CN117164004A - Preparation method of rutile phase nano titanium dioxide with controllable particle size - Google Patents
Preparation method of rutile phase nano titanium dioxide with controllable particle size Download PDFInfo
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- CN117164004A CN117164004A CN202311046674.0A CN202311046674A CN117164004A CN 117164004 A CN117164004 A CN 117164004A CN 202311046674 A CN202311046674 A CN 202311046674A CN 117164004 A CN117164004 A CN 117164004A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002245 particle Substances 0.000 title claims abstract description 41
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 143
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000843 powder Substances 0.000 claims abstract description 72
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000008367 deionised water Substances 0.000 claims abstract description 50
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 50
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 40
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 35
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 33
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 79
- 238000005406 washing Methods 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 24
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 abstract description 26
- 239000011265 semifinished product Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 9
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 19
- 239000013078 crystal Substances 0.000 description 13
- 239000012467 final product Substances 0.000 description 13
- 239000004408 titanium dioxide Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000007619 statistical method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application discloses a preparation method of rutile phase nano titanium dioxide with controllable particle size, which comprises the steps of constructing a water bath reaction environment by utilizing a mixed solution of absolute ethyl alcohol and ultra-dry acetonitrile, adding benzoic acid, enabling the benzoic acid to react with tetrabutyl titanate in the reaction environment, controlling the hydrolysis process of the tetrabutyl titanate, adding a proper amount of hydrolysis sites into a formed tetrabutyl titanate-benzoic acid complex by preparing a mixed solution containing deionized water, then treating a precipitate, grinding the precipitate into semi-finished product powder, and finally carrying out microwave hydrothermal reaction on the semi-finished product powder and the anhydrous oxalic acid to finally obtain the rutile phase nano titanium dioxide with controllable particle size. The preparation method of the rutile phase nano titanium dioxide with the controllable particle size effectively avoids the high-temperature and long-time reaction required by the traditional high-temperature calcination, and has the advantages of simple steps, convenient operation, relatively low cost of used materials, safe and controllable process, cleanness and environmental protection.
Description
Technical Field
The application belongs to the technical field of nano material preparation, and particularly relates to a preparation method of rutile phase nano titanium dioxide with controllable particle size.
Background
Multilayer ceramic capacitors (MLCCs) are among the most widely used and rapidly developed chip components in the world, and have the characteristics of wide capacity range, good frequency characteristics, small loss of operating voltage and operating temperature range, and ultra-small volume. With the development of various electronic industries such as computers, network devices, 5G mobile phones, new energy automobiles and the like and the miniaturization trend of the devices, MLCCs become the first choice capacitor types of the electronic industries, and the market demand and the use amount are continuously increasing, so that the MLCCs are also called as "pillars of the electronic ceramic industry". With the development of new electronic components toward chip, miniaturization, high frequency, broadband, high precision, integration and environmental protection, the MLCC technology is continuously and rapidly developed, and high-end MLCCs with high capacity, ultra-small volume, high frequency and high temperature, high withstand voltage and higher reliability are always pursued in the electronic industry. One of the important points to be studied in order to achieve these performance requirements is titanium dioxide (TiO 2 ) A material.
TiO 2 Is an important raw material for synthesizing barium titanate powder by a solid phase method or a hydrothermal method, the particle size of the barium titanate powder is directly proportional to the particle size of titanium dioxide and inversely proportional to the specific surface area of the titanium dioxide, so that how to control TiO 2 Is to solve the problem of BaTiO 3 Powder homogeneity and dispersibility. BaTiO 3 Is an inorganic ferroelectric material with high dielectric property, low dielectric loss, good dielectric adjustability and medium breakdown field strength (BDS). Research shows that BaTiO 3 The grain size of the barium titanate is increased along with the increase of the relative dielectric constant of the dielectric layer and the number of dielectric layers, and the increase of the number of dielectric layers and the reduction of the thickness of the dielectric layer are both dependent on smallBaTiO of particle size 3 And (3) powder. Thus TiO 2 The particle size of the powder has a decisive influence on the performance of the MLCC product.
The rutile phase titanium dioxide has excellent heat resistance, thermal stability and chemical stability, and can be widely applied to the fields of paint, cosmetics, ceramics and the like. The preparation method mainly comprises a liquid phase method, a solid phase method and a gas phase method. The solid phase method and the gas phase method consume more energy, the purity of the product is lower, and the shape and the size of the product cannot be accurately controlled, so that the industrial production is difficult; the liquid phase method comprises a sol-gel method, a hydrothermal method, a liquid phase precipitation method and a microemulsion method, however, when the preparation is carried out by the liquid phase method, the titanium precursor is too fast in hydrolysis rate, so that the uniform rutile phase titanium dioxide powder with high sphericity is difficult to prepare in high yield, the conventional preparation scheme needs to be subjected to high-temperature calcination, and the energy consumption is too high. Accordingly, there is a need to develop a suitable process for preparing highly uniform and highly dispersed rutile titanium dioxide powders.
