CN113000068B - Preparation method of ZnO @ ZIF-8 core-shell nanocomposite material with high photocatalytic performance - Google Patents
Preparation method of ZnO @ ZIF-8 core-shell nanocomposite material with high photocatalytic performance Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 title abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 195
- 239000011787 zinc oxide Substances 0.000 claims abstract description 64
- 239000002073 nanorod Substances 0.000 claims abstract description 53
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 238000004108 freeze drying Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000005303 weighing Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 24
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- 230000000593 degrading effect Effects 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- -1 zeolite imidazole ester Chemical class 0.000 claims description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 5
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract 1
- 239000011257 shell material Substances 0.000 description 20
- 239000002131 composite material Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 6
- 238000001782 photodegradation Methods 0.000 description 6
- 239000004246 zinc acetate Substances 0.000 description 6
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of a ZnO @ ZIF-8 core-shell nano composite material with high-efficiency photocatalytic performance, which is prepared from H 2 In an O-organic solvent, enabling a zinc oxide nanorod to react with a 2-methylimidazole molecule in the organic solvent, repeatedly washing a reaction product with alcohol and water, and performing freeze drying treatment to obtain a ZnO @ ZIF-8 nanocomposite material with a core-shell structure; the method specifically comprises the following steps: 1) weighing 0.1-0.5g of ZnO nano-rod for later use; 2) 20mL of 2-methylimidazole organic solvent solution with the mass concentration of 0.5-12mg/mL is prepared for later use; 3) and (3) mixing the step (1) and the step (2), pouring the mixture into a polyfluortetraethylene reaction kettle, adding 0.01-0.2ml of deionized water, reacting the zinc oxide nano rod with 2-methylimidazole molecules under a solvothermal condition, and sealing for 8-72 hours.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a preparation method of a ZnO @ ZIF-8 core-shell nanocomposite material with high photocatalytic performance by taking ZnO as a core ZIF-8 as a shell.
Background
The photocatalysis technology has the advantages of high catalytic activity, simple equipment, convenient operation, low energy consumption, strong oxidation capability, no secondary pollution and the like, and is widely researched in the treatment of organic wastewater and comprehensive wastewater which are difficult to degrade. Zinc oxide is a common n-type semiconductor photocatalyst, however, the application of zinc oxide photocatalysts is greatly limited due to the wide band gap energy and the rapid recombination of electron-hole pairs generated by light excitation. The heterostructure material is an important way for improving the photocatalytic performance of the zinc oxide semiconductor due to the advantages that the heterostructure material is easy to control the structure, the appearance and the function of the material, can promote electrons to transfer from a block body to an interface and the like. Metal-Organic Frameworks (MOFs) are a class of Organic-inorganic hybrid materials formed by bonding Metal ions or Metal clusters to Organic ligands through coordination bonds or ion-coordination bonds. Zeolite Imidazolate Framework (ZIF-8) is one of MOFs materials, is formed by coordination of zinc ions and 2-Methylimidazole (MleM), and has attracted attention because of its topology structure of inorganic zeolite molecular sieves.
Under certain conditions, ZnO is placed in an organic solution of 2-methylimidazole, ZIF-8 can uniformly grow on the surface of ZnO, and the ZnO @ ZIF-8 composite material is formed. For example, the literature (J.Am.chem.Soc.,2013,135:1926-1933.) uses ZnO nanorods as self-sacrifice templates in H 2 Preparing ZnO @ ZIF-8 nano rods with the shell thickness of about 300 +/-25 nm by using the O-DMF mixed hot solution; the literature (mater.Lett.2015,156:50-53.) modifies this process and produces ZnO @ ZIF-8 nanospheres with shell thicknesses of about 100 nm; the patent (CN104549082A) prepares ZnO @ ZIF-8 nanospheres with shell thickness of 40-60nm in a 2-methylimidazole organic solvent. Although some documents report the preparation method of the ZnO @ ZIF-8 composite material, the thickness of the prepared ZIF-8 layer is large (both are larger than 40nm), and the photocatalytic efficiency of the composite material cannot be remarkably improved. When the ZIF-8 covered outside the ZnO @ ZIF-8 core-shell material is thinner, the separation and the transmission of photogenerated electron holes are more facilitated, so that the photodegradability of the composite material is improved. Therefore, the preparation of the ZnO @ ZIF-8 composite material with the core-shell structure, the ultrathin ZIF-8 covering layer (below 5 nm) and high light degradation efficiency has important significance and great difficulty.
