CN109289830B - Method for preparing rare earth cerium doped zinc oxide - Google Patents
Method for preparing rare earth cerium doped zinc oxide Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 70
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 26
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 19
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000012153 distilled water Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 20
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims abstract description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004246 zinc acetate Substances 0.000 claims abstract description 11
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 10
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- YQFSZFSGFIVQDY-UHFFFAOYSA-K cerium(3+);triacetate;pentahydrate Chemical compound O.O.O.O.O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O YQFSZFSGFIVQDY-UHFFFAOYSA-K 0.000 claims abstract description 6
- 239000002086 nanomaterial Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 14
- 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 description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000011701 zinc Substances 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 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 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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Abstract
The invention discloses a method for preparing rare earth cerium doped zinc oxide, which comprises the following steps: (1) mixing zinc acetate or zinc nitrate, 2-methylimidazole and distilled water according to a molar ratio of 1: 25: 500, and adding the mixture in a molar ratio of 2-methylimidazole to the 2-methylimidazole: 25 of 1, 5-diazabicyclo [4.3.0] non-5-ene or 1, 8-diazabicyclo [5.4.0] undec-7-ene to give a milky white suspension; (2) adding cerium acetate pentahydrate or cerium nitrate hexahydrate with the mass percent of 0.5-5% of zinc source into the milky white suspension to obtain beige suspension; (3) transferring the beige suspension to a reaction kettle, and placing the reaction kettle in an oven to react at 120 ℃ to obtain a light yellow powdery solid; (4) and calcining the light yellow powdery solid in a tube furnace at 500 ℃ to obtain the Ce/ZnO material. The method has the advantages of mild reaction conditions, good dispersion degree of the rare earth cerium, controllable Ce/ZnO morphology and the like.
Description
Technical Field
The invention relates to the technical field of functional material preparation, in particular to a method for preparing rare earth cerium doped zinc oxide.
Background
Zinc oxide (ZnO) is a common photocatalyst and can generate hydroxyl free radical (. OH) and superoxide free radical (. O) under the action of ultraviolet light with the wavelength of less than 387nm2 –) And the like, and can be used for photocatalytic degradation of pollutants such as organic dyes and the like. As a typical II-VI group direct band gap n-type semiconductor material, the room temperature forbidden band width of ZnO is 3.37eV, so that the utilization rate of the ZnO to sunlight is low. In addition, ZnO is susceptible to recombination of photo-generated electron-hole pairs under illumination, thereby limiting its photocatalytic activity. Therefore, the improvement of the photoresponse range of ZnO and the reduction of the recombination rate of photo-generated electron-hole pairs so as to improve the utilization rate of the ZnO to sunlight become important research points for improving the performance of ZnO materials.
Research shows that rare earth/ZnO nano materials prepared by doping rare earth and other elements can generate more electron energy levels to capture photo-generated electrons and holes, so that the recombination of photo-generated electron-hole pairs is effectively inhibited, and the method becomes an important means for improving the photocatalytic activity of ZnO. Among them, rare earth cerium (Ce) element has incomplete 4f orbital and empty 5d orbital, is easy to generate multi-electron configuration, can effectively inhibit the recombination of photo-generated electrons and holes, and the energy of the ground state and the excited state of Ce is relatively close, can absorb part of visible light, and is an ideal doping element. Liubaoliliang and the like use triethanolamine as a template to synthesize a Ce/ZnO mesoporous material, and the discovery shows that the Ce/ZnO mesoporous material can efficiently degrade methylene blue under sunlight (Liubaoliliang and the like, modern chemical industry, 2015,35:109-112), which shows that the Ce/ZnO mesoporous material has good photocatalytic performance and application prospect. Therefore, the preparation of the rare earth cerium/ZnO nano material has become a research hotspot.