Disclosure of Invention
The technical problem to be solved by the application is to provide a preparation method of the rutile phase nano titanium dioxide with controllable particle size, which solves the defects of non-uniform particle size, difficult particle size regulation, easy agglomeration and the like of the nano rutile titanium dioxide powder.
The technical scheme for solving the technical problems is as follows:
a preparation method of rutile phase nano titanium dioxide with controllable particle size comprises the following steps:
s1, putting absolute ethyl alcohol and ultra-dry acetonitrile into a reaction vessel for mixing, and after complete mixing, slowly dripping benzoic acid into the mixed solution in a stirring environment of 500r/min for water bath reaction until the benzoic acid is completely dispersed in the mixed solution to obtain a system A;
s2, continuously taking tetrabutyl titanate and slowly dripping the tetrabutyl titanate into the system A in a stirring environment of 500r/min to perform water bath reaction until the mixed solution is light yellow to obtain a system B;
s3, firstly, putting absolute ethyl alcohol and ultra-dry acetonitrile into a reaction vessel for mixing, and dripping deionized water into the mixed solution in a stirring environment of 500r/min for water bath reaction after complete mixing to obtain a system C;
s4, continuously pouring the system C into the system B rapidly in a stirring environment of 500r/min for water bath reaction to obtain a system D;
s5, washing and precipitating the system D, drying, and grinding the dried product until the product has fine sense to obtain semi-finished powder;
s6, pouring the semi-finished powder into deionized water for stirring until the semi-finished powder is completely dispersed in water, then adding anhydrous oxalic acid for carrying out microwave hydrothermal reaction, and obtaining a reaction solution after the reaction is finished;
s7, sequentially carrying out ultrasonic treatment, washing, centrifugation and drying treatment on the reaction liquid to obtain uniform rutile phase nano titanium dioxide;
the volume ratio of the absolute ethyl alcohol to the ultra-dry acetonitrile solution in the step S1 to the volume ratio of the absolute ethyl alcohol to the ultra-dry acetonitrile solution in the step S3 is 1:4, and the addition ratio of the absolute ethyl alcohol to the ultra-dry acetonitrile is 1:1;
wherein the molar ratio of the benzoic acid to the tetrabutyl titanate is 0.05-0.5:1.
Preferably, the molar ratio of the benzoic acid to the tetrabutyl titanate is 0.15-0.4:1.
Specifically, the volume ratio of the addition amount of tetrabutyl titanate to the total addition amount of the absolute ethyl alcohol and the ultra-dry acetonitrile is 1:50.
Preferably, in the step S1, the stirring time is at least 30min, and the reaction temperature of the water bath reaction is 25-35 ℃.
Preferably, in the step S2, the stirring time is at least 1h, and the reaction temperature of the water bath reaction is 25-35 ℃.
Specifically, in the step S3, the volume ratio of the added amount of water to the added amount of the absolute ethyl alcohol and the ultra-dry acetonitrile is 1-20:200; the stirring time is at least 30min, and the water bath temperature is 25-35 ℃.
Preferably, in the step S4, the stirring time is at least 2 hours, and the reaction temperature of the water bath reaction is 25-35 ℃.
Specifically, in the step S6, the mass ratio of the semi-finished powder to the anhydrous oxalic acid is 5-15:1-3; the volume of the deionized water is 25-50 mL; the reaction time of the microwave hydrothermal reaction is 20min, and the reaction temperature is 160-220 ℃.
Preferably, in the step S5, the washing includes a deionized water washing and an absolute ethanol washing, wherein the deionized water washing is performed for 1 time, and the absolute ethanol washing is performed for two times; the drying is carried out by adopting a vacuum drying oven, the drying temperature is 60 ℃, and the drying time is 8 hours.
The application has the following beneficial effects: the acetonitrile is adopted to ensure the reliable reaction environment of titanium dioxide dispersion, the benzoic acid is utilized to realize the formation of amorphous titanium dioxide and the regulation and control of the particle size of the titanium dioxide in extremely short induction time, and finally the microwave hydrothermal mode is adopted to solidify the titanium dioxide to form stable and uniform rutile phase nano titanium dioxide, so that the high-temperature and long-time reaction required by the traditional high-temperature calcination is effectively avoided, the whole scheme has the advantages of simple steps, convenient operation and control, relatively low cost of used materials, safe and controllable process, cleanness and environmental protection.
Drawings
FIG. 1 is an electron microscope image of the semi-finished powder (left) and the final product (right) of example 1 of the present application.
FIG. 2 shows XRD diffraction patterns of the semi-finished powder (a) and the final product (b) in example 1 of the present application.
FIG. 3 is an electron microscope image of the semi-finished powder (left) and the final product (right) of example 2 of the present application.
FIG. 4 is an electron microscope photograph of the final product of comparative example 1 of the present application.
Fig. 5 is an electron microscope photograph of the final product of comparative example 2 of the present application.
Detailed Description
The present application will be described in detail with reference to the accompanying drawings.