The invention provides a preparation method of a ZnO @ ZIF-8 core-shell nano composite material with high-efficiency photocatalytic performance, the ZIF-8 shell thickness of the prepared composite material is only 2-5nm, and the composite material shows extremely high photodegradability under the condition of visible light.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a preparation method of a ZnO @ ZIF-8 core-shell nano composite material with the thickness of only 2-5nm and high-efficiency photocatalytic performance.
In an organic solvent, the core-shell composite material with the thickness of only 2-5nm is obtained by controlling the mass ratio of the 2-methylimidazole to the zinc oxide nano-rod, and the photocatalytic performance of the core-shell composite material is remarkably improved.
To solveThe invention solves the technical problem and provides a preparation method of a ZnO @ ZIF-8 core-shell nano composite material with high-efficiency photocatalytic performance, which is prepared from H 2 In an O-organic solvent, enabling a zinc oxide nanorod to react with a 2-methylimidazole molecule in the organic solvent, repeatedly washing a reaction product with alcohol and water, and performing freeze drying treatment to obtain a ZnO @ ZIF-8 nanocomposite material with a core-shell structure;
the method specifically comprises the following steps:
1) weighing 0.1-0.5g of ZnO nano-rod for later use;
2) 20mL of 2-methylimidazole organic solvent solution with the mass concentration of 0.5-12mg/mL is prepared for later use;
3) pouring the mixture obtained in the step 1 and the step 2 into a polyfluortetraethylene reaction kettle, adding 0.01-0.2ml of deionized water, reacting the zinc oxide nano rod with 2-methylimidazole molecules under the solvothermal condition, and carrying out closed reaction for 8-72 hours;
4) repeatedly washing the reaction product obtained in the step (3) with alcohol and water, and then carrying out freeze drying treatment at the freezing temperature of-20-40 ℃ for 8-16h to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure;
Further, ZnO nanorods were prepared as follows:
a. adding 14.8g of zinc acetate and 60ml of methanol solution into a 250ml round-bottom flask, stirring and dissolving;
b. adding 7.4g of potassium hydroxide and 32ml of methanol solution into a 100ml beaker, and cooling after complete dissolution;
c. adding the potassium hydroxide solution dissolved in the step b into the zinc acetate solution in the step a, and stirring and reacting for 3 days at 70 ℃;
d. and (c) repeatedly washing the reaction product in the step (c) by using methanol and deionized water, and finally, freeze-drying to obtain white powder of the zinc oxide nano rod for later use.
Further, the preparation method of the ZnO @ ZIF-8 core-shell nanocomposite material with high photocatalytic performance comprises the following steps:
weighing 0.3g of ZnO nanorod and 20mL of 2.0mg/mL ethanol solution of 2-methylimidazole, adding the ethanol solution into a 50mL of polyfluortetraethylene reaction kettle, adding 0.1mL of deionized water, carrying out closed reaction at 80 ℃ for 24 hours, repeatedly washing the reaction product with alcohol and water, and carrying out freeze drying treatment at-30 ℃ for 12 hours to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure.
Furthermore, the core-shell structure takes a zinc oxide nanorod (ZnO) as an inner core and takes a zeolite imidazole ester framework material (ZIF-8) as an outer shell; wherein the average shell thickness of the zeolite imidazole ester framework material is 2-5 nm.
Further, the average shell thickness of the zeolite imidazolate framework material is 2-3 nm.
Further, the organic solvent is any one of methanol, ethanol, or propanol.
Further, said H 2 O-H of organic solvent 2 The volume ratio of O to the organic solvent is 1: 2000-1:100.
Further, the mass ratio of the 2-methylimidazole added at the beginning of the reaction to the zinc oxide nano-rod is 1: 0.8-1:30.
Further, the temperature of the thermal condition reaction is controlled to be 30-120 ℃, and the reaction time is 8-72 h.
