CN116139867A - MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof - Google Patents
MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 229910020599 Co 3 O 4 Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 23
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical group [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 36
- 230000001699 photocatalysis Effects 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
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- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
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- 239000002994 raw material Substances 0.000 abstract 1
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- 239000003054 catalyst Substances 0.000 description 3
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- 239000011701 zinc Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- WCYJXDMUQGVQQS-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1 WCYJXDMUQGVQQS-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 239000010457 zeolite Substances 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
Abstract
The invention belongs to the field of nano materials, and in particular relates to a MOFs-derived ZnO@CDs@Co 3 O 4 A composite photocatalyst, a preparation method and application thereof. The invention synthesizes the ZIF-8 structure, loads carbon points, synthesizes the ZIF-67 in situ, and prepares ZnO@CDs@Co through calcination 3 O 4 The composite photocatalyst forms a unique core-shell structure. From the structure characterization and performance characterization experiments, it can be found thatThe prepared ZnO@CDs@Co 3 O 4 The composite photocatalyst has the advantages of stable chemical property, uniform morphology, high catalytic efficiency and the like, and has certain research and application values because the composite photocatalyst has the advantages of easily available raw materials, low preparation cost and the like.
Description
Technical Field
The invention belongs to the field of nano materials, and in particular relates to a MOFs-derived ZnO@CDs@Co 3 O 4 A composite photocatalyst, a preparation method and application thereof.
Background
Energy sourceShortages and environmental problems have become significant challenges for today's human society. 80% of the world's energy consumption still comes from fossil energy sources, mainly petroleum, coal, natural gas, etc. With the increase of human social activities, not only the consumption of fossil energy is accelerated, but also CO is used in the atmosphere 2 The increase of the emission of the main greenhouse gases seriously disturbs the carbon circulation in the nature, and leads to global warming.
In recent years, semiconductor materials have included metal oxides (ZnO and Co 3 O 4 ) Metal sulfides (CdS and In) 2 S 3 ) Carbon-based material (C 3 N 4 And carbon quantum dots), a metal organic framework (UIO-66-NH) 2 And MIL-125 amino), and the like, CO has been reported 2 Light conversion. Among them, znO has been called as a most promising semiconductor because of its high stability, low cost, and reasonable carbon dioxide oxidation-reduction capability. However, the broadband band gap is as high as 3.2eV, and the high charging speed is compounded to limit the photocatalytic CO 2 In conversion, the efficiency of bare ZnO when used as a photocatalyst to improve photocatalytic performance, there are many strategies employing techniques including surface engineering, various morphological adjustments, cocatalyst loading, heteroatom doping, heterojunction architecture, and the like.
The metal-organic frameworks (MOFs) have high specific surface area, semiconductor property and abundant active sites, so that the metal-organic frameworks (MOFs) are widely applied to the field of photocatalysis, wherein zeolite type imidazole acid framework structures represented by ZIF-67 and ZIF-8 have the characteristics of exposed metal sites, accessible carbon-nitrogen ligands, good chemical stability and the like, and are ideal materials for solar hydrogen production. Wang et al report ZIF-67/Ni-Fe LDHs composites in which ZIF-67 has a higher specific surface area and well-matched energy band structure, thus exhibiting higher photocatalytic hydrogen rates. ZIF-8/ZIF-67 has better stability and adhesion than other MOFs. In addition, when the photocatalytic system releases a large amount of carbon dioxide, the carbon dioxide can rapidly pass through the porous layer, thereby accelerating the kinetics of the chemical reaction.
In our previous work, we have passed through a multi-step synthetic CD-modified Metal Organic Framework (MOF) shapeCo of the product 3 O 4 /In 2 O 3 Nanotube (CDs-M-CIO) heterostructures exhibit higher solar driven CO generation rates, up to 2.05 μmol h, without sacrificing agent -1 g -1 . In the invention, the ZnO@CDs@Co with unique core-shell structure derived from ZIF-8@CDs@ZIF-67 is prepared by one-step pyrolysis 3 O 4 The method is applied to the field of photocatalysis for the first time and can greatly improve the reduction performance of the photocatalytic carbon dioxide.
