CN114870843B - Photocatalyst for reducing carbon dioxide by flower-like structure, preparation method and application thereof - Google Patents
Photocatalyst for reducing carbon dioxide by flower-like structure, preparation method and application thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910002515 CoAl Inorganic materials 0.000 claims abstract description 16
- 239000003245 coal Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 238000011282 treatment Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 17
- 150000001869 cobalt compounds Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- -1 aluminum compound Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000001000 micrograph Methods 0.000 description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- 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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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a photocatalyst for reducing carbon dioxide by a flower-like structure, and a preparation method and application thereof. The invention adopts different temperature treatments to convert thinner 3D flower-shaped CoAl-LDHs into ultrathin 3D porous CoAl 2 O 4 The method improves the shortcoming of CoAl-LDHs and simultaneously further improves the catalysis of CO by the photocatalyst 2 Efficiency of reduction. The composite material is used for photocatalysis of CO under the irradiation of visible light with the wavelength of 200-800 nm 2 During reduction, the method can detect the reaction product at room temperature without a heating system, and has low working temperature and mild operation condition; under the irradiation of visible light at room temperature, namely 20-40 ℃, the composite material catalyzes CO 2 Reduction to CH 4 And CO at a maximum yield of 58.98. Mu. Mol/g and 33.11. Mu. Mol/g, respectively, with high stability. The invention also provides a simple preparation method, which has low cost and is convenient to popularize and apply.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a photocatalyst for reducing carbon dioxide in a flower-like structure, and a preparation method and application thereof. Adopts different temperature treatments to convert thinner 3D flower-shaped CoAl-LDHs into ultrathin 3D porous CoAl 2 O 4 The catalytic reduction efficiency of the photocatalyst is further improved while the defect of thinner 3D flower-shaped CoAl-LDH is overcome.
Background
In recent years, researchers have created more efficient and highly productive carbon dioxide collection and storage technologies in order to cope with global warming and climate change. Inspired by the photosynthesis of the nature, the artificial photocatalysis emission reduction enters the field of view of researchers, so that the resource exhaustion caused by the consumption of a large amount of stone fuel can be relieved, and the environmental problem caused by the greenhouse effect can be effectively solved.
The carbon dioxide photocatalyst prepared at present generally adopts transition metal to load the composite material, but has the problems of low load and low catalytic efficiency of the preparation process. The problem of low carrier mobility of the carbon dioxide photocatalyst, which exhibits low quantum efficiency, is in need of solving.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a photocatalyst for reducing carbon dioxide by a flower-shaped structure, and a preparation method and application thereof, which can effectively improve quantum efficiency and catalytic efficiency.
In order to solve the technical problems, the invention provides the following technical scheme:
in a first aspect, the present invention provides a method for preparing a photocatalyst for reducing carbon dioxide in a flower-like structure, comprising the steps of:
(1) Preparation of 3D flower-like CoAl-LDHs precursor
Dissolving cobalt compound, aluminum compound, ammonium salt and urea/thiourea in water, stirring and mixing, placing the mixed solution in a closed container, controlling pressure to perform heating reaction, naturally cooling to room temperature, washing and drying to obtain a CoAl-LDHs precursor;
(2) Post-treatment
Calcining the precursor of the CoAl-LDHs in air atmosphere to obtain the 3D porous flower-shaped CoAl 2 O 4 A catalyst.
Further, the cobalt compound in step (1) is selected from cobalt chloride or cobalt nitrate; the aluminum compound is selected from aluminum chloride or aluminum nitrate. Preferably, the cobalt compound is cobalt nitrate and the aluminum compound is aluminum nitrate.
Further, in the step (1), the mass ratio of the cobalt compound to the aluminum compound is 1-3:1. Preferably 2:1.
Further, in the step (1), the ammonium salt is ammonium fluoride or ammonium chloride, and the amount is 64% of the weight of the cobalt compound. Preferably, the ammonium salt is ammonium fluoride in an amount of 64% by weight of the cobalt compound.
Further, the urea/thiourea is used in the step (1) in an amount of 7.29 times by weight of the cobalt compound. Urea is preferred.
Further, the water in the step (1) is selected from drinking water, tap water or deionized water. Preferably, the solvent is deionized water.
Further, the heating reaction temperature in the step (1) is 60-120 ℃, and the heating time is 6-10h. Preferably, the heating reaction temperature is 90℃and the heating time is 8 hours.