The preparation method of the rutile phase nano titanium dioxide with the controllable particle size in the embodiment 1 of the application comprises the following steps:
s1, adding 20mL of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent and the molecular weight of 46.07 and 20mL of ultra-dry acetonitrile with the molecular weight of 41.05 into a reaction vessel-a beaker for mixing, after complete mixing, slowly dripping 0.287g of benzoic acid with the purity of 99.5 percent and the molecular weight of 122.12 into the mixed solution for carrying out water bath reaction, wherein the water bath reaction is carried out by placing the beaker into a water bath kettle, the water bath temperature is 25 ℃, the stirring environment of 500r/min is continuously maintained in the process of carrying out, and the stirring time is at least 30min until the benzoic acid is completely dispersed in the mixed solution, thus obtaining a system A.
S2, continuously taking tetrabutyl titanate (C) with the purity of 99.0 percent and the molecular weight of 340.32 by a liquid-transfering gun in a stirring environment of 500r/min 16 H 36 O 4 Ti) 4mL is slowly dripped into the system A for water bath reaction, wherein the water bath temperature is kept at 25 ℃ in the step, and stirring is continued for 30 minutes, so that benzoic acid and tetrabutyl titanate fully react until the mixed solution is light yellow, and a system B is obtained; in the step, the hydrolysis rate of tetrabutyl titanate can be effectively controlled due to the reaction process of benzoic acid and tetrabutyl titanate, so that the uniformity of particles after the reaction is finished is ensured.
S3, firstly, 80mL of absolute ethyl alcohol and 80mL of ultra-dry acetonitrile are put into another beaker to be mixed, 1mL of deionized water is dripped into the mixed solution to carry out water bath reaction in a stirring environment of 500r/min after complete mixing, the water bath temperature is 25 ℃, and the stirring time is 30 minutes, so that water is uniformly distributed in the mixed solution, and a system C is obtained;
s4, continuously pouring the system C into the system B rapidly in a stirring environment of 500r/min for water bath reaction, wherein the water bath temperature is 25 ℃, and the stirring time is 2h, so as to obtain a system D;
s5, washing and precipitating the system D, drying, and grinding the dried product until the product has fine sense to obtain semi-finished powder; preferably, the washing comprises deionized water washing and absolute ethyl alcohol washing, wherein the washing is that the system D is firstly washed 1 time by deionized water, then is washed twice by absolute ethyl alcohol, and then is left to stand for precipitation to obtain white precipitate; and (3) introducing the precipitate into a clean crucible, drying in a vacuum drying oven at 60 ℃ for 8 hours, and grinding the precipitate with a grinder until the precipitate is ground into fine powder, namely the semi-finished product powder.
S6, pouring the semi-finished powder into deionized water for stirring until the semi-finished powder is completely dispersed in water, then adding anhydrous oxalic acid for carrying out microwave hydrothermal reaction, and obtaining a reaction solution after the reaction is finished; specifically, 40mL of deionized water was poured into a microwave hydrothermal reaction vessel, followed by weighing 1.0g of a semi-finished powder and 0.1g of anhydrous oxalic acid (C) having a purity of 99.0% and a molecular weight of 90.03 2 H 2 O 4 ) Respectively pouring the mixture into a microwave hydrothermal reaction kettle, stirring the liquid in the reaction kettle until the semi-finished powder and the anhydrous oxalic acid are uniformly dispersed in deionized water, then starting a microwave hydrothermal reaction instrument to perform microwave hydrothermal reaction, setting the reaction temperature to 190 ℃, and obtaining the reaction liquid after the reaction is finished for 20 minutes.
And S7, sequentially carrying out ultrasonic treatment, washing, centrifugation and drying treatment on the reaction liquid to obtain the uniform rutile phase nano titanium dioxide.
The semi-finished powder and the final product in this example were subjected to scanning electron microscopy imaging and XRD analysis to obtain an electron micrograph as shown in FIG. 1 and an XRD diffraction pattern as shown in FIG. 2, and the particle condition in the obtained electron micrograph was specifically analyzed by counting the particle sizes of 100-200 particles in the image, calculating the average value, and analyzing the change condition of the crystal form of the obtained powder after microwave hydrothermal reaction by the XRD diffraction pattern. The average grain diameter of the semi-finished product powder is 434.66nm after statistical analysis, and the crystal form is amorphous; the average grain diameter of the final product after the microwave hydrothermal reaction is 204.92nm, and the crystal form is rutile, which belongs to the rutile phase nano titanium dioxide to be obtained by the application.
The preparation method of the rutile phase nano titanium dioxide with the controllable particle size in the embodiment 2 of the application comprises the following steps:
s1, adding 20mL of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent and the molecular weight of 46.07 and 20mL of ultra-dry acetonitrile with the molecular weight of 41.05 into a reaction vessel-a beaker for mixing, after complete mixing, slowly dripping 0.287g of benzoic acid with the purity of 99.5 percent and the molecular weight of 122.12 into the mixed solution for carrying out water bath reaction, wherein the water bath reaction is carried out by placing the beaker into a water bath kettle, the water bath temperature is 25 ℃, the stirring environment of 500r/min is continuously maintained in the process of carrying out, and the stirring time is at least 30min until the benzoic acid is completely dispersed in the mixed solution, thus obtaining a system A.
