CN115043432A - General synthesis method of three-dimensional ordered macroporous perovskite lithium tantalate photocatalytic hydrogen production material - Google Patents
General synthesis method of three-dimensional ordered macroporous perovskite lithium tantalate photocatalytic hydrogen production material Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 14
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- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 22
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- 238000003828 vacuum filtration Methods 0.000 claims abstract description 14
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- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
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- 239000000706 filtrate Substances 0.000 description 5
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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- B01J35/39—
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- B01J35/60—
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- C01—INORGANIC CHEMISTRY
- 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
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- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
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- 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
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to the field of hydrogen production by photocatalytic decomposition, and provides a three-dimensional ordered macroporous perovskite lithium tantalate (LiTaO) 3 ) A general synthesis method of a photocatalytic hydrogen production material. The surface area of the photocatalytic material is improved by modifying the appearance of the perovskite, so that the surface active sites are increased. The nanometer skeleton structure of the three-dimensional ordered macroporous perovskite lithium tantalate shortens the migration distance of carriers, and the ordered pore channel structure improves the mass transfer efficiency and finally improves the efficiency of generating hydrogen. And synthesizing the three-dimensional ordered macroporous perovskite lithium tantalate material by using a crystal fixed-point nucleation control technology. The synthesis steps are as follows: dissolving Ta source in absolute ethyl alcohol solution, stirring to accelerate dissolutionFiltering to remove impurities, adding a proper amount of opal globule template agent, dipping, filtering and drying. The aim is to uniformly distribute tantalum ions, occupy crystal nucleation points and obtain opal spheres with gaps containing the tantalum ions. And dissolving the Li source by using a mixed solution of water and ethanol in a certain ratio. And then mixing and dipping the dissolved Li source and the opal globules containing tantalum ions, and carrying out vacuum filtration and drying. Tantalum ions form tantalate ion fixed points in the template agent to attract Li ions, so that the aim of mixing and solid dissolving of two cation sources is fulfilled. And finally, placing the mixture in a tubular furnace, solidifying the structure in an inert atmosphere, and then placing the mixture in a muffle furnace for secondary calcination to remove the template agent. LiTaO prepared using the method 3 Has a highly ordered three-dimensional ordered macroporous structure, and can efficiently decompose water to produce hydrogen.
Description
Technical Field
The invention relates to the field of photocatalytic decomposition of hydrogen produced by water, in particular to three-dimensional ordered macroporous perovskite lithium tantalateLiTaO 3 ) A general synthesis method of a photocatalytic hydrogen production material.
Background
The traditional fossil energy makes a great contribution to the development of industrial society, but the defects of non-regeneration and high pollution of the traditional fossil energy become more and more obvious along with the wide and deep research and application of the fossil energy. It is important to find clean, efficient and green energy sources for replacing fossil energy sources. Solar energy is almost unlimited for the earth, full utilization of solar energy becomes a promising way for finding alternative energy, and a photocatalytic technology converts solar energy into hydrogen energy, so that the method is a reliable method for clean, efficient and green utilization of solar energy. Compared with the traditional fossil energy, the hydrogen energy is cleaner; compared with green energy sources such as wind energy, tidal energy and the like, the hydrogen energy is more efficient. Therefore, the use of solar energy to split water to produce hydrogen has great technical and industrial prospects. The high carrier recombination rate and the few surface active sites of the semiconductor photocatalytic material are the keys for restricting the photocatalytic technology from going from laboratories to industrial application. Therefore, the synthesis of efficient, cheap and clean photocatalyst is a key problem to be solved urgently.
Perovskite LiTaO 3 Has good photocatalytic performance and photo-thermal stability. In addition, LiTaO 3 Is a wide band gap semiconductor photocatalytic material (4.7 eV), LiTaO 3 Is at a position lower than H + /H 2 Redox potential (0 eV). According to thermodynamic calculations, LiTaO 3 Has great potential of photocatalytic water decomposition. However, the high temperature calcination of the particulate structure proper to the conventional method inherently has surface defects such that the reactive active sites are decreased and the recombination rate of carriers is increased, thereby resulting in low photocatalytic performance. To convert LiTaO 3 Constructing a three-dimensional ordered macroporous structure would be expected to improve these drawbacks. We have found that by synthesizing three-dimensionally ordered macroporous LiTaO 3 The structure can effectively improve the problems. Calcination of LiTaO at relatively high temperatures 3 Structurally, three-dimensionally ordered macroporous LiTaO 3 The photocatalytic performance of the structure is effectively improved.