Disclosure of Invention
The invention aims to solve the technical problems that: based on the above problems, it is an object of the present invention to provide a MOFs-derived ZnO@CDs@Co 3 O 4 A composite photocatalyst, a preparation method and application thereof.
The invention adopts a technical scheme for solving the technical problems that: MOFs derived ZnO@CDs@Co 3 O 4 The composite photocatalyst takes ZnO as a core, carbon points are distributed on the surface of ZnO, and Co is used as a catalyst 3 O 4 The preparation method of the composite photocatalyst with the shell-core-shell structure comprises the following steps:
(1) Preparation of ZIF-8: zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) adding the mixture into methanol, adding a methanol solution containing 2-methylimidazole, stirring to uniformly mix, washing the mixture with methanol for a plurality of times, and drying to obtain ZIF-8;
(2) Preparation of ZIF-8@CDs@ZIF-67: dissolving the prepared ZIF-8 in methanol, adding ethanol solution of carbon dots, adding cobalt chloride, slowly adding methanol solution containing 2-methylimidazole into the suspension, stirring to complete the reaction, and washing with methanol for several times to obtain ZIF-8@CDs@ZIF-67;
(3)ZnO@CDs@Co 3 O 4 is prepared from the following steps: putting the prepared ZIF-8@CDs@ZIF-67 into a crucible, and calcining in a muffle furnace to obtain a product ZnO@CDs@Co 3 O 4 。
Further, zn (NO 3 ) 2 ·6H 2 The ratio of the amount of O to the amount of 2-methylimidazole substance is 2-3:5-7; preferably 2.7:6.4. The size of ZIF-8 prepared in the proportion is about 2 μm,and different proportions can influence the morphology and the size of ZIF-8, thereby influencing the compounding and catalytic effects.
Further, in the step (2), ZIF-8 and CoCl are adopted 2 The mass ratio of the 2-methylimidazole is 0.1-0.3:1-1.5:10-11; preferably 0.1 to 0.3:1.4:10.9; further preferably 0.2:1.4:10.9. At this ratio, the morphology and size of the ZIF-67 formed is such as to ensure that the ZIF-8 and CDs are encapsulated to form a core-shell structure.
Further, in the step (2), the CDs are dispersed in the ethanol solution so that the CDs can be uniformly dispersed, preferably, the concentration of the ethanol solution of the CDs is 1mg/ml; the adding amount of CDs is 1-5% of the mass of ZIF-8; it is further preferable that the amount of CDs to be added is 3% by mass of ZIF-8.
Further, the calcination temperature in the step (3) is 450 ℃, and the calcination time is 2h. The calcination temperature and time will affect the morphology and particle size of the calcined product, preferably at 450 ℃ for 2 hours, resulting in a final ZnO@CDs@Co 3 O 4 The morphology of the composite photocatalyst is a regular-shaped dodecahedron with uniform folds.
ZnO@CDs@Co prepared by the method 3 O 4 The composite photocatalyst is used for photocatalytic carbon dioxide reduction, and ZnO@CDs@Co prepared by the method 3 O 4 The composite photocatalyst is used for producing carbon monoxide by photocatalytic reduction of carbon dioxide.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention synthesizes the ZIF-8 structure, then carries carbon dots through mechanical stirring, and finally produces ZIF-67 in situ to prepare ZnO@CDs@Co 3 O 4 The composite photocatalyst takes ZnO as a core, CDs particles are distributed on the surface of the ZnO, and finally Co is coated 3 O 4 As the shell of the whole structure, a unique core-shell structure is formed. The ZIF-8@CDs@ZIF-67 composite photocatalyst prepared by the method has regular shape and uniform dodecahedron shape; znO@CDs@Co 3 O 4 The morphology of the composite photocatalyst is a regular-shaped dodecahedron with uniform folds;
(2) The supported Carbon Dots (CDs) have good electron transfer characteristics, so that the recombination of photoexcitation electron-hole pairs is inhibited, and the CDs have a conjugated p structure and can preferentially adsorb and activate carbon dioxide, so that the CDs have excellent photocatalytic activity;
(3) Compared with the cube structure in the prior art, the ZnO@CDs@Co of the invention 3 O 4 The specific surface area of the composite photocatalyst is obviously increased, the composite photocatalyst has better stability, no secondary pollution and catalytic efficiency, and can realize ZnO@CDs@Co in 180min 3 O 4 The speed of photocatalytic carbon dioxide can reach 2123 mu mol g -1 h -1 ；
(4) ZnO@CDs@Co of the invention 3 O 4 The preparation method of the composite photocatalyst is simple, the preparation condition is easy to control, the secondary pollution is avoided, and the preparation method has certain research and application values.