S2, continuously taking tetrabutyl titanate (C) with the purity of 99.0 percent and the molecular weight of 340.32 by a liquid-transfering gun in a stirring environment of 500r/min 16 H 36 O 4 Ti) 4mL is slowly dripped into the system A for water bath reaction, wherein the water bath temperature is kept at 25 ℃ in the step, and stirring is continued for 30 minutes, so that benzoic acid and tetrabutyl titanate fully react until the mixed solution is light yellow, and the system B is obtained.
S3, firstly, 80mL of absolute ethyl alcohol and 80mL of ultra-dry acetonitrile are put into another beaker to be mixed, 1mL of deionized water is dripped into the mixed solution to carry out water bath reaction in a stirring environment of 500r/min after complete mixing, the water bath temperature is 25 ℃, and the stirring time is 30 minutes, so that water is uniformly distributed in the mixed solution, and a system C is obtained;
s4, continuously pouring the system C into the system B rapidly in a stirring environment of 500r/min for water bath reaction, wherein the water bath temperature is 25 ℃, and the stirring time is 2h, so as to obtain a system D;
s5, washing and precipitating the system D, drying, and grinding the dried product until the product has fine sense to obtain semi-finished powder; preferably, the washing comprises deionized water washing and absolute ethyl alcohol washing, wherein the washing is that the system D is firstly washed 1 time by deionized water, then is washed twice by absolute ethyl alcohol, and then is left to stand for precipitation to obtain white precipitate; and (3) introducing the precipitate into a clean crucible, drying in a vacuum drying oven at 60 ℃ for 8 hours, and grinding the precipitate with a grinder until the precipitate is ground into fine powder, namely the semi-finished product powder.
S6, pouring the semi-finished powder into deionized water for stirring until the semi-finished powder is completely dispersed in water, then adding anhydrous oxalic acid for carrying out microwave hydrothermal reaction, and obtaining a reaction solution after the reaction is finished; specifically, 50mL of deionized water was poured into a microwave hydrothermal reaction vessel, followed by weighing 1.5g of a semi-finished powder and 0.1g of anhydrous oxalic acid (C) having a purity of 99.0% and a molecular weight of 90.03 2 H 2 O 4 ) Respectively pouring the mixture into a microwave hydrothermal reaction kettle, stirring the liquid in the reaction kettle until the semi-finished powder and the anhydrous oxalic acid are uniformly dispersed in deionized water, then starting a microwave hydrothermal reaction instrument to perform microwave hydrothermal reaction, setting the reaction temperature to 190 ℃, and obtaining the reaction liquid after the reaction is finished for 20 minutes.
And S7, sequentially carrying out ultrasonic treatment, washing, centrifugation and drying treatment on the reaction liquid to obtain the uniform rutile phase nano titanium dioxide.
Scanning electron microscope imaging is carried out on the semi-finished product powder and the final product in the embodiment to obtain an electron microscope photo shown in figure 3, and the average particle size of the semi-finished product powder is 421.32nm after statistical analysis, and the crystal form is amorphous; the average grain diameter of the final product after the microwave hydrothermal reaction is 252.52nm, and the crystal form is rutile, which belongs to the rutile phase nano titanium dioxide to be obtained by the application.
The preparation method of the rutile phase nano titanium dioxide with the controllable particle size in the embodiment 3 of the application comprises the following steps:
s1, taking 20mL of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent and the molecular weight of 46.07, and 20mL of ultra-dry acetonitrile with the molecular weight of 41.05, putting into a reaction vessel-a beaker, mixing, then, in a stirring environment of 500r/min, taking 0.4305g of benzoic acid with the purity of 99.5 percent and the molecular weight of 122.12, slowly dripping into the mixed solution, and carrying out water bath reaction, wherein the water bath reaction is carried out by placing the beaker into a water bath kettle, the water bath temperature is 25 ℃, the stirring environment of 500r/min is continuously maintained in the process, and the stirring time is at least 30min until the benzoic acid is completely dispersed in the mixed solution, thus obtaining a system A.
S2, continuously taking tetrabutyl titanate (C) with the purity of 99.0 percent and the molecular weight of 340.32 by a liquid-transfering gun in a stirring environment of 500r/min 16 H 36 O 4 Ti) 4mL is slowly dripped into the system A for water bath reaction, wherein the water bath temperature is kept at 25 ℃ in the step, and stirring is continued for 30 minutes, so that benzoic acid and tetrabutyl titanate fully react until the mixed solution is light yellow, and the system B is obtained.