At present, the methods for preparing rare earth/ZnO nano materials mainly comprise a pyrolysis method, a hydrothermal method, a gel template method, a chemical precipitation method and the like. The above methods generally require the addition of a surfactant or templating agent during the preparation process and the procedure is relatively complicated. The method for preparing the rare earth/ZnO nano material by the pyrolysis method has the advantages of easily obtained raw materials, simplicity in operation and the like, so that the method is widely applied to the preparation of rare earth doped zinc oxide materials in laboratories. The precursor for preparing the rare earth/ZnO nano material by the pyrolysis method mainly comprises zinc hydroxide or ZIF-8 and the like. Wherein the zinc hydroxide is formed by Zn2+The ZIF-8 is prepared by adding alkaline substances such as ammonia water or sodium hydroxide into the aqueous solution2+Coordinated with an imidazolyl ligand such as 2-methylimidazole (2-MI). At present, the problems of low doping amount of rare earth elements, nonuniform dispersion, easy loss and the like mainly exist in the preparation of rare earth/ZnO nano materials by a pyrolysis method, which is caused by weak interaction between a rare earth source and a precursor in the process of preparing zinc hydroxide or a ZIF-8 precursor. Therefore, the discovery of the preparation method of the rare earth/ZnO material which is simple to operate and has uniformly dispersed rare earth elements has very important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a method for preparing rare earth cerium doped zinc oxide by using zinc acetate or zinc nitrate and 2-methylimidazole as raw materials, cerium pentahydrate acetate or cerium nitrate hexahydrate as a rare earth source, 1, 5-diazabicyclo [4.3.0] non-5-ene or 1, 8-diazabicyclo [5.4.0] undec-7-ene as a catalyst, and firstly self-assembling to form a rare earth cerium doped Ce/ZIF-8 precursor and then performing high-temperature pyrolysis, and has the advantages of simple operation, mild reaction conditions, good dispersion degree of rare earth cerium elements, controllable morphology of Ce/ZnO nano materials and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing rare earth cerium doped zinc oxide specifically comprises the following steps:
(1) mixing zinc acetate or zinc nitrate, 2-methylimidazole and distilled water according to a molar ratio of 1: 25: 500, stirring and mixing evenly at room temperature, and then adding a mixture of 2: 25 of 1, 5-diazabicyclo [4.3.0] non-5-ene or 1, 8-diazabicyclo [5.4.0] undec-7-ene, stirring uniformly at room temperature to obtain a milky white suspension;
(2) adding cerium acetate pentahydrate or cerium nitrate hexahydrate with the mass percent of 0.5-5% of zinc acetate or zinc nitrate into the milky white suspension prepared in the step (1), and stirring until the mixture is completely dissolved to obtain beige suspension;
(3) transferring the beige suspension prepared in the step (2) to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven to perform hydrothermal reaction at 120 ℃, and after the reaction, cooling, settling, centrifuging, washing and drying to obtain a light yellow powdery solid, namely a Ce/ZIF-8 precursor;
(4) and (4) placing the light yellow powdery solid prepared in the step (3) into a tubular furnace, calcining at 500 ℃ in air atmosphere, and naturally cooling to obtain the Ce/ZnO nano material.
In the step (3), the hydrothermal reaction time is 1-3 h, after the reaction, the reaction liquid is cooled, settled and centrifuged to obtain a light yellow solid, the light yellow solid is alternately washed by ethanol and distilled water for 3-6 times respectively, and finally washed by distilled water, and then the light yellow solid is dried in vacuum at 60-80 ℃ for 2-4 h to obtain a light yellow powdery solid.
In the step (4), the calcination time is 2-4 h in the air atmosphere.
Further, the reason why the light yellow solid is washed with distilled water and ethanol in the step (3) is mainly to remove residual organic substances such as 2-methylimidazole.
The invention has the following beneficial effects:
(1) adding a certain amount of catalyst 1, 5-diazabicyclo [4.3.0] into the mixed aqueous solution of zinc source, rare earth source and 2-methylimidazole (2-MI)]Non-5-ene (DBN) or 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU) using 1, 5-diazabicyclo [4.3.0]Non-5-ene (DBN) or 1, 8-diazabicyclo [5.4.0]The lone pair of N atoms in the undec-7-ene (DBU) molecule is capable of accepting H+The active hydrogen on the N-H group in the 2-methylimidazole molecule is promoted to carry out proton transfer to form proton type ionic liquid [ DBUH][2-MI]Or [ DBNH ]][2-MI]And rendering the partial 2-MI molecule to [2-MI]-Negative ions, thereby increasing 2-methylimidazole and Zn2+Interaction between them, promoting 2-MI and Zn2+Effective self-assembly to form ZIF-8;
(2) after proton type ionic liquid is spontaneously generated by 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN) or 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 2-methylimidazole (2-MI), the polarity of the aqueous solution is increased, the diffusion of rare earth ions is facilitated, rare earth cerium cations in the solution are uniformly adsorbed and dispersed into ZIF-8 to form a Ce/ZIF-8 precursor, the loss of rare earth elements in the aqueous solution is reduced, the preparation efficiency and the separation performance of the Ce/ZIF-8 precursor are improved, the dispersity of the rare earth cerium elements is ensured, and the subsequent preparation of rare earth cerium element doped ZnO with good dispersity and controllable shape is guaranteed.
Drawings
FIG. 1 is an SEM spectrum of a Ce/ZnO nanomaterial prepared according to example 1 of the present invention;
FIG. 2 is an SEM spectrum of a Ce/ZnO nanomaterial prepared according to example 2 of the present invention;
FIG. 3 is an SEM spectrum of a Ce/ZnO nanomaterial prepared according to example 3 of the present invention;
FIG. 4 is an SEM spectrum of a Ce/ZnO nanomaterial prepared according to example 4 of the present invention;
FIG. 5 is a TEM spectrum of a Ce/ZnO nanomaterial according to example 1 of the present invention;
FIG. 6 is a TEM spectrum of a Ce/ZnO nanomaterial according to example 2 of the present invention;
FIG. 7 is a TEM spectrum of Ce/ZnO nanomaterial prepared according to example 3 of the present invention;
FIG. 8 is a TEM spectrum of a Ce/ZnO nanomaterial according to example 4, according to the present invention;
FIG. 9 shows XRD contrast spectra of ZnO nanomaterial and Ce/ZnO nanomaterial: (a) is the standard XRD profile of ZnO nanomaterial, (b) is the XRD profile of Ce/ZnO nanomaterial prepared according to example 3;
FIG. 10 is an EDS spectrum of a Ce/ZnO nanomaterial according to example 1 of the present invention;
FIG. 11 is an EDS spectrum of a Ce/ZnO nanomaterial made according to example 2 of the present invention;
FIG. 12 is an EDS spectrum of a Ce/ZnO nanomaterial made according to example 3 of the present invention;
FIG. 13 is an EDS spectrum of a Ce/ZnO nanomaterial according to example 4 of the present invention.
Detailed Description
The invention is further described with reference to the accompanying drawings and the detailed description below:
example 1
(1) Mixing zinc acetate, 2-methylimidazole and distilled water according to a molar ratio of 1: 25: 500, stirring and mixing evenly at room temperature, and then adding a mixture of 2: 25 of 1, 5-diazabicyclo [4.3.0] non-5-ene, stirring uniformly at room temperature to obtain a milky white suspension;
(2) adding cerium nitrate hexahydrate with the mass percent of 0.5% of zinc acetate into the milky white suspension prepared in the step (1), and stirring until the cerium nitrate hexahydrate is completely dissolved to obtain beige suspension;
(3) transferring the beige suspension prepared in the step (2) to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven to perform hydrothermal reaction for 1h at 120 ℃, cooling, settling and centrifuging the reaction liquid after the reaction to obtain light yellow solids, washing the light yellow solids by using ethanol and distilled water alternately for 3 times, washing the light yellow solids by using distilled water for the last time, and performing vacuum drying at 60 ℃ for 4h to obtain light yellow powdery solids, namely a Ce/ZIF-8 precursor;
(4) and (4) placing the light yellow powdery solid prepared in the step (3) into a tubular furnace, calcining for 2 hours at 500 ℃ in air atmosphere, and naturally cooling after calcining to obtain the Ce/ZnO nano material.
As can be seen from fig. 1 and 5, the ZnO doped with Ce is uniformly distributed in a globular shape, has an average particle size of 30nm, and is uniformly dispersed; table 1 shows EDS measurement results of Ce/ZnO nanomaterials prepared according to different examples, and it can be seen from fig. 10 and table 1 that the product prepared according to example 1 contains three elements, namely Zn, Ce and O, and the mass fraction of Ce element in the Ce/ZnO nanomaterials is 0.67%, which is substantially consistent with the experimental addition amount.
Example 2
(1) Mixing zinc nitrate, 2-methylimidazole and distilled water in a molar ratio of 1: 25: 500, stirring and mixing evenly at room temperature, and then adding a mixture of 2: 25 of 1, 8-diazabicyclo [5.4.0] undec-7-ene, and stirring the mixture evenly at room temperature to obtain milky white suspension;
(2) adding 1% cerium nitrate hexahydrate in mass percent with zinc nitrate into the milky white suspension prepared in the step (1), and stirring until the cerium nitrate hexahydrate is completely dissolved to obtain a beige suspension;
(3) transferring the beige suspension prepared in the step (2) to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for carrying out hydrothermal reaction for 3 hours at 120 ℃, cooling, settling and centrifuging the reaction liquid after the reaction to obtain light yellow solids, washing the light yellow solids by using ethanol and distilled water alternately for 3 times, washing the light yellow solids by using distilled water for the last time, and then carrying out vacuum drying for 2 hours at 80 ℃ to obtain light yellow powdery solids, namely a Ce/ZIF-8 precursor;
(4) and (4) placing the light yellow powdery solid prepared in the step (3) into a tubular furnace, calcining for 3h at 500 ℃ in air atmosphere, and naturally cooling after calcining to obtain the Ce/ZnO nano material.
As can be seen from fig. 2 and 6, the ZnO doped with Ce is uniformly distributed in a globular shape, has an average particle size of 50nm, and is relatively uniformly dispersed; table 1 shows the EDS measurement results of the Ce/ZnO nanomaterials prepared according to different examples, and it can be seen from fig. 11 and table 1 that the product prepared according to example 2 contains three elements, namely Zn, Ce and O, and the mass fraction of Ce element in the Ce/ZnO nanomaterials is 0.99%, which is substantially the same as the experimental addition amount.
Example 3
(1) Mixing zinc acetate, 2-methylimidazole and distilled water according to a molar ratio of 1: 25: 500, stirring and mixing evenly at room temperature, and then adding a mixture of 2: 25 of 1, 8-diazabicyclo [5.4.0] undec-7-ene, and stirring the mixture evenly at room temperature to obtain milky white suspension;
(2) adding cerium nitrate hexahydrate with the mass percentage of 2% of zinc acetate into the milky white suspension prepared in the step (1), and stirring until the cerium nitrate hexahydrate and the zinc acetate are completely dissolved to obtain beige suspension;
(3) transferring the beige suspension prepared in the step (2) to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for carrying out hydrothermal reaction for 2 hours at 120 ℃, cooling, settling and centrifuging the reaction liquid after the reaction to obtain light yellow solids, washing the light yellow solids by using ethanol and distilled water alternately for 5 times, washing the light yellow solids by using distilled water for the last time, and then carrying out vacuum drying for 3 hours at 70 ℃ to obtain light yellow powdery solids, namely a Ce/ZIF-8 precursor;
(4) and (4) placing the light yellow powdery solid prepared in the step (3) into a tubular furnace, calcining for 3h at 500 ℃ in air atmosphere, and naturally cooling after calcining to obtain the Ce/ZnO nano material.
As can be seen from fig. 3 and 7, ZnO doped with Ce is uniformly distributed in a globular shape, has an average particle size of 30nm, and is uniformly dispersed; as can be seen from FIG. 9, (in which (a) is a standard XRD curve of the ZnO nanomaterial and (b) is an XRD curve of the Ce/ZnO nanomaterial manufactured according to example 3), the XRD curve of the Ce/ZnO nanomaterial manufactured according to example 3 includes a diffraction peak of wurtzite structure and the diffraction peak is relatively sharp, and in addition, a CeO is generated2The diffraction peak corresponding to the crystal plane (diffraction peak at the diffraction angle 2 theta of 28.614 degrees) shows that the Ce/ZnO nano-material prepared according to the example 3 has better crystallinity, and part of Ce is CeO2Is present between ZnO; table 1 shows the EDS measurement results of the Ce/ZnO nanomaterials prepared according to different examples, and it can be seen from fig. 12 and table 1 that the product prepared according to example 3 contains three elements, namely Zn, Ce and O, and the mass fraction of Ce element in the Ce/ZnO nanomaterials is 2.11%, which is substantially the same as the experimental addition amount.
