CN108408765B - A kind of preparation method of rectangular tubular calcium titanate micron particles - Google Patents
A kind of preparation method of rectangular tubular calcium titanate micron particles Download PDFInfo
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- CN108408765B CN108408765B CN201810229964.1A CN201810229964A CN108408765B CN 108408765 B CN108408765 B CN 108408765B CN 201810229964 A CN201810229964 A CN 201810229964A CN 108408765 B CN108408765 B CN 108408765B
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The present invention relates to a kind of preparation method of rectangular tubular calcium titanate micron particles, includes the following steps: that butyl titanate 1) is dissolved in ethyl alcohol, and water is added, obtain white precipitate；2) white precipitate is dispersed in water, and KOH is added, carry out hydro-thermal reaction, it is post-treated to obtain potassium titanate；3) potassium titanate is dispersed in water, and calcium nitrate and KOH is added, the molar concentration of the KOH in the reaction system is 0.1-1mol/L, carries out hydro-thermal reaction, post-treated to obtain rectangular tubular calcium titanate, two concave ends of the rectangular tubular calcium titanate.Present invention process process is simple, easily controllable, non-environmental-pollution, needs not move through high-temperature calcination, at low cost, is easy to large-scale production.
Description
Technical field
The present invention relates to inorganic material to synthesize field, and in particular to a kind of preparation side of rectangular tubular calcium titanate micron particles
Method.
Background technique
Perofskite type oxide is a kind of new inorganic material with unique physical and chemical property, and general molecular formula is
ABO3, it is widely used in fields such as optics, air-sensitive, catalysis, biologies at present.
Calcium titanate (CaTiO3) be perovskite-type compounds Typical Representative, have good crystal structural stability and heat
Stability and good dielectric properties and catalytic performance have been applied to manufacture capacitor, Photocatalyzed Hydrogen Production, photocatalytic degradation
Organic matter is one of the hot spot material paid close attention at present.
Currently, the method for preparing calcium titanate powder mainly has high temperature solid-state method, sol-gal process, hydrothermal synthesis method etc..Its
In, high temperature solid-state method all has the disadvantages of needing higher temperature, spending the time long, be easily introduced impurity with sol-gal process.Phase
Lower than the temperature required for both methods, hydrothermal synthesis method, the time is short, can directly obtain dispersibility and uniformity is preferable
Powdered product, not only can prepare the problem of calcium titanate easily causes to avoid solid reaction process and sol-gal process, but also can
To obtain different patterns by controlling experiment condition.Therefore, started more and more by the method for hydrothermal synthesis calcium titanate
It is concerned.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of system of rectangular tubular calcium titanate micron particles
Preparation Method, the patterns of product calcium titanate micron particles are rectangular tubular, and two concave ends.
Technical solution provided by the present invention are as follows:
A kind of preparation method of rectangular tubular calcium titanate micron particles, includes the following steps:
1) butyl titanate is dissolved in ethyl alcohol, and water is added, obtain white precipitate；
2) white precipitate is dispersed in water, and KOH is added, carry out hydro-thermal reaction, it is post-treated to obtain potassium titanate；
3) potassium titanate is dispersed in water, and calcium nitrate and KOH is added, the molar concentration of the KOH in the reaction system
For 0.1-1mol/L, hydro-thermal reaction is carried out, it is post-treated to obtain rectangular tubular calcium titanate, the both ends of the rectangular tubular calcium titanate
Recess.
White precipitate is titanium hydroxide in the present invention, and tetrabutyl titanate hydrolysis reacts to obtain titanium hydroxide, later and KOH into
Row hydro-thermal reaction obtains potassium titanate.Continue to react with calcium nitrate, KOH using intermediate product potassium titanate, available calcium titanate is micro-
Rice grain, the patterns of product calcium titanate micron particles are rectangular tubular, and two concave ends.Potassium titanate is formed by hydro-thermal reaction,
Calcium titanate is prepared by titanium source of potassium titanate again, reaction can be made to obtain rectangular tubular metatitanic acid under conditions of taking water as a solvent
Calcium avoids CaTi2O4(OH)2The generation of miscellaneous phase.
Preferably, the molar concentration of butyl titanate in ethanol is 0.07-0.35mol/L in the step 1).Into
One step is preferably 0.1-0.25mol/L.
Preferably, the molar concentration of KOH in the reaction system is 6-10mol/L in the step 2).Further preferably
For 8mol/L.
Preferably, the reaction temperature of hydro-thermal reaction is 190-210 DEG C in the step 2), reaction time 14-18h.
Further preferably, the reaction temperature of hydro-thermal reaction is 190-200 DEG C in the step 2), reaction time 14-16h.
Preferably, post-processing includes: to be washed with deionized place the product in cooling in air in the step 2).
Preferably, potassium titanate and calcium nitrate are with the ratio between amount of substance of Ca and Ti for 1:0.9-1.1 in the step 3)
It feeds intake.Further preferably 1:1 feeds intake.
Preferably, the reaction temperature of hydro-thermal reaction is 190-210 DEG C in the step 3), reaction time 4-20h.Into
One step is preferred, and the reaction temperature of hydro-thermal reaction is 190-200 DEG C in the step 3), reaction time 4-16h.
