CN115924968A - Method for preparing rare earth metal doped zirconia by using metal organic framework as precursor - Google Patents
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 152
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 30
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 30
- 239000002243 precursor Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 139
- 239000002245 particle Substances 0.000 claims abstract description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 zirconium ions Chemical class 0.000 claims abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000005342 ion exchange Methods 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 61
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 6
- 150000003754 zirconium Chemical class 0.000 claims description 6
- 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 description 5
- JVYYYCWKSSSCEI-UHFFFAOYSA-N europium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JVYYYCWKSSSCEI-UHFFFAOYSA-N 0.000 claims description 5
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- HDCOFJGRHQAIPE-UHFFFAOYSA-N samarium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HDCOFJGRHQAIPE-UHFFFAOYSA-N 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- UTCARTSNNKGRTD-UHFFFAOYSA-N terbium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O UTCARTSNNKGRTD-UHFFFAOYSA-N 0.000 claims description 5
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 4
- 150000003503 terephthalic acid derivatives Chemical class 0.000 claims description 4
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims description 3
- WIOZZYWDYUOMAY-UHFFFAOYSA-N 2,5-diaminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=C(N)C=C1C(O)=O WIOZZYWDYUOMAY-UHFFFAOYSA-N 0.000 claims description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 claims description 2
- ZPXGNBIFHQKREO-UHFFFAOYSA-N 2-chloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1 ZPXGNBIFHQKREO-UHFFFAOYSA-N 0.000 claims description 2
- FFHNZBHCEGONDG-UHFFFAOYSA-N 2-sulfanylterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(S)=C1 FFHNZBHCEGONDG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 claims description 2
- RQHUQJCIAFYPAI-UHFFFAOYSA-K praseodymium(3+);trichloride;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Pr+3] RQHUQJCIAFYPAI-UHFFFAOYSA-K 0.000 claims description 2
- LXXCECZPOWZKLC-UHFFFAOYSA-N praseodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LXXCECZPOWZKLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 2
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 claims description 2
- FDFPDGIMPRFRJP-UHFFFAOYSA-K trichlorolanthanum;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] FDFPDGIMPRFRJP-UHFFFAOYSA-K 0.000 claims description 2
- ULJUVCOAZNLCJZ-UHFFFAOYSA-K trichloroterbium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Tb+3] ULJUVCOAZNLCJZ-UHFFFAOYSA-K 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of powder materials, and particularly discloses a method for preparing rare earth metal doped zirconia by using a metal organic framework as a precursor, which comprises the following steps: assembling terephthalic acid ligands substituted by different functional groups with zirconium ions to form a metal organic framework material, and then performing metal ion exchange with rare earth metal salt in deionized water in a metal ion exchange manner, centrifuging, washing and drying to obtain binuclear metal organic framework material powder; and calcining the binuclear metal organic framework material powder in a tubular furnace at high temperature, and introducing nitrogen gas to finally obtain the rare earth metal oxide doped zirconia particles. According to the method, the synthesized metal organic framework material is used as a precursor, a binuclear metal organic framework material is synthesized by utilizing a metal ion exchange reaction, and the rare earth metal oxide doped zirconia particles with regular shapes and uniform sizes are obtained through high-temperature calcination.
Description
Technical Field
The invention relates to the technical field of powder materials, and particularly discloses a method for preparing rare earth metal doped zirconia by using a metal organic framework as a precursor.
Background
The zirconia has excellent physical and chemical properties such as high hardness, high strength, high toughness, high wear resistance, high chemical corrosion resistance and the like, so that the zirconia becomes a high-grade refractory material and is applied to various fields. However, zirconia has some defects, because pure zirconia has three morphologies of monoclinic phase, tetragonal phase and cubic phase at different temperatures, the change of crystalline phase can cause the change of material volume to cause the cracking of the prepared product, and the insufficient stability of zirconia limits the application of the zirconia.
