CN111484072A - Method for preparing titanate or titanium-based composite oxide material by low-temperature crystalline phase conversion - Google Patents
Method for preparing titanate or titanium-based composite oxide material by low-temperature crystalline phase conversion Download PDFInfo
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- CN111484072A CN111484072A CN202010329194.5A CN202010329194A CN111484072A CN 111484072 A CN111484072 A CN 111484072A CN 202010329194 A CN202010329194 A CN 202010329194A CN 111484072 A CN111484072 A CN 111484072A
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Abstract
The invention relates to a method for preparing titanate or titanium-based composite oxide material by low-temperature crystalline phase conversion. The method comprises the following steps: (1) mixing Ti (SO)4)2·9H2Dissolving O in ethanol, and adding H2O2To produce TiO2A material; (2) to prepare TiO2Dispersing in NaOH solution, and then adding soluble salt of M element to prepare mixture suspension; (3) carrying out constant-temperature crystal phase conversion on the obtained suspension at the temperature of 25-80 ℃ for 1-24h under a closed condition, and finally cooling; to obtain the titanate or titanium-based composite oxide material. The synthesis process has the advantages of simple operation method, mild reaction conditions, energy conservation, environmental protection and good stability, and can be converted and synthesized even at room temperature. The composition proportion of the prepared material can be regulated and controlled by simply regulating and controlling the amount of the added M component, and the method is simple and easy to implement.
Description
Technical Field
The invention relates to a method for preparing titanate and a titanium-based composite oxide material by low-temperature crystalline phase conversion, belonging to the technical field of functional materials.
Background
Titanate is a typical perovskite ABO3The oxide material with the structure has the characteristics of good thermal stability, low dielectric loss, high dielectric constant and the like, and is widely applied to the fields of ceramic functional industry, electronics and machinery. The main preparation methods of titanate include a high-temperature solid-phase reaction synthesis method, a sol-gel method, a hydrothermal method and the like. In the former two methods, the calcination temperature of the sol-gel method needs to reach about 700 ℃ even if the calcination temperature is low, and the high temperature has the disadvantages of high energy consumption, high production cost and poor safety of the preparation process, and is easy to cause serious agglomeration of materials. The low-temperature liquid phase synthesis has the advantages of simple method, easy control of the chemical composition of the product and the like, and although the temperature required by the hydrothermal method is relatively low, the crystallization temperature for directly synthesizing titanate is far over 100 ℃, and the crystallization needs to be carried out in a pressure container. TiO 22The method for synthesizing titanate material by crystal phase conversion has been reported (advanced chemical research and development, 2011,32,2490), even if nano TiO is adopted2The fiber is taken as a precursor and is treated in 1M NaOH solution for 24 hours at the temperature of 150 ℃ to prepare SrTiO3. The method generally accepts a 'dissolution-crystallization' mechanism, so that precursor TiO2The more porous the structure, the more advantageous the conversion reaction proceeds. In addition, most of the reported synthetic processes are relatively complex, high in production cost and almost difficult to realize large-scale production. Therefore, the development of a method for simply and stably synthesizing titanate and a titanium-based composite oxide material at low temperature even room temperature has important significance for the theoretical research and industrial application of perovskite type oxides.
Disclosure of Invention
The invention aims to provide a method for synthesizing titanate and a titanium-based composite oxide material by low-temperature crystalline phase conversion aiming at the defects in the prior art. The method takes inorganic titanium salt as a titanium source and adopts ethanol thermal crystallization to synthesize TiO2(ii) a Then the titanate material is synthesized by low-temperature crystal phase conversion in an alkaline system. The amount and the variety of substances for adding the M element into the system in the crystalline phase conversion process are controlled to regulate and control the prepared materialThe proportion of titanate is reduced, thereby preparing titanate or titanium-based composite oxide material. The invention has simple operation, stability and easy control.
