CN106927502B - A kind of method that citric acid-combustion method prepares zirconic acid yttrium - Google Patents
A kind of method that citric acid-combustion method prepares zirconic acid yttrium Download PDFInfo
- Publication number
- CN106927502B CN106927502B CN201710233570.9A CN201710233570A CN106927502B CN 106927502 B CN106927502 B CN 106927502B CN 201710233570 A CN201710233570 A CN 201710233570A CN 106927502 B CN106927502 B CN 106927502B
- Authority
- CN
- China
- Prior art keywords
- solution
- citric acid
- obtains
- yttrium
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
A kind of method that citric acid-combustion method prepares zirconic acid yttrium obtains solution A for yttrium nitrate is soluble in water, and zirconium nitrate is soluble in water, obtains solution B, and solution A and solution B are mixed, mixed solution is obtained；Aqueous citric acid solution is added drop-wise in mixed liquor, adjusting pH value is 2~6, obtains vitreosol；After vitreosol is stirred at room temperature, reheating obtains white gels；White gels heating burning is obtained into fluffy block；Fluffy block is heat-treated 1~3h at 500 DEG C~700 DEG C, obtains zirconic acid yttrium.Present invention process is simple, convenient, strong operability, and preparation cost is lower；The NO in carbonyl functional group and presoma of citric acid in the present invention as complexing agent and incendiary agent, in citric acid3 ‑Ion carbonyl functional group in xerogel combustion process can play reducing agent.Product made from the method is in there is hole bulk morphologies, and crystallinity is high, and test measurement has the photocatalysis performance of greater activity.
Description
Technical field
The invention belongs to field of material preparation, and in particular to a kind of method that citric acid-combustion method prepares zirconic acid yttrium.
Background technique
Material, information and the energy are known as three big pillars of this century science and technology, and material is information and energy skill
The material base of art, material science development function and significance be it is self-evident [Zhang Lide, Mu Ji beauty nano material with receive
The Beijing rice structure [M]: science tech publishing house, 2001,1~10.].
As a kind of important functional material, rare earth zirconate material is because have high-melting-point, lower thermal conductivity, high thermal expansion
The features such as coefficient, high chemical stability, relatively low transition temperature, excellent ionic conducting property and high irradiation stability,
Many necks such as main body of actinides are fixed in refractory material, heat barrier coat material, high-temperature solid electrolyte material and nuke rubbish
Domain is used widely, and [Liu Zhanguo, Ou Yangjiahu, Xia Jiaoliang wait novel rare-earth zirconate material progress [J] China material
Material progress, 2011,30 (1): 32-40.].
And one kind as rare earth zirconate material, zirconic acid yttrium (Y2Zr2O7) there is randomness defect fluorite structure, belong to vertical
Prismatic crystal system.With good electron transport ability, mechanical performance and optical property.Therefore, in thermal barrier coating, photocatalysis and light
Photoluminescence field has huge research potential.
The zirconic acid yttrium preparation method of existing report is mainly sol-gal process, hydro-thermal method and high-temperature solid-phase sintering method.Such as
[Jovan í Marc, Sanz Ana, the et al.New red-shade environmental-friendly such as Jovan í Marc
multifunctional pigment based on Tb and Fe doped Y2Zr2O7for ceramic
Applications and cool roof coatings [J] .Dyes and Pigments, 133 (2016) 33-40.],
[Linhui Gao, Yue An, the et al.Hydrothermal synthesis and such as Linhui Gao
photoluminescence properties of Y2Zr2O7:Tb3+phosphors[J].Journal of Materials
Science, 46 (2011): 1337-1340.] and Hui Li et al. [Hui Li, Qiang Tao, et al.Pressure-
induced structural transition of Y2Zr2O7[J].Journal of Alloys and Compounds,
660 (2016): 446-449.] it is all made of the obtained target product of method mentioned above.In above method, high temperature solid-phase sintering
Method disadvantage be synthesis temperature height, generate Product size it is larger, not can control partial size, due to component is unevenly distributed and there are impure
Phase has stoichiometry loss；The shortcomings that simple sol-gal process, is that the generation temperature of reactant is higher, the reaction time compared with
It is long.The advantages of hydro-thermal method, is the shortcomings that overcoming component is unevenly distributed, and there are stoichiometry losses, however equipment is wanted
Ask higher, and the reaction time is longer.
