CN111482200A - Preparation method of Zn-Bim-His/GQDs composite visible-light-driven photocatalyst - Google Patents
Preparation method of Zn-Bim-His/GQDs composite visible-light-driven photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 230000007547 defect Effects 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000009396 hybridization Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000005406 washing 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
- 230000002950 deficient Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 238000005303 weighing Methods 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
- 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
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000007704 wet chemistry method Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 3
- 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 6
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000013153 zeolitic imidazolate framework 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
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003446 ligand Substances 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
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 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
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 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
- 239000005431 greenhouse 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
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 230000004298 light response Effects 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
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000013139 quantization Methods 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
- 230000007847 structural defect Effects 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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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
Abstract
The invention belongs to the technical field of photocatalytic nano materials, and relates to a preparation method of a GQDs/Zn-Bim-His composite visible-light-induced photocatalyst. The method comprises the following steps: preparing Zn-Bim by a wet chemical method; performing surface defect treatment on the Zn-Bim prepared in the step one to obtain defect Zn-Bim-His; GQDs hybridization defects Zn-Bim-His are adopted to obtain the GQDs/Zn-Bim-His photocatalyst. 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-driven photocatalyst is a green pollution-free high-performance catalyst, can efficiently convert greenhouse-effect gas carbon dioxide into fuel, and has a certain application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalytic nano materials, and relates to a preparation method of a GQDs/Zn-Bim-His composite visible-light-induced photocatalyst.
Background
Due to the large consumption of fossil fuels and the increasing energy demand of human beings, serious environmental pollution and energy crisis occur. At present, CO is produced by using inexhaustible solar energy2Conversion to fuels is one of the most promising technologies, and thus photocatalytic CO2Reduction is becoming a growing concern for researchers. The key to the development of the technology lies in the development of a novel efficient visible-light-driven photocatalyst. Currently, people mainly capture visible light by a photocatalyst through two ways: firstly, the existing photocatalyst (such as titanium dioxide, zinc oxide and the like) is modified, so that the response range of the photocatalyst is expanded to a visible light region; and secondly, developing a novel photocatalyst with visible light response.
Metal-organic frameworks (MOFs) are crystalline porous organic-inorganic hybrid materials, which are generally formed by connecting metal ions or clusters and polydentate organic ligands containing oxygen, nitrogen and other elements 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, diversity of functions, adjustable pore size, high crystallinity and highly ordered pore structure. In recent years, MOFs have been widely used in the fields of energy storage, photoelectricity, sensing, catalysis, etc. due to their special structures and excellent physicochemical properties. Metal organic framework compounds (ZIFs) based on imidazolyl ligands have similar properties to zeolite and metal oxide photocatalysts, and have attracted considerable attention. Because ZIFs structure and composition are changeable, the ZIFs has the advantage of combining most characteristics of most existing photoresponse materials and photocatalysts, and therefore has great application potential in the field of photocatalysis. The defect Zn-Bim-His is a mixed ligand metal organic framework compound which is formed by bridging an organic ligand benzimidazole, histidine and a metal ion zinc ion and has a sodalite structure, and has a crystal structure similar to ZIF-7. Although the defect Zn-Bim-His can absorb visible light, the quantization efficiency of the defect Zn-Bim-His is still very low, and the photocatalytic performance is weak. Therefore, it is a new idea to develop a new photocatalyst based on the defect Zn-Bim-His to improve the photocatalytic performance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: based on the problems, the invention provides a preparation method for preparing a high-efficiency GQDs/Zn-Bim-His composite visible-light-driven photocatalyst.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a GQDs/Zn-Bim-His composite visible light catalyst.
One aspect of the invention provides a preparation method of a GQDs/Zn-Bim-His photocatalyst, and a novel efficient visible photocatalyst is obtained by regulating and controlling surface defects of Zn-Bim and hybridizing the surface with the GQDs.
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 step three, adopting GQDs to hybridize the defect Zn-Bim-His to obtain the GQDs/Zn-Bim-His photocatalyst.