The technical scheme of the invention is as follows:
a method for preparing titanate or titanium-based composite oxide material by low-temperature crystal phase conversion comprises the following steps:
(1) mixing Ti (SO)4)2·9H2Dissolving O in ethanol, and adding H2O2Stirring the mixed solution for 5-30 minutes, heating to 90-120 ℃, and crystallizing for 2-24 hours to obtain TiO2A material;
wherein, Ti (SO)4)2·9H2The concentration of the O ethanol solution is 5-100 g/L, H2O2The volume of (a) is 5-20% of the volume of the mixed liquid;
(2) to prepare TiO2Dispersing in NaOH solution, and then adding soluble salt of M element to prepare mixture suspension;
wherein the molar ratio of M to Ti is 0.01-2, and the solubility of NaOH solution is 0.2-2 mol/L2The mass ratio of the M to the NaOH solution is 2-50%, wherein M is Sr, Ba, Ni or L a;
(3) carrying out constant-temperature crystal phase conversion on the obtained suspension at the temperature of 25-80 ℃ for 1-24h under a closed condition, and finally cooling;
(4) and after cooling, filtering, washing and drying the obtained particles to obtain the titanate or titanium-based composite oxide material.
Wherein, the soluble salt of the M element in the step (2) is one or more soluble salts of elements, and the soluble salt is hydrochloride or nitrate.
When M is more than or equal to 1, the synthesized material is titanate, and when M is less than 1, the synthesized material is a titanium-based composite oxide material.
The invention has the beneficial effects that:
1. the method takes the inorganic titanium salt as the titanium source, the operation method of the used synthesis process is simple, the reaction condition is mild, the inorganic titanium salt can be converted and synthesized even at room temperature, and the method is energy-saving, environment-friendly and good in stability.
2. The composition proportion of the material prepared by the invention can be regulated and controlled by simply regulating and controlling the amount of the added M component, and the method is simple and easy to implement.
3. The material has mild preparation process conditions, and does not need special environment (such as inert atmosphere protection and the like); the microstructure of the material is more easily maintained and is less prone to damage.
Drawings
FIG. 1 is an XRD pattern of a sample of strontium titanate as described in example 1;
FIG. 2 is an XRD pattern of a sample of barium titanate as described in example 2;
FIG. 3 is an XRD pattern of a sample of strontium titanate as described in example 3;
FIG. 4 is an SEM photograph of a sample of strontium titanate as described in example 3;
figure 5 is an XRD pattern of a sample of strontium titanate as described in example 4.
Detailed Description
The present invention is illustrated below by examples, which are described only for further explaining and explaining the present invention in detail, but the scope of the present invention is not limited to the following examples, and the insubstantial modifications and adaptations made by those skilled in the art based on the contents of the present invention still belong to the scope of the present invention.
Example 1:
ti (SO) with a concentration of 10 g/L was prepared under magnetic stirring4)2·9H2O ethanol solution, and adding H of 7.5% of the total volume of the solution2O2With Ti4+Complexing for 20min, crystallizing for 12 hr, suction filtering, and washing to obtain TiO2Then dispersing the mixture in a 1 mol/L NaOH solution to obtain TiO2The concentration is 5 wt%, and a certain amount of SrCl is added into the system2Stirring for 20min so that the molar ratio of Sr to Ti is 50%, placing the obtained suspension into a crystallization kettle, and carrying out crystal phase transformation for 4h and 12h respectively at the temperature of 25 ℃ under a sealed condition to obtain two samples. Cooling to room temperature, filtering, washing and drying the obtained particles. The XRD characterization results of the samples are shown in FIG. 1, and it can be seen from the results that at normal temperature, SrTiO is present in the sample after 4h of crystal phase transformation3Formation of material and formation with extended conversion timeSrTiO3The amount of (c) increases.
Example 2:
ti (SO) with a concentration of 10 g/L was prepared under magnetic stirring4)2·9H2O ethanol solution, and adding H of 7.5% of the total volume of the solution2O2With Ti4+Complexing for 20min, crystallizing for 12 hr, suction filtering, and washing to obtain TiO2Then dispersing the mixture in a 1 mol/L NaOH solution to obtain TiO2The concentration is 1 wt%, and a certain amount of SrCl is added into the system2And stirring for 20min until the molar ratio of Sr to Ti is 50%, and then carrying out closed crystal phase transformation for 4h at 40 ℃ to obtain a material sample. XRD characterization of the samples is shown in FIG. 2, from which it can be seen that SrTiO is formed with a slight increase in the phase transition temperature3The amount of (c) is significantly increased.