Disclosure of Invention
The invention aims to provide a three-dimensional ordered macroporous perovskite LiTaO 3 A general synthesis method of a photocatalytic hydrogen production material. Effectively cope with LiTaO 3 The semiconductor catalyst has low specific surface area and high carrier recombination rate, so that the photocatalytic hydrogen production efficiency is improved.
The technical scheme of the invention is as follows:
ta ions and Li ions are not uniformly mixed in a solid solution mode through the assistance of a chelating agent, but are formed into a uniformly mixed solid solution in a mode of self-priming Li ions by tantalate ions. The method has the advantages of lower cost and wider application range.
The invention specifically adopts the following technical scheme:
s1, taking opal globules with the globule diameter of 150-300 nm as a template agent;
s2 taking 0.6-1.2 g of TaCl 5 Adding into absolute ethyl alcohol solution, stirring and dissolving;
s3, naturally filtering the solution obtained in the step S2 to leave a clear solution;
s4, adding an opal template agent into the clear liquid, and soaking for 2-6 h at room temperature;
s5, carrying out vacuum filtration on the solution after standing, wherein the negative pressure is 0.01-0.05 MPa;
s6, mixing water and ethanol according to a certain proportion to dissolve a Li source;
s7, soaking the sample obtained in the step S5 in S6 for 2-6 h, and carrying out vacuum filtration under the negative pressure of 0.01-0.05 MPa;
s8, calcining the sample obtained in the step S7 in nitrogen atmosphere, slowly heating to 623K, keeping for 2-6 h, cooling to room temperature, and taking out;
s9, calcining the sample obtained in the step S8 in an air atmosphere, slowly heating to 873K, and keeping for 0.5-2 h; after cooling to room temperature, the sample was washed, dried and collected.
Preferably, the opal beads used in S1 are selected from polymethylmethacrylate beads.
Preferably, the suction filtration negative pressure in S5 is 0.01-0.04 MPa.
Preferably, S6 uses a ratio of water to ethanol solution of 3: 7.
preferably, the Li source in S6 is aceto.
Preferably, the volume ratio of templating agent to pre-polymer is 2: 3.
Preferably, the temperature rising rate in S8 and S9 should be 0.5-2 deg.C/min.
The invention constructs three-dimensional ordered macroporous perovskite LiTaO by using opal globules as a template agent at room temperature 3 . In the process, TaCl is added 5 Dissolving in absolute ethanol solution, stirring for accelerating dissolution, filtering to remove impurities, adding an appropriate amount of opal globule template agent, soaking, filtering, and drying. The aim is to uniformly distribute tantalum ions, occupy crystal nucleation points and obtain opal spheres with gaps containing the tantalum ions. And dissolving the Li source by using a mixed solution of water and ethanol in a certain ratio. And then mixing and dipping the dissolved Li source and the opal globules containing tantalum ions, and carrying out vacuum filtration and drying. Tantalum ions form tantalate ion fixed points in the template agent to attract Li ions, so that the aim of mixing and solid dissolving of two cation sources is fulfilled. And finally, placing the mixture in a tubular furnace, solidifying the structure in an inert atmosphere, and then placing the mixture in a muffle furnace for secondary calcination to remove the template agent. LiTaO prepared by the method 3 Has highly ordered three-dimensional ordered macroporous structure, and can efficiently decompose water to produce hydrogen. Therefore, the method for controlling crystal nucleation is used for constructing the three-dimensional ordered macroporous perovskite LiTaO 3 The method for regulating the morphology of the catalyst is expected to be widely applied to various photocatalysts.
The invention has the advantages and beneficial effects that:
1. the invention takes opal globules as a template agent to construct the catalyst with a three-dimensional ordered macroporous structure, the specific surface area of the photocatalyst is obviously increased, the reaction active sites are increased, and the catalyst and the high-temperature calcined LiTaO are used 3 Compared with the prior art, the hydrogen generation capacity is improved.
2. According to the invention, a chelating agent is not used, the catalyst with the three-dimensional ordered macroporous structure is constructed by a tantalum radical ion self-priming Li ion uniform nucleation method, the carrier migration distance is shortened, the service life of a photon-generated carrier is prolonged, and the carriers of the reaction which are migrated to the surface of the catalyst are increased, so that the efficiency of decomposing water to generate hydrogen of the catalyst is improved.
3. According to the invention, the perovskite catalyst with the three-dimensional ordered macroporous structure is constructed, the catalyst structure obtains high porosity, the mass transfer efficiency is improved, the product release efficiency is improved, and the photocatalytic reaction is facilitated.
4. The perovskite catalyst with the three-dimensional ordered macroporous structure is constructed, the aim of uniformly mixing and dissolving two cations is fulfilled without using a chelating agent, and the method is low in cost and high in universality, and is expected to be applied to construction of three-dimensional ordered macroporous structures of other perovskite materials.