Preferably, in the step one, the specific process for preparing 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 as follows: 0.250-0.550 g, 1.200-1.500 g, and the stirring time is 12-36 h.
Preferably, the zinc salt is zinc nitrate hexahydrate.
Preferably, in the second step, the specific process of carrying out surface oxygen defect treatment on Zn-Bim-His comprises the steps of weighing Zn-Bim prepared in the first step, adding the Zn-Bim into deionized water, carrying out ultrasonic dispersion, transferring to a reaction vessel, adding polyvinylpyrrolidone (PVP) and L-histidine, then putting into an oil bath pot, stirring and heating, naturally cooling to room temperature after the reaction is finished, washing with deionized water, centrifuging, and carrying out freeze drying to obtain the defective Zn-Bim-His.
Preferably, in the second step, the using amount of Zn-Bim, deionized water, PVP and L-histidine is 0.050-0.200 g, 20-100 m L, 0.100-0.500 g and 0.300-0.800 g, the oil bath heating temperature is 90-150 ℃, and the oil bath heating time is 15-30 hours.
Preferably, in the third step, the specific process of adopting GQDs hybridization defect Zn-Bim-His is as follows: and weighing the defect Zn-Bim-His prepared in the step two, adding the defect Zn-Bim-His into anhydrous n-hexane, performing ultrasonic dispersion, stirring at room temperature, simultaneously dropwise adding a GQDs aqueous solution, washing with anhydrous ethanol and deionized water in sequence after reaction, centrifuging, and performing freeze drying to obtain the defect GQDs/Zn-Bim-His photocatalyst.
Preferably, the dosage ratio of the defect Zn-Bim-His to the anhydrous n-hexane is 10-50 mg: 20-100 m L, the ultrasonic dispersion time is 5-60 min, the addition amount of the GQDs aqueous solution is 5-20 mu L, the concentration of the aqueous solution is 100-250 mg/m L, 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 hybridizing the Zn-Bim with GQDs.
The invention also provides an application of the GQDs/Zn-Bim-His photocatalyst in the photocatalytic conversion of carbon dioxide.
The invention has the beneficial effects that: the used raw materials are easy to obtain, the preparation method is simple, the preparation conditions are easy to control, the prepared GQDs/Zn-Bim-His composite visible-light-driven photocatalyst 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 sample of a defective Zn-Bim-His 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 GQDs/Zn-Bim-His composite photocatalyst prepared in examples 1-4 of the present invention on the photocatalytic conversion of carbon dioxide.
Detailed Description
The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative of the invention and are not intended to be a further limitation of the invention.
Example 1: the preparation method of the GQDs/Zn-Bim-His composite visible light catalyst comprises the following specific steps:
(1) and the preparation of Zn-Bim comprises the steps of adding 0.250g of zinc nitrate hexahydrate and 1.200g of benzimidazole into 50m L DMF, stirring at room temperature for 12 hours to obtain a reaction product, washing the reaction product with deionized water, centrifuging and drying to obtain the Zn-Bim.
(2) Preparation of defect Zn-Bim-His, weighing 0.050g of Zn-Bim, adding 20m L deionized water, ultrasonically dispersing for 5min, transferring the mixture into a round bottom flask, adding 0.100g of polyvinylpyrrolidone (PVP) and 0.300g of L-histidine, then putting the mixture into an oil bath pot, stirring and heating, setting the heating temperature to be 90 ℃, stopping heating after reacting for 15h, continuing stirring for 20h, then sequentially washing with absolute ethyl alcohol and water, and freeze-drying for 36h to obtain the defect Zn-Bim-His.
(3) Weighing 10mg of defective Zn-Bim-His, adding the defective Zn-Bim-His into 20m L anhydrous n-hexane, ultrasonically dispersing for 5min, stirring at room temperature, simultaneously dropwise adding a 5 mu L GQDs aqueous solution (100mg/m L), sequentially washing with anhydrous ethanol and deionized water for two times respectively, and freeze-drying for 48h to obtain the defective 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) and the preparation of Zn-Bim comprises the steps of adding 0.400g of zinc nitrate hexahydrate and 1.400g of benzimidazole into 50m L DMF, stirring at room temperature for 24 hours to obtain a reaction product, washing the reaction product with deionized water, centrifuging and drying to obtain the Zn-Bim.