Compared with the prior art, the invention has the beneficial effects that:
the invention is achieved by 2 Zn on the surface of a ZnO nano rod in an O-organic solvent 2+ And reacting with 2-methylimidazole molecules in the solution to obtain the ZnO @ ZIF-8 nano composite material. By regulating and controlling the mass ratio of the 2-methylimidazole to the zinc oxide nano rod, the ZnO @ ZIF-8 composite material with different ZIF-8 shell thicknesses (2-5nm) can be obtained through regulation and control. When visible light irradiates for 6min, the degradation rate of Methylene Blue (MB) can reach 100%, and the photocatalytic performance is obviously improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of ZnO nanorods;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a ZnO @ ZIF-8 nanocomposite;
FIG. 3 is a Transmission Electron Microscope (TEM) image of a ZnO @ ZIF-8 nanocomposite;
FIG. 4 is an X-ray diffraction (XRD) pattern of ZnO nanorods, ZIF-8, and ZnO @ ZIF-8 nanocomposites;
FIG. 5 is a graph of X-ray diffraction (XRD) comparison of ZnO @ ZIF-8 nanocomposites with 2-methylimidazolium methanol solutions at concentrations of 2mg/mL, 5mg/mL, and 10 mg/mL;
FIG. 6 is a graph of the UV-VIS absorption spectrum of ZnO @ ZIF-8 degrading methylene blue under visible light irradiation (the inset is a photograph of the color of the solution as a function of time);
FIG. 7 is a graph showing the stability degradation of ZnO @ ZIF-8 in degrading methylene blue under visible light irradiation;
FIG. 8 is a graph comparing the results of the preparation of ZnO @ ZIF-8 nanocomposites with 2-methylimidazolium methanol solutions at concentrations of 2mg/mL and 10mg/mL, respectively, for the degradation of methylene blue under visible light irradiation;
FIG. 9 is a diagram of the ultraviolet-visible absorption spectrum of a ZnO nanorod degrading methylene blue under irradiation of visible light (the inset is a photograph of the color of the solution changing with time);
FIG. 10 is a chart of the UV-VIS absorption spectrum of ZIF-8 degrading methylene blue under visible light irradiation (the inset is a photograph of the color of the solution as a function of time);
FIG. 11 is the result of the degradation of methylene blue by the ZnO nanorods and ZnO @ ZIF-8 nanocomposites under visible light irradiation;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
As shown in figures 1-11, a preparation method of ZnO @ ZIF-8 core-shell nano composite material with high photocatalytic performance is carried out in H 2 In an O-organic solvent, a zinc oxide nanorod reacts with a 2-methylimidazole molecule in the organic solvent, and the reaction product is repeatedly washed by alcohol and water and then is subjected to freeze drying treatment to obtain the ZnO @ ZIF-8 nano rod with the core-shell structureA rice composite;
the method specifically comprises the following steps:
1) weighing 0.1-0.5g of ZnO nano-rod for later use;
2) proportioning a 2-methylimidazole organic solvent, wherein the mass concentration of the 2-methylimidazole organic solvent is 20mL and 0.5-12mg/mL for later use;
3) pouring the mixture obtained in the step 1 and the step 2 into a polyfluortetraethylene reaction kettle, adding 0.01-0.2ml of deionized water, reacting the zinc oxide nano rod with 2-methylimidazole molecules under the solvothermal condition, and carrying out closed reaction for 8-72 hours;
4) Repeatedly washing the reaction product obtained in the step (3) with alcohol and water, and then carrying out freeze drying treatment at the freezing temperature of-20-40 ℃ for 8-16h to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure;
the ZnO nanorod is prepared as follows:
a. adding 14.8g of zinc acetate and 60ml of methanol solution into a 250ml round-bottom flask, stirring and dissolving;
b. adding 7.4g of potassium hydroxide and 32ml of methanol solution into a 100ml beaker, and cooling after complete dissolution;
c. adding the potassium hydroxide solution dissolved in the step b into the zinc acetate solution in the step a, and stirring and reacting for 3 days at 70 ℃;
d. and (c) repeatedly washing the reaction product in the step (c) by using methanol and deionized water, and finally, freeze-drying to obtain white powder of the zinc oxide nano rod for later use.
Said H 2 O-H of organic solvent 2 The volume ratio of O to the organic solvent is 1: 2000-1:100.
Example 1
Adding 14.8g of zinc acetate and 60ml of methanol solution into a 250ml round-bottom flask, stirring and dissolving; adding 7.4g of potassium hydroxide and 32m l methanol solution into a 100ml beaker, and cooling after complete dissolution; adding a potassium hydroxide solution into a zinc acetate solution, and stirring and reacting for 3 days at 70 ℃; and repeatedly washing the reaction product with methanol and deionized water, and finally freeze-drying to obtain white ZnO nanorod powder for later use.
