CN114684786A - Method for efficiently producing hydrogen and oxygen based on perovskite titanium dioxide heterostructure - Google Patents
Method for efficiently producing hydrogen and oxygen based on perovskite titanium dioxide heterostructure Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 25
- 239000001257 hydrogen Substances 0.000 title claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 24
- 239000001301 oxygen Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000004753 textile Substances 0.000 claims abstract description 70
- 239000011941 photocatalyst Substances 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 32
- 238000002791 soaking Methods 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- JTDNNCYXCFHBGG-UHFFFAOYSA-L Tin(II) iodide Inorganic materials I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000969 carrier Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- -1 orthotitanic acid ester Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- 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
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- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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Abstract
The invention provides a method for efficiently producing hydrogen and oxygen based on a perovskite titanium dioxide heterostructure. The invention provides a high-efficiency hydrogen and oxygen production method which is realized by depositing a heterostructure photocatalyst formed by coupling perovskite titanium dioxide on a textile net. The perovskite material has the advantages of narrow band gap, long carrier diffusion distance and the like, and can not only solve the problem of TiO semiconductor material by utilizing the synergistic effect of the titanium dioxide and the perovskite material2The photocatalyst has a large band gap, only responds to ultraviolet light, can inhibit photon-generated carrier recombination, improves the carrier transmission performance, and obviously improves the hydrogen production and oxygen production efficiency. The invention provides a titanium dioxide heterogenous material based on perovskiteThe method for producing hydrogen and oxygen with high-efficiency structure is realized by preparing the photocatalytic textile net with the hydrogen and oxygen production function, the photocatalytic textile net has visible light response performance, the absorption and the utilization of visible light are greatly improved, the photocatalytic textile net can be recycled, and economic benefits are brought to the society.
Description
Technical Field
The invention belongs to the field of application of photocatalytic hydrogen production and oxygen production, and particularly relates to a method for efficiently producing hydrogen and oxygen based on a perovskite titanium dioxide heterostructure.
Background
In recent years, energy consumption and environmental deterioration become major challenges for human beings, and replacement of non-renewable fossil energy by clean renewable energy is an effective way to solve environmental pressure. The hydrogen energy is a clean, renewable and high-calorific-value fuel, is hopeful to replace fossil energy such as coal and petroleum in the future, and occupies the leading position of the energy pattern. The semiconductor photocatalysis method can utilize inexhaustible solar energy in the nature as an excitation light source of a semiconductor to realize hydrogen production and oxygen production by decomposing water, has the advantages of simplicity, convenience, economy, high efficiency and the like, and is widely concerned. Among them, the photocatalyst is the core of the photocatalytic water splitting reaction, and is usually a semiconductor material that can finally convert light energy into chemical energy. When the photocatalyst of the semiconductor material absorbs photons with energy larger than the band gap of the photocatalyst, the generated photo-generated electrons can jump to a conduction band, and a photo-generated hole is generated in a valence band. The generated photo-generated electrons and holes can diffuse to the surface of the semiconductor and respectively generate reduction reaction and oxidation reaction with water molecules on the surface of the semiconductor to generate hydrogen and oxygen. The titanium dioxide material has the advantages of no toxicity, sterilization, deodorization, good stability, strong oxidation-reduction capability and the like, and has great potential and good prospect in the field of hydrogen production and oxygen production by photolysis of water.
However, the photocatalytic material of titanium dioxide for photolysis of water to produce hydrogen and oxygen faces the following problems: (ii) TiO2The material is a wide-band-gap semiconductor material, and only responds to about 6% of ultraviolet light in sunlight, so that the absorption utilization rate of the sunlight is low; (II) TiO2The problem that photo-generated electrons and holes generated by illumination excitation are easy to recombine also exists, so that the light quantum efficiency is low; meanwhile, the traditional photocatalyst is powdery, is usually applied to sewage treatment in modes such as throwing, and has the problems of difficult recovery and difficult reuse.
