CN111099691A - Preparation method of porous microcrystalline glass containing titanium dihydrogen phosphate dihydrate and anatase crystalline phase and obtained product - Google Patents

Preparation method of porous microcrystalline glass containing titanium dihydrogen phosphate dihydrate and anatase crystalline phase and obtained product Download PDF

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CN111099691A
CN111099691A CN202010012067.2A CN202010012067A CN111099691A CN 111099691 A CN111099691 A CN 111099691A CN 202010012067 A CN202010012067 A CN 202010012067A CN 111099691 A CN111099691 A CN 111099691A
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dihydrogen phosphate
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tio
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刘世权
陈�峰
张维娟
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University of Jinan
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Abstract

The invention discloses a preparation method of porous glass ceramics containing titanium dihydrogen phosphate dihydrate and anatase crystalline phase and an obtained product. The porous material comprises 0-40 mol% of ZnO, 0-40 mol% of CuO and 30mol% of TiO2，30mol%P2O5The glass is obtained after heat treatment and acid treatment. The methodThe prepared porous material has high specific surface area, open pore structure and multilevel pores, has photocatalytic performance and is expected to be used as an adsorption and photocatalytic material.

Description

Preparation method of porous microcrystalline glass containing titanium dihydrogen phosphate dihydrate and anatase crystalline phase and obtained product
Technical Field
The invention relates to a preparation method of porous microcrystalline glass containing titanium dihydrogen phosphate dihydrate and an anatase crystalline phase and an obtained product, belonging to the technical field of porous materials.
Background
The porous titanium phosphate material has excellent ion exchange performance, can be subjected to intercalation modification, and has potential application prospects in the fields of ion exchange, adsorption, catalysis and the like. At present, the porous titanium hydrogen phosphate material is mainly prepared by a wet chemical method and a hydrothermal method. Such as Ko ̋ ro ̈ si, using titanium isopropoxide and phosphoric acid as starting materials, the synthesized precursor is refluxed to a temperature of 90 deg.CoIn C dipropanol/water mixture, after refluxing for 144 hours, rectangular flaky titanium dihydrogen phosphate dihydrate (Ti) is finally synthesized2O3(H2PO4)2·2H2O) crystals. The anatase titanium dioxide photocatalyst is the most widely used photocatalytic material, has extremely strong oxidation-reduction capability and has a good degradation effect on most organic pollutants. The synthesis method of anatase titanium dioxide mainly comprises a sol-gel method, an alcoholysis method, a hydrothermal method, a high-temperature combustion synthesis method and the like. The main raw materials for synthesizing the material comprise titanium tetrachloride, tetrabutyl titanate, titanium isopropoxide and the like, and the price is high.
The titanium dioxide modified moderately by phosphate can improve the photocatalysis effect of the latter, for example, L.K ő r ö si and the like adopt isopropanol, titanium isopropoxide and phosphoric acid as raw materials, and a series of titanium dioxide (P-TiO) with different phosphate contents and high specific surface area is prepared by a sol-gel method2) And (3) sampling. Experiments show that the content of phosphate is P-TiO2The activity of the sample for degrading phenol by photocatalysis has obvious influence, and the P-TiO with lower phosphate content (the P/Ti molar ratio is less than 0.01) has obvious influence2The sample has higher phenol degradation rate than pure titanium dioxide.
The invention aims to prepare the porous material containing titanium phosphate and anatase crystalline phase by using cheap oxide raw materials, and is easy to carry out industrial large-scale production.
Disclosure of Invention
Aiming at the problems of large-scale production of the porous material containing titanium phosphate and anatase crystalline phase. The invention aims to provide titanium dihydrogen phosphate (Ti) containing dihydrate2O3(H2PO4)2·2H2O) and anatase type titanium dioxide(TiO2) A preparation method of porous microcrystalline glass with composite crystalline phase and an obtained product.
The method of the invention firstly adopts a high-temperature melting-water quenching method to obtain ZnO-CuO-TiO2-P2O5A glass of composition; crystallizing and heat treating the obtained glass to obtain microcrystalline glass; after the microcrystalline glass is treated by hot hydrochloric acid solution, titanium dihydrogen phosphate (Ti) containing dihydrate is obtained2O3(H2PO4)2·2H2O) and anatase type titanium dioxide (TiO)2) Porous glass ceramics with composite crystal phase.