Drawings
FIG. 1 shows three-dimensional ordered macroporous perovskite LiTaO 3 And standard card LiTaO 3 (PDF # 29-0836).
FIG. 2 shows three-dimensional ordered macroporous perovskite LiTaO 3 SEM images at different magnifications.
FIG. 3 is a three-dimensional ordered network LiTaO 3 XPS chart of (a).
FIG. 4 shows three-dimensional ordered macroporous perovskite LiTaO in pure water 3 And high temperature calcination of LiTaO 3 The hydrogen production performance of the catalyst.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
Firstly, taking TaCl 5 (0.7 g) is added into absolute ethyl alcohol (10 mL) solution to be stirred and dissolved, impurities are filtered, then 4 g of PMMA pellet template is added into the filtrate, the mixture is kept stand for 3 hours and is filtered in vacuum, and the negative pressure is 0.05 MPa, so that a sample 1 is obtained. Dissolving lithium acetate in a mixed solution of 3 mL of deionized water and 7 mL of absolute ethyl alcohol, mixing the sample 1 with the solution, soaking for 5 hours, and performing vacuum filtration under the negative pressure of 0.05 MPa to obtain a sample 2. And placing the sample 2 in a tube furnace, introducing nitrogen, slowly heating to 623K, keeping for 2 hours, cooling to room temperature, and taking out. It was next placed in a muffle furnace, slowly warmed to 873K, and held for 1 h. Obtaining the three-dimensional ordered macroporous perovskite LiTaO 3 。
Example 2
Firstly, TaCl is taken 5 (0.8 g) was added to a solution of anhydrous ethanol (12 mL) and dissolved with stirring, and impurities were filtered off, after whichAnd adding 4.5 g of PMMA pellet template into the filtrate, standing for 4 h, and carrying out vacuum filtration under the negative pressure of 0.05 MPa to obtain a sample 1. And (3) dissolving lithium acetate in a mixed solution of 3 mL of deionized water and 7 mL of absolute ethyl alcohol, mixing the sample 1 with the solution, soaking for 6 hours, and performing vacuum filtration under the negative pressure of 0.06 MPa to obtain a sample 2. And placing the sample 2 in a tube furnace, introducing nitrogen, slowly heating to 623K, keeping for 2 hours, cooling to room temperature, and taking out. It was next placed in a muffle furnace, slowly warmed to 873K, and held for 1 h. Obtaining the three-dimensional ordered macroporous perovskite LiTaO 3 。
Example 3
Firstly, taking TaCl 5 (0.7 g) is added into absolute ethyl alcohol (9 mL) solution to be stirred and dissolved, impurities are filtered, then 3.5 g of PMMA pellet template is added into the filtrate, the mixture is kept stand for 3 h and is filtered in vacuum, and the negative pressure is 0.02 MPa, so that a sample 1 is obtained. Dissolving lithium acetate in a mixed solution of 3 mL of deionized water and 7 mL of absolute ethyl alcohol, mixing the sample 1 with the solution, soaking for 4 hours, and performing vacuum filtration under the negative pressure of 0.04 MPa to obtain a sample 2. And placing the sample 2 in a tube furnace, introducing nitrogen, slowly heating to 623K, keeping for 1 h, cooling to room temperature, and taking out. It was next placed in a muffle furnace, slowly warmed to 873K, and held for 1.5 h. Obtaining the three-dimensional ordered macroporous perovskite LiTaO 3 。
Example 4
Firstly, TaCl is taken 5 (1.1 g) adding the mixture into an absolute ethyl alcohol (10 mL) solution, stirring and dissolving, filtering to remove impurities, then adding 4 g of PMMA pellet template into the filtrate, standing for 3 h, and carrying out vacuum filtration under the negative pressure of 0.04 MPa to obtain a sample 1. Dissolving lithium acetate in a mixed solution of 3 mL of deionized water and 7 mL of absolute ethyl alcohol, mixing the sample 1 with the solution, soaking for 4 hours, and performing vacuum filtration under the negative pressure of 0.04 MPa to obtain a sample 2. And placing the sample 2 in a tube furnace, introducing nitrogen, slowly heating to 623K, keeping for 1 h, cooling to room temperature, and taking out. It was next placed in a muffle furnace, slowly warmed to 873K, and held for 1.5 h. Obtaining the three-dimensional ordered macroporous perovskite LiTaO 3 。
Example 5
Firstly, TaCl is taken 5 (1 g) Adding the mixture into absolute ethyl alcohol (10 mL) solution, stirring and dissolving, filtering out impurities, then adding 4.2 g of PMMA (polymethyl methacrylate) pellet template into the filtrate, standing for 3 hours, and carrying out vacuum filtration with the negative pressure of 0.03 MPa to obtain a sample 1. Dissolving lithium acetate in a mixed solution of 3 mL of deionized water and 7 mL of absolute ethyl alcohol, mixing the sample 1 with the solution, soaking for 4 hours, and performing vacuum filtration under the negative pressure of 0.04 MPa to obtain a sample 2. And placing the sample 2 in a tube furnace, introducing nitrogen, slowly heating to 623K, keeping for 1 h, cooling to room temperature, and taking out. It was next placed in a muffle furnace, slowly warmed to 873K, and held for 1.5 h. Obtaining the three-dimensional ordered macroporous perovskite LiTaO 3 。
The morphology and structure, and properties of the product obtained in the comparative example are shown in FIGS. 1-4.