Aiming at the problems, the invention provides a perovskite titanium dioxide heterostructure-based high-efficiency hydrogen and oxygen production methodThe method of (1). Perovskite is a structure of ABX3The semiconductor material has the advantages of simple preparation, adjustable band gap, large-area attachment to a flexible substrate and the like, and is often applied to photoelectric devices such as solar cells, LEDs, photoelectric detectors and the like due to excellent photoelectric properties. The invention adopts the material compounding method to compound the traditional TiO2Modifying the photocatalyst to obtain TiO2Coupled with the perovskite to form a heterojunction. On one hand, the perovskite semiconductor material has narrow forbidden band width, can absorb incident light with lower energy and has visible light response characteristic. Besides being used as a photocatalyst to decompose water to produce hydrogen and oxygen, the catalyst can also be mixed with TiO2The material is compounded into a heterojunction, and solves the problem of TiO2The photocatalyst only responds to ultraviolet light due to large band gap. Further, the photogenerated electrons generated by the perovskite semiconductor material may be transported to the TiO through the heterojunction2The conduction band and the photoproduction cavity are left in the perovskite valence band, so that the spectral response range of the perovskite titanium dioxide heterostructure photocatalyst is widened, and the utilization rate of the photocatalyst to sunlight is greatly improved. On the other hand, as the heterojunction exists at the perovskite-titanium dioxide interface, a built-in electric field can be formed by the concentration difference of current carriers at two sides of the junction, the transmission of photon-generated current carriers is promoted, the recombination of electron-hole pairs is reduced, and the catalytic activity of the heterojunction photocatalyst is further improved by the coordination effect of the perovskite and titanium dioxide. And finally, the perovskite titanium dioxide heterostructure photocatalyst is loaded on the textile, so that the problem that the powdery photocatalyst is difficult to recycle and reuse is solved. The method for efficiently producing hydrogen and oxygen based on the perovskite titanium dioxide heterostructure provided by the invention has a wide range, and comprises but is not limited to the field of producing hydrogen and oxygen by solar energy hydrolysis.
Disclosure of Invention
The invention aims to provide a method for efficiently producing hydrogen and oxygen based on a perovskite titanium dioxide heterostructure. According to the invention, the perovskite titanium dioxide heterojunction is constructed by a material compounding method, so that the response wavelength range of the perovskite titanium dioxide heterostructure photocatalyst is expanded to a visible light wave band, and TiO is improved2The photocatalyst has insufficient response only in an ultraviolet light wave band; simultaneous interestThe separation and transmission of photon-generated carriers are promoted by using a built-in electric field at the perovskite titanium dioxide heterojunction, and the recombination of photon-generated electrons and holes is effectively inhibited. The textile is used as the photocatalyst to serve as a carrier, so that the problem that the conventional powdery photocatalyst is difficult to recycle is solved, and the reuse rate of the photocatalyst is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-efficiency hydrogen and oxygen production method based on a perovskite titanium dioxide heterostructure is realized by preparing a textile mesh loaded with a perovskite titanium dioxide heterostructure photocatalyst.
The preparation method of the visible light response perovskite titanium dioxide heterostructure photocatalytic textile comprises the following steps:
(1) preparing a perovskite precursor solution: dissolving the precursor A and the precursor B in a certain amount of organic polar solvent, and magnetically stirring for a period of time to obtain a perovskite precursor solution A.
(2)TiO2Preparing sol: adding a certain amount of simple organic acid into lower alcohol to obtain a mixed solution B, and slowly adding ortho-titanate into the mixed solution B to prepare a solution C. The solution C is stirred vigorously under heating conditions to obtain the TiO2And (3) sol.