The specific technical scheme of the invention is as follows:
crystalline phase (Ti) containing titanium dihydrogen phosphate dihydrate2O3(H2PO4)2·2H2O) and anatase type titanium dioxide (TiO)2) A method for preparing a crystalline phase porous glass ceramic, the method comprising the steps of:
(1) according to the weight percentage of 0-40 mol% ZnO, 0-40 mol% CuO and 30mol% TiO2，30mol%P2O5Weighing the raw materials according to the component content;
(2) uniformly mixing the raw materials, heating the uniformly mixed batch to a melting temperature, and keeping the temperature for a certain time to obtain a molten liquid for water quenching;
(3) drying the water-quenched sample for later use;
(4) preserving heat of the sample in the step (3) at 569-600 ℃, preserving heat at 670-693 ℃, performing two-section type heat treatment, and then cooling along with a furnace;
(5) immersing the sample in the step (4) in a hydrochloric acid solution for acid corrosion;
(6) and collecting a sample, and drying to obtain the porous glass ceramics.
Further, in the step (1), ZnO, CuO and TiO2Respectively provided by zinc oxide, copper oxide and titanium dioxide raw materials, P2O5Introduced from a phosphoric acid solution. In the formula, the total molar weight of all the components is 100%.
Further, in the step (2), zinc oxide, copper oxide and titanium dioxide powder are uniformly mixed, and then distilled water and phosphoric acid solution are added and uniformly mixed; adding distilled water in an amount based on that a stirring rod can freely stir the mixture; the mixture was heat-treated at 200 ℃ for 24 hours and then pulverized to obtain a batch.
Further, in the step (2), the batch materials are heated from room temperature to 600 ℃ at the heating rate of 10 ℃/min, then heated from 600 ℃ to 1100 ℃ at the heating rate of 5 ℃/min, then heated from 1100 ℃ to 1250 ℃ at the heating rate of 3 ℃/min, and kept at the melting temperature of 1250 ℃ for 1 hour, so that the batch materials are completely melted.
Further, in the step (4), the sample is heated to 569-600 ℃ and is subjected to heat preservation for 1 hour, and the first-stage heat preservation is carried out at the temperature; and after the first-stage heat preservation is finished, continuously raising the temperature, preserving the heat for 2 hours at 670-693 ℃, and carrying out second-stage heat preservation.
Further, in the step (5), the concentration of the hydrochloric acid solution is 3 mol/L; acid etching is carried out at 100 ℃ for 24 hours.
The crystal phase (Ti) containing the dihydrate titanium dihydrogen phosphate obtained by the invention2O3(H2PO4)2·2H2O) and anatase type titanium dioxide crystal phase (TiO)2) The mechanism of formation of the porous material of (a) is: firstly, all raw material components fully react in a high-temperature molten state, and a molten liquid is quenched into granules; the particles are subjected to two-stage heat preservation treatment to separate out copper titanium phosphate (CuTi)2(PO4)3) Zinc phosphate (Zn)3(PO4)2) Anatase type titanium dioxide (anatase TiO)2) And rutile titanium dioxide (rutile TiO)2) A crystalline phase; when the particles containing the crystal phases are treated in a hot hydrochloric acid solution, the corrosion speed and the corrosion degree of each crystal phase and components are different, and complex in-situ chemical reaction also occurs while corrosion is carried out, and finally, a crystal phase (Ti) containing titanium dihydrogen phosphate dihydrate is formed2O3(H2PO4)2·2H2O) and anatase type titanium dioxide crystal phase (TiO)2) The porous material of (1).
Further, the porous material obtained by the invention isAnd (4) granular. SEM test shows that the interior of the sample is composed of nano sheets, and the thickness of the nano sheets is about 10-150 nm; XRD analysis result shows that the porous microcrystalline glass has titanium dihydrogen phosphate dihydrate crystal phase (Ti)2O3(H2PO4)2·2H2O) (2 θ =8.78 °, 12.16 °, 17.13 °, 18.65 °, 27.05 °, 27.98 °, 33.22 °) and anatase type titanium dioxide crystal phase (TiO crystal phase)2). Wherein when the content of zinc oxide in the glass composition is less than or equal to the content of copper oxide, the dihydrate titanium dihydrogen phosphate crystal phase (Ti)2O3(H2PO4)2·2H2O) is the main crystal phase, anatase titanium dioxide crystal phase (TiO)2) Is a secondary crystalline phase. When the glass composition is free of zinc oxide, the base glass is devitrified and a copper titanium phosphate crystalline phase (CuTi) is precipitated2(PO4)3) Therefore, the glass composition not only has the main crystal phase of titanium dihydrogen phosphate dihydrate (Ti)2O3(H2PO4)2·2H2O), and also a secondary crystalline phase of anatase titanium dioxide (TiO)2) And a titanium copper phosphate crystalline phase (CuTi)2(PO4)3). Anatase titanium dioxide crystalline phase (TiO) when the zinc oxide content is greater than the copper oxide content in the glass composition2) Is a main crystal phase, a titanium dihydrogen phosphate dihydrate crystal phase (Ti)2O3(H2PO4)2·2H2O) is a secondary crystalline phase. The relative content of the crystal phase can be judged from the intensity of diffraction peaks in an XRD pattern.