Summary of the invention
It is an object of the invention to propose that a kind of method that citric acid-combustion method prepares zirconic acid yttrium, the method can be prepared
The lesser zirconic acid yttrium superfine powder of size out, and present invention process is simple, synthesis temperature is low, and the time is short, combines colloidal sol-
The advantages of gel method and low temperature auto-combustion method, can prepare the zirconic acid yttrium powder body of high reaction activity.
To achieve the above object, technical scheme is as follows:
A kind of method that citric acid-combustion method prepares zirconic acid yttrium, comprising the following steps:
1) by Y (NO3)3·6H2O is soluble in water to obtain solution A, by Zr (NO3)4·5H2O is soluble in water, obtains solution B,
Solution A and solution B are mixed, mixed solution is obtained；Wherein, the molar ratio of Y and Zr is 1:1 in mixed liquor；
2) aqueous citric acid solution is added drop-wise in mixed solution, drop finishes, and adjusting pH value is 2~6, obtains vitreosol；
3) after vitreosol being stirred at room temperature, reheating obtains white gels；
4) white gels heating burning is obtained into fluffy block；
5) fluffy block is heat-treated to 1~3h at 500 DEG C~700 DEG C, obtains zirconic acid yttrium.
A further improvement of the present invention lies in that in step 1) solution A 0.025~0.5mol/L of concentration；The concentration of solution B
0.025~0.5mol/L.
A further improvement of the present invention lies in that Y (NO in mixed solution in step 1)3)3·6H2The concentration 0.0125 of O~
0.25mol/L。
A further improvement of the present invention lies in that ammonium hydroxide is used to adjust pH value as 2~6 in step 2).
A further improvement of the present invention lies in that citric acid and Y (NO in step 2)3)3·6H2The molar ratio of O be 0.3~
0.5:1。
A further improvement of the present invention lies in that the concentration of aqueous citric acid solution is 0.1~0.5mol/L in step 2).
A further improvement of the present invention lies in that the revolving speed stirred at room temperature in step 3) is 350~500 revs/min, the time
For 6~12h.
A further improvement of the present invention lies in that the temperature heated in step 3) is 60~80 DEG C, the time is 4~8h.
A further improvement of the present invention lies in that step 4) high temperature heating temperature be 300~350 DEG C, the time be 10~
20min。
A further improvement of the present invention lies in that being ground before being heat-treated.
Compared with prior art, a kind of beneficial effect that the present invention has: low, preparation that the present invention provides synthesis temperatures
New synthetic method-citric acid-combustion method of simple process prepares zirconic acid yttrium.The Y of method therefor preparation of the present invention2Zr2O7Powder
The advantage of body is: (1) present invention uses non-explosive redox exothermic reaction, and burning generates a large amount of gas, and can
Self―sustaining can obtain the oxide powder of high-specific surface area；(2) early period, reaction process was in the solution by preparing gel
It carries out, it can be ensured that the uniformity of the accuracy of stoichiometric ratio and product component, gained powder particles are relatively thin and are distributed
Uniformly (up to submicron order, even nanoscale), and powder is without apparent hard aggregation；(3) present invention process is simple, convenient,
Special equipment is not needed, strong operability, preparation cost is lower；(4) citric acid in the present invention is as complexing agent and burning
Agent, the NO in carbonyl functional group and presoma in citric acid3 -Ion carbonyl functional group in xerogel combustion process can rise
The effect of reducing agent.(5) for product made from the method in there is hole bulk morphologies, crystallinity is high, and test measurement is with higher
Active photocatalysis performance.
Detailed description of the invention
Fig. 1, which is that the present invention is obtained under conditions of embodiment 2, hole bulk Y2Zr2O7X-ray diffraction (XRD) map.
Fig. 2 is the present invention Y under 20,000 enlargement ratios prepared under the conditions of embodiment 22Zr2O7SEM figure.
Fig. 3 is present invention Y prepared under the conditions of embodiment 22Zr2O7Photocatalytic degradation sieve under 500W Hg lamp irradiation
Red bright B performance map.
Specific embodiment
Present invention will now be described in detail with reference to the accompanying drawings..
Embodiment 1
1) analytically pure Y (NO is weighed respectively3)3·6H2O and Zr (NO3)4·5H2O uses deionization in beaker respectively
Water dissolution, obtains solution Y (NO3)3·6H2O concentration is A and the Zr (NO of 0.025mol/L3)4·5H2O concentration is 0.025mol/L
Solution B, solution A and solution B are mixed, Y (NO is configured to3)3·6H2O concentration is the mixed solution of 0.0125mol/L.Wherein
The molar ratio of Y and Zr is 1:1 in mixed liquor.