S3, firstly, 80mL of absolute ethyl alcohol and 80mL of ultra-dry acetonitrile are put into another beaker to be mixed, 5mL of deionized water is dripped into the mixed solution to carry out water bath reaction in a stirring environment of 500r/min after complete mixing, the water bath temperature is 25 ℃, the stirring time is 30 minutes, and water is uniformly distributed in the mixed solution to obtain a system C.
S4, continuously pouring the system C into the system B rapidly in a stirring environment of 500r/min for water bath reaction, wherein the water bath temperature is 25 ℃, and the stirring time is 2h, so as to obtain a system D;
s5, washing and precipitating the system D, drying, and grinding the dried product until the product has fine sense to obtain semi-finished powder; preferably, the washing comprises deionized water washing and absolute ethyl alcohol washing, wherein the washing is that the system D is firstly washed 1 time by deionized water, then is washed twice by absolute ethyl alcohol, and then is left to stand for precipitation to obtain white precipitate; and (3) introducing the precipitate into a clean crucible, drying in a vacuum drying oven at 60 ℃ for 8 hours, and grinding the precipitate with a grinder until the precipitate is ground into fine powder, namely the semi-finished product powder.
S6, pouring the semi-finished powder into deionized water for stirring until the semi-finished powder is completely dispersed in water, then adding anhydrous oxalic acid for carrying out microwave hydrothermal reaction, and obtaining a reaction solution after the reaction is finished; specifically, 40mL of deionized water was poured into a microwave hydrothermal reaction vessel, followed by weighing 1.0g of a semi-finished powder and 0.1g of anhydrous oxalic acid (C) having a purity of 99.0% and a molecular weight of 90.03 2 H 2 O 4 ) Respectively pouring into a microwave hydrothermal reaction kettleStirring the liquid in the reaction kettle until the semi-finished powder and the anhydrous oxalic acid are uniformly dispersed in deionized water, then starting a microwave hydrothermal reaction instrument to carry out microwave hydrothermal reaction, setting the reaction temperature to 190 ℃, and obtaining the reaction liquid after the reaction is finished, wherein the reaction time is 20 min.
And S7, sequentially carrying out ultrasonic treatment, washing, centrifugation and drying treatment on the reaction liquid to obtain the uniform rutile phase nano titanium dioxide.
The average grain diameter of the semi-finished product powder is 372.72nm after statistical analysis, and the crystal form is amorphous; the average grain diameter of the final product after the microwave hydrothermal reaction is 287.60nm, and the crystal form is rutile, which belongs to the rutile phase nano titanium dioxide to be obtained by the application.
The preparation method of the rutile phase nano titanium dioxide with the controllable particle size in the embodiment 4 of the application comprises the following steps:
s1, adding 20mL of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent and the molecular weight of 46.07 and 20mL of ultra-dry acetonitrile with the molecular weight of 41.05 into a reaction vessel-a beaker for mixing, after complete mixing, slowly dripping 0.287g of benzoic acid with the purity of 99.5 percent and the molecular weight of 122.12 into the mixed solution for carrying out water bath reaction, wherein the water bath reaction is carried out by placing the beaker into a water bath kettle, the water bath temperature is 25 ℃, the stirring environment of 500r/min is continuously maintained in the process of carrying out, and the stirring time is at least 30min until the benzoic acid is completely dispersed in the mixed solution, thus obtaining a system A.
S2, continuously taking tetrabutyl titanate (C) with the purity of 99.0 percent and the molecular weight of 340.32 by a liquid-transfering gun in a stirring environment of 500r/min 16 H 36 O 4 Ti) 4mL is slowly dripped into the system A for water bath reaction, wherein the water bath temperature is kept at 25 ℃ in the step, and stirring is continued for 30 minutes, so that benzoic acid and tetrabutyl titanate fully react until the mixed solution is light yellow, and the system B is obtained.
S3, firstly, 80mL of absolute ethyl alcohol and 80mL of ultra-dry acetonitrile are put into another beaker to be mixed, 5mL of deionized water is dripped into the mixed solution to carry out water bath reaction in a stirring environment of 500r/min after complete mixing, the water bath temperature is 25 ℃, the stirring time is 30 minutes, and water is uniformly distributed in the mixed solution to obtain a system C.
S4, continuously pouring the system C into the system B rapidly in a stirring environment of 500r/min to perform water bath reaction, wherein the water bath temperature is 25 ℃, and the stirring time is 2h, so as to obtain the system D.
S5, washing and precipitating the system D, drying, and grinding the dried product until the product has fine sense to obtain semi-finished powder; preferably, the washing comprises deionized water washing and absolute ethyl alcohol washing, wherein the washing is that the system D is firstly washed 1 time by deionized water, then is washed twice by absolute ethyl alcohol, and then is left to stand for precipitation to obtain white precipitate; and (3) introducing the precipitate into a clean crucible, drying in a vacuum drying oven at 60 ℃ for 8 hours, and grinding the precipitate with a grinder until the precipitate is ground into fine powder, namely the semi-finished product powder.
