CN109289830A - A method of preparing rare-earth cerium doped zinc oxide - Google Patents
A method of preparing rare-earth cerium doped zinc oxide Download PDFInfo
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- CN109289830A CN109289830A CN201811441653.8A CN201811441653A CN109289830A CN 109289830 A CN109289830 A CN 109289830A CN 201811441653 A CN201811441653 A CN 201811441653A CN 109289830 A CN109289830 A CN 109289830A
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- suspension
- methylimidazole
- alkene
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 68
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 21
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 29
- 239000000725 suspension Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012153 distilled water Substances 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
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004246 zinc acetate Substances 0.000 claims abstract description 10
- AERUOEZHIAYQQL-UHFFFAOYSA-K cerium(3+);triacetate;hydrate Chemical class O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AERUOEZHIAYQQL-UHFFFAOYSA-K 0.000 claims abstract description 4
- 239000002086 nanomaterial Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 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
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- -1 Hydroxyl radical free radical Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 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
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000008614 2-methylimidazoles Chemical class 0.000 description 1
- 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229910000238 buergerite Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 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
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005945 translocation Effects 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
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of methods for preparing rare-earth cerium doped zinc oxide, the following steps are included: (1) is by zinc acetate or zinc nitrate, 1:25:500 is mixed in molar ratio with 2-methylimidazole, distilled water, 1 with 2-methylimidazole molar ratio for 2:25 is added, 5- diazabicyclo [4.3.0] nonyl- 5- alkene or 1,11-7- alkene of 8- diazabicyclo [5.4.0], obtains milky suspension；(2) five hydrate cerium acetates or six nitric hydrate ceriums that are 0.5~5% with zinc source mass percent are added in milky suspension, obtain ecru suspension；(3) ecru suspension is transferred to reaction kettle, is placed in 120 DEG C of reactions in baking oven, obtains pale yellow powder shape solid；(4) pale yellow powder shape solid is placed in 500 DEG C of tube furnace calcinings, obtains Ce/ZnO material.The present invention has many advantages, such as that reaction condition is mild, cerium good dispersion degree, Ce/ZnO morphology controllable.
Description
Technical field
The present invention relates to functional material preparation technical fields, more particularly to a kind of side for preparing rare-earth cerium doped zinc oxide
Method.
Background technique
Zinc oxide (ZnO) is that the common photochemical catalyst of one kind can generate under action of ultraviolet light of the wavelength lower than 387nm
Hydroxyl radical free radical (OH) and superoxide radical (O2 –) isoreactivity free radical, it can be used for the pollution such as photocatalytically degradating organic dye
Object.As a kind of typical II-VI group direct band gap n-type semiconductor, ZnO room temperature forbidden bandwidth is 3.37eV, leads to it
It is lower to the utilization rate of sunlight.In addition, ZnO is easy to happen the compound of photo-generate electron-hole pair under light illumination, to limit
Its photocatalytic activity.Therefore, the optical response range of ZnO is improved, the recombination rate of photo-generate electron-hole pair is reduced, to improve it
To sun light utilization efficiency, it has also become improve the research emphasis of ZnO material performance.
Studies have shown that preparing rare earth/ZnO nano material by rare earth doped equal elements, more electronics energy can produce
Grade captures light induced electron and hole, to effectively inhibit the compound of photo-generate electron-hole pair, has become the light for improving ZnO
The important means of catalytic activity.Wherein, cerium (Ce) element has incomplete 4f track and empty 5d track, is also easy to produce more
Electron configuration can effectively inhibit the compound of light induced electron and hole, and the ground state of Ce and excited energy are relatively, can inhale
Receiving portions visible light is a kind of more satisfactory doped chemical.Liu Baoliang etc. has synthesized Ce/ using triethanolamine as template
The mesoporous material of ZnO, find its under sunlight can efficient degradation methylene blue (Liu Baoliang etc., modern chemical industry, 2015,35:
109-112), this shows that Ce/ZnO material has good photocatalysis performance and application prospect.Therefore, related cerium/ZnO receives
The preparation of rice material has become research hotspot.
Mainly there are pyrolysismethod, hydro-thermal method, gel template and chemistry heavy currently, preparing rare earth/ZnO nano material method
Shallow lake method etc..The above method generally requires is added surface-active or template during the preparation process, and operating process is relative complex.