As can be seen from FIG. 1, the three-dimensional ordered macroporous perovskite LiTaO 3 And standard card LiTaO 3 Compared with the XRD pattern of (PDF # 29-0836), the peak patterns are consistent, so that the three-dimensional ordered macroporous perovskite LiTaO 3 Is pure phase LiTaO 3 。
As can be seen from FIG. 2, the three-dimensional ordered macroporous perovskite LiTaO 3 The three-dimensional ordered macroporous structure is successfully constructed, and SEM pictures under different multiples show that the three-dimensional ordered macroporous perovskite LiTaO 3 Maintaining high porosity and integrity.
As can be seen from FIG. 3, the three-dimensional ordered macroporous perovskite LiTaO 3 Does not change the surface chemistry state.
As can be seen from FIG. 4, in pure water, the three-dimensionally ordered macroporous perovskite LiTaO 3 The performance of generating hydrogen is better than that of calcining LiTaO at high temperature 3 . Shows that the introduction of the three-dimensional ordered macroporous structure greatly improves the perovskite LiTaO 3 The performance of (c).
The results of the examples show that the three-dimensional ordered macroporous perovskite LiTaO prepared by the invention 3 Has excellent photodecomposition water performance. The foregoing description merely represents preferred embodiments of the present invention, which are described in some detail and detail, and should not be construed as limiting the scope of the present invention. It should be noted that it will occur to those skilled in the artIt is understood that various changes, modifications and substitutions may be made without departing from the spirit of the invention and these are within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (5)
1. A general synthesis method of a three-dimensional ordered macroporous perovskite lithium tantalate photocatalytic hydrogen production material is characterized by comprising the following steps:
ta ions and Li ions are not uniformly mixed through the assistance of a chelating agent, but form a uniformly mixed solid solution through a mode of self-priming Li ion nucleation by tantalate ions.
2. The general synthesis method of three-dimensional ordered macroporous perovskite lithium tantalate as claimed in claim 1, wherein:
the method specifically comprises the following steps:
s1, taking opal globules with the globule diameter of 150-;
s2 taking 0.6-1.2 g of TaCl 5 Adding into absolute ethyl alcohol solution, stirring and dissolving;
s3, naturally filtering the solution obtained in the step S2 to leave a clear solution;
s4, adding an opal template agent into the clear liquid, and soaking for 2-6 h at room temperature;
s5, carrying out vacuum filtration on the solution after standing, wherein the negative pressure is 0.01-0.05 MPa;
s6, mixing water and ethanol according to a certain proportion to dissolve a Li source;
s7, soaking the sample obtained in the step S5 in S6 for 2-6 h, and carrying out vacuum filtration under the negative pressure of 0.01-0.05 MPa;
s8, calcining the sample obtained in the step S7 in nitrogen atmosphere, slowly heating to 623K, keeping for 2-6 h, cooling to room temperature, and taking out;
s9, calcining the sample obtained in the step S8 in an air atmosphere, slowly heating to 873K, and keeping for 0.5-2 h; after cooling to room temperature, the sample was washed, dried and collected.
3. The general synthesis method of the three-dimensional ordered macroporous perovskite lithium tantalate photocatalytic hydrogen production material according to claim 2 comprises the following steps: the water and ethanol solution used in the S6 in a certain proportion is 3: 7.
4. the general synthesis method of the three-dimensional ordered macroporous perovskite lithium tantalate photocatalytic hydrogen production material according to claim 2, is characterized in that: the Li source in S6 uses acetogen.
5. The general synthesis method of the three-dimensional ordered macroporous perovskite lithium tantalate photocatalytic hydrogen production material according to claim 2, is characterized in that: the temperature rise rate in S8 and S9 should be 0.5-2 deg.C/min.
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