Furthermore, the pores of the porous material mainly come from the gaps among the nano sheets, the nano sheets also have pores, and the pore diameter ranges from mesopores to macropores.
The preparation process of the porous material is easy to industrialize, and the obtained material has a high specific surface area, the pore diameter is distributed in the range from mesopores to macropores, and the material has the functions of adsorption and photocatalysis. Thus, the above process produces a crystalline phase (Ti) containing titanium dihydrogen phosphate dihydrate2O3(H2PO4)2·2H2O) and anatase type titanium dioxide crystal phase (TiO)2) Are also within the scope of the inventionWithin.
The invention prepares the porous material containing the crystalline phase of the dihydrate dihydrogen titanyl phosphate and the crystalline phase of the anatase titanium dioxide by the steps of melting, heat treatment and acid treatment, and is a good photocatalyst material. The method has the advantages of low price of the adopted raw materials, easily controlled production process, suitability for industrial application and popularization, and provides a new idea for the preparation of the porous titanium dioxide photocatalytic material.
Drawings
FIG. 1 is an XRD diffraction pattern of the samples obtained in examples 1-5.
FIG. 2 is a SEM photograph of a sample obtained in example 3.
FIG. 3 shows N in the sample obtained in example 32Adsorption isotherm curve.
Fig. 4 is a BJH pore size distribution curve of the sample obtained in example 3.
FIG. 5 is a graph showing the removal rate of the product of example 3 and P25 from a methylene blue solution in the application examples.
Detailed Description
The invention is further described with reference to the following drawings and detailed description, which are illustrative only and not limiting in nature.
Sample N was measured using a nitrogen isothermal adsorption apparatus (AutosorbiQ-C)2An isothermal adsorption curve, calculating specific surface area according to a BET model, obtaining a pore size distribution curve according to a BJH model, determining pore size according to curve peak point data, and determining pore volume from N2The adsorption curve is determined relative to the amount of adsorption at the maximum pressure.
Example 1
1. According to 40mol percent of CuO and 30mol percent of TiO2、30mol%P2O5Selecting the raw materials, CuO and TiO2The starting materials of (A) are the oxides themselves, P2O5The starting material of (2) was a phosphoric acid solution (85 wt%).
2. Uniformly mixing copper oxide and titanium dioxide powdery raw materials, adding a proper amount of distilled water and phosphoric acid solution, uniformly mixing, heating at 200 ℃ for 24 hours after uniform mixing, and crushing for later use to obtain a batch.
3. And (3) putting the batch in the step (2) into a crucible, heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min, then heating from 600 ℃ to 1100 ℃ at a heating rate of 5 ℃/min, finally heating from 1100 ℃ to 1250 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 h at the temperature to completely melt the batch, pouring the molten sample into cold water for quenching by water to obtain a granular sample, and then putting the sample into an oven, preserving heat for 12 h and keeping for later use at 100 ℃.
4. And (3) heating the sample to 600 ℃ at the heating rate of 5 ℃/min, preserving heat for 1 h, then heating to 672 ℃ from 600 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 3 mol/L hydrochloric acid at 100 ℃ for 24 hours, taking out the sample and drying the sample.
The obtained product contains titanium dihydrogen phosphate dihydrate crystal phase (Ti)2O3(H2PO4)2·2H2O) and anatase type titanium dioxide crystal phase (TiO)2) A small amount of a titanium copper phosphate crystal phase (CuTi)2(PO4)3) (see FIG. 1). Warp of N2The BET surface area of the product, determined by isothermal adsorption analysis, was 69 m2Per g, pore volume of 0.18 cm3The pore diameter is 2.04 nm.