S6, pouring the semi-finished powder into deionized water for stirring until the semi-finished powder is completely dispersed in water, then adding anhydrous oxalic acid for carrying out microwave hydrothermal reaction, and obtaining a reaction solution after the reaction is finished; specifically, 40mL of deionized water was poured into a microwave hydrothermal reaction vessel, followed by weighing 1.0g of a semi-finished powder and 0.1g of anhydrous oxalic acid (C) having a purity of 99.0% and a molecular weight of 90.03 2 H 2 O 4 ) Respectively pouring the mixture into a microwave hydrothermal reaction kettle, stirring the liquid in the reaction kettle until the semi-finished powder and the anhydrous oxalic acid are uniformly dispersed in deionized water, then starting a microwave hydrothermal reaction instrument to perform microwave hydrothermal reaction, setting the reaction temperature to 190 ℃, and obtaining the reaction liquid after the reaction is finished for 20 minutes.
And S7, sequentially carrying out ultrasonic treatment, washing, centrifugation and drying treatment on the reaction liquid to obtain the uniform rutile phase nano titanium dioxide.
The average grain diameter of the semi-finished product powder is 368.93nm after statistical analysis, and the crystal form is amorphous; the average grain diameter of the final product after the microwave hydrothermal reaction is 237.07nm, and the crystal form is rutile, which belongs to the rutile phase nano titanium dioxide to be obtained by the application.
The preparation method of the rutile phase nano titanium dioxide with the controllable particle size in the embodiment 5 of the application comprises the following steps:
s1, taking 20mL of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent and the molecular weight of 46.07, and 20mL of ultra-dry acetonitrile with the molecular weight of 41.05, putting into a reaction vessel-a beaker, mixing, then, in a stirring environment of 500r/min, taking 0.4305g of benzoic acid with the purity of 99.5 percent and the molecular weight of 122.12, slowly dripping into the mixed solution, and carrying out water bath reaction, wherein the water bath reaction is carried out by placing the beaker into a water bath kettle, the water bath temperature is 25 ℃, the stirring environment of 500r/min is continuously maintained in the process, and the stirring time is at least 30min until the benzoic acid is completely dispersed in the mixed solution, thus obtaining a system A.
S2, continuously taking tetrabutyl titanate (C) with the purity of 99.0 percent and the molecular weight of 340.32 by a liquid-transfering gun in a stirring environment of 500r/min 16 H 36 O 4 Ti) 4mL is slowly dripped into the system A for water bath reaction, wherein the water bath temperature is kept at 25 ℃ in the step, and stirring is continued for 30 minutes, so that benzoic acid and tetrabutyl titanate fully react until the mixed solution is light yellow, and a system B is obtained; in the step, the hydrolysis rate of tetrabutyl titanate can be effectively controlled due to the reaction process of benzoic acid and tetrabutyl titanate, so that the uniformity of particles after the reaction is finished is ensured.
S3, firstly, 80mL of absolute ethyl alcohol and 80mL of ultra-dry acetonitrile are put into another beaker to be mixed, 10mL of deionized water is dripped into the mixed solution to carry out water bath reaction in a stirring environment of 500r/min after complete mixing, the water bath temperature is 25 ℃, the stirring time is 30 minutes, and water is uniformly distributed in the mixed solution to obtain a system C.
S4, continuously pouring the system C into the system B rapidly in a stirring environment of 500r/min to perform water bath reaction, wherein the water bath temperature is 25 ℃, and the stirring time is 2h, so as to obtain the system D.
S5, washing and precipitating the system D, drying, and grinding the dried product until the product has fine sense to obtain semi-finished powder; preferably, the washing comprises deionized water washing and absolute ethyl alcohol washing, wherein the washing is that the system D is firstly washed 1 time by deionized water, then is washed twice by absolute ethyl alcohol, and then is left to stand for precipitation to obtain white precipitate; and (3) introducing the precipitate into a clean crucible, drying in a vacuum drying oven at 60 ℃ for 8 hours, and grinding the precipitate with a grinder until the precipitate is ground into fine powder, namely the semi-finished product powder.
S6, pouring the semi-finished powder into deionized water for stirring until the semi-finished powder is completely dispersed in water, then adding anhydrous oxalic acid for carrying out microwave hydrothermal reaction, and obtaining a reaction solution after the reaction is finished; specifically, 25mL of deionized water was poured into a microwave hydrothermal reaction vessel, followed by weighing 0.5g of a semi-finished powder and 0.1g of anhydrous oxalic acid (C) having a purity of 99.0% and a molecular weight of 90.03 2 H 2 O 4 ) Respectively pouring the mixture into a microwave hydrothermal reaction kettle, stirring the liquid in the reaction kettle until the semi-finished powder and the anhydrous oxalic acid are uniformly dispersed in deionized water, then starting a microwave hydrothermal reaction instrument to perform microwave hydrothermal reaction, setting the reaction temperature to 190 ℃, and obtaining the reaction liquid after the reaction is finished for 20 minutes.
And S7, sequentially carrying out ultrasonic treatment, washing, centrifugation and drying treatment on the reaction liquid to obtain the uniform rutile phase nano titanium dioxide.
The average grain diameter of the semi-finished product powder is 314.65nm after statistical analysis, and the crystal form is amorphous; the average grain diameter of the final product after the microwave hydrothermal reaction is 182.34nm, and the crystal form is rutile, which belongs to the rutile phase nano titanium dioxide to be obtained by the application.
The preparation method of the rutile phase nano titanium dioxide with the controllable particle size in the embodiment 6 of the application comprises the following steps:
s1, adding 20mL of absolute ethyl alcohol with the purity of more than or equal to 99.7 percent and the molecular weight of 46.07 and 20mL of ultra-dry acetonitrile with the molecular weight of 41.05 into a reaction vessel-a beaker for mixing, after complete mixing, slowly dripping 0.287g of benzoic acid with the purity of 99.5 percent and the molecular weight of 122.12 into the mixed solution for carrying out water bath reaction, wherein the water bath reaction is carried out by placing the beaker into a water bath kettle, the water bath temperature is 25 ℃, the stirring environment of 500r/min is continuously maintained in the process of carrying out, and the stirring time is at least 30min until the benzoic acid is completely dispersed in the mixed solution, thus obtaining a system A.
S2, continuously taking tetrabutyl titanate (C) with the purity of 99.0 percent and the molecular weight of 340.32 by a liquid-transfering gun in a stirring environment of 500r/min 16 H 36 O 4 Ti) 4mL is slowly dripped into the system A for water bath reaction, wherein the water bath temperature is kept at 25 ℃ in the step, and stirring is continued for 30 minutes, so that benzoic acid and tetrabutyl titanate fully react until the mixed solution is light yellow, and a system B is obtained; in the step, the hydrolysis rate of tetrabutyl titanate can be effectively controlled due to the reaction process of benzoic acid and tetrabutyl titanate, so that the uniformity of particles after the reaction is finished is ensured.
S3, firstly, 80mL of absolute ethyl alcohol and 80mL of ultra-dry acetonitrile are put into another beaker to be mixed, 10mL of deionized water is dripped into the mixed solution to carry out water bath reaction in a stirring environment of 500r/min after complete mixing, the water bath temperature is 25 ℃, the stirring time is 30 minutes, and water is uniformly distributed in the mixed solution to obtain a system C.
S4, continuously pouring the system C into the system B rapidly in a stirring environment of 500r/min to perform water bath reaction, wherein the water bath temperature is 25 ℃, and the stirring time is 2h, so as to obtain the system D.
S5, washing and precipitating the system D, drying, and grinding the dried product until the product has fine sense to obtain semi-finished powder; preferably, the washing comprises deionized water washing and absolute ethyl alcohol washing, wherein the washing is that the system D is firstly washed 1 time by deionized water, then is washed twice by absolute ethyl alcohol, and then is left to stand for precipitation to obtain white precipitate; and (3) introducing the precipitate into a clean crucible, drying in a vacuum drying oven at 60 ℃ for 8 hours, and grinding the precipitate with a grinder until the precipitate is ground into fine powder, namely the semi-finished product powder.
S6, pouring the semi-finished powder into deionized water for stirring until the semi-finished powder is completely dispersed in water, then adding anhydrous oxalic acid for carrying out microwave hydrothermal reaction, and obtaining a reaction solution after the reaction is finished; specifically, 40mL of deionized water was poured into a microwave hydrothermal reaction vessel, followed by weighing 1.0g of a semi-finished powder and 0.1g of anhydrous oxalic acid (C) having a purity of 99.0% and a molecular weight of 90.03 2 H 2 O 4 ) Respectively pouring the mixture into a microwave hydrothermal reaction kettle, stirring the liquid in the reaction kettle until the semi-finished powder and the anhydrous oxalic acid are uniformly dispersed in deionized water, then starting a microwave hydrothermal reaction instrument to perform microwave hydrothermal reaction, setting the reaction temperature to 190 ℃, and obtaining the reaction liquid after the reaction is finished for 20 minutes.
And S7, sequentially carrying out ultrasonic treatment, washing, centrifugation and drying treatment on the reaction liquid to obtain the uniform rutile phase nano titanium dioxide.
The average grain diameter of the semi-finished product powder is 270.77nm after statistical analysis, and the crystal form is amorphous; the average grain diameter of the final product after the microwave hydrothermal reaction is 179.05nm, and the crystal form is rutile, which belongs to the rutile phase nano titanium dioxide to be obtained by the application.
The preparation method of nano titanium dioxide according to comparative example 1 of the present application is basically the same as that of example 1, except that in step S1, benzoic acid is not added, and the image of the product after SEM scanning is shown in fig. 4, it can be seen that the particle size distribution is not uniform, and the particle size cannot be controlled, so that it can be proved that in the preparation method, in the absence of benzoic acid, tetrabutyl titanate is hydrolyzed too fast to cause the particle size distribution to be uneven, and the steric hindrance effect of benzene ring is lost to cause unavoidable agglomeration of titanium dioxide, thereby causing the result of the particle size distribution to be uneven.