In order to stabilize the stability of a crystalline phase of zirconia, other metal elements are generally introduced into zirconia, and a common synthesis method at present is a coprecipitation method mainly. In recent years, a method of taking an organic framework as a precursor and adopting a complex adsorption method is slowly developed, and zirconium and other metal elements are introduced into the framework, so that the product defects of a coprecipitation method are improved, however, the chemical composition uniformity of the metal-doped zirconia prepared by adopting the adsorption method is poor, and the structural stability of the organic framework before and after the metal ions are adsorbed is damaged to a certain extent, so that the morphology regularity and the size uniformity of the metal-doped zirconia particles prepared after calcination cannot reach ideal levels. Therefore, there is a need to propose new strategies and develop new synthesis methods to solve the problems of stability of zirconia and non-uniformity of particles during the preparation process.
Disclosure of Invention
In order to solve the problems of the existing zirconia, the invention aims to provide a method for preparing rare earth metal doped zirconia by using a metal organic framework material as a precursor, namely, a binuclear metal organic framework material is synthesized by using a metal ion exchange reaction and then calcined at a high temperature to obtain particles with regular shapes and uniform sizes.
The invention discloses a method for preparing rare earth metal doped zirconia by using a metal organic framework as a precursor, which adopts the following technical scheme:
a method for preparing rare earth metal doped zirconia by using a metal organic framework as a precursor comprises the following steps:
(1) Preparing a metal organic framework material: different functional group substituted terephthalic acid derivative ligands and zirconium salt are mixed according to the mass ratio of 1:0.5 to 10 portions of the raw materials are mixed, N-dimethylformamide is added, the mixture is stirred until solid powder is dissolved until the mixture is clear and transparent, and clear liquid is placed at the temperature of between 50 and 200 ℃ for hydrothermal reaction for 2 to 24 hours; centrifuging and washing reactants obtained by the hydrothermal reaction for 3-5 times, collecting and adding 50-100 mL of ethanol, stirring at room temperature for 24 hours, filtering the suspension, and vacuum-drying the filtered solid powder at 50-100 ℃ for 2-6 hours to obtain the metal organic framework material;
(2) Preparing a binuclear metal-organic framework material: mixing a metal organic framework material and a rare earth metal salt according to a mass ratio of 1: 0.1-5, adding deionized water, stirring uniformly, carrying out metal ion exchange reaction at 50-200 ℃ for 2-24 h, cooling, filtering, and vacuum drying at 50-100 ℃ for 2-6 h to obtain the binuclear metal-organic framework material;
(3) Preparation of rare earth metal doped zirconia particles: the binuclear metal-organic framework material is calcined at 600-1000 ℃ for 0.5-5 h, and nitrogen is introduced for protection.
Preferably, the terephthalic acid ligand substituted by different functional groups is one or more of terephthalic acid, 2-aminoterephthalic acid, 2-hydroxyterephthalic acid, 2-mercaptoterephthalic acid, 2, 5-diaminoterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 2-nitroterephthalic acid, 2, 5-dihydroxyterephthalic acid and 2-carboxyterephthalic acid.
Preferably, the zirconium salt is one or more of zirconium nitrate pentahydrate, zirconium tetrachloride and zirconium oxychloride octahydrate; the rare earth metal salt is one or more of lanthanum nitrate hexahydrate, cerium nitrate hexahydrate, terbium nitrate hexahydrate, praseodymium nitrate hexahydrate, samarium nitrate hexahydrate, europium nitrate hexahydrate, lanthanum chloride heptahydrate, cerium chloride heptahydrate, terbium chloride hexahydrate, praseodymium chloride heptahydrate and samarium chloride.
Preferably, the mass ratio of the terephthalic acid-derived ligand to the zirconium salt is 1:0.5 to 5.
Preferably, the concentration of the terephthalic acid-derived ligand in N, N-dimethylformamide is from 5 to 50g/L.
Preferably, the conditions of the hydrothermal reaction are: keeping the temperature for 2 to 10 hours at the temperature of between 100 and 180 ℃.
Preferably, the mass ratio of the metal organic framework material to the rare earth metal salt is 1:0.1 to 1.
Preferably, the concentration of the metal organic framework material in deionized water is 5-50 g/L.
Preferably, the conditions of the metal ion exchange reaction are: keeping the temperature for 2 to 10 hours at the temperature of between 100 and 180 ℃.