Example 2
1. According to the proportion of 10mol ZnO, 30mol percent CuO and 30mol percent TiO2、30 mol% P2O5Selecting the raw materials of ZnO, CuO and TiO according to the molar composition2The starting materials of (A) are the oxides themselves, P2O5The starting material of (2) was a phosphoric acid solution (85 wt%).
2. Uniformly mixing zinc oxide, copper oxide and titanium dioxide powdery raw materials, adding a proper amount of distilled water and phosphoric acid solution, uniformly mixing, heating at 200 ℃ for 24 hours after uniform mixing, and crushing for later use to obtain a batch.
3. And (3) putting the batch in the step (2) into a crucible, heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min, then heating from 600 ℃ to 1100 ℃ at a heating rate of 5 ℃/min, finally heating from 1100 ℃ to 1250 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 h at the temperature to completely melt the batch, pouring the molten sample into cold water for quenching by water to obtain a granular sample, and then putting the sample into an oven, preserving heat for 12 h and keeping for later use at 100 ℃.
4. The sample is heated to 587 ℃ at the heating rate of 5 ℃/min and is kept warm for 1 h, and then is heated from 587 ℃ to 670 ℃ at the heating rate of 5 ℃/min and is kept warm for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 3 mol/L hydrochloric acid at 100 ℃ for 24 hours, taking out the sample and drying the sample.
The obtained product contains a main crystal phase of titanium dihydrogen phosphate dihydrate (Ti)2O3(H2PO4)2·2H2O) and a secondary crystalline phase of anatase titanium dioxide (TiO)2) The porous material of (1) (see fig. 1). Warp of N2The BET surface area of the product, determined by isothermal adsorption analysis, was 72 m2Per g, pore volume of 0.19 cm3The pore diameter is 1.99 nm.
Example 3
1. According to the proportion of 20mol% ZnO, 20mol% CuO and 30mol% TiO2、30 mol% P2O5Selecting the raw materials of ZnO, CuO and TiO according to the molar composition2The starting materials of (A) are the oxides themselves, P2O5The starting material of (2) was a phosphoric acid solution (85 wt%).
2. Uniformly mixing zinc oxide, copper oxide and titanium dioxide powdery raw materials, adding a proper amount of distilled water and phosphoric acid solution, uniformly mixing, heating at 200 ℃ for 24 hours after uniform mixing, and crushing for later use to obtain a batch.
3. And (3) putting the batch in the step (2) into a crucible, heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min, then heating from 600 ℃ to 1100 ℃ at a heating rate of 5 ℃/min, finally heating from 1100 ℃ to 1250 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 h at the temperature to completely melt the batch, pouring the molten sample into cold water for quenching by water to obtain a granular sample, and then putting the sample into an oven, preserving heat for 12 h and keeping for later use at 100 ℃.
4. The sample is heated to 574 ℃ at the heating rate of 5 ℃/min and is kept warm for 1 h, and then is heated from 574 ℃ to 673 ℃ at the heating rate of 5 ℃/min and is kept warm for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 3 mol/L hydrochloric acid at 100 ℃ for 24 hours, taking out the sample and drying the sample.
The obtained product contains titanium dihydrogen phosphate dihydrate crystal phase (Ti)2O3(H2PO4)2·2H2O) and anatase type titanium dioxide crystal phase (TiO)2) The porous material of (1). Wherein the main crystal phase is titanium dihydrogen phosphate dihydrate (Ti)2O3(H2PO4)2·2H2O), the secondary crystal phase is anatase type titanium dioxide (TiO)2) (see FIG. 1). SEM analysis of the product, as shown in figure 2, shows that: the product is composed of nano sheets, and macropores exist between the nano sheets. Subjecting the product to N2Isothermal adsorption analysis, product N2The adsorption isotherms and BJH pore size distribution curves are shown in fig. 3 and 4. The BET surface area of this product is 59 m2Per g, pore volume of 0.19 cm3The pore diameter is 1.99 nm.
Example 4
1. According to the proportion of 30mol% ZnO, 10 mol% CuO and 30mol% TiO2、30 mol% P2O5Selecting the raw materials of ZnO, CuO and TiO according to the molar composition2The starting materials of (A) are the oxides themselves, P2O5The starting material of (2) was a phosphoric acid solution (85 wt%).
2. Uniformly mixing zinc oxide, copper oxide and titanium dioxide powdery raw materials, adding a proper amount of distilled water and phosphoric acid solution, uniformly mixing, heating at 200 ℃ for 24 hours after uniform mixing, and crushing for later use to obtain a batch.