2) using citric acid as complexing agent and incendiary agent, by 0.1mol/L aqueous citric acid solution by the way of being added dropwise
It is added in the mixed liquor stirred evenly, wherein keeping citric acid: the molar ratio of Y=0.3:1.Concentrated ammonia liquor adjusting is slowly added dropwise again
Its pH=6, obtains vitreosol.
3) at room temperature by clear gel revolving speed be 350 revs/min under stir 12h, obtain stable sol solutions.It will stablize
Sol solutions be put into temperature constant magnetic stirring pot, controlled at 60 DEG C, after water-bath 8h, obtain white gels.
4) resulting white gels are collected into alumina crucible, are placed in Muffle furnace, react 20min at 300 DEG C,
Promote citric acid to burn, obtains fluffy block.
5) the fluffy block of acquisition is placed in agate mortar and grinds 5min, be subsequently placed in Muffle furnace, in 500 DEG C of temperature
Target product zirconic acid yttrium (Y can be obtained in lower heat treatment 3h2Zr2O7)。
Embodiment 2
1) analytically pure Y (NO is weighed respectively3)3·6H2O and Zr (NO3)4·5H2O uses deionization in beaker respectively
Water dissolution, obtains solution Y (NO3)3·6H2O concentration is A and the Zr (NO of 0.5mol/L3)4·5H2O concentration is the molten of 0.5mol/L
Solution A and solution B are mixed, are configured to Y (NO by liquid B3)3·6H2O concentration is the mixed solution of 0.25mol/L.Wherein mixed liquor
The molar ratio of middle Y and Zr is 1:1.
2) using citric acid as complexing agent and incendiary agent, by 0.5mol/L aqueous citric acid solution by the way of being added dropwise
It is added to the mixed liquor stirred evenly, wherein keeping citric acid: the molar ratio of Y=0.4:1.Concentrated ammonia liquor is slowly added dropwise again and adjusts it
PH=2 obtains vitreosol.
3) at room temperature by clear gel revolving speed be 500 revs/min under stir 6h, obtain stable sol solutions.It will stablize
Sol solutions be put into temperature constant magnetic stirring pot, controlled at 80 DEG C, after water-bath 5h, obtain white gels.
4) resulting white gels are collected into alumina crucible, are placed in Muffle furnace, react 10min at 350 DEG C,
Promote citric acid to burn, obtains fluffy block.
5) the fluffy block of acquisition is placed in agate mortar and grinds 5min, be subsequently placed in Muffle furnace, in 600 DEG C of temperature
Target product zirconic acid yttrium (Y can be obtained in lower heat treatment 2h2Zr2O7)。
It will be seen from figure 1 that the present invention successfully prepares Y using citric acid-combustion method2Zr2O7(comparison ICDD card number:
01-074-9311)。
Figure it is seen that using citric acid-combustion method preparation Y2Zr2O7In there is hole bulk pattern.
From figure 3, it can be seen that zirconic acid yttrium is in 2h to concentration prepared by this patent under conditions of 500W Hg lamp irradiation
It can achieve 78% (subtracting product absorption and result after the effect of dyestuff self-degradation) for the rhodamine B degradation rate of 10mg/L,
2.5h just can reach degradable.
Embodiment 3
1) analytically pure Y (NO is weighed respectively3)3·6H2O and Zr (NO3)4·5H2O uses deionization in beaker respectively
Water dissolution, obtains solution Y (NO3)3·6H2O concentration is A and the Zr (NO of 0.0125mol/L3)4·5H2O concentration is 0.3mol/L
Solution B, solution A and solution B are mixed, Y (NO is configured to3)3·6H2O concentration is the mixed solution of 0.2mol/L.Wherein mix
The molar ratio for closing Y and Zr in liquid is 1:1.
2) using citric acid as complexing agent and incendiary agent, by 0.3mol/L aqueous citric acid solution by the way of being added dropwise
It is added in the mixed liquor stirred evenly, wherein keeping citric acid: the molar ratio of Y=0.5:1.Concentrated ammonia liquor adjusting is slowly added dropwise again
Its pH=3, obtains vitreosol.
3) at room temperature by clear gel revolving speed be 400 revs/min under stir 9h, obtain stable sol solutions.It will stablize
Sol solutions be put into temperature constant magnetic stirring pot, controlled at 70 DEG C, after water-bath 7h, obtain white gels.
