CN112357955A - Method for preparing titanium dioxide powder with different morphologies by solid phase method - Google Patents
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Abstract
The invention discloses a method for preparing titanium dioxide powder with different morphologies by a solid phase method, which comprises the following steps: s1: weighing titanyl sulfate solid and sodium carbonate solid in a ceramic mortar, and carrying out S2: adding different surfactants into a ceramic mortar, S3: a small amount of water was added to the solid mixture, and the milling was continued, S4: transferring the mixture to a centrifuge tube, centrifuging on a centrifuge, pouring out the supernatant after the end, adding water, stirring for 2min-5min by a glass rod, centrifuging again, repeating the centrifugation for five times, S5: drying the washed solid in an oven at 110 ℃ for 1h, and carrying out S6: and (3) putting the dried powder into a muffle furnace for calcining, wherein S7: the calcined sample was filled into a sample bag. The solid-phase synthesis method of titanium dioxide powder has the advantages of simple process conditions, low cost, low requirement on equipment, environmental protection, small particle size of titanium dioxide, high yield, continuous and adjustable operation program and easy industrial production.
Description
Technical Field
The invention relates to a preparation method of titanium dioxide powder, in particular to a method for preparing titanium dioxide powder with different shapes by a solid phase method.
Background
Titanium dioxide (TiO)2) The photocatalyst has the advantages of high photocatalytic activity, good stability, no toxicity to human bodies, low price and the like, and is widely applied to the fields of degradation of organic wastewater, reduction of heavy metal ions, air purification, sterilization, antifogging and the like.
The preparation method of nano titanium dioxide mainly includes gas phase method, liquid phase method and solid phase method [ Chen X B, Mao S. titanium dioxide nanomaterials: synthesis, properties, modifications, and applications, chem. Rev.,2007,107(7):2891-]. The vapor phase method generally comprises gasifying a reaction precursor by a specific means, allowing the reaction precursor to undergo physical or chemical changes under vapor phase conditions, then nucleating and growing in a cooling process, and finally forming nano titanium dioxide [ Akurati K, vitamin A, Klotz U E, et al]. The prepared superfine particles have the characteristics of high purity, fine granularity, strong chemical activity, large surface activity, good monodispersity, less condensed particles and the like. The disadvantages are high process temperature, strict requirements on equipment materials, accurate control requirements on process parameters and high product cost. The liquid phase method is the most important and most researched method in the field of nano titanium dioxide particle preparation in the world at present, has the advantages of low raw material price, wide source, easy operation, simple equipment and the like, and is widely adopted in laboratory research by [ Wang H, Liu P G, Cheng X S, et al2 nano-particles by homogeneous precipitation method,Powder Technol.,2008,188(1):52-54]The liquid phase method can be subdivided into a micro-emulsion method, a hydrothermal method/solvothermal method, a precipitation method, a sol-gel method and the like. Microemulsions are generally a transparent, isotropic thermodynamically stable system consisting of four components, water (or electrolyte solution), oil (usually hydrocarbons), surfactant and co-surfactant (usually alcohols) [ Kim K D, Kim S H, Kim H T.applying the method to the optimization for the synthesis of TiO2 nanoparticles by hydrolysis of TEOT in micelles,Coll.Surf.A.,2005,254(1-3):99-105]. Wherein the uniform monodisperse microemulsion is due to its dispersionThe phase is uniform nanometer-scale liquid drop and is widely adopted in the preparation of nanometer materials. It can be classified into water-in-oil (W/O) and oil-in-water (O/W) types according to the difference between the dispersed phase and the continuous phase. Sol-gel method [ Neppolan B, Wang Q, Jung H, et al. ultrasonic-assisted sol-gel method of preparation of TiO2 nano-particles:Characterization,properties and 4-chlorophenol removal application,Ultrason Sonochem.,2008,15(4):649-658]The preparation of the nano titanium dioxide is usually carried out at normal temperature, the equipment is simple, the investment is low, and the nano titanium dioxide has the advantages of high purity, good chemical uniformity, high activity, fine particles, easiness in dispersion and suspension