Example 3:
ti (SO) with a concentration of 10 g/L was prepared under magnetic stirring4)2·9H2O ethanol solution, and adding H of 7.5% of the total volume of the solution2O2With Ti4+Complexing for 20min, crystallizing for 12 hr, suction filtering, and washing to obtain TiO2Then dispersing the mixture in a 1 mol/L NaOH solution to obtain TiO2The concentration is 1 wt%, and a certain amount of SrCl is added into the system2And stirring for 20min until the molar ratio of Sr to Ti is 50%, and then carrying out closed crystal phase transformation for 4h at 60 ℃ to obtain a material sample. The XRD characterization results of the sample are shown in FIG. 3, and the scanning electron micrograph is shown in FIG. 4, from which it can be seen that the SrTiO is formed by continuously increasing the transformation temperature of the crystal phase3The amount of (a) is more significantly increased.
Example 4:
ti (SO) with a concentration of 10 g/L was prepared under magnetic stirring4)2·9H2O ethanol solution, and adding H of 7.5% of the total volume of the solution2O2With Ti4+Complexing for 20min, crystallizing for 12 hr, suction filtering, and washing to obtain TiO2Then dispersing the mixture in a 1 mol/L NaOH solution to obtain TiO2The concentration is 1 wt%, and a certain amount of BaCl is added into the system2Stirring for 20min until the molar ratio of Ba to Ti is 50%, and sealing at 60 deg.C for crystal phase conversion 4h to prepare a material sample. The XRD characterization results of the samples are shown in FIG. 5, from which BaCl is observed2Replacement of SrCl2Can prepare BaTiO3A material.
Example 5:
ti (SO) with a concentration of 20 g/L was prepared under magnetic stirring4)2·9H2O ethanol solution, and adding H of 7.5% of the total volume of the solution2O2With Ti4+Complexing for 20min, crystallizing for 8 hr, suction filtering, and washing to obtain TiO2Then dispersing the mixture in a 1 mol/L NaOH solution to obtain TiO2The concentration is 10 wt%, and a certain amount of Sr (NO) is added into the system3)2And stirring for 20min until the molar ratio of Sr to Ti is 50%, and then carrying out closed crystal phase transformation for 4h at 60 ℃ to obtain a material sample.
Example 6:
ti (SO) with a concentration of 10 g/L was prepared under magnetic stirring4)2·9H2O ethanol solution, and adding H of 7.5% of the total volume of the solution2O2With Ti4+Complexing for 20min, crystallizing for 12 hr, suction filtering, and washing to obtain TiO2Then dispersing the mixture in a 1 mol/L NaOH solution to obtain TiO2The concentration is 5 wt%, and a certain amount of SrCl is added into the system2And stirring for 20min, and then carrying out closed crystal phase transformation for 8h at 80 ℃ to obtain a material sample.
Example 7:
ti (SO) with the concentration of 40 g/L is prepared under the magnetic stirring4)2·9H2O ethanol solution, and adding H of 7.5% of the total volume of the solution2O2With Ti4+Complexing for 20min, crystallizing for 20 hr, suction filtering, and washing to obtain TiO2Then dispersing the mixture in a 1 mol/L NaOH solution to obtain TiO2The concentration is 1 wt%, and a certain amount of SrCl is added into the system2And BaCl2The material sample was prepared by stirring the mixture so that the molar ratio (Sr + Ba) to Ti was 100% for 20min and then converting the crystal phase in a closed state at 80 ℃ for 4 hours.
In conclusion, the synthesis of titanate or titanate-containing material through low-temperature crystalline phase conversion is reported in the inventionThe method of titanate composite material is based on 'dissolving-crystallizing' mechanism, firstly titanium ion and hydrogen peroxide are utilized to complex polyhydroxy hydrate, TiO is formed by heat treatment2The hydrate is decomposed to generate oxygen in the process, so that the material structure is looser; the loose structure of the precursor is beneficial to the action of Ti and NaOH, and the transformation of a crystalline phase is further promoted. The composition of the synthesized sample can be regulated by controlling the amount of the added M element, for example, when the amount of Sr is insufficient, the obtained material is TiO2-SrTiO3When sufficient or excessive Sr is added into the system, the SrTiO is3(ii) a Namely, when M is more than or equal to 1, the synthesized material is titanate, M is Ti<The material synthesized in the step 1 is a titanium-based composite oxide material.