Preferably, the molar concentration of KOH in the reaction system is 0.4-0.6mol/L in the step 3).It is further excellent
It is selected as 0.5mol/L.
Preferably, in the step 3) post-processing include: place the product in being cooled to room temperature in air, successively spend from
Sub- water, dust technology, deionized water and dehydrated alcohol washing, the dry 10-14h at 55-65 DEG C.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) present invention process process is simple, easily controllable, non-environmental-pollution, needs not move through high-temperature calcination, at low cost, easily
In large-scale production.
(2) present invention prepares calcium titanate by intermediate product potassium titanate, avoids CaTi2O4(OH)2The generation of miscellaneous phase.
(3) the calcium titanate particle prepared of the present invention is rectangular tubular, two concave ends, and length is at 2-5 μm, draw ratio about 3:
1, uniformity and good dispersion, surface smoothness are good with integrality.
Detailed description of the invention
Fig. 1 is the XRD diagram of the product rectangular tubular calcium titanate prepared in embodiment 1；
Fig. 2 is the SEM figure of the product rectangular tubular calcium titanate prepared in embodiment 1；
Fig. 3 is the SEM figure of the product rectangular tubular calcium titanate prepared in embodiment 2；
Fig. 4 is the SEM figure of the product rectangular tubular calcium titanate prepared in embodiment 3；
Fig. 5 is the SEM figure of the product rectangular tubular calcium titanate prepared in embodiment 4；
Fig. 6 is the SEM figure of the product rectangular tubular calcium titanate prepared in embodiment 5；
Fig. 7 is the XRD diagram of the product prepared in comparative example 1；
Fig. 8 is the SEM figure of the product prepared in comparative example 1；
Fig. 9 is the SEM figure of the product prepared in comparative example 2；
Figure 10 is the SEM figure of the product prepared in comparative example 3.
Specific embodiment
Below in conjunction with specific embodiment and Figure of description, the invention will be further described.
Embodiment 1
1) 6mmol butyl titanate is taken to be dissolved in 60ml dehydrated alcohol, stirring 10min makes it uniformly, is gone with dropper instillation
Ionized water obtains white precipitate, through being filtered, washed to obtain titanium hydroxide.
2) disperse titanium hydroxide in deionized water, be added 17.92g KOH, stirring 10min make its uniformly, add from
Sub- water is settled to 40ml, and the concentration of KOH is 8mol/L at this time.Suspension is moved into 50ml ptfe autoclave and is carried out
200 DEG C, 16h hydro-thermal reaction obtains potassium titanate after cooling, washing, the pattern of intermediate product potassium titanate is threadiness.
3) it disperses obtained potassium titanate in deionized water, sequentially adds 1.42g calcium nitrate tetrahydrate and 1.12g
KOH, addition deionized water is settled to 40ml after stirring 10min, and the ratio between concentration of Ca and Ti is 1:1 at this time, and the concentration of KOH is
0.50mol/L.Suspension is moved into and carries out 200 DEG C in 50ml ptfe autoclave, 16h hydro-thermal reaction.Allow reaction later
Kettle naturally cools to 25 DEG C of room temperature, after precipitated product is successively washed with deionized water, dust technology, deionized water, dehydrated alcohol
12h is dried at 60 DEG C to get rectangular tubular calcium titanate micron particles are arrived.
Object phase and structural analysis are carried out to the product calcium titanate in embodiment 1 using XRD and SEM, respectively such as Fig. 1 and 2 institute
Show.When preparing potassium titanate with butyl titanate, then by the available calcium titanate of the secondary hydro-thermal of potassium titanate, and without obvious impurity, institute
Obtaining calcium titanate is in rectangular tubular, and two concave ends, length is between 2~5 μm, draw ratio about 3:1.
Embodiment 2~3
It is prepared according to the method for embodiment 1, the difference is that, during calcium titanate is prepared in step 3),
The concentration for being successively set on KOH after being settled to 40mL is 0.25mol/L, 1.0mol/L, remaining condition is constant.Embodiment 2 and 3
Product morphology is rectangular tubular, two concave ends.The SEM figure of embodiment 2,3 is as shown in Figure 3,4 respectively.
Embodiment 4
It is prepared according to the method for embodiment 1, the difference is that, during potassium titanate is prepared in step 1),
Be arranged be added butyl titanate amount be 10mmol, during preparing calcium titanate, be added calcium nitrate tetrahydrate after make Ca with
The ratio between amount of substance of Ti is still 1:1, remaining condition is constant.The product morphology of embodiment 4 is rectangular tubular, and two concave ends are real
The SEM figure for applying example 4 is as shown in Figure 5.
Embodiment 5
It is prepared according to the method for embodiment 1, the difference is that, during calcium titanate is prepared in step 3),
The setting hydro-thermal time is 4h, cooling in air, remaining condition is constant.The product morphology of embodiment 5 is similarly rectangular tubular, and two
The SEM figure of concave end, embodiment 5 is as shown in Figure 6.