Further, in the step (1), the drying temperature is 40-80 ℃ and the drying time is 10-14h. Preferably, the drying temperature is 60 ℃ and the drying time is 12 hours.
Further, in the step (2), the calcination temperature is 600-900 ℃, the calcination time is 0.5-4 h, and the temperature rising rate is 1-10 ℃/min. Preferably, the calcination temperature is 750 ℃, the calcination time is 3 hours, and the temperature rising rate is 5 ℃/min.
The invention takes cobalt compound and aluminum compound as main raw materials for preparing catalyst, and adds ammonium salt and urea, the urea is used as pH buffering agent to slowly and continuously release OH - And simultaneously provides carbonate ions during the hydrolysis process to precipitate Co 2+ Provides a basic environment, and in addition, due to the reducibility of urea, it may prevent Co 2+ Is a metal oxide semiconductor device. The F ion in ammonium fluoride acts as a functional template in the formation of LDHs. Al (Al) 3+ By AlO 2 And OH (OH) - The complex exists and forms [ Al 13 (OH) 32 (H 2 O)] 7+ ，Co 2+ By alpha-Co (OH) 2 Precipitation exists, al increases with the reaction time 3+ The complex rapidly transfers to alpha-Co (OH) 2 Substitution of Co in the unit cell 2+ Forming the CoAl-LDH. The preparation method provided by the invention can further obtain a regular and uniform thinner (0.9-4.0 nm) 3D flower-like structure by controlling the reaction temperature and the reaction pressure so as toThe obtained active adsorption sites have higher specific surface area and richer, and are favorable for nucleation and growth of the CoAl-LDH under the experimental conditions of the reaction temperature of 90 ℃ and the reaction pressure of 2 MPa. The thinner 3D flower-shaped CoAl-LDH has the advantages of strong conduction band and a large number of Co active sites, however, under solar irradiation, the 3D flower-shaped CoAl-LDH photocatalyst has lower quantum efficiency due to low carrier mobility and rapid recombination of photo-generated electrons and photo-generated holes. Therefore, in order to improve the quantum yield of the catalyst, on the basis of preparing a thinner 3D flower-like structure, the invention controls proper calcination temperature and heating rate, so that the thinner 3D flower-like structure is further thinned (0.2-0.4 nm) to further increase the specific surface area so as to maintain more photo-generated charges and photo-generated hole activities, and further can effectively improve the photo-catalytic efficiency.
In a second aspect, the present invention provides a flower-like structure CoAl prepared by the method of the first aspect 2 O 4 A photocatalyst for reducing carbon dioxide.
In a third aspect, the present invention provides a method of using the flower-like structure CoAl of the second aspect 2 O 4 Preparation of photocatalytic CO by reduction of carbon dioxide 2 The method for reducing the film comprises the following steps: placing a photocatalyst in a glass culture dish, and adding deionized water; dispersing the catalyst by ultrasonic wave; placing the culture dish in an oven for drying; finally, evenly distributing deionized water on the surface of the dried catalyst to obtain the photocatalytic CO 2 And (5) reducing the film.
The beneficial effects of the invention are as follows:
the invention converts thinner 3D flower-shaped CoAl-LDHs into ultrathin 3D porous CoAl by adopting proper calcination temperature treatment 2 O 4 A composite material. The catalyst has the advantages of narrow band gap, strong response to visible light and high stability, the lamellar porous structure of the catalyst is favorable for absorbing light, the light can be reflected repeatedly, and the porous petal nano-sheet structure and the high specific surface area are CO 2 Reduction provides rich adsorption sites; optimized ultrathin 3D porous CoAl 2 O 4 The charge transmission path can effectively inhibit carrier recombination and retain photogenerated charge and photogenerationActivity of holes. The composite material is used for photocatalysis of CO under irradiation of visible light 2 During reduction, the method can detect the reaction product at room temperature without a heating system, and has low working temperature and mild operation condition. Under the irradiation of visible light with the wavelength of 200-800 nm at the room temperature of 20-40 ℃, the composite material catalyzes CO by photocatalysis 2 Reduction to CH 4 And the maximum yield of CO is 58.98 mu mol/g and 33.11 mu mol/g respectively, and the preparation method provided by the invention has high stability, is simple to operate, has low cost and is convenient to popularize.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
In the drawings:
FIG. 1 is a scanning electron microscope image of a thinner 3D flower-like CoAl-LDHs precursor material obtained in example 1;
FIG. 2 is a scanning electron microscope image of the calcination of the thinner 3D flower-like CoAl-LDHs precursor obtained in example 1 at 650 ℃;
FIG. 3 is a scanning electron microscope image of a calcination of the thinner 3D flower-like CoAl-LDHs precursor obtained in example 2 at 750 ℃;
FIG. 4 is a transmission electron microscope image of a thin 3D flower-like CoAl-LDHs precursor calcined at 750deg.C obtained in example 2;
FIG. 5 is an X-ray diffraction pattern of a composite material of the thinner 3D flower-like CoAl-LDHs precursor calcined at 750deg.C obtained in example 2; from the figure it can be seen that ultra thin 3D porous CoAl 2 O 4 A composite material is formed.