Weighing 0.3g of ZnO nanorod (shown in figure 1) and 20mL of 2.0mg/mL methanol solution of 2-methylimidazole, adding the methanol solution into a 50mL of polyfluortetraethylene reaction kettle, adding 0.1mL of deionized water, carrying out closed reaction at 80 ℃ for 24 hours, repeatedly washing the reaction product with alcohol and water, and carrying out freeze drying treatment at-30 ℃ for 12 hours to obtain the ZnO @ ZIF-8 nanocomposite (shown in figures 2 and 3a) with the core-shell structure, wherein the shell thickness of the zeolite imidazolate framework material is 3 nm.
Through detection, the mass ratio of the 2-methylimidazole to the zinc oxide nanorod is regulated and controlled, and the ZnO @ ZIF-8 composite material with different ZIF-8 shell thicknesses (2-5nm) can be obtained through regulation and control.
FIG. 2 shows that the prepared ZnO @ ZIF-8 nano composite material has the same morphology as the original ZnO nano rod.
FIG. 3 is a Transmission Electron Microscope (TEM) image of ZnO @ ZIF-8 nanocomposite. FIG. 3(a) shows that the mass ratio of 2-methylimidazole to zinc oxide nanorods is 1: 7.5, obtaining the ZnO @ ZIF-8 composite material with the thickness of the ZIF-8 shell layer of 3 nm; FIG. 3(b) shows that the mass ratio of 2-methylimidazole to zinc oxide nanorods is 1: and when 1.5 hours, obtaining the ZnO @ ZIF-8 composite material with the ZIF-8 shell thickness of 5 nm.
FIG. 4 shows that a diffraction peak of ZIF-8 appears in diffraction peaks of ZnO @ ZIF-8, indicating that a ZnO @ ZIF-8 complex is formed.
FIG. 5 is a comparison graph of X-ray diffraction (XRD) of 2-methylimidazole methanol solutions at concentrations of 2mg/mL, 5mg/mL, and 10mg/mL to prepare ZnO @ ZIF-8 nanocomposites with mass ratios of 2-methylimidazole to zinc oxide nanorods of 1: 7.5, 1: 3.0 and 1: 1.5; the result shows that the intensity of the diffraction peak of the ZIF-8 is increased along with the increase of the mass ratio of the 2-methylimidazole to the zinc oxide nano-rod, and the quantity of the generated ZIF-8 is higher and higher.
Example 2
Weighing 0.3g of ZnO nanorod and 20mL of 0.5mg/mL ethanol solution of 2-methylimidazole, adding the ethanol solution into a 50mL of polyfluortetraethylene reaction kettle, adding 0.1mL of deionized water, carrying out closed reaction at 75 ℃ for 48 hours, repeatedly washing the reaction product with alcohol and water, and carrying out freeze drying treatment at-25 ℃ for 13 hours to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure.
The preparation of white powder of ZnO nanorods was the same as in embodiment 1, and the ZnO nanorods were used in the following examples.
Example 3
Weighing 0.3g of ZnO nanorod and 20mL of 2.0mg/mL methanol solution of 2-methylimidazole, adding the methanol solution into a 50mL of polyfluortetraethylene reaction kettle, adding 0.01mL of deionized water, carrying out closed reaction at 120 ℃ for 72 hours, repeatedly washing the reaction product with alcohol and water, and carrying out freeze drying treatment at the freezing temperature of-20 ℃ for 16 hours to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure, wherein the shell thickness of the zeolite imidazolate framework material is 5nm (shown in figure 3 b).
Example 4
Weighing 0.3g of ZnO nanorod and 20mL of 5.0mg/mL propanol solution of 2-methylimidazole, adding the obtained mixture into a 50mL polyfluortetraethylene reaction kettle, adding 0.2mL deionized water, carrying out closed reaction at 30 ℃ for 72 hours, repeatedly carrying out alcohol washing and water washing on a reaction product, and carrying out freeze drying treatment at the freezing temperature of-40 ℃ for 8 hours to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure.
Example 5
Weighing 0.3g of ZnO nanorod and 20mL of 12mg/mL propanol solution of 2-methylimidazole, adding the mixture into a 50mL polyfluortetraethylene reaction kettle, adding 0.1mL deionized water, carrying out closed reaction at 100 ℃ for 36 hours, repeatedly carrying out alcohol washing and water washing on a reaction product, and carrying out freeze drying treatment at-30 ℃ for 12 hours to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure.
Example 6
Weighing 0.1g of ZnO nanorod and 20mL of 2.0mg/mL propanol solution of 2-methylimidazole, adding the obtained mixture into a 50mL polyfluortetraethylene reaction kettle, adding 0.2mL deionized water, carrying out closed reaction at 60 ℃ for 60 hours, repeatedly carrying out alcohol washing and water washing on a reaction product, and carrying out freeze drying treatment at the freezing temperature of-20 ℃ for 8 hours to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure.