3. And (3) putting the batch in the step (2) into a crucible, heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min, then heating from 600 ℃ to 1100 ℃ at a heating rate of 5 ℃/min, finally heating from 1100 ℃ to 1250 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 h at the temperature to completely melt the batch, pouring the molten sample into cold water for quenching by water to obtain a granular sample, and then putting the sample into an oven, preserving heat for 12 h and keeping for later use at 100 ℃.
4. The sample is heated to 569 ℃ at the heating rate of 5 ℃/min and is kept warm for 1 h, and then is heated from 569 ℃ to 679 ℃ at the heating rate of 5 ℃/min and is kept warm for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 3 mol/L hydrochloric acid at 100 ℃ for 24 hours, taking out the sample and drying the sample.
The obtained product contains titanium dihydrogen phosphate dihydrate crystal phase (Ti)2O3(H2PO4)2·2H2O) and anatase type titanium dioxide crystal phase (TiO)2) The porous material of (1). As can be seen from FIG. 1, anatase type titanium dioxide (TiO)2) Main crystal phase, titanium dihydrogen phosphate dihydrate (Ti)2O3(H2PO4)2·2H2O) is a secondary crystalline phase. Warp of N2The BET surface area of the product, determined by isothermal adsorption analysis, was 55 m2Per g, pore volume of 0.22 cm3The pore diameter is 2.04 nm.
Example 5
1. According to 40mol ZnO, 30mol% TiO2、30 mol% P2O5Selecting raw materials, ZnO and TiO2The starting materials of (A) are the oxides themselves, P2O5The starting material of (2) was a phosphoric acid solution (85 wt%).
2. Uniformly mixing zinc oxide and titanium dioxide powdery raw materials, adding a proper amount of distilled water and phosphoric acid solution, uniformly mixing, heating at 200 ℃ for 24 hours after uniform mixing, and crushing for later use to obtain a batch.
3. And (3) putting the batch in the step (2) into a crucible, heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min, then heating from 600 ℃ to 1100 ℃ at a heating rate of 5 ℃/min, finally heating from 1100 ℃ to 1250 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 h at the temperature to completely melt the batch, pouring the molten sample into cold water for quenching by water to obtain a granular sample, and then putting the sample into an oven, preserving heat for 12 h and keeping for later use at 100 ℃.
4. The temperature of the sample is increased to 570 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 1 h, then the temperature is increased from 570 ℃ to 693 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 3 mol/L hydrochloric acid at 100 ℃ for 24 hours, taking out the sample and drying the sample.
The obtained product contains titanium dihydrogen phosphate dihydrate crystal phase (Ti)2O3(H2PO4)2·2H2O) and anatase type titanium dioxide crystal phase (TiO)2) The porous material of (1) (see fig. 1).
Application example
In order to verify the performance of the porous material containing a crystalline phase of titanium dihydrogen phosphate dihydrate and a crystalline phase of anatase titanium dioxide, the following experiment was conducted by selecting the prepared sample to adsorb and photocatalytically degrade an organic dye methylene blue solution. And (3) measuring the absorbances of the porous material before and after the absorption and photocatalytic degradation of the methylene blue solution at the 665 nm wavelength by using a spectrophotometer, and calculating the concentration of the methylene blue in the solution according to a standard curve. The experimental procedure was as follows:
300mg of the product prepared in example 3 (ground by a standard sieve of 18-120 meshes) and commercially available P25 were put into 100mL of methylene blue solution with a concentration of 10mg/L respectively, and stirred and adsorbed in the dark when the time for adding the product was 0 hour, and after the adsorption equilibrium was reached, an ultraviolet lamp (30W) was turned on for irradiation, and the methylene blue in the solution was degraded by magnetic stirring. The adsorption efficiency of the sample on methylene blue in the methylene blue solution is shown as the formula At=(C0−Ct)/C0X 100%, the adsorption and photocatalytic total dye removal rate is calculated according to the formula = ((C)0−Ct)/C0X 100% calculation. In the formula, AtFor the adsorption efficiency at time t, C0Concentration of the original solution, CtIs the concentration of the solution at time t.