(3) Soaking the textile in the form of rope, cloth and the like in the perovskite precursor solution A, then taking out the textile completely covered with the solution A, annealing for a period of time at a certain temperature to form uniform perovskite crystals on the textile, and then placing the textile with the perovskite material on TiO2Fully soaking the sol, and then putting the sol into an oven for drying to coat a compact TiO layer on the textile loaded with the perovskite layer2Obtaining a textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst; or soaking the textile in the form of rope or cloth in TiO2In sol, then will be impregnated with TiO2Taking out the sol textile, putting the sol textile into an oven for drying, and growing compact TiO2The crystal textile is soaked in the perovskite precursor solution A, taken out after being soaked for a period of time,annealing for a period of time at a certain temperature to obtain a textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst; or mixing the perovskite precursor solution A with TiO2Mixing the sol to obtain perovskite and TiO2And then soaking the textiles in the forms of ropes, cloth and the like in the mixed solution D, finally taking out the textiles soaked with the mixed solution D, and putting the textiles into an oven for drying to obtain the textile mesh loaded with the perovskite titanium dioxide heterostructure photocatalyst.
Further, in the step (1), the precursor a may be one or more of MAI, CsI, and FAI; the precursor B can be PbI2、SnI2One or more of; the organic polar solvent is one or more of N, N-dimethylformamide or dimethyl sulfoxide.
Further, in the step (1), the molar ratio of the precursor A to the precursor B is 0.8-1.5: 1; the mass concentration of the precursor A in the solution A is 0.8-1.5 mol/L; the mass concentration of the precursor B in the solution A is 0.53-1.88 mol/L.
Further, in the step (1), the magnetic stirring time is 5-12 hours.
Further, in the step (2), the lower alcohol is absolute ethyl alcohol; the simple organic acid is glacial acetic acid; the orthotitanate is butyl titanate.
Further, in the step (2), the pH value of the mixed solution B is 1-3; the mass ratio of the ortho-titanate to the lower alcohol to the simple organic acid is 13.27-24.12: 54.39-66.24: 0.71-5.13; the heating and stirring temperature is 80-150 ℃; the heating and stirring time is 1-6 h.
Further, in the step (3), the perovskite precursor solution A is soaked for 0.5-5 hours; the annealing temperature after the dipping solution A is 80-110 ℃; the annealing time after the dipping of the solution A is 0.5-1.5 h; said at TiO2Soaking in the sol for 0.5-1 h; the impregnated TiO2Drying at 100-130 ℃ after sol; the impregnated TiO2Drying time after sol dissolving is 15-30 min; what is needed isPerovskite and TiO2The soaking time in the mixed solution D is 0.5-1 h; the drying temperature after the mixed solution D is soaked is 100-110 ℃; and the drying time after the mixed solution D is soaked is 0.5-1 h.
The invention has the advantages that: conventional TiO2The defects of the photocatalyst include that the photocatalyst can only be excited by ultraviolet light, the recombination rate of photon-generated carriers is high, and the like. According to the invention, the perovskite and the titanium dioxide are compounded to form the heterostructure photocatalyst in a material compounding mode, and as the perovskite material has a narrow band gap and a large light absorption coefficient, and the heterostructure exists at the interface of the perovskite and the titanium dioxide, the spectral response range of the photocatalyst can be expanded to a visible light region, so that the utilization rate of sunlight is improved; and the recombination of electron holes is inhibited, and the activity of the photocatalyst is obviously improved. In addition, the textile is used as a catalyst carrier, so that the aim of recycling the photocatalyst can be fulfilled. The invention can be applied to the field of hydrogen production and oxygen production by solar photolysis of water and has great significance for improving environmental benefits and economic benefits.
Drawings
FIG. 1 is a schematic structural diagram of a basic embodiment of the present invention
FIG. 2 is a real object diagram of the textile net loaded with titanium dioxide perovskite photocatalyst capable of realizing efficient hydrogen and oxygen production
FIG. 3 shows the combination of MAI and PbI according to the present invention2X-ray diffraction pattern of perovskite crystal prepared
FIG. 4 shows the combination of MAI and PbI according to the present invention2Scanning Electron microscopy of the prepared perovskite Crystal (Scale: 5 μm)
Detailed Description
The schematic structural diagram of the basic embodiment of the present embodiment is shown in fig. 1, in which: textile 1, TiO in the form of rope, cloth, or the like2Photocatalyst 2, perovskite 3.