The invention is not the best known technology.
Claims (3)
1. A method for preparing titanate or titanium-based composite oxide material by low-temperature crystal phase conversion is characterized by comprising the following steps:
(1) mixing Ti (SO)4)2·9H2Dissolving O in ethanol, and adding H2O2Stirring the mixed solution for 5-30 minutes, heating to 90-120 ℃, and crystallizing for 2-24 hours to obtain TiO2A material;
wherein, Ti (SO)4)2·9H2The concentration of the O ethanol solution is 5-100 g/L, H2O2The volume of (a) is 5-20% of the volume of the mixed liquid;
(2) to prepare TiO2Dispersing in NaOH solution, and then adding soluble salt of M element to prepare mixture suspension;
wherein the molar ratio of M to Ti is 0.01-2, and the solubility of NaOH solution is 0.2-2 mol/L2The mass ratio of the M to the NaOH solution is 2-50%, wherein M is Sr, Ba, Ni or L a;
(3) carrying out constant-temperature crystal phase conversion on the obtained suspension at the temperature of 25-80 ℃ for 1-24h under a closed condition, and finally cooling;
(4) and after cooling, filtering, washing and drying the obtained particles to obtain the titanate or titanium-based composite oxide material.
2. The method for preparing titanate or titanium-based composite oxide material by low-temperature crystal phase transformation according to claim 1, wherein the soluble salt of M element in step (2) is one or more soluble salts of elements, and the soluble salt is hydrochloride or nitrate.
3. The method of claim 1, wherein the titanate or Ti-based composite oxide material is prepared by low temperature crystal phase transformation, when M: Ti is more than or equal to 1, the titanate is synthesized, and when M: Ti is less than 1, the Ti-based composite oxide material is synthesized.
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Citations (7)
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| US20050186133A1 (en) * | 2002-09-24 | 2005-08-25 | Jianfeng Chen | Process for preparing a strontium titanate powder |
| CN101045554A (en) * | 2007-03-12 | 2007-10-03 | 胜利油田华鑫石油材料有限公司 | Method for preparing uniform dispersion square phase barium titanate nanocrystal |
| CN101595059A (en) * | 2006-09-21 | 2009-12-02 | 托库森美国股份有限公司 | The temperature production method of the TiO 2 particles of nanometer size |
| CN102101697A (en) * | 2011-01-04 | 2011-06-22 | 上海大学 | Rapid preparation method of high-dispersible TiO2 nano crystal sol |
| CN103833076A (en) * | 2012-11-27 | 2014-06-04 | 王泰林 | Nickel oxide-titanium dioxide nano composite material |
| CN104098125A (en) * | 2013-04-10 | 2014-10-15 | 中国科学院大学 | Preparation method for nanometer strontium titanate cube |
| CN106268747A (en) * | 2016-08-16 | 2017-01-04 | 曹健 | A kind of preparation method of La doped TiO2 |
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2020
- 2020-04-23 CN CN202010329194.5A patent/CN111484072A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050186133A1 (en) * | 2002-09-24 | 2005-08-25 | Jianfeng Chen | Process for preparing a strontium titanate powder |
| CN101595059A (en) * | 2006-09-21 | 2009-12-02 | 托库森美国股份有限公司 | The temperature production method of the TiO 2 particles of nanometer size |
| CN101045554A (en) * | 2007-03-12 | 2007-10-03 | 胜利油田华鑫石油材料有限公司 | Method for preparing uniform dispersion square phase barium titanate nanocrystal |
| CN102101697A (en) * | 2011-01-04 | 2011-06-22 | 上海大学 | Rapid preparation method of high-dispersible TiO2 nano crystal sol |
| CN103833076A (en) * | 2012-11-27 | 2014-06-04 | 王泰林 | Nickel oxide-titanium dioxide nano composite material |
| CN104098125A (en) * | 2013-04-10 | 2014-10-15 | 中国科学院大学 | Preparation method for nanometer strontium titanate cube |
| CN106268747A (en) * | 2016-08-16 | 2017-01-04 | 曹健 | A kind of preparation method of La doped TiO2 |
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