FIG. 6 is a scanning electron microscope image of the calcination of the thinner 3D flower-like CoAl-LDHs precursor obtained in example 3 at 850 ℃;
FIG. 7 is a graph of CO and CH light irradiation for 7 hours from visible light irradiation of composite materials calcined at different temperatures to give thinner 3D flower-like CoAl-LDHs precursors for examples 1-3 4 Comparison of yields, wherein A represents CoAl-LDHs of example 1, B represents CoAl-650, C represents CoAl-750, and D represents CoAl-850.
Detailed Description
The invention is further illustrated below in connection with specific examples, the content of which is not limited at all.
Example 1
0.233g of cobalt nitrate, 0.15g of aluminum nitrate, 0.15g of ammonium fluoride and 1.7g of urea were dissolved in 40mL of deionized water, and magnetically stirred at room temperature for one hour. The precursor was transferred to a 100 ml polytetrafluoroethylene stainless steel autoclave, which was then placed in a constant temperature oven and heated in a sealed manner at 90 ℃ for 8 hours. After naturally cooling to room temperature, the mixture is thoroughly washed with deionized water and ethanol. The powder obtained was dried in air at 60℃for 12 hours and then designated as CoAl-LDHs.
FIG. 7 shows CH of uncalcined precursor CoAl-LDHs catalyst 4 And CO yields of 40.37. Mu. Mol/g and 20.24. Mu. Mol/g, respectively.
Placing the obtained precursor powder in a porcelain crucible, and under air atmosphere at 5deg.C for min -1 The temperature rise rate of (2) was heated in a muffle furnace and calcined to 650 ℃ for 3 hours, and the resulting product was designated as CoAl-650. A scanning electron microscope image of the thinner 3D flower-like CoAl-LDH precursor material obtained in example 1 is shown in fig. 1. A scanning electron microscope image of calcination of the CoAl-LDH precursor obtained in example 1 at 650℃is shown in FIG. 2. Example 1 obtaining 3D porous flower-like CoAl 2 O 4 CO and CH of the composite material irradiated by visible light of 200-800 nm for 7 hours 4 The comparison of the yields is shown in FIG. 7.
FIG. 7 shows that 3D porous flower-like CoAl obtained by calcination at 650 DEG C 2 O 4 CH of catalyst 4 And CO yields of 49.06. Mu. Mol/g and 26.30. Mu. Mol/g, respectively.
Example 2
This example is identical to the process used in example 1, except that the calcination procedure is different, in this example to 750℃and the product obtained is designated CoAl-750. A scanning electron microscope image of the thinner 3D flower-like CoAl-LDHs precursor obtained in example 2 at 750 ℃ is shown in fig. 3. Fig. 4 is a transmission electron micrograph of the thinner 3D flower-like CoAl-LDHs precursor obtained in example 2 calcined at 750 ℃. FIG. 5 is a thin 3D flower-like CoAl-LDHs obtained in example 2An X-ray diffraction pattern of the composite material with the precursor calcined at 750 ℃; from the figure it can be seen that ultra thin 3D porous CoAl 2 O 4 A composite material is formed. Example 2 obtaining 3D porous flower-like CoAl 2 O 4 CO and CH of the composite material irradiated by visible light of 200-800 nm for 7 hours 4 The comparison of the yields is shown in FIG. 7.
FIG. 7 shows that 3D porous flower-like CoAl obtained by calcination at 750 ℃ 2 O 4 CH of catalyst 4 And CO yields of 58.98. Mu. Mol/g and 33.11. Mu. Mol/g, respectively.