Example 1:
a method for efficiently producing hydrogen and oxygen based on a perovskite titanium dioxide heterostructure comprises the following steps:
(1) 0.158g of MAI and 0.461g of PbI were mixed2Dissolving in 1mL of N, N-dimethylformamide, and magnetically stirringStirring for 12h to obtain a perovskite precursor solution A.
(2) Adding glacial acetic acid into absolute ethyl alcohol to obtain a mixed solution B, and slowly adding ortho-titanate into the mixed solution B to prepare a solution C. Wherein the mass ratio of the raw materials of the orthotitanic acid ester, the lower alcohol, the simple organic acid and the like is 17.82: 60.33: 3.76; the solution C is stirred vigorously at a temperature of 130 ℃ for 1.5h to obtain the TiO2And (3) sol.
(3) Soaking the fabric in the form of rope or cloth in TiO2Soaking in the sol for 1h, and soaking with TiO2Taking out the sol textile, drying in an oven at 100 deg.C for 15min, and growing dense TiO2And soaking the crystal textile in the perovskite precursor solution A, taking out after soaking for 0.5h, and annealing for 0.5h at the temperature of 100 ℃ to obtain the textile mesh loaded with the perovskite titanium dioxide heterostructure photocatalyst.
Example 2
The procedure is as in example 1, except that in example 1, 0.158g of MAI and 0.461g of PbI are used20.175g of MAI and 0.461g of PbI were dissolved in 1mL of N, N-dimethylformamide2Dissolved in a mixed solvent of 200. mu.L of dimethyl sulfoxide and 800. mu. L N, N-dimethylformamide.
Example 3
The procedure is as in example 1, except that in example 1, 0.158g of MAI and 0.369g of PbI are added20.175g of MAI and 0.461g of PbI were dissolved in 1mL of N, N-dimethylformamide2Dissolved in a mixed solvent of 200. mu.L of dimethyl sulfoxide and 800. mu. L N, N-dimethylformamide.
Example 4
The steps are the same as the example 1, except that the mass ratio of the raw materials of the orthotitanate, the lower alcohol, the simple organic acid and the like in the example 1 is changed to be 23.54: 63.87: 4.36, and the mass ratio of the raw materials of the orthotitanate, the lower alcohol, the simple organic acid and the like is 15.04: 58.12: 2.32; the stirring time was changed from 1.5h to 2 h.
Example 5
The procedure is as in example 1, except thatAnd (3) soaking the textile in the form of rope, cloth and the like in the perovskite precursor solution A for 0.5h, taking out the textile completely covered with the solution A, and annealing at the temperature of 100 ℃ for 0.5h to form uniform perovskite crystals on the textile. The textile with the perovskite material grown on TiO2Fully soaking the sol for 1h, and then putting the sol into an oven for drying for 15min at the temperature of 100 ℃ to coat a compact TiO layer on the textile loaded with the perovskite layer2And obtaining the textile with the perovskite titanium dioxide heterostructure.
The steps are the same as example 1, except that the step (3) is changed into perovskite precursor solution A and TiO2Mixing the sol to obtain perovskite and TiO2And soaking the textiles in the forms of ropes, cloth and the like in the mixed solution D for 0.5h, finally taking out the textiles soaked with the mixed solution D, and putting the textiles into an oven at the temperature of 110 ℃ for drying for 0.5h to obtain the textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A method for efficiently producing hydrogen and oxygen based on a perovskite titanium dioxide heterostructure is characterized by comprising the following steps: the efficient hydrogen and oxygen production method is realized by preparing a textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst.
2. A method of preparing the textile web loaded with perovskite titanium dioxide heterostructure photocatalyst of claim 1, characterized in that: the titanium dioxide sol synthesized by a hydrothermal method is coupled with a perovskite material grown by a solution infiltration method to form a heterostructure, and then the heterostructure is deposited on a textile to prepare the composite material.