Description of the drawings:
the invention is further described below with reference to the accompanying drawings.
FIG. 1 shows a pure ZIF-67, a pure ZIF-8, a ZIF-8@ZIF-67, a ZIF-8@CDs@ZIF-67, a pure Co prepared in example 1 of the present invention 3 O 4 Pure ZnO, znO@Co 3 O 4 And ZnO@CDs@Co 3 O 4 An X-ray diffraction pattern of the composite photocatalyst;
FIG. 2 is a pure ZIF-67 (FIG. 2 a), a pure ZIF-8 (FIG. 2 b), a ZIF-67@ZIF-8 (FIG. 2 c), a ZIF-8@CDs@ZIF-67 (FIG. 2 d), a pure Co, prepared in example 1 of the present invention 3 O 4 (FIG. 2 e), pure ZnO (FIG. 2 f), co 3 O 4 @ZnO (FIG. 2 g), and ZnO@CDs@Co 3 O 4 (FIG. 2 h) scanning electron microscope image of the composite photocatalyst; ZIF-8@CDs@ZIF-67 (FIG. 2 i) and ZnO@CDs@Co 3 O 4 (FIG. 2 j) a transmission electron microscope image; znO@CDs@Co 3 O 4 (FIG. 2 k) high power transmission electron microscopy; znO@CDs@Co 3 O 4 (FIG. 2 l) EDX profile;
FIG. 3 is a graph showing ZnO@Co prepared in example 1 of the present invention 3 An O composite photocatalyst photocatalytic carbon dioxide rate diagram;
FIG. 4 is a graph showing ZnO@CDs@Co obtained in example 1 of the present invention 3 An O composite photocatalyst photocatalytic carbon dioxide rate diagram;
FIG. 5 is a graph showing the 3% -ZnO@CDs@Co obtained in example 1 of the present invention 3 O and 3% -ZnO@Co 3 And (3) an O@CDs composite photocatalyst photocatalytic carbon dioxide rate comparison chart.
Detailed Description
The invention will now be further illustrated with reference to specific examples, which are intended to illustrate the invention and not to limit it further.
The general method for carrying out photocatalytic carbon dioxide reduction by using the composite photocatalyst in the invention is as follows: 10mg of the sample and 10mg of ruthenium pyridine were added to 20ml of acetonitrile, 5ml of water, 5ml of triethanolamine, and further sonicated for 30 minutes to prepare a uniformly dispersed catalyst sample. Then, the prepared catalyst sample and 30ml of the solution were put into a 120ml Pyrex glass reactor and bubbled with a carbon dioxide system for 30min, ensuring anaerobic conditions for 30 min. The photocatalytic experiment used a 300W xenon lamp (simulating the full spectrum of sunlight, wavelength range 200-2500 nm). Three hours after the reaction time, samples were taken and detected by gas chromatography (GC-7860 plus, TCD detector).
The reagents used in the invention are all analytically pure unless specified.