Wherein, pyrolysismethod prepare rare earth/ZnO nano material be easy to get with raw material, simple operation and other advantages, therefore prepare in laboratory dilute
It is widely used in terms of native doped zinc oxide material.Pyrolysismethod, which prepares rare earth/ZnO nano material presoma, mainly to be had
Zinc hydroxide or ZIF-8 etc..Wherein, zinc hydroxide is by Zn2+Aqueous solution adds the preparation of the alkaline matters such as ammonium hydroxide or sodium hydroxide
And obtain, ZIF-8 is by Zn2+It is formed with imidazole radicals ligands such as 2-methylimidazoles (2-MI).Currently, pyrolysismethod prepare rare earth/
ZnO nano material is primarily present the problems such as rare earth doped amount is low, dispersion is uneven, easy loss, this, which is derived from, is preparing
During zinc hydroxide or ZIF-8 presoma, caused by the interaction of rare earth source and presoma is weaker.Thus, it is found that one
Easy to operate, the finely dispersed rare earth/ZnO material of rare earth element the preparation method of kind has a very important significance.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, one kind is provided with zinc acetate or zinc nitrate and 2-
Methylimidazole be raw material, using five hydrate cerium acetates or six nitric hydrate ceriums as rare earth source, with 1,5- diazabicyclo [4.3.0]
Nonyl- 5- alkene or 1,11-7- alkene of 8- diazabicyclo [5.4.0] are catalyst, and first autonomous dress forms rare-earth cerium doped Ce/
ZIF-8 presoma, then the method for preparing by high temperature pyrolysis rare-earth cerium doped zinc oxide, have easy to operate, reaction condition
Mildly, rare earth Ce elements good dispersion degree, the advantages that Ce/ZnO appearance of nano material is controllable.
To achieve the goals above, the present invention adopts the following technical scheme:
A method of preparing rare-earth cerium doped zinc oxide, this method specifically includes the following steps:
(1) by zinc acetate or zinc nitrate and 2-methylimidazole, distilled water in molar ratio 1:25:500 be stirred at room temperature it is mixed
It closes and uniformly adds 1,5- diazabicyclo [4.3.0] the nonyl- 5- alkene or 1 for being 2:25 with 2-methylimidazole molar ratio, 8- phenodiazine
Miscellaneous bicyclic [5.4.0] 11-7- alkene is stirred at room temperature and uniformly obtains milky suspension；
(2) in the milky suspension made from step (1), being added with zinc acetate or zinc nitrate mass percent is 0.5
~5% five hydrate cerium acetates or six nitric hydrate ceriums stir to being completely dissolved, obtain ecru suspension；
(3) ecru suspension made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will
Reaction kettle, which is placed in baking oven, carries out hydro-thermal reaction under the conditions of 120 DEG C, after reaction through cooling-sedimentation, centrifugation, wash, be dried to obtain
Pale yellow powder shape solid, as Ce/ZIF-8 presoma；
(4) pale yellow powder shape solid made from step (3) is placed in tube furnace, 500 DEG C of calcinings in air atmosphere,
After calcining natural cooling to get arrive Ce/ZnO nano material.
In the step (3), the hydro-thermal reaction time be 1~3h, after reaction by reaction solution cooling-sedimentation, centrifugation obtain it is yellowish
Color solid is replaced washing faint yellow solid each 3~6 times with distilled water using ethyl alcohol, adopts be washed with distilled water for the last time, then
In 60~80 DEG C of 2~4h of vacuum drying, pale yellow powder shape solid is obtained.
In the step (4), in air atmosphere, calcination time is 2~4h.
Further, use distilled water with ethanol washing faint yellow solid primarily to removal is remaining in step (3)
The organic matters such as 2-methylimidazole.
Beneficial effects of the present invention are as follows:
(1) a certain amount of catalyst 1 is added in the mixed aqueous solution in zinc source, rare earth source and 2-methylimidazole (2-MI),
5- diazabicyclo [4.3.0] nonyl- 5- alkene (DBN) or 1,11-7- alkene (DBU) of 8- diazabicyclo [5.4.0], utilizes 1,5-
N atom in diazabicyclo [4.3.0] nonyl- 5- alkene (DBN) or 1,8- diazabicyclo [5.4.0] 11-7- alkene (DBU) molecule
Lone pair electrons can receive H+Ability, promote active hydrogen in 2-methylimidazole molecule on N-H group that proton translocation, shape occurs
At proton type ionic liquid [DBUH] [2-MI] or [DBNH] [2-MI], and part 2-MI molecule is made to become [2-MI]-Bear from
Son, to increase 2-methylimidazole and Zn2+Between interaction, promote 2-MI and Zn2+Effectively it is self-assembly of ZIF-8；
(2) in 11-7- of 1,5- diazabicyclo [4.3.0] nonyl- 5- alkene (DBN) or 1,8- diazabicyclo [5.4.0]
After alkene (DBU) and 2-methylimidazole (2-MI) spontaneously generate proton type ionic liquid, the polarity of aqueous solution is increased, is conducive to
The diffusion of rare earth ion makes the rare earth cerium cation in solution equably adsorb, be dispersed in ZIF-8, before forming Ce/ZIF-8
Body is driven, the loss of rare earth element in aqueous solution is reduced, which not only improves the preparation efficiency of Ce/ZIF-8 presoma and is divided
From performance, and the dispersibility of rare earth Ce elements is ensured, thus for the cerium member of subsequent acquisition good dispersion, morphology controllable
The ZnO of element doping provides guarantee.