The preparation method of nano titanium dioxide in comparative example 2 is basically the same as that in example 1, and the difference is that in step S3, the added deionized water is 20mL, and the image of the product after SEM scanning is shown in fig. 5, and the particle size distribution is also uneven in the range of 150-300 nm, because in step S3, the ratio of the added deionized water to the total added absolute ethyl alcohol and ultra-dry acetonitrile 160mL in the step is 1:8, and exceeds the maximum addition limit 1:10 (i.e. 20:200) specified in the application, resulting in excessive hydrolysis sites of the tetrabutyl titanate-benzoic acid complex, thus proving that the added deionized water is not suitable for excessive.
The foregoing is a further detailed description of the application in connection with the preferred embodiments, and it is not intended that the application be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the application, and these should be considered to be within the scope of the application.
Claims (8)
1. The preparation method of the rutile phase nano titanium dioxide with controllable particle size is characterized by comprising the following steps:
s1, putting absolute ethyl alcohol and ultra-dry acetonitrile into a reaction vessel for mixing, and after complete mixing, slowly dripping benzoic acid into the mixed solution in a stirring environment of 500r/min for water bath reaction until the benzoic acid is completely dispersed in the mixed solution to obtain a system A;
s2, continuously taking tetrabutyl titanate and slowly dripping the tetrabutyl titanate into the system A in a stirring environment of 500r/min to perform water bath reaction until the mixed solution is light yellow to obtain a system B;
s3, firstly, putting absolute ethyl alcohol and ultra-dry acetonitrile into a reaction vessel for mixing, and dripping deionized water into the mixed solution in a stirring environment of 500r/min for water bath reaction after complete mixing to obtain a system C;
s4, continuously pouring the system C into the system B rapidly in a stirring environment of 500r/min for water bath reaction to obtain a system D;
s5, washing and precipitating the system D, drying, and grinding the dried product until the product has fine sense to obtain semi-finished powder;
s6, pouring the semi-finished powder into deionized water for stirring until the semi-finished powder is completely dispersed in water, then adding anhydrous oxalic acid for carrying out microwave hydrothermal reaction, and obtaining a reaction solution after the reaction is finished;
s7, sequentially carrying out ultrasonic treatment, washing, centrifugation and drying treatment on the reaction liquid to obtain uniform rutile phase nano titanium dioxide;
the volume ratio of the absolute ethyl alcohol to the ultra-dry acetonitrile solution in the step S1 to the volume ratio of the absolute ethyl alcohol to the ultra-dry acetonitrile solution in the step S3 is 1:4, and the addition ratio of the absolute ethyl alcohol to the ultra-dry acetonitrile is 1:1;
wherein the molar ratio of the benzoic acid to the tetrabutyl titanate is 0.05-0.5:1.
2. The method for preparing the rutile phase nano titanium dioxide with controllable particle size according to claim 1, which is characterized in that: the volume ratio of the adding amount of tetrabutyl titanate to the total adding amount of the absolute ethyl alcohol and the ultra-dry acetonitrile is 1:50.
3. The method for preparing the rutile phase nano titanium dioxide with controllable particle size according to claim 1, which is characterized in that: in the step S1, the stirring time is at least 30min, and the reaction temperature of the water bath reaction is 25-35 ℃.
4. The method for preparing the rutile phase nano titanium dioxide with controllable particle size according to claim 1, which is characterized in that: in the step S2, the stirring time is at least 1h, and the reaction temperature of the water bath reaction is 25-35 ℃.
5. The method for preparing the rutile phase nano titanium dioxide with controllable particle size according to claim 1, which is characterized in that: in the step S3, the volume ratio of the addition amount of the water to the addition amount of the absolute ethyl alcohol and the ultra-dry acetonitrile is 1-20:200; the stirring time is at least 30min, and the water bath temperature is 25-35 ℃.
6. The method for preparing the rutile phase nano titanium dioxide with controllable particle size according to claim 1, which is characterized in that: in the step S4, the stirring time is at least 2 hours, and the reaction temperature of the water bath reaction is 25-35 ℃.
7. The method for preparing rutile phase nano titanium dioxide with controllable particle size according to any one of claims 1 to 6, which is characterized in that: in the step S6, the addition mass ratio of the semi-finished powder to the anhydrous oxalic acid is 5-15:1-3; the volume of the deionized water is 25-50 mL; the reaction time of the microwave hydrothermal reaction is 20min, and the reaction temperature is 160-220 ℃.
8. The method for preparing the rutile phase nano titanium dioxide with controllable particle size according to claim 7, which is characterized in that: in the step S5, the washing includes deionized water washing and absolute ethyl alcohol washing, wherein the deionized water washing is performed for 1 time, and the absolute ethyl alcohol washing is performed for two times; the drying is carried out by adopting a vacuum drying oven, the drying temperature is 60 ℃, and the drying time is 8 hours.
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