3. The method according to claim 2, characterized by the steps of:
(1) preparing a perovskite precursor solution: dissolving the precursor A and the precursor B in a certain amount of organic polar solvent, and magnetically stirring for a period of time to obtain a perovskite precursor solution A.
(2)TiO2Preparing sol: adding a certain amount of simple organic acid into lower alcohol to obtain a mixed solution B, and slowly adding ortho-titanate into the mixed solution B to prepare a solution C. The solution C is stirred vigorously under heating conditions to obtain the TiO2And (3) sol.
(3) Soaking the textile in the forms of rope, cloth and the like in the perovskite precursor solution A, then taking out the textile completely covered with the solution A, annealing for a period of time at a certain temperature to form uniform perovskite crystals on the textile, and then placing the textile with the perovskite materials grown on the textile on TiO2Fully soaking the sol, and then putting the sol into an oven for drying to coat a compact TiO layer on the textile loaded with the perovskite layer2Obtaining a textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst; or soaking textile in form of rope or cloth in TiO2In sol, then soaking with TiO2Taking out the sol textile, putting the sol textile into an oven for drying, and growing compact TiO2Soaking the textile of the crystal in the perovskite precursor solution A, taking out after soaking for a period of time, and annealing for a period of time at a certain temperature to obtain a textile mesh loaded with the perovskite titanium dioxide heterostructure photocatalyst; or mixing the perovskite precursor solution A with TiO2Mixing the sol to obtain perovskite and TiO2And (3) soaking the textiles in the forms of ropes, cloth and the like in the mixed solution D, finally taking out the textiles soaked with the mixed solution D, and putting the textiles into an oven for drying to obtain the textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst.
4. The method for preparing the textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst as claimed in claim 3, wherein the textile net is characterized in that: in the step (1), the precursor A can be one or more than one of MAI, CsI and FAI; the precursor B can be PbI2、SnI2And/orThe above step (1); the organic polar solvent is one or more of N, N-dimethylformamide or dimethyl sulfoxide.
5. The method for preparing the textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst as claimed in claim 3, wherein the textile net is characterized in that: in the step (1), the molar ratio of the precursor A to the precursor B is 0.8-1.5: 1; the mass concentration of the precursor A in the solution A is 0.8-1.5 mol/L; the mass concentration of the precursor B in the solution A is 0.53-1.88 mol/L.
6. The method for preparing the textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst as claimed in claim 3, wherein the textile net is characterized in that: in the step (1), the magnetic stirring time is 5-12 h.
7. The method for preparing the textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst as claimed in claim 3, wherein the textile net is characterized in that: in the step (2), the lower alcohol is absolute ethyl alcohol; the simple organic acid is glacial acetic acid; the orthotitanate is butyl titanate.
8. The method for preparing the textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst as claimed in claim 3, wherein the textile net is characterized in that: in the step (2), the pH value of the mixed solution B is 1-3; the mass ratio of the ortho-titanate to the lower alcohol to the simple organic acid is 13.27-24.12: 54.39-66.24: 0.71-5.13; the heating and stirring temperature is 80-150 ℃; the heating and stirring time is 1-6 h.
9. The method for preparing the textile net loaded with the perovskite titanium dioxide heterostructure photocatalyst as claimed in claim 3, wherein the textile net is characterized in that: in the step (3), the perovskite precursor solution A is soaked for 0.5-5 h; the annealing temperature after the dipping solution A is 80-110 ℃; the annealing time after the dipping of the solution A is 0.5-1.5 h; said at TiO2Soaking in the sol for 0.5-1 h; the impregnated TiO2Drying at 100-130 ℃ after sol; the impregnated TiO2Drying time after sol dissolving is 15-30 min; the perovskite and TiO2The soaking time in the mixed solution D is 0.5-1 h; the drying temperature after the mixed solution D is soaked is 100-110 ℃; and the drying time after the mixed solution D is soaked is 0.5-1 h.
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