Comparative example 1
1) 6mmol butyl titanate is taken to be dissolved in 60ml dehydrated alcohol, stirring 10min makes it uniformly, is gone with dropper instillation
Ionized water obtains white precipitate, through being filtered, washed to obtain titanium hydroxide.
2) it disperses titanium hydroxide in deionized water, sequentially adds 1.42g calcium nitrate tetrahydrate and 0.56g KOH is solid
Body with deionized water is settled to 40ml after stirring 10min, and the ratio between concentration of Ca and Ti is 1:1 at this time, and the concentration of KOH is
0.25mol/L。
3) suspension in step 2) is moved into and carries out 200 DEG C in 50ml ptfe autoclave, 16h hydro-thermal reaction.
It allows reaction kettle to naturally cool to 25 DEG C of room temperature later, precipitated product is successively used to deionized water, dust technology, deionized water, anhydrous
Dry 12h obtains calcium titanate micron particles at 60 DEG C after ethanol washing.
The resulting product of comparative example 1 carries out XRD and SEM characterization, as shown in Fig. 7~8, products therefrom CaTiO3, but contain
There is CaTi2O4(OH)2.By Fig. 7 and Fig. 8 to be clearly seen that, when directly preparing calcium titanate with butyl titanate, although can make
Standby calcium titanate out, but contain sheet impurity, pattern is irregular, is unable to get rectangular tubular.
Comparative example 2
It is prepared according to the method for comparative example 1, the difference is that, the KOH mass being added in step 2) is
1.12g, the concentration of KOH is 0.50mol/L after being settled to 40mL at this time.The SEM of the product of comparative example 2 schemes as shown in figure 9, same
Sample is unable to get rectangular tubular.
Comparative example 3
1) 6mmol butyl titanate is taken to be dissolved in 60ml dehydrated alcohol, stirring 10min makes it uniformly, is gone with dropper instillation
Ionized water obtains white precipitate, through being filtered, washed to obtain titanium hydroxide.
2) disperse titanium hydroxide in deionized water, be added 17.92g KOH, stirring 10min make its uniformly, add from
Sub- water is settled to 40ml, and the concentration of KOH is 8mol/L at this time.Suspension is moved into 50ml ptfe autoclave and is carried out
200 DEG C, 16h hydro-thermal reaction obtains potassium titanate after cooling, washing, the pattern of intermediate product potassium titanate is threadiness.
3) it disperses obtained potassium titanate in deionized water, sequentially adds 1.42g calcium nitrate tetrahydrate and 8.96g
KOH, addition deionized water is settled to 40ml after stirring 10min, and the ratio between concentration of Ca and Ti is 1:1 at this time, and the concentration of KOH is
4mol/L.Suspension is moved into and carries out 200 DEG C in 50ml ptfe autoclave, 16h hydro-thermal reaction.Allow later reaction kettle from
25 DEG C of room temperature so are cooled to, 60 after precipitated product is successively washed with deionized water, dust technology, deionized water, dehydrated alcohol
12h is dried at DEG C to get tetragonal body calcium titanate micron particles are arrived.
SEM characterization, which is carried out, for product calcium titanate is equally unable to get rectangular tubular, product morphology four if Figure 10 shows
Cube, three ribs are mutually perpendicular to, and side length is at 1-5 μm, main reason is that the concentration of KOH is larger in step 3).
Claims (4)
1. a kind of preparation method of rectangular tubular calcium titanate micron particles, which comprises the steps of:
1) butyl titanate is dissolved in ethyl alcohol, and water is added, obtain white precipitate；The molar concentration of butyl titanate in ethanol
For 0.07-0.35mol/L；
2) white precipitate is dispersed in water, and KOH is added, carry out hydro-thermal reaction, it is post-treated to obtain potassium titanate；KOH is anti-
Answering the molar concentration in system is 6-10mol/L；The reaction temperature of hydro-thermal reaction is 190-210 DEG C, reaction time 14-18h；
3) potassium titanate is dispersed in water, and calcium nitrate and KOH is added, the molar concentration of the KOH in the reaction system is
0.1-1mol/L carries out hydro-thermal reaction, and post-treated to obtain rectangular tubular calcium titanate, the both ends of the rectangular tubular calcium titanate are recessed
It falls into；Potassium titanate and calcium nitrate are fed intake with the ratio between amount of substance of Ca and Ti for 1:0.9-1.1；The reaction temperature of hydro-thermal reaction
It is 190-210 DEG C, reaction time 4-20h.
2. the preparation method of rectangular tubular calcium titanate micron particles according to claim 1, which is characterized in that the step
2) post-processing includes: and is washed with deionized place the product in cooling in air in.
3. the preparation method of rectangular tubular calcium titanate micron particles according to claim 1, which is characterized in that the step
3) molar concentration of KOH in the reaction system is 0.4-0.6mol/L in.
4. the preparation method of rectangular tubular calcium titanate micron particles according to claim 1, which is characterized in that the step
3) post-processing includes: successively to use deionized water, dust technology, deionized water and nothing place the product in being cooled to room temperature in air in
Water-ethanol washing, the dry 10-14h at 55-65 DEG C.
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