Detailed description of the invention
Fig. 1 is the SEM spectrogram of the invention according to Ce/ZnO nano material made from embodiment 1；
Fig. 2 is the SEM spectrogram of the invention according to Ce/ZnO nano material made from embodiment 2；
Fig. 3 is the SEM spectrogram of the invention according to Ce/ZnO nano material made from embodiment 3；
Fig. 4 is the SEM spectrogram of the invention according to Ce/ZnO nano material made from embodiment 4；
Fig. 5 is the TEM spectrogram of the invention according to Ce/ZnO nano material made from embodiment 1；
Fig. 6 is the TEM spectrogram of the invention according to Ce/ZnO nano material made from embodiment 2；
Fig. 7 is the TEM spectrogram of the invention according to Ce/ZnO nano material made from embodiment 3；
Fig. 8 is the TEM spectrogram of the invention according to Ce/ZnO nano material made from embodiment 4；
Fig. 9 is the XRD comparison spectrogram of ZnO nano material and Ce/ZnO nano material: (a) being the standard of ZnO nano material
XRD curve, (b) for according to the XRD curve of Ce/ZnO nano material made from embodiment 3；
Figure 10 is the EDS spectrogram of the invention according to Ce/ZnO nano material made from embodiment 1；
Figure 11 is the EDS spectrogram of the invention according to Ce/ZnO nano material made from embodiment 2；
Figure 12 is the EDS spectrogram of the invention according to Ce/ZnO nano material made from embodiment 3；
Figure 13 is the EDS spectrogram of the invention according to Ce/ZnO nano material made from embodiment 4.
Specific embodiment
Present invention will be further described below with reference to the accompanying drawings and specific embodiments:
Embodiment 1
(1) by zinc acetate and 2-methylimidazole, distilled water, 1:25:500 is stirred at room temperature and is uniformly mixed in molar ratio, then
1,5- diazabicyclo [4.3.0] the nonyl- 5- alkene for being 2:25 with 2-methylimidazole molar ratio is added, uniform obtain is stirred at room temperature
To milky suspension；
(2) in the milky suspension made from step (1), six water for being 0.5% with zinc acetate mass percent are added
Cerous nitrate is closed, stirs to being completely dissolved, obtains ecru suspension；
(3) ecru suspension made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will
Reaction kettle is placed in baking oven under the conditions of 120 DEG C progress hydro-thermal reaction 1h, obtains reaction solution cooling-sedimentation, centrifugation after reaction light
Yellow solid is replaced washing faint yellow solid each 3 times with distilled water using ethyl alcohol, adopts be washed with distilled water for the last time, then
In 60 DEG C of vacuum drying 4h, pale yellow powder shape solid, as Ce/ZIF-8 presoma are obtained；
(4) pale yellow powder shape solid made from step (3) is placed in tube furnace, 500 DEG C of calcinings in air atmosphere
2h, after calcining natural cooling to get arrive Ce/ZnO nano material.
In conjunction with Fig. 1, Fig. 5 it is found that the ZnO after doping Ce is uniformly distributed in coccoid, average grain diameter 30nm, and disperse equal
It is even；Table 1 be according to Ce/ZnO nano material made from different embodiments EDS measurement result, in conjunction with Figure 10 and table 1 it is found that according to
According to tri- kinds of elements containing Zn, Ce and O in product obtained by embodiment 1, the mass fraction of Ce element in the Ce/ZnO nano material
It is 0.67%, it is almost the same with experiment additive amount.