Example 1
(1) Preparation of CDs:
two graphite rods are used as carbon sources, and ultrasonic cleaning is carried out in deionized water for 15min to remove surface impurities. Two graphite rods are respectively connected with the anode and the cathode and then inserted into a beaker filled with ultrapure water to serve as an anode and a cathode. The two electrodes were spaced apart by about 7.5cm and protruded outwardly from the electrolyte surface by 3-5cm, and a voltage of 30V was applied between the two electrodes by a DC power supply. And (3) electrolyzing the graphite rod for about half a month, filtering with a chronic quantitative filter paper for three times when the aqueous solution in the beaker turns into brown black, or centrifuging at 22000rpm of a centrifuge for about 15-30min to remove precipitated graphite oxide and larger graphite particles, and finally obtaining the aqueous solution of pure CDs. The CDs powder is obtained by freeze-drying a certain amount of an aqueous solution of CDs. And finally, dispersing the CDs powder into an ethanol solution for later use, wherein the concentration of the ethanol solution of the CDs is 1mg/ml.
(2) Preparation of ZIF-67 and ZIF-8: will 0.177g CoCl 2 Dissolving in 15mL of methanol, slowly adding 15mL of methanol solution containing 0.895g of 2-methylimidazole into the suspension, stirring for 3h, and washing with methanol for several times to obtain ZIF-67; 0.810g Zn (NO) 3 ) 2 ·6H 2 O was added to 15mL of methanol, then 40mL of a methanol solution containing 0.526g of 2-methylimidazole was added to the above suspension, and after stirring for 3 hours, the mixture was washed 3 times with methanol and dried at 60℃to give ZIF-8 as a sample.
(3)ZnO@Co 3 O 4 Preparation of a composite photocatalyst:
40mg of ZIF-8 or 50mg of ZIF-8 or 60mg of ZIF-8 are dissolved in 15ml of methanol, and 0.177g of CoCl is added 2 . Then, 15mL of methanol solution containing 0.895g of 2-methylimidazole is slowly put into the suspension, and after stirring for 3 hours, the product ZIF-8@ZIF-67 is obtained by washing with methanol for several times; putting the prepared ZIF-8@ZIF-67 into a crucible, and calcining for 2 hours at 450 ℃ in a muffle furnace to obtain products respectively marked as 40mg-ZnO@Co 3 O 4 、50mg-ZnO@Co 3 O 4 、60mg-ZnO@Co 3 O 4 。
As can be seen from FIG. 3, 50mg of-ZnO@Co 3 O 4 The highest CO production efficiency of catalyzing carbon dioxide reaches 1032 mu mol g -1 h -1 Compared with ZnO and Co 3 O 4 The improvement is 2.96 times and 2.30 times respectively.
(4)ZnO@CDs@Co 3 O 4 Preparation of a composite photocatalyst:
1％-ZnO@CDs@Co 3 O 4 preparation of a composite photocatalyst: 50mg ZIF-8 was dissolved in 15ml of methanol, 0.5ml of CDs in ethanol (1 mg/ml) was added, and 0.177g of CoCl was added 2 . Then, 15mL of a methanol solution containing 0.895g of 2-methylimidazole was slowly put into the above suspension. After stirring for 3 hours, washing with methanol for several times to obtain a product ZIF-8@CDs@ZIF-67; putting the prepared ZIF-8@CDs@ZIF-67 into a crucible, calcining at 450 ℃ in a muffle furnace for 2 hours to obtain a product 1% -ZnO@CDs@Co 3 O 4 。
3％-ZnO@CDs@Co 3 O 4 Preparation of a composite photocatalyst: and 1％-ZnO@CDs@Co 3 O 4 The preparation method of the composite photocatalyst is different in that the addition amount of the ethanol solution of 1mg/ml CDs is 1.5ml.
5％-ZnO@CDs@Co 3 O 4 Preparation of a composite photocatalyst: with 1% -ZnO@CDs@Co 3 O 4 The preparation method of the composite photocatalyst is different in that the addition amount of the ethanol solution of 1mg/ml CDs is 2.5ml.