(2) Preparation of defect Zn-Bim-His, weighing 0.100g of Zn-Bim, adding 50m L deionized water, ultrasonically dispersing for 30min, transferring the mixture into a round-bottom flask, adding 0.300g of polyvinylpyrrolidone (PVP) and 0.500g of L-histidine, then putting the mixture into an oil bath pot, stirring and heating, setting the heating temperature at 110 ℃, stopping heating after reacting for 20h, continuing stirring for 24h, then sequentially washing with absolute ethyl alcohol and water, and freeze-drying for 48h to obtain the defect Zn-Bim-His.
(3) Weighing 20mg of defective Zn-Bim-His, adding the defective Zn-Bim-His into 40m L anhydrous n-hexane, ultrasonically dispersing for 30min, stirring at room temperature, simultaneously dropwise adding 10 mu L GQDs aqueous solution (150mg/m L), sequentially washing with anhydrous ethanol and deionized water for two times respectively, and freeze-drying for 48h to obtain the defective 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) and the preparation of Zn-Bim comprises the steps of adding 0.480g of zinc nitrate hexahydrate and 1.450g of benzimidazole into 60m L DMF, stirring at room temperature for 24 hours to obtain a reaction product, washing the reaction product with deionized water, centrifuging and drying to obtain the Zn-Bim.
(2) Preparation of defect Zn-Bim-His, weighing 0.150g of Zn-Bim, adding 80m L deionized water, ultrasonically dispersing for 40min, transferring the mixture into a round-bottom flask, adding 0.400g of polyvinylpyrrolidone (PVP) and 0.600g of L-histidine, then putting the mixture into an oil bath pot, stirring and heating, setting the heating temperature at 120 ℃, stopping heating after reacting for 26h, continuing stirring for 30h, then sequentially washing with absolute ethyl alcohol and water, and freeze-drying for 60h to obtain the defect Zn-Bim-His.
(3) Weighing 30mg of defective Zn-Bim-His, adding the defective Zn-Bim-His into 60m L anhydrous n-hexane, ultrasonically dispersing for 45min, stirring at room temperature, simultaneously dropwise adding a 15 mu L GQDs aqueous solution (200mg/m L), sequentially washing with anhydrous ethanol and deionized water for two times respectively, and freeze-drying for 55h to obtain the defective GQDs/Zn-Bim-His photocatalyst.
FIG. 1 is a transmission electron microscope image of a sample with defect Zn-Bim-His prepared in the above example 3, and it can be seen that many structural defect small holes are formed on the surface of the Zn-Bim-His nano particle; FIG. 2 is a transmission electron microscope image of the GQDs/Zn-Bim-His composite visible light catalyst prepared in example 3, which shows that the GQDs can be well dispersed on the surface of the defect Zn-Bim-His-1 nanoparticle, and the agglomeration phenomenon of the GQDs is not observed.
Example 4: the preparation method of the GQDs/Zn-Bim-His composite visible light catalyst comprises the following specific steps:
(1) and the preparation of Zn-Bim comprises the steps of adding 0.550g of zinc nitrate hexahydrate and 1.500g of benzimidazole into 80m L DMF, stirring at room temperature for 36 hours to obtain a reaction product, washing the reaction product with deionized water, centrifuging and drying to obtain the Zn-Bim.
(2) Preparation of defect Zn-Bim-His, weighing 0.200g of Zn-Bim, adding 100m L deionized water, ultrasonically dispersing for 60min, transferring the mixture into a round-bottom flask, adding 0.500g of polyvinylpyrrolidone (PVP) and 0.800g of L-histidine, then putting the mixture into an oil bath pot, stirring and heating, setting the heating temperature at 150 ℃, stopping heating after reacting for 30h, continuing stirring for 36h, then sequentially washing with absolute ethyl alcohol and water, and freeze-drying for 72h to obtain the defect Zn-Bim-His.