Preferably, the binuclear metal-organic framework material used for high-temperature calcination has a mass of 1 to 10g, and 1 to 10g of the binuclear metal-organic framework material is placed in a crucible, and the crucible is placed in a tube furnace for calcination.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes the synthesized metal organic framework material as a precursor, and utilizes metal ion exchange reaction to synthesize the binuclear metal organic framework material, and the binuclear metal organic framework material has a regular structure, so that particles with regular appearance and uniform size can be obtained by calcining the binuclear metal organic framework material at high temperature. The method of the invention improves the stability of the zirconia while obtaining regular particles. In addition, the preparation method of the rare earth metal doped zirconia particles is simple, low in cost, universal and suitable for large-scale industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern of the metal-organic framework material and the binuclear metal-organic framework material obtained in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of the rare earth metal-doped zirconia particles prepared in example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of rare earth metal-doped zirconia particles produced in example 6 of the present invention.
FIG. 4 is a scanning electron micrograph of rare earth metal-doped zirconia particles produced in example 11 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example 1
A method for preparing rare earth metal doped zirconia by using a metal organic framework as a precursor comprises the following steps:
(1) Preparation of metal organic framework material:
adding 1g of terephthalic acid and 1g of zirconium tetrachloride into a single-neck flask, adding 100mL of N, N-dimethylformamide, mechanically stirring until an organic ligand and metal ions are dissolved to be clear and transparent, transferring clear liquid into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a hydrothermal reaction kettle, and reacting for 10 hours at 100 ℃; after the obtained reactant is centrifugally washed for 3 times, collecting solid powder in a single-neck flask, adding 80mL of ethanol, and stirring at room temperature for 24 hours to exchange out N, N-dimethylformamide molecules remained in pores; and filtering the suspension, and drying the filtered solid powder at 80 ℃ for 3 hours in vacuum to obtain the metal organic framework material.
(2) Preparing a binuclear metal-organic framework material:
adding 1g of the metal organic framework material and 0.2g of lanthanum nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, mechanically stirring uniformly, reacting at 100 ℃ for 6h, cooling, filtering, and vacuum drying the obtained solid powder at 80 ℃ for 3h to obtain the binuclear metal organic framework material.
(3) Preparation of lanthanum-doped zirconia particles:
and (2) placing 1g of the binuclear metal-organic framework material in a crucible, paving, placing the crucible in a tubular furnace, continuously introducing nitrogen, and calcining at 600 ℃ for 4 hours to obtain the lanthanum-doped zirconia particles.
The X-ray diffraction patterns of the metal-organic framework material and the binuclear metal-organic framework material prepared in example 1 are shown in fig. 1, and the scanning electron microscope of the rare earth metal-doped zirconia particles obtained by high-temperature calcination is shown in fig. 2.
Example 2
(1) Preparing a metal organic framework material:
the preparation of the metal-organic framework material was carried out as in example 1.
(2) Preparing a binuclear metal-organic framework material:
adding 1g of the metal organic framework material prepared in the embodiment 1 and 0.2g of cerous nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, reacting at 100 ℃ for 6h after mechanically stirring uniformly, then cooling and filtering, and drying the obtained solid powder at 80 ℃ for 3h in vacuum to obtain the binuclear metal organic framework material.
(3) Preparation of cerium-doped zirconia particles:
1g of the binuclear metal-organic framework material prepared in example 2 was placed in a crucible, laid flat, and the crucible was placed in a tube furnace, and nitrogen was continuously introduced, and calcined at 600 ℃ for 4 hours, to obtain cerium-doped zirconia particles.
Example 3
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material was carried out as in example 1.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 1 and 0.2g of terbium nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, mechanically stirring uniformly, reacting at 100 ℃ for 6h, cooling, filtering, and vacuum drying the obtained solid powder at 80 ℃ for 3h to obtain the binuclear metal organic framework material.