in aqueous solution and the like; but also has the defects of poor sintering property, large drying shrinkage and long preparation period. The solvothermal method is a new titanium dioxide preparation method derived on the basis of a hydrothermal method [ Li G H, Gray K A. preparation of mixed-phase titanium dioxide nanocomposites via solvothermal processing, chem. Mater.,2007,19(5): 1143-1146-]The preparation principle is similar to that of a hydrothermal method, and the difference of the method from the hydrothermal method is that water in the hydrothermal method is replaced by an organic solvent or a nonaqueous solvent. At present, most of the titanium dioxide thermally synthesized by the solvent is still in the theoretical exploration or laboratory exploration stage, and the aspects of selecting which organic solvent and optimizing the process conditions need to be further studied. The precipitation method is to prepare nano TiO2Simpler methods [ Wang H, Liu P G, Cheng X S, et al. Effect of surfactants on synthesis of TiO2 nano-particles by homogeneous precipitation method,Powder Technol.,2008,188(1):52-54]The direct precipitation is usually carried out by taking inorganic titanium salt as raw material, directly adding precipitant such as ammonia water to promote hydrolysis reaction to generate insoluble hydroxide, separating precipitate, washing, drying and calcining to obtain TiO2And (3) granules. However, the obtained precipitate is generally jelly, so that the washing and the filtration are difficult; and the product is easy to introduce impurities, so the product is rarely used at present. The homogeneous precipitation method is a method in which chemical reactions are used to uniformly and slowly generate crystal-forming ions in a solution. The method can avoid the phenomenon of uneven concentration as long as the speed of generating the precipitate is well controlled, has high product purity and uniform granularity, is convenient to wash, and effectively solves the problem of excessive local concentration in the direct precipitation methodHigh results in the problem of impurities being included in the precipitate. The solid phase method is to prepare TiO by solid phase to solid phase change2Powders, typically obtained by grinding and comminuting solid materials by mechanical action [ Gajovic A, Furic K, Tomasic N, et al, mechanical compaction of nanocrystalline TiO ]2powders and their behavior at high temperatures,J.Alloys Compd.,2005,398(1-2):188-199]. The solid phase method has simple process, low cost and high yield, can be used for mass production, but has the defects of easy introduction of impurities and the like in the process, and limits the development of the solid phase method preparation. In recent years, with the improvement of mechanical processes, solid phase methods have attracted attention in the field of preparing nanomaterials.
A solid phase method for preparing nano titanium dioxide powder with different shapes is a method for providing alkaline environment by utilizing hydrolysis of sodium carbonate, obtaining nano products by chemical reaction with titanyl sulfate, calcination and other processes, and adding a surfactant has a regulating effect on the particle size and the shape of titanium dioxide. The innovation point is that the chemical reaction is controlled by a solid phase method, and the method is simple, quick and easy to operate; meanwhile, the influence of water dosage, surfactant type and calcination temperature on the crystal type and particle morphology of titanium dioxide is systematically researched by adopting orthogonal experimental design, while the common method for synthesizing titanium dioxide is a liquid phase method, and most documents do not study the influence of different surfactant types on the crystal type and morphology of titanium dioxide in detail. Therefore, the method utilizes the surfactant, and can provide brand new theoretical basis and practical reference for the titanium dioxide through the solid phase method.
There are many patents that have been published to produce titanium dioxide, including: a method for preparing high-efficiency nano titanium dioxide photocatalyst at normal temperature (publication number: CN107519852A), a method for preparing echinoid rutile type nano titanium oxide (publication number: CN105439197A), a method for preparing liquid phase silicon deposition modified nano titanium dioxide (publication number: CN105131655B), a method for preparing lithiation nano titanium oxide and application thereof (publication number: CN101475213A), and the like, but titanium dioxide powder is synthesized by a solid phase method, but related literature reports are rare.