Example 7
Weighing 0.5g of ZnO nanorod and 20mL of propanol solution of 12mg/mL 2-methylimidazole, adding the mixture into a 50mL of polyfluortetraethylene reaction kettle, adding 0.01mL of deionized water, carrying out closed reaction at 120 ℃ for 8 hours, repeatedly washing the reaction product with alcohol and water, and carrying out freeze drying treatment at-40 ℃ for 16 hours to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure.
Application example 1
ZnO @ ZIF-8 powder prepared in example 1 was used as a catalytic material, and 50ml of the powder was degraded by irradiation with visible light at 1.0X 10 -5 M in methylene blue, and testing the catalytic performance of the material. The test procedure was as follows:
0.5g of the prepared ZnO @ ZIF-8 powder was weighed out separately from 50mL of MB solution (10X 10) -5 M) was magnetically stirred in the dark for 3min to uniformly disperse the powder in the solution, and then the mixture was exposed to sunlight to test its photocatalytic properties. And tracking and testing the photodegradation effect by using an ultraviolet-visible spectrophotometer. In the photocatalytic stability test, the catalyst was recovered by centrifugation and then redispersed in the same MB solution in the next cycle, with the other experimental procedures being identical to the first test.
FIG. 6 shows that the ZnO @ ZIF-8 nanocomposite can completely degrade methylene blue at 6 min under visible light irradiation.
FIG. 7 shows that the ZnO @ ZIF-8 nano composite material shows higher stability after repeating 4 cycles, and has excellent photodegradation performance.
Application example 2
50ml of 1.0X 10 ZnO @ ZIF-8 powder prepared in example 1 and example 4, respectively, was degraded under irradiation of visible light to obtain a catalytic material -5 M in methylene blue, and testing the catalytic performance of the material.
FIG. 8 is a graph showing the results of the degradation of methylene blue under visible light irradiation of ZnO @ ZIF-8 nanocomposites prepared with 2-methylimidazole methanol solutions at concentrations of 2mg/mL and 10mg/mL, respectively, wherein the mass ratios of 2-methylimidazole to zinc oxide nanorods are 1: 7.5 and 1: 1.5.
FIG. 8 shows that the higher the concentration of 2-methylimidazole under visible light irradiation, the lower the photodegradation efficiency of the prepared ZnO @ ZIF-8 nanocomposite. The reason for this phenomenon is that the ZIF-8 layer of the ZnO @ ZIF-8 nanocomposite becomes thicker with the increase of the concentration of 2-methylimidazole, and the increase of the thickness of the ZIF-8 shell layer can improve the specific surface area of the photocatalyst, thereby improving the adsorption performance of the surface of the catalyst. However, since ZIF-8 itself absorbs visible light weakly, the absorption of visible light inside ZnO is hindered by the excessive thickness of the shell layer. The photodegradation of the composite catalyst benefits from the excitation of light, so the inhibition effect of the increase of the shell thickness is greater than the promotion effect, and the integral photodegradation effect of the photocatalyst is finally reduced.
Comparative example 1
50ml of 1.0X 10 ZnO nano-rod prepared in example 1 is used as a catalytic material and degraded under the irradiation of visible light -5 M in methylene blue, and testing the catalytic performance of the material.
FIG. 9 shows that the ZnO nanorods can degrade methylene blue under the irradiation of visible light, and the time for completely degrading the methylene blue needs 15 min.
Comparative example 2
In a 200mL beaker, 3.0g of zinc nitrate hexahydrate and 35mL of methanol were added and mixed with stirring. 4.4g of 2-methylimidazole and 35ml of methanol are added into a 50ml beaker, after complete dissolution, the 2-methylimidazole solution is added into a zinc nitrate solution, and stirring is carried out at room temperature for 6 hours to obtain a milky white suspension. And repeatedly washing the reaction product with alcohol and water, and performing freeze drying treatment to obtain ZIF-8 powder. The prepared ZIF-8 powder is used as a catalytic material, and 50ml of the ZIF-8 powder is degraded under the irradiation of visible light, wherein the volume of the ZIF-8 powder is 1.0 multiplied by 10 -5 M in methylene blue, and testing the catalytic performance of the material.