(3) Preparation of Terbium-doped zirconia particles
1g of the binuclear metal-organic framework material prepared in example 3 was placed in a crucible, spread, and the crucible was placed in a tube furnace, and nitrogen was continuously introduced, and the mixture was calcined at 600 ℃ for 4 hours, to obtain terbium-doped zirconia particles.
Example 4
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material was carried out as in example 1.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 1 and 0.2g of samarium nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, mechanically stirring uniformly, reacting at 100 ℃ for 6h, cooling, filtering, and drying the obtained solid powder at 80 ℃ for 3h in vacuum to obtain the binuclear metal organic framework material.
(3) Preparation of samarium-doped zirconia particles
Placing 1g of the binuclear metal-organic framework material prepared in example 4 in a crucible, paving, placing the crucible in a tube furnace, continuously introducing nitrogen, and calcining at 600 ℃ for 4 hours to obtain the samarium-doped zirconium oxide particles.
Example 5
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material was carried out as in example 1.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 1 and 0.2g of europium nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, reacting at 100 ℃ for 6 hours after mechanically stirring uniformly, then cooling and filtering, and drying the obtained solid powder at 80 ℃ for 3 hours in vacuum to obtain the binuclear metal organic framework material.
(3) Preparation of europium-doped zirconia particles
1g of the binuclear metal-organic framework material prepared in example 5 was placed in a crucible, laid flat, and the crucible was placed in a tube furnace, and nitrogen was continuously introduced, and calcined at 600 ℃ for 4 hours, to obtain europium-doped zirconia particles.
Example 6
(1) Preparation of metal organic framework material
Adding 1g of 2-hydroxy terephthalic acid and 0.9g of zirconium oxychloride octahydrate into a single-neck flask, adding 100mL of N, N-dimethylformamide, mechanically stirring until organic ligands and metal ions are dissolved until the mixture is clear and transparent, transferring the clear liquid into a polytetrafluoroethylene lining, then putting the polytetrafluoroethylene lining into a hydrothermal reaction kettle, and reacting for 6 hours at 150 ℃. After the resultant reaction was washed by 3 times of centrifugation, the solid powder was collected in a single-neck flask, and 80mL of ethanol was added thereto and stirred at room temperature for 24 hours to exchange the N, N-dimethylformamide molecules remaining in the pores. And filtering the suspension, and drying the filtered solid powder at 80 ℃ for 3 hours in vacuum to obtain the metal organic framework material.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 6 and 0.2g of lanthanum nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, reacting at 100 ℃ for 6 hours after mechanically stirring uniformly, then cooling and filtering, and drying the obtained solid powder at 80 ℃ in vacuum for 3 hours to obtain the binuclear metal organic framework material.
(3) Preparation of lanthanum-doped zirconia particles
Placing 1g of the binuclear metal-organic framework material prepared in example 6 in a crucible, paving, placing the crucible in a tube furnace, continuously introducing nitrogen, and calcining at 800 ℃ for 2h to obtain lanthanum-doped zirconia particles.
A scanning electron microscope of the rare earth metal-doped zirconia particles prepared from example 6 above is shown in fig. 3.
Example 7
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material was carried out as in example 6.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 6 and 0.2g of cerous nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, reacting at 100 ℃ for 6h after mechanically stirring uniformly, then cooling and filtering, and drying the obtained solid powder at 80 ℃ for 3h in vacuum to obtain the binuclear metal organic framework material.
(3) Preparation of cerium-doped zirconia particles
1g of the binuclear metal-organic framework material prepared in example 7 was placed in a crucible, laid flat, placed in a tube furnace, continuously purged with nitrogen, and calcined at 800 ℃ for 2 hours to obtain cerium-doped zirconia particles.
Example 8
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material was carried out as in example 6.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 6 and 0.2g of terbium nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, mechanically stirring uniformly, reacting at 100 ℃ for 6h, cooling, filtering, and vacuum drying the obtained solid powder at 80 ℃ for 3h to obtain the binuclear metal organic framework material.
(3) Preparation of terbium-doped zirconia particles
1g of the binuclear metal-organic framework material prepared in example 8 was placed in a crucible, spread, and the crucible was placed in a tube furnace, and nitrogen was continuously introduced, and the mixture was calcined at 800 ℃ for 2 hours, to obtain terbium-doped zirconia particles.
Example 9
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material was carried out as in example 6.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 6 and 0.2g of samarium nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, mechanically stirring uniformly, reacting at 100 ℃ for 6h, cooling, filtering, and drying the obtained solid powder at 80 ℃ for 3h in vacuum to obtain the binuclear metal organic framework material.
(3) Preparation of samarium-doped zirconia particles
Placing 1g of the binuclear metal-organic framework material prepared in example 9 in a crucible, paving, placing the crucible in a tube furnace, continuously introducing nitrogen, and calcining at 800 ℃ for 2h to obtain samarium-doped zirconium oxide particles.
Example 10
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material is as in example 6.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 6 and 0.2g of europium nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, reacting at 100 ℃ for 6 hours after mechanically stirring uniformly, then cooling and filtering, and drying the obtained solid powder at 80 ℃ in vacuum for 3 hours to obtain the binuclear metal organic framework material.
(3) Preparation of europium-doped zirconia particles
1g of the binuclear metal-organic framework material prepared in example 10 was placed in a crucible, laid flat, and the crucible was placed in a tube furnace, nitrogen was continuously introduced, and calcined at 800 ℃ for 2 hours, to obtain europium-doped zirconia particles.
Example 11
(1) Preparation of metal organic framework material
Adding 1g of 2-carboxyl terephthalic acid and 0.8g of zirconium nitrate pentahydrate into a single-neck flask, adding 100mL of N, N-dimethylformamide, mechanically stirring until the organic ligand and the metal ions are dissolved to be clear and transparent, transferring clear liquid into a polytetrafluoroethylene lining, then putting into a hydrothermal reaction kettle, and reacting for 8 hours at 120 ℃. After the resultant reaction mass was washed by 3 times of centrifugation, the solid powder was collected in a one-necked flask, and 80mL of ethanol was added thereto and stirred at room temperature for 24 hours to exchange the N, N-dimethylformamide molecules remaining in the pores. And filtering the suspension, and drying the filtered solid powder at 80 ℃ for 3 hours in vacuum to obtain the metal organic framework material.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 11 and 0.2g of lanthanum nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, reacting at 100 ℃ for 6h after mechanically stirring uniformly, then cooling and filtering, and drying the obtained solid powder at 80 ℃ for 3h in vacuum to obtain the binuclear metal organic framework material.
(3) Preparation of lanthanum-doped zirconia particles
Placing 1g of the binuclear metal-organic framework material prepared in example 11 in a crucible, paving, placing the crucible in a tube furnace, continuously introducing nitrogen, and calcining at 1000 ℃ for 1h to obtain lanthanum-doped zirconia particles.
A scanning electron microscope of the rare earth metal-doped zirconia particles prepared by the above example 11 is shown in fig. 4.
Example 12
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material was carried out as in example 11.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 11 and 0.2g of cerous nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, reacting at 100 ℃ for 6h after mechanically stirring uniformly, then cooling and filtering, and drying the obtained solid powder at 80 ℃ for 3h in vacuum to obtain the binuclear metal organic framework material.
(3) Preparation of cerium-doped zirconia particles
1g of the binuclear metal-organic framework material prepared in example 12 was placed in a crucible, laid flat, and the crucible was placed in a tube furnace, and nitrogen was continuously introduced, and calcined at 1000 ℃ for 1 hour, to obtain cerium-doped zirconia particles.
Example 13
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material was carried out as in example 11.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 11 and 0.2g of terbium nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, mechanically stirring uniformly, reacting at 100 ℃ for 6h, cooling, filtering, and vacuum drying the obtained solid powder at 80 ℃ for 3h to obtain the binuclear metal organic framework material.
(3) Preparation of Terbium-doped zirconia particles
1g of the binuclear metal-organic framework material prepared in example 13 was placed in a crucible, spread, and the crucible was placed in a tube furnace, nitrogen was continuously introduced, and calcination was carried out at 1000 ℃ for 1 hour to obtain terbium-doped zirconia particles.
Example 14
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material is as in example 11.
(2) Preparation of binuclear metal-organic framework material
Adding 1g of the metal organic framework material prepared in the embodiment 11 and 0.2g of samarium nitrate hexahydrate into a single-neck flask, adding 80mL of deionized water, mechanically stirring uniformly, reacting at 100 ℃ for 6h, cooling, filtering, and drying the obtained solid powder at 80 ℃ for 3h in vacuum to obtain the binuclear metal organic framework material.
(3) Preparation of samarium-doped zirconia particles
Placing 1g of the binuclear metal-organic framework material prepared in example 14 in a crucible, paving, placing the crucible in a tube furnace, continuously introducing nitrogen, and calcining at 1000 ℃ for 1h to obtain samarium-doped zirconium oxide particles.
Example 15
(1) Preparation of metal organic framework material
The preparation of the metal-organic framework material was carried out as in example 11.
(2) Preparation of binuclear metal-organic framework material
1g of the metal organic framework material prepared in example 11 and 0.2g of europium nitrate hexahydrate are added into a single-neck flask, 80mL of deionized water is added, the mixture is mechanically stirred uniformly and then reacts at 100 ℃ for 6 hours, then the mixture is cooled and filtered, and the obtained solid powder is dried in vacuum at 80 ℃ for 3 hours, so that the binuclear metal organic framework material is obtained.
(3) Preparation of europium-doped zirconia particles
1g of the binuclear metal-organic framework material prepared in example 15 was placed in a crucible, laid flat, and the crucible was placed in a tube furnace, nitrogen was continuously introduced, and calcined at 1000 ℃ for 1 hour, to obtain europium-doped zirconia particles.
The crystal form and the structure of the binuclear metal organic framework material prepared by the above examples 1-15 are kept good, and the X-ray diffraction pattern in fig. 1 shows that the diffraction peaks of the metal organic framework material before and after the metal ion exchange are kept consistent, which shows that the method of the present invention is different from the existing method of complex adsorption on the organic framework, and the crystal form and the structural stability of the original framework are not changed after the rare earth metal ions are introduced. According to the invention, terephthalic acid derived ligands and zirconium ions are adopted to form a metal organic framework material with a stable structure through coordination, the synthesized metal organic framework material and rare earth metal salt are subjected to reflux reaction in deionized water, the added rare earth metal ions can be coordinated with carboxyl on the terephthalic acid derived ligands, so that part of zirconium ions are exchanged, and the purpose of forming a binuclear metal organic framework material is achieved.
In addition, the binuclear metal-organic framework material is calcined at high temperature, organic matters can be completely decomposed, and gases such as water vapor, carbon dioxide and the like generated by high-temperature calcination can be timely discharged by continuously introducing nitrogen, so that carbon impurities are prevented from being carried in pores of zirconia particles, and the final residue after calcination is the metal oxide/zirconia material. As can be seen from the scanning electron microscope images shown in fig. 2-4, the rare earth metal doped zirconia particles obtained by the preparation method of the present invention have regular shape and uniform size, and it is found that the rare earth metal doped zirconia particles with uniform particles can be obtained by raising the reaction temperature and prolonging the reaction time in the powder calcination process.
In summary, the invention provides a preparation method of a binuclear metal-organic framework material by using a metal ion exchange mode with a metal-organic framework material as a precursor, which is mainly characterized in that the metal-organic framework material is of a very regular structure, after the metal-organic framework material is calcined at a high temperature, organic matters are completely decomposed into carbon dioxide and water vapor, and the carbon dioxide and the water vapor are discharged along with nitrogen, and the remainder is oxide of binuclear metal, namely the rare earth metal doped zirconia. The method can obtain the zirconium oxide particles with regular shapes and uniform sizes, and simultaneously improves the stability of the zirconium oxide particles.