Disclosure of Invention
The invention aims to provide a method for preparing titanium dioxide powder with different shapes by a solid phase method, which has the advantages of simple process condition, low cost, low requirement on equipment, environmental protection, high yield of the titanium dioxide powder, continuous and adjustable operation procedure, easy control of the experimental process and easy industrial production; titanium dioxide with different crystal forms (anatase type, anatase and rutile mixed crystal form and rutile type) and different appearances (irregular, rod-shaped and cubic) can be prepared by adjusting experimental parameters (water using amount, surfactant category and calcining temperature); the method adopts simpler solid phase grinding, has obvious difference from the preparation environment of the common liquid phase method, and can simply and quickly prepare the titanium dioxide.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing titanium dioxide powder with different morphologies by a solid phase method comprises the following steps:
s1, weighing titanyl sulfate solid and sodium carbonate solid in a ceramic mortar, wherein the molar ratio of the titanyl sulfate solid to the sodium carbonate solid is 1: 1;
s2, adding different surfactants into a ceramic mortar and grinding for 3min, wherein the cationic surfactant is cetyl trimethyl ammonium bromide, the anionic surfactant is sodium dodecyl benzene sulfonate, the nonionic surfactant is polyethylene glycol with the molecular weight of 10000, and the proportion of the dosage of the surfactants in the total dosage of the reactants is 2-6%;
s3, adding 3-7 mL of water into the solid mixture, and continuing to grind for 60 min;
s4, transferring the mixture into a centrifuge tube after grinding, centrifuging on a centrifuge, pouring out supernatant after finishing the centrifuging, adding water, stirring for 2-5 min by a glass rod, centrifuging again, repeating the centrifuging for five times, and finishing the washing process for five times;
s5, drying the washed solid in an oven at 110 ℃ for 1 h;
s6, putting the dried powder into a muffle furnace to be calcined for 1.5h, wherein the calcining temperature is 500-900 ℃;
s7, finally, filling the calcined sample into a sample bag for standby.
Further, the sodium carbonate in S1 is anhydrous sodium carbonate or hydrated sodium carbonate.
Further, the surfactant in S2 is a cationic surfactant, an anionic surfactant or a nonionic surfactant.
Furthermore, the cationic surfactant cetyl trimethyl ammonium bromide, the anionic surfactant sodium dodecyl benzene sulfonate and the nonionic surfactant polyethylene glycol with the molecular weight of 10000 are used, and the proportion of the dosage of the surfactant in the total dosage of the reactants is 2-6%.
Furthermore, the using amount of water in the S3 is 3mL-7mL, and the grinding time is 30min-90 min.
Further, the number of water washes in S4 is 3 to 7.
Further, the drying temperature in the S5 is 100-120 ℃, and the drying time is 0.5-2 h.
Further, the calcining temperature in the S6 is 500-900 ℃, and the calcining time is 1-2 h.
The invention has the beneficial effects that:
1. the method for preparing the titanium dioxide powder has the advantages of simple process conditions, low cost, low requirement on equipment, environmental protection, high yield of the titanium dioxide powder, continuous and adjustable operation program, easy control of the experimental process and easy industrial production;
2. the method for preparing titanium dioxide powder prepares titanium dioxide with different crystal forms (anatase type, anatase and rutile mixed crystal form and rutile type) and different appearances (irregular, rod-shaped and cubic) by adjusting experimental parameters (water dosage, surfactant category and calcining temperature);
3. the method for preparing titanium dioxide powder adopts simpler solid phase grinding, has obvious difference from the preparation environment of the common liquid phase method, and simply and quickly prepares titanium dioxide.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction (XRD) pattern of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of titanium dioxide No. 1 of the present invention;
FIG. 3 is an SEM image of titanium dioxide No. 2 according to the present invention;
FIG. 4 is an SEM image of titanium dioxide No. 3 according to the present invention;
FIG. 5 is an SEM image of titanium dioxide No. 4 of the present invention;
FIG. 6 is an SEM image of titanium dioxide No. 5 of the present invention;
FIG. 7 is an SEM image of titanium dioxide No. 6 according to the present invention;
FIG. 8 is an SEM image of titanium dioxide No. 7 of the present invention;
FIG. 9 is an SEM image of titanium dioxide No. 8 of the present invention;
FIG. 10 is an SEM photograph of titanium dioxide No. 9 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
S1, weighing 8.00g (0.05mol) of titanyl sulfate solid and 5.30g (0.05mol) of sodium carbonate solid in a ceramic mortar;
s2, adding Cetyl Trimethyl Ammonium Bromide (CTAB) as a surfactant, grinding in a ceramic mortar for 3min, wherein the proportion of the surfactant in the total amount of reactants is 2%;
s3, adding 3mL of water into the solid mixture, and continuing to grind for 60 min;
s4, after grinding is finished, transferring the mixture into a centrifuge tube, performing centrifugal separation on the centrifuge tube, pouring out supernatant after finishing the centrifugal separation, adding water, stirring the mixture for 2 to 5 minutes by using a glass rod, performing centrifugation again, repeating the centrifugation for 3 times, and finishing the washing process for 3 times;
s5, drying the washed solid in an oven at 110 ℃ for 1 h;
s6, placing the dried powder into a muffle furnace to be calcined for 1.5h, wherein the calcining temperature range is 500 ℃;
s7, and finally, filling the calcined sample into a sample bag for later use.