(3) Weighing 50mg of defective Zn-Bim-His, adding the defective Zn-Bim-His into 100m L anhydrous n-hexane, ultrasonically dispersing for 60min, stirring at room temperature, simultaneously dropwise adding a 20 mu L GQDs aqueous solution (250mg/m L), sequentially washing with anhydrous ethanol and deionized water for two times respectively, and freeze-drying for 72h to obtain the defective GQDs/Zn-Bim-His photocatalyst.
FIG. 3 is a diagram showing the effect of the GQDs/Zn-Bim-His composite photocatalyst prepared in the above examples 1-4 on the photocatalytic conversion of carbon dioxide, and it can be seen that all the GQDs/Zn-Bim-His composite photocatalysts can catalyze gas CO under the visible light2Conversion to CH4And CO, and also small amounts of H2In which CH is generated4The conversion efficiency of (a) is highest.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. A preparation method of a 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;
step two, carrying out surface defect treatment on the Zn-Bim prepared in the step one to obtain defect Zn-Bim-His;
and step three, adopting GQDs to hybridize the defect Zn-Bim-His to obtain the GQDs/Zn-Bim-His photocatalyst.
2. The method for preparing a GQDs/Zn-Bim-His photocatalyst as claimed in claim 1, wherein in the first step, the specific process for preparing Zn-Bim by wet chemistry method is as follows: adding zinc salt 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.
3. The method for preparing GQDs/Zn-Bim-His photocatalyst as claimed in claim 2, wherein in the first step, the ratio of the zinc salt to the benzimidazole is as follows: 0.250-0.550 g, 1.200-1.500 g, and the stirring time is 12-36 h.
4. The method of claim 3, wherein the zinc salt is zinc nitrate hexahydrate.
5. The method for preparing GQDs/Zn-Bim-His photocatalyst according to claim 4, wherein in the second step, Zn-Bim-His is subjected to surface defect treatment by weighing Zn-Bim prepared in the first step, adding the Zn-Bim into deionized water, ultrasonically dispersing, transferring to a reaction vessel, adding polyvinylpyrrolidone and L-histidine, stirring and heating in an oil bath kettle, cooling to room temperature after reaction, washing with absolute ethyl alcohol and water in sequence, and freeze-drying to obtain defective Zn-Bim-His.
6. The method for preparing GQDs/Zn-Bim-His photocatalyst according to claim 5, wherein in the second step, the dosage ratios of Zn-Bim, deionized water, polyvinylpyrrolidone and L-histidine are 0.050-0.200 g, 20-100 m L, 0.100-0.500 g and 0.300-0.800 g, the oil bath heating temperature is 90-150 ℃, and the oil bath heating time is 15-30 h.
7. The method for preparing GQDs/Zn-Bim-His photocatalyst according to claim 6, wherein in the third step, the specific process of adopting GQDs hybridization defect Zn-Bim-His is as follows: and weighing the defect Zn-Bim-His prepared in the step two, adding the defect Zn-Bim-His into anhydrous n-hexane, performing ultrasonic dispersion, stirring at room temperature, simultaneously dropwise adding a GQDs aqueous solution, washing with anhydrous ethanol and deionized water in sequence after reaction, centrifuging, and performing freeze drying to obtain the defect GQDs/Zn-Bim-His photocatalyst.
8. The preparation method of the GQDs/Zn-Bim-His photocatalyst according to claim 7, wherein the dosage ratio of the defect Zn-Bim-His to the anhydrous n-hexane is 10-50 mg: 20-100 m L, the ultrasonic dispersion time is 5-60 min, the addition amount of the GQDs aqueous solution is 5-20 μ L, the concentration of the aqueous solution is 100-250 mg/m L, and the stirring time is 1-5 h.
9. Use of a GQDs/Zn-Bim-His photocatalyst as claimed in any one of claims 1 to 8 for the photocatalytic conversion of carbon dioxide.
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