The technical solutions provided by the present invention are described in detail above, and the principle and the implementation of the present invention are explained in this document by applying specific examples, and the descriptions of the above examples are only used to help understanding the method and the core idea of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. A method for preparing rare earth metal doped zirconia by using a metal organic framework as a precursor is characterized by comprising the following steps:
(1) Preparing a metal organic framework material: different functional group substituted terephthalic acid derivative ligands and zirconium salt are mixed according to the mass ratio of 1:0.5 to 10 percent of the raw materials are mixed, N-dimethylformamide is added, the mixture is stirred until solid powder is dissolved to be clear and transparent, and clear liquid is placed at the temperature of between 50 and 200 ℃ for hydrothermal reaction for 2 to 24 hours; centrifuging and washing reactants obtained by the hydrothermal reaction for 3-5 times, collecting and adding 50-100 mL of ethanol, stirring at room temperature for 24 hours, filtering the suspension, and vacuum-drying the filtered solid powder at 50-100 ℃ for 2-6 hours to obtain the metal organic framework material;
(2) Preparation of the binuclear metal-organic framework material: mixing a metal organic framework material and a rare earth metal salt according to a mass ratio of 1: 0.1-5, adding deionized water, stirring uniformly, carrying out metal ion exchange reaction at 50-200 ℃ for 2-24 h, cooling, filtering, and vacuum drying at 50-100 ℃ for 2-6 h to obtain the binuclear metal-organic framework material;
(3) Preparation of rare earth metal doped zirconia particles: the binuclear metal-organic framework material is calcined at 600-1000 ℃ for 0.5-5 h, and nitrogen is introduced for protection.
2. The method for preparing rare earth metal doped zirconia by using metal organic framework as precursor according to claim 1, wherein the terephthalic acid ligand substituted by different functional groups is one or more of terephthalic acid, 2-amino terephthalic acid, 2-hydroxy terephthalic acid, 2-mercapto terephthalic acid, 2, 5-diamino terephthalic acid, 2-chloro terephthalic acid, 2-bromo terephthalic acid, 2-nitro terephthalic acid, 2, 5-dihydroxy terephthalic acid and 2-carboxy terephthalic acid.
3. The method for preparing rare earth metal doped zirconia by using the metal organic framework as the precursor according to claim 1, wherein the zirconium salt is one or more of zirconium nitrate pentahydrate, zirconium tetrachloride and zirconium oxychloride octahydrate; the rare earth metal salt is one or more of lanthanum nitrate hexahydrate, cerium nitrate hexahydrate, terbium nitrate hexahydrate, praseodymium nitrate hexahydrate, samarium nitrate hexahydrate, europium nitrate hexahydrate, lanthanum chloride heptahydrate, cerium chloride heptahydrate, terbium chloride hexahydrate, praseodymium chloride heptahydrate and samarium chloride.
4. The method for preparing rare earth metal doped zirconia by using metal organic framework as precursor according to claim 1, wherein the mass ratio of the terephthalic acid derivative ligand to the zirconium salt is 1:0.5 to 5.
5. The method for preparing rare earth metal doped zirconia by using metal organic framework as precursor according to claim 1, wherein the concentration of the terephthalic acid derivative ligand in N, N-dimethylformamide is 5-50 g/L.
6. The method for preparing rare earth metal doped zirconia by using metal organic framework as precursor according to claim 1, wherein the hydrothermal reaction conditions are as follows: keeping the temperature for 2 to 10 hours at the temperature of between 100 and 180 ℃.
7. The method for preparing rare earth metal doped zirconia by using metal organic framework as precursor according to claim 1, wherein the mass ratio of the metal organic framework material to the rare earth metal salt is 1:0.1 to 1.
8. The method for preparing rare earth metal doped zirconia by using the metal organic framework as the precursor according to claim 1, wherein the concentration of the metal organic framework material in deionized water is 5 to 50g/L.
9. The method for preparing rare earth metal doped zirconia by using metal organic framework as precursor according to claim 1, characterized in that the conditions of metal ion exchange reaction are as follows: keeping the temperature for 2 to 10 hours at the temperature of between 100 and 180 ℃.
10. The method for preparing rare earth metal-doped zirconia using a metal organic framework as a precursor according to claim 1, wherein the binuclear metal organic framework material used for the high-temperature calcination has a mass of 1 to 10g, and 1 to 10g of the binuclear metal organic framework material is placed in a crucible, and the crucible is placed in a tube furnace for calcination.
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