4) resulting white gels are collected into alumina crucible, are placed in Muffle furnace, react 20min at 300 DEG C,
Promote citric acid to burn, obtains fluffy block.
5) the fluffy block of acquisition is placed in agate mortar and grinds 5min, be subsequently placed in Muffle furnace, in 700 DEG C of temperature
Target product zirconic acid yttrium (Y can be obtained in lower heat treatment 1h2Zr2O7)。
Embodiment 4
1) 1) analytically pure Y (NO is respectively weighed3)3·6H2O and Zr (NO3)4·5H2O in beaker, and spend respectively from
Sub- water dissolution, obtains solution Y (NO3)3·6H2O concentration is A and the Zr (NO of 0.05mol/L3)4·5H2O concentration is 0.4mol/L
Solution B, solution A and solution B are mixed, Y (NO is configured to3)3·6H2O concentration is the mixed solution of 0.2mol/L.Wherein mix
The molar ratio for closing Y and Zr in liquid is 1:1.
2) using citric acid as complexing agent and incendiary agent, by 0.4mol/L aqueous citric acid solution by the way of being added dropwise
It is added in the mixed liquor stirred evenly, wherein keeping citric acid: the molar ratio of Y=0.4:1.Concentrated ammonia liquor adjusting is slowly added dropwise again
Its pH=5, obtains vitreosol.
3) at room temperature by clear gel revolving speed be 450 revs/min under stir 8h, obtain stable sol solutions.It will stablize
Sol solutions be put into temperature constant magnetic stirring pot, controlled at 80 DEG C, after water-bath 4h, obtain white gels.
4) resulting white gels are collected into alumina crucible, are placed in Muffle furnace, react 15min at 350 DEG C,
Promote citric acid to burn, obtains fluffy block.
5) the fluffy block of acquisition is placed in agate mortar and grinds 5min, be subsequently placed in Muffle furnace, in 600 DEG C of temperature
Target product zirconic acid yttrium (Y can be obtained in lower heat treatment 2h2Zr2O7)。
The invention has the following advantages that
1) for product made from the method in there is hole bulk morphologies, crystallinity is high.
2) the method manufacture craft is simple, does not need special installation, strong operability, and preparation cost is lower.
3) the method can accurately control stoichiometric ratio, the uniform product of prepared composition.
4) the zirconic acid yttrium powder body of the method preparation has the photocatalysis performance of greater activity through test measurement.
Claims (4)
1. a kind of method that citric acid-combustion method prepares zirconic acid yttrium, which comprises the following steps:
1) by Y (NO3)3·6H2O is soluble in water to obtain solution A, by Zr (NO3)4·5H2O is soluble in water, obtains solution B, will be molten
Liquid A and solution B mixing, obtain mixed solution；Wherein, the molar ratio of Y and Zr is 1:1 in mixed solution；Y in mixed solution
(NO3)3·6H20.0125~0.25mol/L of concentration of O；
2) aqueous citric acid solution is added drop-wise in mixed solution, drop finishes, and uses ammonium hydroxide to adjust pH value as 2~6, obtains transparent molten
Glue；Wherein, middle citric acid and Y (NO3)3·6H2The molar ratio of O is 0.3~0.5:1；
3) after vitreosol being stirred at room temperature, reheating obtains white gels；
4) white gels heating burning is obtained into fluffy block；
5) fluffy block is heat-treated to 1~3h at 500 DEG C~700 DEG C, obtains zirconic acid yttrium；
The revolving speed stirred at room temperature in step 3) is 350~500 revs/min, and the temperature of heating is 60~80 DEG C, the time is 4~
8h；
The temperature of heating burning is 300~350 DEG C in step 4), and the time is 10~20min.
2. the method that a kind of citric acid-combustion method according to claim 1 prepares zirconic acid yttrium, which is characterized in that step 1)
0.025~0.5mol/L of concentration of middle solution A；0.025~0.5mol/L of concentration of solution B.
3. the method that a kind of citric acid-combustion method according to claim 1 prepares zirconic acid yttrium, which is characterized in that step 2)
The concentration of middle aqueous citric acid solution is 0.1~0.5mol/L.