The obtained titanium dioxide powder was subjected to XRD detection, and as shown in FIG. 1(a), it was anatase titanium dioxide having a particle diameter of 11.19 nm. The observation result by SEM shows that the titanium dioxide at this time has a random morphology as shown in FIG. 2.
Example 2
S1, weighing 8.00g (0.05mol) of titanyl sulfate solid and 5.30g (0.05mol) of sodium carbonate solid in a ceramic mortar;
s2, adding Sodium Dodecyl Benzene Sulfonate (SDBS) as a surfactant, grinding the SDBS in a ceramic mortar for 3min, wherein the proportion of the surfactant to the total amount of reactants is 4%;
s3, adding 3mL of water into the solid mixture, and continuing to grind for 60 min;
s4, after grinding is finished, transferring the mixture into a centrifuge tube, performing centrifugal separation on the centrifuge tube, pouring out supernatant after finishing the centrifugal separation, adding water, stirring the mixture for 2 to 5 minutes by using a glass rod, performing centrifugation again, repeating the centrifugation for 4 times, and finishing the washing process for 4 times;
s5, drying the washed solid in an oven at 100 ℃ for 2 h;
s6, placing the dried powder into a muffle furnace to be calcined for 1h, wherein the calcining temperature range is 700 ℃;
s7, and finally, filling the calcined sample into a sample bag for later use.
XRD examination of the obtained product was carried out, as shown in FIG. 1(b), and it was revealed that the particle diameter of titanium dioxide was 29.84nm and the crystal type was anatase type. The corresponding SEM is shown in fig. 3, indicating that the titanium dioxide is now a mixed structure of rods (small amount) and irregular (large amount).
Example 3
S1, weighing 8.00g (0.05mol) of titanyl sulfate solid and 5.30g (0.05mol) of sodium carbonate solid in a ceramic mortar;
s2, adding a nonionic surfactant which is polyethylene glycol (PEG-10000) with the molecular weight of 10000, wherein the dosage of the surfactant accounts for 6 percent of the total dosage of reactants;
s3, adding 3mL of water into the solid mixture, and continuing to grind for 60 min;
s4, after grinding is finished, transferring the mixture into a centrifuge tube, performing centrifugal separation on the centrifuge tube, pouring out supernatant after finishing the centrifugal separation, adding water, stirring the mixture for 2 to 5 minutes by using a glass rod, performing centrifugation again, repeating the centrifugation for 3 times, and finishing the washing process for 3 times;
s5, drying the washed solid in an oven at 100 ℃ for 1 h;
s6, placing the dried powder into a muffle furnace to be calcined for 1h, wherein the calcining temperature range is 900 ℃;
s7, and finally, filling the calcined sample into a sample bag for later use.
XRD examination of the obtained product was carried out, as shown in FIG. 1(c), and it was revealed that the particle diameter of titanium dioxide was 42.59nm and the crystal type was rutile type. The corresponding SEM is shown in fig. 4, indicating that the titanium dioxide is now a mixed structure of cubic (large amount) and rod-like (small amount).
Example 4
S1, weighing 8.00g (0.05mol) of titanyl sulfate solid and 5.30g (0.05mol) of sodium carbonate solid in a ceramic mortar;
s2, adding a surfactant which is anionic surfactant Sodium Dodecyl Benzene Sulfonate (SDBS), wherein the dosage of the surfactant accounts for 2% of the total dosage of reactants;
s3, adding 5mL of water into the solid mixture, and continuing to grind for 60 min;
s4, after grinding is finished, transferring the mixture into a centrifuge tube, performing centrifugal separation on the centrifuge tube, pouring out supernatant after finishing the centrifugal separation, adding water, stirring the mixture for 2 to 5 minutes by using a glass rod, performing centrifugation again, repeating the centrifugation for 4 times, and finishing the washing process for 4 times;
s5, drying the washed solid in an oven at 120 ℃ for 0.5 h;
s6, placing the dried powder into a muffle furnace to be calcined for 1.5h, wherein the calcining temperature range is 900 ℃;
s7, and finally, filling the calcined sample into a sample bag for later use.
XRD examination of the obtained product showed that the particle diameter of titanium dioxide was 38.53nm and the crystal type was rutile type, as shown in FIG. 1 (d). The corresponding SEM is shown in FIG. 5, indicating that the titanium dioxide is now cubic.
Example 5
S1, weighing 8.00g (0.05mol) of titanyl sulfate solid and 5.30g (0.05mol) of sodium carbonate solid in a ceramic mortar;
s2, adding a surfactant which is anionic surfactant Sodium Dodecyl Benzene Sulfonate (SDBS), wherein the proportion of the dosage of the surfactant in the total dosage of the reactants is 4%;
s3, adding 5mL of water into the solid mixture, and continuing to grind for 60 min;
s4, after grinding is finished, transferring the mixture into a centrifuge tube, performing centrifugal separation on the centrifuge tube, pouring out supernatant after finishing the centrifugal separation, adding water, stirring the mixture for 2 to 5 minutes by using a glass rod, performing centrifugation again, repeating the centrifugation for 4 times, and finishing the washing process for 4 times;
s5, drying the washed solid in an oven at 100 ℃ for 2 h;
s6, placing the dried powder into a muffle furnace to be calcined for 2 hours, wherein the calcining temperature range is 500 ℃;
s7, and finally, filling the calcined sample into a sample bag for later use.
XRD detection of the obtained product was carried out, as shown in FIG. 1(e), and it was revealed that the particle diameter of titanium dioxide was 17.90nm and the crystal type was anatase type. The corresponding SEM is shown in FIG. 6, which shows that the titanium dioxide is in a random structure.
Example 6
S1, weighing 8.00g (0.05mol) of titanyl sulfate solid and 5.30g (0.05mol) of sodium carbonate solid in a ceramic mortar;
s2, adding a cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) as the surfactant, wherein the proportion of the surfactant to the total amount of reactants is 6%;
s3, adding 5mL of water into the solid mixture, and continuing to grind for 60 min;
s4, after grinding is finished, transferring the mixture to a centrifuge tube, carrying out centrifugal separation on the centrifuge tube, pouring out supernatant after finishing the centrifugal separation, adding water, stirring for 2-5 min by using a glass rod, centrifuging again, repeating the centrifugation for five times, and finishing the washing process for five times;
s5, drying the washed solid in an oven at 110 ℃ for 2 h;
s6, placing the dried powder into a muffle furnace to be calcined for 1h, wherein the calcining temperature range is 700 ℃;
s7, and finally, filling the calcined sample into a sample bag for later use.
XRD examination of the obtained product was carried out, and as shown in FIG. 1(f), it was revealed that the particle diameter of titanium dioxide was 25.43nm and the crystal type was a mixed crystal phase of rutile type and anatase type, wherein the rutile phase accounted for 59.17%, and the anatase phase accounted for 40.83%. The corresponding SEM is shown in FIG. 7, which shows that the titanium dioxide is in a random structure.
Example 7
S1, weighing 8.00g (0.05mol) of titanyl sulfate solid and 5.30g (0.05mol) of sodium carbonate solid in a ceramic mortar;
s2, adding a nonionic surfactant which is polyethylene glycol (PEG-10000) with the molecular weight of 10000, wherein the dosage of the surfactant accounts for 2% of the total dosage of reactants;
s3, adding 7mL of water into the solid mixture, and continuing to grind for 60 min;
s4, after grinding is finished, transferring the mixture to a centrifuge tube, carrying out centrifugal separation on the centrifuge tube, pouring out supernatant after finishing the centrifugal separation, adding water, stirring for 2-5 min by using a glass rod, centrifuging again, repeating the centrifugation for five times, and finishing the washing process for five times;
s5, drying the washed solid in an oven at 100 ℃ for 0.5 h;
s6, placing the dried powder into a muffle furnace to be calcined for 1.5h, wherein the calcining temperature range is 700 ℃;
s7, and finally, filling the calcined sample into a sample bag for later use.
XRD examination of the obtained product was carried out, and as shown in FIG. 1(g), it was revealed that the particle diameter of titanium dioxide was 20.37nm, and the crystal type was a mixed crystal phase of rutile type and anatase type, wherein the rutile phase accounted for 48.71%, and the anatase phase accounted for 51.29%. The corresponding SEM is shown in FIG. 8, which shows that the titanium dioxide is in a random structure.
Example 8
S1, weighing 8.00g (0.05mol) of titanyl sulfate solid and 5.30g (0.05mol) of sodium carbonate solid in a ceramic mortar;
s2, adding a cationic surfactant which is Cetyl Trimethyl Ammonium Bromide (CTAB), wherein the dosage of the surfactant accounts for 4% of the total dosage of the reactants;
s3, adding 7mL of water into the solid mixture, and continuing to grind for 60 min;
s4, after grinding is finished, transferring the mixture into a centrifuge tube, performing centrifugal separation on the centrifuge tube, pouring out supernatant after finishing the centrifugal separation, adding water, stirring the mixture for 2 to 5 minutes by using a glass rod, performing centrifugation again, repeating the centrifugation for 6 times, and finishing the washing process for 6 times;
s5, drying the washed solid in an oven at 110 ℃ for 2 h;
s6, placing the dried powder into a muffle furnace to be calcined for 2 hours, wherein the calcining temperature range is 900 ℃;
s7, and finally, filling the calcined sample into a sample bag for later use.
XRD examination of the obtained product was carried out, as shown in FIG. 1(h), and it was revealed that the particle diameter of titanium dioxide was 47.61nm and the crystal type was rutile type. The corresponding SEM is shown in fig. 9, indicating that the titanium dioxide is now a mixed structure of rod-like (minor amount) and cubic (major amount).
Example 9
S1, weighing 8.00g (0.05mol) of titanyl sulfate solid and 5.30g (0.05mol) of sodium carbonate solid in a ceramic mortar;
s2, adding a surfactant which is anionic surfactant and is Sodium Dodecyl Benzene Sulfonate (SDBS), wherein the proportion of the dosage of the surfactant in the total dosage of reactants is 6%;
s3, adding 7mL of water into the solid mixture, and continuing to grind for 60 min;
s4, after grinding is finished, transferring the mixture into a centrifuge tube, performing centrifugal separation on the centrifuge tube, pouring out supernatant after finishing the centrifugal separation, adding water, stirring the mixture for 2 to 5 minutes by using a glass rod, performing centrifugation again, repeating the centrifugation for 7 times, and finishing the washing process for 7 times;
s5, drying the washed solid in an oven at 120 ℃ for 1 h;
s6, placing the dried powder into a muffle furnace to be calcined for 2 hours, wherein the calcining temperature range is 500 ℃;
s7, and finally, filling the calcined sample into a sample bag for later use.
XRD examination of the obtained product was carried out, as shown in FIG. 1(i), and it was revealed that the particle diameter of titanium dioxide was 16.11nm and the crystal type was anatase type. The corresponding SEM is shown in FIG. 10, which shows that the titanium dioxide is in a random structure.
XRD (X-ray diffraction) detection is carried out on the titanium dioxide powder obtained in the above embodiment, and as shown in figure 1, the result shows that the crystal form of the titanium dioxide is changed by changing four factors (water using amount, surfactant type and calcination temperature) in an orthogonal table. The XRD patterns of titanium dioxide samples from nos. 1 to 9 are shown in fig. 1(a) - (i) in turn as 1-9, respectively, and the particle sizes thereof are constantly changing (fig. 1, table 2), the minimum particle size is 11.19nm, and the maximum particle size is 47.61nm, and nos. 1,2, 5 and 9 all give pure anatase type titanium dioxide, nos. 3, 4 and 8 all give pure rutile type titanium dioxide, and nos. 6 and 7 all give mixed crystal phases of anatase and rutile. The orthogonal data is analyzed by a range method, as shown in table 2, four factors (water dosage, surfactant category and calcination temperature) have influence on the particle size of the titanium dioxide, the influence degrees of the four factors are calcination temperature, surfactant dosage, surfactant category and water dosage from large to small, the optimal scheme is determined that the calcination temperature is 500 ℃, the surfactant dosage is 2%, the surfactant category is polyethylene glycol (PEG-10000) with the molecular weight of 10000, the water dosage is 5mL, and the particle size of the titanium dioxide prepared according to the parameters is theoretically lower than 11.19 nm.