As can be seen from FIG. 4, within 180min, 1% -ZnO@CDs@Co 3 O 4 、3％-ZnO@CDs@Co 3 O 4 、5％-ZnO@CDs@Co 3 O 4 Compared with 50mg-ZnO@Co, the composite photocatalyst 3 O 4 Respectively improves by 1.22 times, 2.06 times and 1.35 times, wherein 3% -ZnO@CDs@Co 3 O 4 The rate of CO production by photocatalytic carbon dioxide reduction can reach 2123 mu mol g -1 h -1 The CO selectivity was 62%. Thus, the prepared ZnO@CDs@Co can be seen 3 O 4 The composite photocatalyst has high photocatalytic activity.
(5) Preparation of 3% -ZnO@Co 3 O 4 @CDs, examining the effect of the doping mode of CDs on the activity of the photocatalyst
According to the step (3) ZnO@Co 3 O 4 Preparation method of composite photocatalyst, weighing 50mg ZIF-8, and preparing 50mg-ZnO@Co 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the 50mg of-ZnO@Co 3 O 4 Dissolving in 15ml methanol, adding 1.5ml ethanol solution (1 mg/ml) of CDs, stirring for 24h, and washing with methanol for several times to obtain 3% -ZnO@Co product 3 O 4 @CDs。
As can be seen from FIG. 5, the doping mode of CDs has a significant effect on the activity of the photocatalyst, and ZnO@Co is prepared first 3 O 4 3% -ZnO@Co prepared by loading CDs 3 O 4 CO formation rate at 1528. Mu. Mol g for @ CDs -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the 3% -ZnO@CDs@Co prepared by loading CDs 3 O 4 CO formation rate of 2123. Mu. Mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Compared with the two, the speed of the composite photocatalysis prepared by the prior doping method for catalyzing carbon dioxide to generate CO is improved by 1.39 times.
X-ray diffractometer split using Japanese D/MAX2500Analysis of the pure ZIF-67, pure ZIF-8, ZIF-8@ZIF-67, ZIF-8@CDs@ZIF-67 prepared in example 1, pure Co 3 O 4 Pure ZnO, co 3 O 4 @ZnO, and ZnO@CDs@Co 3 O 4 Crystalline phase structure of composite photocatalyst, wherein X-ray is Cu target K alpha
The voltage is 40kV, the current is 100mA, the step size is 0.02 DEG, and the scanning range is 5 DEG-80 deg. As shown in FIG. 1, it can be seen from the graph that characteristic diffraction peaks at 7.4 °,10.4 °,12.8 °,14.7 °,16.4 ° and 17.8 ° of ZIF-8 correspond to (011), (002), (112), (022), (013), and (222) crystal planes of ZIF-8, respectively, (011), (002), (112), (013), and (222) crystal planes of ZIF-67, respectively, and that characteristic diffraction peaks at 7.4 °,10.4 °,12.8 °,14.7 °,16.4 ° and 17.8 ° correspond to (011), (002), (112), (022), (013), and (222) crystal planes of ZIF-67, respectively, in the XRD diffraction pattern of the prepared ZIF-8@CDs@ZIF-67 composite photocatalyst. 22.5 DEG and 42.3 DEG are characteristic diffraction peaks of CDs corresponding to (002) and (100) crystal planes of CDs, respectively. However, the ZIF-8@CDs@ZIF-67 composite material has no obvious CDs peak in the X-ray diffraction pattern, which is related to low CDs loading, small volume and good dispersibility. Therefore, the composite photocatalyst only contains ZIF-8 and ZIF-67, and the chemical structures and crystal forms of the ZIF-8 and the ZIF-67 are not changed in the composite process. Likewise, the prepared ZnO@CDs@Co 3 O 4 Co appears at 31.2, 37.1, 44.7, 59.3, and 65.3 as seen in the XRD diffraction patterns of the composite photocatalyst 3 O 4 The characteristic diffraction peaks respectively correspond to Co 3 O 4 (220), (311), (400), (511), and (440) crystal planes of 31.9 °,34.5 °,36.3 °,47.5 °,56.6 °,62.9 °,66.4 °,68.0 °, and 69.1 ° are characteristic diffraction peaks of ZnO corresponding to (100), (002), (101), (102), (110), (103), (200), (112), and (201) crystal planes of ZnO, respectively. 22.5 DEG and 42.3 DEG are characteristic diffraction peaks of CDs corresponding to (002) and (100) crystal planes of CDs, respectively. But ZnO@CDs@Co in X-ray diffraction pattern 3 O-composites have no distinct CDs peaks, which is associated with low CDs loadings, small volumes, good dispersibility. Therefore, the composite photocatalyst contains only Co 3 O 4 And ZnO, andthe chemical structure and crystal form of the two are not changed in the compounding process.