4. the method that a kind of citric acid-combustion method according to claim 1 prepares zirconic acid yttrium, which is characterized in that carry out heat
It is ground before processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710233570.9A CN106927502B (en) | 2017-04-11 | 2017-04-11 | A kind of method that citric acid-combustion method prepares zirconic acid yttrium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710233570.9A CN106927502B (en) | 2017-04-11 | 2017-04-11 | A kind of method that citric acid-combustion method prepares zirconic acid yttrium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106927502A CN106927502A (en) | 2017-07-07 |
| CN106927502B true CN106927502B (en) | 2019-01-25 |
Family
ID=59426337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710233570.9A Active CN106927502B (en) | 2017-04-11 | 2017-04-11 | A kind of method that citric acid-combustion method prepares zirconic acid yttrium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106927502B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030368A (en) * | 2010-11-18 | 2011-04-27 | 西南科技大学 | Preparation method of pure-phase high-performance rare earth zirconate material |
| CN102515752A (en) * | 2011-12-20 | 2012-06-27 | 中国科学院上海硅酸盐研究所 | Transparent ceramic material and preparation method thereof |
-
2017
- 2017-04-11 CN CN201710233570.9A patent/CN106927502B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030368A (en) * | 2010-11-18 | 2011-04-27 | 西南科技大学 | Preparation method of pure-phase high-performance rare earth zirconate material |
| CN102515752A (en) * | 2011-12-20 | 2012-06-27 | 中国科学院上海硅酸盐研究所 | Transparent ceramic material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| (Y,Ce)2Zr2O7纳米粉体的制备及其发光性能的研究;王蕾等;《中国计量学院学报》;20160331;第27卷(第1期);第108-120页 |
| 燃烧法合成La2Zr2O7粉及其光谱性能;刘小珍等;《光谱学与光谱分析》;20161231;第36卷(第12期);第4063-4066页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106927502A (en) | 2017-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | A homogeneous co-precipitation method to synthesize highly sinterability YAG powders for transparent ceramics | |
| CN102775985B (en) | There is a Sr2MgSi2O7:Eu2+ for long-persistence luminous function, the synthetic method of Dy3+ nano wire | |
| CN103691421B (en) | A kind of CeVO 4micron ball photochemical catalyst and preparation method thereof | |
| CN106745231B (en) | A kind of taper titanium dioxide nano-rod and preparation method thereof | |
| CN101475377A (en) | Preparation of solid oxide electrolytic cell anode barrier layer nano powder and barrier layer | |
| CN102923770A (en) | Preparation method of yttrium-stabilized nanometer zirconium dioxide powder | |
| CN101845668B (en) | Method for preparing nano nickel borate whiskers | |
| CN104528799A (en) | Preparation method of ultrafine magnesium-based rare earth hexaaluminate powder | |
| CN107880884B (en) | Preparation method of cerium-doped rare earth silicate polycrystalline powder | |
| CN102391865A (en) | Preparation method for doping gadolinium oxide nano-powders | |
| CN102718258A (en) | Preparation method of Gd2Zr2O7 nano-powder | |
| CN100411996C (en) | Method for preparting Nano powder of zirconia | |
| CN104030693B (en) | A kind of preparation method of triple cationic Ce:LuAG ceramic fluorescent powder | |
| CN105905944A (en) | Method of preparing Bi2Zr2O7 nano material through non-hydrolytic sol-gel method | |
| CN101767997B (en) | Method for preparing NiTiO3 nano-powder by sol-gel | |
| CN102730756A (en) | Preparation method for pyrochlore type rare-earth zirconate | |
| CN102134089B (en) | Fusiform large-scale cerium based composite oxide powder and preparation method thereof | |
| CN101367539A (en) | Preparation of nano- luminescent powder body with colloidal sols gel rubber method | |
| CN102491416A (en) | Method for preparing Eu2Zr207 nanometer powder | |
| Wu et al. | Influence of pH on nano-phosphor YPO4: 2% Sm3+ and luminescent properties | |
| CN105272252A (en) | Fluorite-type Eu-doped Y2Ce2O7 nano ceramic pigment and preparation method | |
| CN106927502B (en) | A kind of method that citric acid-combustion method prepares zirconic acid yttrium | |
| Huang et al. | Morphology controllable synthesis of yttrium oxide-based phosphors from yttrium citrate precursors | |
| CN107010662B (en) | A kind of method that nitrate-urea combustion prepares zirconic acid yttrium powder body | |
| Wang et al. | One-step microwave synthesis of (Gd, Eu) PO4 urchin-like hollow spheres: Enhanced luminescence and pH-sensitive drug delivery properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |