CN111482200B - Preparation method of Zn-Bim-His/GQDs composite visible light catalyst - Google Patents
Preparation method of Zn-Bim-His/GQDs composite visible light catalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 230000007547 defect Effects 0.000 claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 9
- 229960002885 histidine Drugs 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 230000002950 deficient Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 3
- 238000009396 hybridization Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000005431 greenhouse gas Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- 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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Abstract
The invention belongs to the technical field of photocatalysis nano materials, and relates to a preparation method of a GQDs/Zn-Bim-His composite visible light catalyst. The method comprises the following steps: preparing Zn-Bim by wet chemical method; performing surface defect treatment on the Zn-Bim prepared in the step one to obtain defect Zn-Bim-His; GQDs/Zn-Bim-His photocatalyst is obtained by adopting GQDs hybridization defect Zn-Bim-His. The raw materials used in the invention are easy to obtain, the preparation method is simple, the preparation conditions are easy to control, and the prepared GQDs/Zn-Bim-His composite visible light catalyst is a green pollution-free high-performance catalyst, can efficiently convert greenhouse gas carbon dioxide into fuel, and has a certain application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalysis nano materials, and relates to a preparation method of a GQDs/Zn-Bim-His composite visible light catalyst.
Background
Due to the massive consumption of fossil fuels and the increasing energy demands of humans, serious environmental pollution and energy crisis occur. At present, inexhaustible solar energy is utilized to convert CO 2 Conversion to fuel is one of the most promising technologies, thus photocatalytic CO 2 Reduction is increasingly attracting attention from researchers. The key to the development of the technology is to develop a novel high-efficiency visible light catalyst. At present, the photocatalyst is mainly made to capture visible light through two ways: firstly, the existing photocatalysts (such as titanium dioxide, zinc oxide and the like) are modified to expand the response range of the photocatalysts to be visibleA light zone; and secondly, developing a novel photocatalyst with visible light response.
Metal-organic frameworks (MOFs) are crystalline porous organic-inorganic hybrid materials, generally formed by connecting metal ions or clusters with multidentate organic ligands containing elements such as oxygen, nitrogen and the like through coordination bonds. Compared with the traditional porous materials, the MOF material has some remarkable characteristics such as ultra-large specific surface area and pore volume, functional diversity, adjustable pore size, high crystallinity and highly ordered pore structure. In recent years, MOFs materials are widely applied in the fields of energy storage, photoelectricity, sensing, catalysis and the like due to the special structure and excellent physical and chemical properties. Metal organic framework compounds (ZIFs) based on imidazolyl ligands have similar properties to zeolites and metal oxide photocatalysts, and have attracted considerable attention. Because ZIFs have variable structures and compositions, have the advantage of combining most of the characteristics of the existing majority of light response materials and photocatalysts, and have great application potential in the field of photocatalysis. The defect Zn-Bim-His is a mixed ligand metal organic framework compound with a sodalite structure and is formed by bridging organic ligands of benzimidazole, histidine and metal ions of zinc ions, and the mixed ligand metal organic framework compound has a crystal structure similar to ZIF-7. Although the defect Zn-Bim-His can absorb visible light, the quantization efficiency is still low, and the photocatalytic performance is weak. Therefore, developing a new photocatalyst with defect Zn-Bim-His as a base point to improve the photocatalytic performance becomes a new idea.
Disclosure of Invention
The invention aims to solve the technical problems that: based on the problems, the invention provides a preparation method for preparing the high-efficiency GQDs/Zn-Bim-His composite visible light catalyst.
The invention solves the technical problems by adopting a technical scheme that: a preparation method of GQDs/Zn-Bim-His composite visible light catalyst.
The invention provides a preparation method of a GQDs/Zn-Bim-His photocatalyst, which is characterized in that a novel high-efficiency visible light catalyst is obtained by regulating and controlling surface defects of Zn-Bim and carrying out GQDs hybridization on the surface.
The preparation method of the GQDs/Zn-Bim-His photocatalyst comprises the following steps:
step one, preparing Zn-Bim by a wet chemical method;
step two, carrying out surface defect treatment on the Zn-Bim prepared in the step one to obtain defect Zn-Bim-His;
and thirdly, adopting GQDs to hybridize with the defect Zn-Bim-His to obtain the GQDs/Zn-Bim-His photocatalyst.
Preferably, in the first step, the specific process for preparing the Zn-Bim by a wet chemical method is as follows: adding zinc nitrate hexahydrate and benzimidazole into Dimethylformamide (DMF), stirring at room temperature to obtain a reaction product, washing the reaction product with deionized water, centrifuging, and drying to obtain Zn-Bim.
Preferably, in the first step, the ratio of the zinc salt to the benzimidazole is: 0.250-0.550 g, 1.200-1.500 g, and stirring time is 12-36 h.
Preferably, the zinc salt is zinc nitrate hexahydrate.
Preferably, in the second step, the specific process of performing surface oxygen defect treatment on the Zn-Bim-His is as follows: weighing Zn-Bim prepared in the first step, adding into deionized water, performing ultrasonic dispersion, transferring to a reaction container, adding polyvinylpyrrolidone (PVP) and L-histidine, then placing into an oil bath, stirring and heating, naturally cooling to room temperature after the reaction is finished, washing with deionized water, centrifuging, and freeze-drying to obtain the defect Zn-Bim-His.
Preferably, in the second step, the mixture ratio of the dosages of Zn-Bim, deionized water, PVP and L-histidine is as follows: 0.050-0.200 g, 20-100 mL, 0.100-0.500 g, 0.300-0.800 g, the heating temperature of the oil bath is 90-150 ℃, and the heating time of the oil bath is 15-30 h.
Preferably, in the third step, the specific process of adopting GQDs to hybridize the defect Zn-Bim-His is as follows: and (3) weighing the defect Zn-Bim-His prepared in the second step, adding the defect Zn-Bim-His into anhydrous n-hexane, performing ultrasonic dispersion, stirring at room temperature, simultaneously dropwise adding a GQDs aqueous solution, sequentially washing with absolute ethyl alcohol and deionized water after reaction, centrifuging, and freeze-drying to obtain the defect GQDs/Zn-Bim-His photocatalyst.
Preferably, the dosage ratio of defect Zn-Bim-His and anhydrous n-hexane is 10-50 mg:20-100 mL, the ultrasonic dispersion time is 5-60 min, the addition amount of GQDs aqueous solution is 5-20 mu L, the concentration of GQDs aqueous solution is 100-250 mg/mL, and the stirring time is 1-5 h.
The GQDs/Zn-Bim-His photocatalyst prepared by the preparation method of the GQDs/Zn-Bim-His photocatalyst is prepared by carrying out surface defect treatment on Zn-Bim and then carrying out GQDs hybridization.
In another aspect, the invention provides an application of the GQDs/Zn-Bim-His photocatalyst in photocatalytic conversion of carbon dioxide.
The beneficial effects of the invention are as follows: the adopted raw materials are easy to obtain, the preparation method is simple, the preparation conditions are easy to control, and the prepared GQDs/Zn-Bim-His composite visible light catalyst is a green pollution-free high-performance catalyst, can efficiently convert greenhouse gas carbon dioxide into fuel, and has a certain application prospect.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a transmission electron microscope image of a defective Zn-Bim-His sample prepared in example 3 of the present invention;
FIG. 2 is a transmission electron microscope image of the GQDs/Zn-Bim-His composite visible light catalyst prepared in example 3 of the present invention;
FIG. 3 is a graph showing the effect of the photocatalytic conversion of carbon dioxide by the GQDs/Zn-Bim-His composite visible light catalyst prepared in examples 1 to 4 of the present invention.
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.
Example 1: the preparation method of the GQDs/Zn-Bim-His composite visible light catalyst comprises the following specific steps:
(1) Preparation of Zn-Bim: 0.250g of zinc nitrate hexahydrate and 1.200g of benzimidazole are added into 50mL of DMF, and the mixture is stirred at room temperature for 12 hours to obtain a reaction product, and the reaction product is washed by deionized water, centrifuged and dried to obtain Zn-Bim.
(2) Preparation of defect Zn-Bim-His: weighing 0.050g of Zn-Bim, adding 20mL of deionized water, performing ultrasonic dispersion for 5min, transferring the mixture into a round-bottom flask, adding 0.100g of polyvinylpyrrolidone (PVP) and 0.300-g L-histidine, then placing into an oil bath, stirring and heating, setting the heating temperature to 90 ℃, stopping heating after reacting for 15h, continuing stirring for 20h, washing with absolute ethyl alcohol and water in sequence, and freeze-drying for 36h to obtain the defect Zn-Bim-His.
(3) Preparation of GQDs/Zn-Bim-His photocatalyst: 10mg of defect Zn-Bim-His is weighed, added into 20mL of anhydrous n-hexane, dispersed for 5min by ultrasonic, stirred at room temperature, added with 5 mu L of GQDs aqueous solution (100 mg/mL) drop by drop, washed twice by absolute ethyl alcohol and deionized water in sequence, and freeze-dried for 48h to obtain the defect GQDs/Zn-Bim-His photocatalyst.
Example 2: the preparation method of the GQDs/Zn-Bim-His composite visible light catalyst comprises the following specific steps:
(1) Preparation of Zn-Bim: 0.400g of zinc nitrate hexahydrate and 1.400g of benzimidazole are added into 50mLDMF, the mixture is stirred at room temperature for 24 hours to obtain a reaction product, and the reaction product is washed by deionized water, centrifuged and dried to obtain Zn-Bim.
(2) Preparation of defect Zn-Bim-His: weighing 0.100g of Zn-Bim, adding 50mL of deionized water, performing ultrasonic dispersion for 30min, transferring the mixture into a round-bottom flask, adding 0.300g of polyvinylpyrrolidone (PVP) and 0.500-g L-histidine, then placing into an oil bath, stirring and heating, setting the heating temperature to 110 ℃, stopping heating after reacting for 20h, continuing stirring for 24h, then washing with absolute ethyl alcohol and water in sequence, and performing freeze drying for 48h to obtain the defect Zn-Bim-His.
(3) Preparation of GQDs/Zn-Bim-His photocatalyst: 20mg of defect Zn-Bim-His is weighed, added into 40mL of anhydrous n-hexane, dispersed for 30min by ultrasonic, stirred at room temperature, simultaneously added with 10 mu L of GQDs aqueous solution (150 mg/mL) dropwise, washed twice by absolute ethyl alcohol and deionized water in sequence, and freeze-dried for 48h to obtain the defect GQDs/Zn-Bim-His photocatalyst.
Example 3: the preparation method of the GQDs/Zn-Bim-His composite visible light catalyst comprises the following specific steps:
(1) Preparation of Zn-Bim: 0.480g of zinc nitrate hexahydrate and 1.450g of benzimidazole are added into 60mL of DMF, and the mixture is stirred at room temperature for 24 hours to obtain a reaction product, and the reaction product is washed by deionized water, centrifuged and dried to obtain Zn-Bim.
(2) Preparation of defect Zn-Bim-His: weighing 0.150g of Zn-Bim, adding 80mL of deionized water, carrying out ultrasonic dispersion for 40min, transferring the mixture into a round bottom flask, adding 0.400g of polyvinylpyrrolidone (PVP) and 0.600-g L-histidine, then placing into an oil bath, stirring and heating, setting the heating temperature to 120 ℃, stopping heating after reaction for 26h, continuing stirring for 30h, washing with absolute ethyl alcohol and water in sequence, and freeze-drying for 60h to obtain the defect Zn-Bim-His.
(3) Preparation of GQDs/Zn-Bim-His photocatalyst: 30mg of defect Zn-Bim-His is weighed, added into 60mL of anhydrous n-hexane, dispersed for 45min by ultrasonic, stirred at room temperature, simultaneously added with 15 mu L of GQDs aqueous solution (200 mg/mL) dropwise, washed twice by absolute ethyl alcohol and deionized water in sequence, and freeze-dried for 55h, thus obtaining the defect GQDs/Zn-Bim-His photocatalyst.
FIG. 1 is a transmission electron microscope image of a defective Zn-Bim-His sample prepared in example 3, and it can be seen that many structure-defective pinholes are formed on the surface of Zn-Bim-His nanoparticles; FIG. 2 is a transmission electron microscope image of the GQDs/Zn-Bim-His composite visible light catalyst prepared in the above example 3, and it is seen that the GQDs can be well dispersed on the surface of the defect Zn-Bim-His-1 nanoparticle, and no agglomeration phenomenon of the GQDs is observed.
Example 4: the preparation method of the GQDs/Zn-Bim-His composite visible light catalyst comprises the following specific steps:
(1) Preparation of Zn-Bim: 0.550g of zinc nitrate hexahydrate and 1.500g of benzimidazole were added to 80mL of DMF and stirred at room temperature for 36 hours to obtain a reaction product, and the reaction product was washed with deionized water, centrifuged and dried to obtain Zn-Bim.
(2) Preparation of defect Zn-Bim-His: weighing 0.200g of Zn-Bim, adding 100mL of deionized water, performing ultrasonic dispersion for 60min, transferring the mixture into a round-bottom flask, adding 0.500g of polyvinylpyrrolidone (PVP) and 0.800-g L-histidine, then placing into an oil bath, stirring and heating, setting the heating temperature to 150 ℃, stopping heating after 30h of reaction, continuing stirring for 36h, then washing with absolute ethyl alcohol and water in sequence, and freeze-drying for 72h to obtain the defect Zn-Bim-His.
(3) Preparation of GQDs/Zn-Bim-His photocatalyst: 50mg of defect Zn-Bim-His is weighed, added into 100mL of anhydrous n-hexane, dispersed for 60min by ultrasonic, stirred at room temperature, simultaneously added with 20 mu L of GQDs aqueous solution (250 mg/mL) dropwise, washed twice by absolute ethyl alcohol and deionized water in sequence, and freeze-dried for 72h to obtain the defect GQDs/Zn-Bim-His photocatalyst.
FIG. 3 is a graph showing the effect of the GQDs/Zn-Bim-His composite photocatalyst prepared in examples 1-4 on the photocatalytic conversion of carbon dioxide, wherein all the GQDs/Zn-Bim-His composite photocatalysts can catalyze CO gas under the visible light 2 Conversion to CH 4 And CO, also a small amount of H 2 Wherein to generate CH 4 The conversion efficiency of (2) is highest.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (2)
1. The preparation method of the GQDs/Zn-Bim-His composite visible light catalyst is characterized by comprising the following steps:
step one, preparing Zn-Bim by a wet chemical method;
adding zinc nitrate hexahydrate and benzimidazole into dimethylformamide, stirring at room temperature to obtain a reaction product, washing the reaction product with deionized water, centrifuging, and drying to obtain Zn-Bim; the ratio of the dosage of the zinc nitrate hexahydrate to the dosage of the benzimidazole is as follows: 0.250-0.550 g, 1.200-1.500 g, and stirring time is 12-36 h;
step two, carrying out surface defect treatment on the Zn-Bim prepared in the step one to obtain defect Zn-Bim-His;
weighing Zn-Bim prepared in the first step, adding into deionized water, ultrasonically dispersing, transferring to a reaction container, adding polyvinylpyrrolidone and L-histidine, then placing into an oil bath kettle, stirring, heating, cooling to room temperature after the reaction is finished, sequentially washing with absolute ethyl alcohol and water, and freeze-drying to obtain defective Zn-Bim-His;
the dosage ratio of Zn-Bim, deionized water, polyvinylpyrrolidone and L-histidine is as follows: 0.050-0.200 g, 20-100 mL, 0.100-0.500 g, 0.300-0.800 g, oil bath heating temperature is 90-150 ℃, and oil bath heating time is 15-30 h;
step three, adopting GQDs to hybridize the defect Zn-Bim-His to obtain a GQDs/Zn-Bim-His photocatalyst;
weighing the defect Zn-Bim-His prepared in the second step, adding the defect Zn-Bim-His into anhydrous n-hexane, performing ultrasonic dispersion, stirring at room temperature, simultaneously dropwise adding a GQDs aqueous solution, sequentially washing with absolute ethyl alcohol and deionized water after reaction, centrifuging, and freeze-drying to obtain the defect GQDs/Zn-Bim-His photocatalyst;
the dosage ratio of defect Zn-Bim-His and anhydrous n-hexane is as follows: 10-50 mg/20-100 mL, ultrasonic dispersion time of 5-60 min, GQDs aqueous solution addition of 5-20 mu L, GQDs aqueous solution concentration of 100-250 mg/mL, and stirring time of 1-5 h.
2. Use of a GQDs/Zn-Bim-His photocatalyst according to claim 1 for the photocatalytic conversion of carbon dioxide.
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