle, reacting for 18 hours at 140 ℃, washing the product to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 2g of NaTaO3Mixing with 20g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia gas released in the urea polycondensation process3Ammoniation treatment is carried out, the temperature is raised to 500 ℃ and kept for 20 hours, and the temperature raising rate is 2.3 ℃/min.
And (3) calcining: placing the obtained composite product in a tubular atmosphere furnace filled with high-purity argon for protection, heating to 900 ℃ at the speed of 9 ℃/min, further calcining for 6 hours to remove polymer carbon nitride formed in the urea polycondensation process, washing the product to be neutral to obtain Ta3N5。
Example 8
Preparation of NaTaO3: 48g NaOH was dissolved in 120mL water, followed by the addition of 8.3075g Ta2O5Stirring for 3 hours, transferring the mixture into a polytetrafluoroethylene lining of a 200mL hydrothermal reaction kettle, reacting for 16 hours at the temperature of 150 ℃, washing the product to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 2g of NaTaO3Mixing with 20g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia gas released in the urea polycondensation process3Ammoniation treatment is carried out, the temperature is raised to 525 ℃ and kept for 5 hours, and the temperature raising rate is 2.7 ℃/min.
And (3) calcining: placing the obtained composite product in a tubular atmosphere furnace filled with high-purity argon for protection, heating to 1200 ℃ at the speed of 10 ℃/min, further calcining for 1 hour to remove polymer carbon nitride formed in the urea polycondensation process, washing the product to be neutral to obtain Ta3N5。
Comparative example 1
Preparation of NaTaO3: 48g NaOH was dissolved in 100mL water, followed by the addition of 8.3075g Ta2O5Stirring for 3 hours, transferring the mixture into a polytetrafluoroethylene lining of a 200mL hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, washing the product to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 2g of NaTaO3Mixing with 0.2g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia released in the urea polycondensation process3Ammoniation treatment is carried out, and the temperature is raised to450℃The temperature is kept for 5 hours, and the heating rate is 2.3 ℃/min.
And (3) calcining: placing the obtained composite catalyst in a tubular atmosphere furnace filled with high-purity argon for protection, heating to 700 ℃ at the speed of 10 ℃/min, further calcining for 1 hour to remove polymer carbon nitride formed in the urea polycondensation process, washing the product to be neutral, and obtaining a sample Ta3N5The content is very low.
Comparative example 2
Preparation of NaTaO3: 48g NaOH was dissolved in 80mL water, followed by the addition of 8.3075g Ta2O5Stirring 3Transferring the reaction product into a polytetrafluoroethylene lining of a 200mL hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, washing the product to be neutral by ultrapure water, and drying to obtain NaTaO3。
An ammoniation step: 2g of NaTaO3Mixing with 20g of urea, grinding uniformly, calcining in a crucible with a sealed opening, and carrying out NaTaO (NaTaO) treatment by using ammonia gas released in the urea polycondensation process3Ammoniation treatment is carried out, the temperature is raised to 550 ℃ and kept for 4 hours, and the temperature raising rate is 2.3 ℃/min.
And (3) calcining: the obtained composite catalystIs placed in air atmosphereCalcining at 10 deg.C/min to 700 deg.C, further calcining for 3 hr to remove carbon nitride polymer formed during urea polycondensation, washing the product with water to neutrality to obtain white powder of Ta2O5This is because: oxygen was mixed into the calcination atmosphere, and thus Ta could not be obtained3N5。
Ta obtained in the above examples 1 to 83N5The photocatalyst can be used for solar hydrogen production.
It should be noted that the prior art in the protection scope of the present invention is not limited to the examples given in the present application, and all the prior art which is not inconsistent with the technical scheme of the present invention, including but not limited to the prior patent documents, the prior publications and the like, can be included in the protection scope of the present invention.
In addition, the combination of the features in the present application is not limited to the combination described in the claims of the present application or the combination described in the embodiments, and all the features described in the present application may be freely combined or combined in any manner unless contradictory to each other.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (10)

1. The preparation method of the photocatalyst with efficient absorption of visible light is characterized in that the photocatalyst comprises Ta3N5The preparation method comprises the following steps: ta is prepared by adopting an ammoniation-calcination two-step method3N5。
2. The method according to claim 1, wherein the two-step ammonification-calcinations method comprises the following steps:
an ammoniation step: uniformly mixing a nitrogen source and a tantalum source, sealing and carrying out ammoniation treatment to obtain a composite product;
and (3) calcining: the composite product is calcined for the second time under inert atmosphere to obtain Ta3N5。
3. The method of manufacturing according to claim 1 or 2, further comprising a washing step: ta prepared by adopting an ammoniation-calcination two-step method3N5Washing with ultrapure water until neutral.
4. The method according to claim 3, wherein the nitrogen source is at least one of urea, cyanamide, dicyandiamide and melamine, and the tantalum source comprises NaTaO3、KTaO3、LiTaO3At least one of (a).
5. The method as claimed in claim 3, wherein in the ammoniation step, the mass ratio of the nitrogen source to the tantalum source is 1: 5-1000: 1, the ammoniation time is 1-24 hours, and the temperature is 500-580 ℃.
6. The preparation method according to claim 3, wherein in the calcination step, the heat preservation time is 2 to 12 hours, and the calcination temperature is 600 to 1200 ℃.
7. The method according to claim 3, wherein in the calcining step, the inert gas is at least one of argon, helium and nitrogen.
8. A photocatalyst having high absorption of visible light, which is produced by the production method according to any one of claims 1 to 7.
9. The photocatalyst of claim 8, wherein the Ta3N5With NaTaO3Is obtained by synthesizing a solid template agent.
10. Use of a photocatalyst having a high absorption of visible light according to claim 8 or 9 for solar hydrogen production.
CN202010641624.7A 2020-07-06 2020-07-06 Photocatalyst with efficient absorption of visible light and preparation method and application thereof Pending CN111790424A (en)

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CN114768851A (en) * 2022-04-18 2022-07-22 西安交通大学苏州研究院 Tantalum-series nitrogen oxide core-shell structure heterojunction and preparation method and application thereof

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CN108751148A (en) * 2018-06-29 2018-11-06 上海交通大学 A kind of tantalum nitride oxide (TaOxNy) and/or tantalum nitride (Ta3N5) nano-photocatalyst preparation method

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Application publication date: 20201020