FIG. 10 shows that the ZIF-8 material still did not completely degrade methylene blue within 140min, indicating that ZIF-8 itself has poor catalytic performance under visible light irradiation.
FIG. 11 shows that the prepared ZnO @ ZIF-8 nanocomposite can completely degrade methylene blue within 6min, and the time for completely degrading the methylene blue by ZnO needs 15min, which shows that the composite strategy of ZIF-8 and ZnO nanorods can actually improve the photocatalytic activity of ZnO.
In the invention, the core-shell structure is characterized in that a zinc oxide nanorod (ZnO) is taken as an inner core, and a zeolite imidazole ester framework material (ZIF-8) is taken as an outer shell; wherein the average shell thickness of the zeolite imidazole ester framework material is 2-5 nm.
Compared with a ZnO material, the ZnO @ ZIF-8 nano composite material compounded with the ZIF-8 has the advantage that the specific surface area of the material is improved, so that more methylene blue molecules are adsorbed on the surface of the catalyst. On the other hand, the ultra-thin ZIF-8 shell layer is beneficial to improving the transfer and separation efficiency of photo-generated electron holes. Through a photocatalytic performance test, under the irradiation of visible light, the ZnO @ ZIF-8 nanocomposite can completely degrade methylene blue within 6min (as shown in figure 6), and shows higher stability after repeating 4 cycles (as shown in figure 7), which indicates that the ZnO @ ZIF-8 nanocomposite has excellent photodegradation performance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. The ZnO @ ZIF-8 core-shell nano composite material is applied to degrading methylene blue and is characterized in that H is 2 In O-organic solvent, zinc oxide nano-rod and 2-methylimidazole molecule are dissolved in organic solventReacting in the presence of a reagent, repeatedly washing the reaction product with alcohol and water, and performing freeze drying treatment to obtain the ZnO @ ZIF-8 nano composite material with the core-shell structure;
the method specifically comprises the following steps:
1) weighing 0.1-0.5 g of ZnO nano-rod for later use;
2) 20mL of 2-methylimidazole organic solvent solution with the mass concentration of 0.5-12 mg/mL is prepared for later use;
3) pouring the mixture obtained in the step 1 and the step 2 into a polyfluortetraethylene reaction kettle, adding 0.01-0.2 ml of deionized water, reacting the zinc oxide nano rod with 2-methylimidazole molecules under the solvothermal condition, and carrying out closed reaction for 8-72 hours;
4) Repeatedly washing the reaction product obtained in the step (3) with alcohol and water, and then carrying out freeze drying treatment and freeze drying at the freezing temperature of-20-40 ℃ for 8-16h to obtain the ZnO @ ZIF-8 nanocomposite with the core-shell structure;
the core-shell structure takes zinc oxide nanorod ZnO as an inner core and takes a zeolite imidazolate framework material ZIF-8 as an outer shell;
wherein the average shell thickness of the zeolite imidazole ester framework material is 2-5nm;
the organic solvent is any one of methanol, ethanol or propanol.
2. The ZnO @ ZIF-8 core-shell nanocomposite applied to methylene degradation according to claim 1 is characterized in that the average shell thickness of the zeolite imidazolate framework material is 2-3 nm.
3. The ZnO @ ZIF-8 core-shell nanocomposite material applied to methylene degradation according to claim 1, wherein H is H 2 O-H of organic solvent 2 The volume ratio of O to the organic solvent is 1: 2000-1:100.
4. The ZnO @ ZIF-8 core-shell nanocomposite applied to methylene degradation according to claim 1 is characterized in that the mass ratio of 2-methylimidazole to zinc oxide nanorods added at the beginning of the reaction is 1: 0.8-1:30.
5. The ZnO @ ZIF-8 core-shell nanocomposite material applied to methylene degradation according to claim 1, wherein the temperature of the thermal condition reaction is controlled to be 30-120 ℃.
6. The application of the ZnO @ ZIF-8 core-shell nanocomposite material in methylene degradation according to any one of claims 1 to 5, wherein 0.3 g of ZnO nanorods and 20mL of 2.0 mg/mL ethanol solution of 2-methylimidazole are weighed and added into a 50mL of polyfluortetraethylene reaction kettle, 0.1 mL of deionized water is added, the reaction is carried out in a sealed manner at the temperature of 80 ℃ for 24 hours, the reaction product is repeatedly washed by alcohol and water, and then is subjected to freeze drying treatment at the freezing temperature of-30 ℃ for 12 hours to obtain the ZnO @ ZIF-8 nanocomposite material with the core-shell structure.
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