SEM detection is carried out on the obtained titanium dioxide powder, as shown in figures 2-10, samples No. 1-9 in the orthogonal table are sequentially represented, and the result shows that the shape of the titanium dioxide is changed by changing four factors (water using amount, surfactant type and calcining temperature) in the orthogonal table. No. 1, No. 5, No. 6, No. 7 and No. 9 titanium dioxide samples are all irregular structures, No. 2 titanium dioxide samples are a small amount of rod-shaped and large amount of irregular mixed structures, No. 3 and No. 8 titanium dioxide samples are a small amount of rod-shaped and large amount of cuboidal mixed structures, and No. 4 titanium dioxide samples are cuboidal structures. Therefore, the titanium dioxide powder with different shapes (irregular, rod-shaped, cubic and cubic) can be obtained by changing different experimental parameters.
TABLE 1 orthogonal experiment parameter table
TABLE 2 analysis table of orthogonal experimental data results calculated by range method
Kn represents the sum of the indicators of the nth level of the factor, Kn represents the average value of Kn, and n is 1,2 and 3.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (8)
1. A method for preparing titanium dioxide powder with different morphologies by a solid phase method is characterized by comprising the following steps:
s1, weighing titanyl sulfate solid and sodium carbonate solid in a ceramic mortar, wherein the molar ratio of the titanyl sulfate solid to the sodium carbonate solid is 1: 1;
s2, adding different surfactants into a ceramic mortar and grinding for 3min, wherein the cationic surfactant is cetyl trimethyl ammonium bromide, the anionic surfactant is sodium dodecyl benzene sulfonate, and the nonionic surfactant is polyethylene glycol with molecular weight of 10000;
s3, adding 3mL-7mL of water into the solid mixture, and continuing to grind for 60 min;
s4, transferring the mixture into a centrifuge tube after grinding, centrifuging on a centrifuge, pouring out supernatant after finishing the centrifuging, adding water, stirring for 2-5 min by a glass rod, centrifuging again, repeating the centrifuging for five times, and finishing the washing process for five times;
s5, drying the washed solid in an oven at 110 ℃ for 1 h;
s6, putting the dried powder into a muffle furnace to be calcined for 1.5h, wherein the calcining temperature is 500-900 ℃;
s7, filling the calcined sample into a sample bag for later use.
2. The method for preparing titanium dioxide powder with different morphologies by the solid phase method according to claim 1, wherein the sodium carbonate in S1 is anhydrous sodium carbonate or hydrated sodium carbonate.
3. The method for preparing titanium dioxide powder with different morphologies by the solid phase method according to claim 1, wherein the surfactant in S2 is a cationic surfactant, an anionic surfactant or a nonionic surfactant.
4. The method for preparing titanium dioxide powder with different morphologies by the solid phase method according to claim 3, wherein the cationic surfactant cetyl trimethyl ammonium bromide, the anionic surfactant sodium dodecyl benzene sulfonate and the nonionic surfactant polyethylene glycol with the molecular weight of 10000 are used, and the proportion of the surfactant in the total amount of the reactants is 2% -6%.
5. The method for preparing titanium dioxide powder with different morphologies by the solid phase method according to claim 1, wherein the amount of water used in S3 is 3mL-7mL, and the grinding time is 30min-90 min.
6. The method for preparing titanium dioxide powder with different morphologies by the solid phase method according to claim 1, wherein the number of washing times in S4 is 3-7.
7. The method for preparing titanium dioxide powder with different morphologies by the solid phase method according to claim 1, wherein the drying temperature in S5 is 100-120 ℃, and the drying time is 0.5-2 h.
8. The method for preparing titanium dioxide powder with different morphologies by the solid phase method according to claim 1, wherein the calcination temperature in S6 is 500-900 ℃, and the calcination time is 1-2 h.
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| CN112919536A (en) * | 2021-03-08 | 2021-06-08 | 安徽景成新材料有限公司 | Method for synthesizing nano zirconia by rheological phase method |
| WO2022078015A1 (en) * | 2020-10-16 | 2022-04-21 | 安徽景成新材料有限公司 | Method for preparing titanium dioxide powder in different morphologies by using solid-phase process |
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| CN115501878B (en) * | 2022-09-29 | 2023-07-25 | 中国科学院青岛生物能源与过程研究所 | Method for synthesizing niobium-cobalt catalyst by in-situ centrifugation and application thereof |
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