Example 3
This example is identical to example 1 except that the calcination procedure is different, in this example, calcination to 850℃is carried out, and the resulting product is designated CoAl-850. A scanning electron microscope image of the calcination of the thinner 3D flower-like CoAl-LDHs precursor obtained in example 3 at 850 ℃ is shown in fig. 6. Example 3 obtaining 3D porous flower-like CoAl 2 O 4 CO and CH of the composite material irradiated by visible light of 200-800 nm for 7 hours 4 The comparison of the yields is shown in FIG. 7.
FIG. 7 shows that 3D porous flower-like CoAl obtained by calcination at 850 deg.C 2 O 4 CH of catalyst 4 And CO yields were 46.12. Mu. Mol/g and 25.29. Mu. Mol/g, respectively.
Example 4
This example is identical to the procedure used in example 1, except that the ammonium fluoride is replaced by ammonium chloride.
Example 6
This example is identical to the process used in example 1, except that urea is replaced with thiourea.
Example 7
Photocatalytic CO 2 Preparation of reduced films
A6 cm diameter glass petri dish was charged with 50 mg of catalyst and 5ml of deionized water was added. The catalyst was dispersed by sonication for 3min. Placing the culture dish in an oven, drying at 60deg.C, and uniformly distributing 500 μl deionized water on the surface of the dried catalyst to obtain photocatalytic CO 2 And (5) reducing the film.
The present invention is not limited to the above-mentioned embodiments, but any modifications, equivalents, improvements and modifications within the scope of the invention will be apparent to those skilled in the art.
Claims (8)
1. The application of flower-like structure photocatalyst in reducing carbon dioxide is characterized in that the product of reducing carbon dioxide is CH 4 And CO; the preparation method of the flower-like structure photocatalyst comprises the following steps:
(1) Preparation of 3D flower-like CoAl-LDHs precursor
Dissolving cobalt compound, aluminum compound, ammonium salt and urea in water, stirring and mixing, placing the mixed solution in a closed container, controlling pressure to perform heating reaction, naturally cooling to room temperature, washing and drying to obtain a CoAl-LDHs precursor; the ammonium salt is ammonium fluoride;
(2) Post-treatment
Calcining the precursor of the CoAl-LDHs in air atmosphere to obtain the 3D porous flower-shaped CoAl 2 O 4 A catalyst; the calcination temperature is 600-900 ℃, the calcination time is 0.5-4 h, and the heating rate is 1-10 ℃/min.
2. Use of a flower structured photocatalyst according to claim 1 for reducing carbon dioxide, characterized in that: the cobalt compound in the step (1) is selected from cobalt chloride or cobalt nitrate; the aluminum compound is selected from aluminum chloride or aluminum nitrate.
3. Use of a flower structured photocatalyst according to claim 1 for reducing carbon dioxide, characterized in that: the mass ratio of the cobalt compound to the aluminum compound in the step (1) is 1-3:1.
4. Use of a flower structured photocatalyst according to claim 1 for reducing carbon dioxide, characterized in that: the ammonium salt in the step (1) is used in an amount of 64% by weight of the cobalt compound.
5. Use of a flower structured photocatalyst according to claim 1 for reducing carbon dioxide, characterized in that: the urea in step (1) is used in an amount of 7.29 times the weight of the cobalt compound.
6. Use of a flower structured photocatalyst according to claim 1 for reducing carbon dioxide, characterized in that: the heating reaction temperature in the step (1) is 60-120 ℃, and the heating time is 6-10h.
7. Use of a flower structured photocatalyst according to claim 1 for reducing carbon dioxide, characterized in that: the drying temperature in the step (1) is 40-80 ℃ and the drying time is 10-14h.
8. The application of the flower-like structure photocatalyst film in reducing carbon dioxide is characterized in that the preparation steps of the flower-like structure photocatalyst film are as follows: placing the flower-like structured photocatalyst used in the application of any one of claims 1 to 7 in a glass culture dish, and adding deionized water; dispersing the catalyst by ultrasonic wave; placing the culture dish in an oven for drying; finally, evenly distributing deionized water on the surface of the dried catalyst to obtain the photocatalytic CO 2 And (5) reducing the film.
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| CN202210399631.XA CN114870843B (en) | 2022-04-15 | 2022-04-15 | Photocatalyst for reducing carbon dioxide by flower-like structure, preparation method and application thereof |
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