Example 4
(1) Mixing zinc nitrate, 2-methylimidazole and distilled water in a molar ratio of 1: 25: 500, stirring and mixing evenly at room temperature, and then adding a mixture of 2: 25 of 1, 8-diazabicyclo [5.4.0] undec-7-ene, and stirring the mixture evenly at room temperature to obtain milky white suspension;
(2) adding cerium pentahydrate acetate which accounts for 5 percent of the mass of zinc nitrate into the milky white suspension prepared in the step (1), and stirring until the cerium pentahydrate acetate is completely dissolved to obtain beige suspension;
(3) transferring the beige suspension prepared in the step (2) to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal reaction at 120 ℃ for 3 hours, cooling, settling and centrifuging the reaction liquid after the reaction to obtain light yellow solids, washing the light yellow solids by using ethanol and distilled water alternately for 6 times, washing the light yellow solids by using distilled water for the last time, and then carrying out vacuum drying at 80 ℃ for 2 hours to obtain light yellow powdery solids, namely a Ce/ZIF-8 precursor;
(4) and (4) placing the light yellow powdery solid prepared in the step (3) into a tubular furnace, calcining for 4 hours at 500 ℃ in the air atmosphere, and naturally cooling to obtain the Ce/ZnO nano material.
As can be seen from fig. 4 and 8, ZnO doped with Ce is uniformly distributed in a globular shape, has an average particle size of 50nm, and is relatively uniformly dispersed; table 1 shows EDS measurement results of Ce/ZnO nanomaterials prepared according to different examples, and it can be seen from fig. 13 and table 1 that the product prepared according to example 4 contains three elements, namely Zn, Ce and O, and the mass fraction of Ce element in the Ce/ZnO nanomaterials is 4.59%, which is substantially consistent with the experimental addition amount.
TABLE 1 EDS measurement results of Ce/ZnO nanomaterials prepared according to different examples
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A method for preparing rare earth cerium doped zinc oxide is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) mixing zinc acetate or zinc nitrate, 2-methylimidazole and distilled water according to a molar ratio of 1: 25: 500, stirring and mixing evenly at room temperature, and then adding a mixture of 2: 25 of 1, 5-diazabicyclo [4.3.0] non-5-ene or 1, 8-diazabicyclo [5.4.0] undec-7-ene, stirring uniformly at room temperature to obtain a milky white suspension;
(2) adding cerium acetate pentahydrate or cerium nitrate hexahydrate with the mass percent of 0.5-5% of zinc acetate or zinc nitrate into the milky white suspension prepared in the step (1), and stirring until the mixture is completely dissolved to obtain beige suspension;
(3) transferring the beige suspension prepared in the step (2) into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven to perform hydrothermal reaction at 120 ℃, and after the reaction, cooling, settling, centrifuging, washing and drying to obtain a light yellow powdery solid, namely a Ce/ZIF-8 precursor;
(4) and (4) placing the light yellow powdery solid prepared in the step (3) into a tubular furnace, calcining at 500 ℃ in air atmosphere, and naturally cooling to obtain the Ce/ZnO nano material.
2. The method of claim 1, wherein the preparation method comprises: in the step (3), the hydrothermal reaction time is 1-3 h, after the reaction, the reaction liquid is cooled, settled and centrifuged to obtain a light yellow solid, the light yellow solid is alternately washed by ethanol and distilled water for 3-6 times respectively, and finally washed by distilled water, and then the light yellow solid is dried in vacuum at 60-80 ℃ for 2-4 h to obtain a light yellow powdery solid.
3. The method of claim 1, wherein the rare earth cerium doped zinc oxide is prepared by: in the step (4), the calcination time is 2-4 h in the air atmosphere.
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