Embodiment 2
(1) by zinc nitrate and 2-methylimidazole, distilled water, 1:25:500 is stirred at room temperature and is uniformly mixed in molar ratio, then
1,8- diazabicyclo [5.4.0], the 11-7- alkene for being 2:25 with 2-methylimidazole molar ratio is added, is stirred at room temperature uniformly
Obtain milky suspension；
(2) in the milky suspension made from step (1), six hydrations for being 1% with zinc nitrate mass percent are added
Cerous nitrate stirs to being completely dissolved, obtains ecru suspension；
(3) ecru suspension made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will
Reaction kettle is placed in baking oven under the conditions of 120 DEG C progress hydro-thermal reaction 3h, obtains reaction solution cooling-sedimentation, centrifugation after reaction light
Yellow solid is replaced washing faint yellow solid each 3 times with distilled water using ethyl alcohol, adopts be washed with distilled water for the last time, then
In 80 DEG C of vacuum drying 2h, pale yellow powder shape solid, as Ce/ZIF-8 presoma are obtained；
(4) pale yellow powder shape solid made from step (3) is placed in tube furnace, 500 DEG C of calcinings in air atmosphere
3h, after calcining natural cooling to get arrive Ce/ZnO nano material.
In conjunction with Fig. 2, Fig. 6 it is found that the ZnO after doping Ce is uniformly distributed in coccoid, average grain diameter 50nm disperses more equal
It is even；Table 1 be according to Ce/ZnO nano material made from different embodiments EDS measurement result, in conjunction with Figure 11 and table 1 it is found that according to
According to tri- kinds of elements containing Zn, Ce and O in product obtained by embodiment 2, the mass fraction of Ce element in the Ce/ZnO nano material
It is 0.99%, it is almost the same with experiment additive amount.
Embodiment 3
(1) by zinc acetate and 2-methylimidazole, distilled water, 1:25:500 is stirred at room temperature and is uniformly mixed in molar ratio, then
1,8- diazabicyclo [5.4.0], the 11-7- alkene for being 2:25 with 2-methylimidazole molar ratio is added, is stirred at room temperature uniformly
Obtain milky suspension；
(2) in the milky suspension made from step (1), six hydrations for being 2% with zinc acetate mass percent are added
Cerous nitrate stirs to being completely dissolved, obtains ecru suspension；
(3) ecru suspension made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will
Reaction kettle is placed in baking oven under the conditions of 120 DEG C progress hydro-thermal reaction 2h, obtains reaction solution cooling-sedimentation, centrifugation after reaction light
Yellow solid is replaced washing faint yellow solid each 5 times with distilled water using ethyl alcohol, adopts be washed with distilled water for the last time, then
In 70 DEG C of vacuum drying 3h, pale yellow powder shape solid, as Ce/ZIF-8 presoma are obtained；
(4) pale yellow powder shape solid made from step (3) is placed in tube furnace, 500 DEG C of calcinings in air atmosphere
3h, after calcining natural cooling to get arrive Ce/ZnO nano material.
In conjunction with Fig. 3, Fig. 7 it is found that the ZnO after doping Ce is uniformly distributed in coccoid, average grain diameter 30nm, and disperse equal
It is even；By can be seen that ((a) is the standard x RD curve of ZnO nano material in figure, (b) for according to made from embodiment 3 in Fig. 9
The XRD curve of Ce/ZnO nano material), according in the XRD curve of Ce/ZnO nano material made from embodiment 3 include buergerite
The diffraction maximum of the structure and diffraction maximum is more sharp, in addition to this, has also appeared a CeO2The corresponding diffraction maximum of crystal face (
2 θ of the angle of diffraction is the diffraction maximum at 28.614 °), show crystallinity according to Ce/ZnO nano material prepared by embodiment 3 compared with
It is good, and part Ce is with CeO2It is present between ZnO；Table 1 is the EDS according to Ce/ZnO nano material made from different embodiments
Measurement result, in conjunction with Figure 12 and table 1 it is found that according to tri- kinds of elements containing Zn, Ce and O in product obtained by embodiment 3, the Ce/
The mass fraction of Ce element is 2.11% in ZnO nano material, almost the same with experiment additive amount.
Embodiment 4
(1) by zinc nitrate and 2-methylimidazole, distilled water, 1:25:500 is stirred at room temperature and is uniformly mixed in molar ratio, then
1,8- diazabicyclo [5.4.0], the 11-7- alkene for being 2:25 with 2-methylimidazole molar ratio is added, is stirred at room temperature uniformly
Obtain milky suspension；
(2) in the milky suspension made from step (1), five hydrations for being 5% with zinc nitrate mass percent are added
Cerous acetate stirs to being completely dissolved, obtains ecru suspension；
(3) ecru suspension made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will
Reaction kettle is placed in baking oven under the conditions of 120 DEG C progress hydro-thermal reaction 3h, obtains reaction solution cooling-sedimentation, centrifugation after reaction light
Yellow solid is replaced washing faint yellow solid each 6 times with distilled water using ethyl alcohol, adopts be washed with distilled water for the last time, then
In 80 DEG C of vacuum drying 2h, pale yellow powder shape solid, as Ce/ZIF-8 presoma are obtained；
(4) pale yellow powder shape solid made from step (3) is placed in tube furnace, 500 DEG C of calcinings in air atmosphere
4h, after calcining natural cooling to get arrive Ce/ZnO nano material.
In conjunction with Fig. 4, Fig. 8 it is found that the ZnO after doping Ce is uniformly distributed in coccoid, average grain diameter 50nm disperses more equal
It is even；Table 1 be according to Ce/ZnO nano material made from different embodiments EDS measurement result, in conjunction with Figure 13 and table 1 it is found that according to
According to tri- kinds of elements containing Zn, Ce and O in product prepared by embodiment 4, the mass fraction of Ce element in the Ce/ZnO nano material
It is 4.59%, it is almost the same with experiment additive amount.
Table 1 according to Ce/ZnO nano material made from different embodiments EDS measurement result
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of method for preparing rare-earth cerium doped zinc oxide, it is characterised in that: this method specifically includes the following steps:
(1) by zinc acetate or zinc nitrate and 2-methylimidazole, distilled water, 1:25:500 is stirred at room temperature and mixes in molar ratio
It is even, 1,5- diazabicyclo [4.3.0] the nonyl- 5- alkene or 1 for being 2:25 with 2-methylimidazole molar ratio is added, 8- diaza is double
11-7- alkene of ring [5.4.0] is stirred at room temperature and uniformly obtains milky suspension；
(2) in the milky suspension made from step (1), being added with zinc acetate or zinc nitrate mass percent is 0.5~5%
Five hydrate cerium acetates or six nitric hydrate ceriums, stir to being completely dissolved, obtain ecru suspension；
(3) ecru suspension made from step (2) is transferred in the hydrothermal synthesis reaction kettle of polytetrafluoro liner, then will reaction
Kettle, which is placed in baking oven, carries out hydro-thermal reaction under the conditions of 120 DEG C, after reaction through cooling-sedimentation, centrifugation, wash, be dried to obtain it is yellowish
Color pulverulent solids, as Ce/ZIF-8 presoma；
(4) pale yellow powder shape solid made from step (3) is placed in tube furnace, 500 DEG C of calcinings in air atmosphere, calcining
Afterwards natural cooling to get arrive Ce/ZnO nano material.
2. a kind of preparation method of rare earth doping zinc oxide as described in claim 1, it is characterised in that: in the step (3), water
The thermal response time is 1~3h, reaction solution cooling-sedimentation, centrifugation is obtained faint yellow solid after reaction, using ethyl alcohol and distilled water
Alternately washing faint yellow solid each 3~6 times, adopt be washed with distilled water for the last time, then 60~80 DEG C be dried in vacuo 2~
4h obtains pale yellow powder shape solid.
3. a kind of method for preparing rare-earth cerium doped zinc oxide as described in claim 1, it is characterised in that: in the step (4),
In air atmosphere, calcination time is 2~4h.
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| CN113713797A (en) * | 2021-09-03 | 2021-11-30 | 巢湖学院 | Preparation method and application of sandwich-shaped zinc oxide-cerium oxide composite nanoparticles |
| CN113797973A (en) * | 2021-08-26 | 2021-12-17 | 福州大学 | Method for rapidly preparing alkaline framework material catalyst and application |
| CN115135604A (en) * | 2020-02-28 | 2022-09-30 | 株式会社村田制作所 | Metal double salt dispersion liquid, method for producing metal double salt dispersion liquid, metal oxide nanoparticle dispersion liquid, and method for producing metal oxide nanoparticle dispersion liquid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115135604A (en) * | 2020-02-28 | 2022-09-30 | 株式会社村田制作所 | Metal double salt dispersion liquid, method for producing metal double salt dispersion liquid, metal oxide nanoparticle dispersion liquid, and method for producing metal oxide nanoparticle dispersion liquid |
| CN113797973A (en) * | 2021-08-26 | 2021-12-17 | 福州大学 | Method for rapidly preparing alkaline framework material catalyst and application |
| CN113797973B (en) * | 2021-08-26 | 2023-11-17 | 福州大学 | Method for rapidly preparing alkaline framework material catalyst and application thereof |
| CN113713797A (en) * | 2021-09-03 | 2021-11-30 | 巢湖学院 | Preparation method and application of sandwich-shaped zinc oxide-cerium oxide composite nanoparticles |
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