ZIF-8@CDs@ZIF-67 and ZnO@CDs@Co prepared in example 1 were observed by using Quanta 200F type field emission scanning electron microscope 3 O 4 The morphology of the composite photocatalyst is shown in a scanning electron microscope image as shown in fig. 2, and as can be seen from the image, the morphology of the ZIF-8@CDs@ZIF-67 composite photocatalyst prepared by the embodiment is regular, and the size of the ZIF-8@CDs@ZIF-67 composite photocatalyst is uniform; whereas ZnO@CDs@Co 3 O 4 The morphology of the composite photocatalyst is a regular-shaped dodecahedron with uniform folds. This can also be further illustrated by the TEM image in fig. 2.
Claims (8)
1. MOFs derived ZnO@CDs@Co 3 O 4 The composite photocatalyst is characterized in that the MOFs derived ZnO@CDs@Co 3 O 4 The composite photocatalyst takes ZnO with carbon dots distributed on the surface as a core and Co 3 O 4 The composite photocatalyst is a core-shell structure of a shell.
2. MOFs-derived zno@cds@co according to claim 1 3 O 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparation of ZIF-8: adding zinc nitrate hexahydrate into methanol, adding a methanol solution containing 2-methylimidazole, stirring to uniformly mix, washing with methanol for several times, and drying to obtain ZIF-8;
(2) Preparation of ZIF-8@CDs@ZIF-67: dissolving the prepared ZIF-8 in methanol, adding ethanol solution of carbon dots, adding cobalt chloride, slowly adding methanol solution containing 2-methylimidazole into the suspension, stirring to complete the reaction, and washing with methanol for several times to obtain ZIF-8@CDs@ZIF-67;
(3)ZnO@CDs@Co 3 O 4 is prepared from the following steps: putting the prepared ZIF-8@CDs@ZIF-67 into a crucible, and calcining in a muffle furnace to obtain a product ZnO@CDs@Co 3 O 4 。
3. MOFs-derived zno@cds@according to claim 2Co 3 O 4 The preparation method of the composite photocatalyst is characterized in that the ratio of the amount of zinc nitrate hexahydrate to the amount of 2-methylimidazole substances in the step (1) is 2-3:5-7.
4. MOFs-derived zno@cds@co according to claim 2 3 O 4 The preparation method of the composite photocatalyst is characterized in that the mass ratio of ZIF-8, cobalt chloride and 2-methylimidazole in the step (2) is 0.1-0.3:1-1.5:10-11.
5. MOFs-derived zno@cds@co according to claim 2 3 O 4 The preparation method of the composite photocatalyst is characterized in that the addition amount of carbon points in the step (2) is 1-5% of the mass of ZIF-8.
6. MOFs-derived zno@cds@co according to claim 2 3 O 4 The preparation method of the composite photocatalyst is characterized in that the calcining temperature in the step (3) is 450 ℃ and the calcining time is 2 hours.
7. MOFs-derived zno@cds@co according to claim 1 3 O 4 The application of the composite photocatalyst is characterized in that the composite photocatalyst is applied to photocatalytic carbon dioxide reduction.
8. The MOFs-derived zno@cds@co of claim 7 3 O 4 The application of the composite photocatalyst is characterized in that the composite photocatalyst is applied to the reduction of carbon dioxide to produce carbon monoxide by photocatalysis.
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