As shown in FIG. 5, the adsorption equilibrium of the product of example 3 and the methylene blue solution in P25 was reached with the adsorption rates of 39% and 12% respectively when the solution was stirred in the dark for 3 hours; the product of example 3 and methylene blue solution in P25 are both close to clear solution after being stirred for 7 hours under the irradiation of an ultraviolet lamp, and the total removal rate of adsorption and photocatalysis reaches 97%, which shows that the porous material prepared by the invention has better adsorption and photocatalysis performance.

Claims (9)

1. A preparation method of porous glass ceramics containing a crystalline phase of titanium dihydrogen phosphate dihydrate and a crystalline phase of anatase titanium dioxide is characterized by comprising the following steps:
(1) according to the weight percentage of 0-40 mol% ZnO, 0-40 mol% CuO and 30mol% TiO2，30mol%P2O5Weighing the raw materials according to the component content;
(2) uniformly mixing the raw materials, heating the uniformly mixed batch to a melting temperature, and keeping the temperature for a certain time to obtain a molten liquid for water quenching;
(3) drying the water-quenched sample for later use;
(4) preserving heat of the sample in the step (3) at 569-600 ℃, preserving heat at 670-693 ℃, performing two-section type heat treatment, and then cooling along with a furnace;
(5) immersing the sample obtained in the step (4) in hydrochloric acid for acid corrosion;
(6) and collecting a sample, and drying to obtain the porous glass ceramics.
2. The method of claim 1, wherein: ZnO, CuO, TiO2The component is introduced by zinc oxide, copper oxide and titanium oxide, P2O5The components are introduced from a phosphoric acid solution.
3. The method of claim 1, wherein: in the step (2), zinc oxide, copper oxide and titanium oxide powder are uniformly mixed; then adding distilled water and phosphoric acid solution, and uniformly mixing, wherein the amount of the added distilled water is based on the condition that a stirring rod can freely stir the mixture; after being uniformly mixed, the mixture is heated and treated for 24 hours at the temperature of 200 ℃ and then is crushed to obtain the batch.
4. The method of claim 1, wherein: in the step (2), during temperature rise, the temperature is raised from room temperature to 600 ℃ at the temperature rise rate of 10 ℃/min, then is raised from 600 ℃ to 1100 ℃ at the temperature rise rate of 5 ℃/min, then is raised from 1100 ℃ to 1250 ℃ at the temperature rise rate of 3 ℃/min, and is kept at the melting temperature of 1250 ℃ for 1 hour, so that the batch is completely melted.
5. The method of claim 1, wherein: in the step (4), the sample is heated to 569-600 ℃ for heat preservation, and the first stage of heat preservation is carried out at the temperature; and (4) after the first-stage heat preservation is finished, continuously raising the temperature, preserving the heat at 670-693 ℃, and carrying out second-stage heat preservation at the temperature.
6. The method of claim 1, wherein: in the step (4), the sample is subjected to heat preservation for 1 hour at 569-600 ℃ and heat preservation for 2 hours at 670-693 ℃.
7. The method of claim 1, wherein: in the step (5), the concentration of the hydrochloric acid is 3 mol/L, the temperature during corrosion is 100 ℃, and the time is 24 hours.
8. A porous material obtained by the production method according to any one of claims 1 to 7, characterized in that: the porous material is composed of nano-sheets and contains titanium dihydrogen phosphate dihydrate (Ti)2O3(H2PO4)2·2H2O) and anatase titanium dioxide crystalline phases.
9. The titanium dihydrogen phosphate dihydrate-containing crystalline phase (Ti) as set forth in claim 82O3(H2PO4)2·2H2O) and anatase titanium dioxide crystal phase as an adsorbent or a photocatalyst.
CN202010012067.2A 2020-01-07 2020-01-07 Preparation method of porous microcrystalline glass containing titanium dihydrogen phosphate dihydrate and anatase crystalline phase and obtained product Pending CN111099691A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109046407A (en) * 2018-08-15 2018-12-21 济南大学 One kind TiO containing Detitanium-ore-type2The preparation method and products obtained therefrom of the porous material of crystal phase and application
CN109336075A (en) * 2018-08-15 2019-02-15 济南大学 The preparation method and products obtained therefrom of POROUS TITANIUM hydrogen orthophosphate material and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109046407A (en) * 2018-08-15 2018-12-21 济南大学 One kind TiO containing Detitanium-ore-type2The preparation method and products obtained therefrom of the porous material of crystal phase and application
CN109336075A (en) * 2018-08-15 2019-02-15 济南大学 The preparation method and products obtained therefrom of POROUS TITANIUM hydrogen orthophosphate material and application

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