CN109485093B - Anatase type titanium dioxide hollow spherical shell with good spherical shape and preparation method thereof - Google Patents
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Abstract
The invention provides an anatase titanium dioxide hollow spherical shell with a good spherical shape and a preparation method thereof, comprising the following steps: step 1, preparing modified PS colloidal microsphere emulsion by a soap-free liquid polymerization method; step 2, coating TiO by a mixed solvent method2Obtaining PS @ TiO through a shell structure2Powder; step 3, PS @ TiO2And (3) carrying out twice calcination treatment on the powder: the primary calcination is carried out for 2h at the temperature of 450-550 ℃; the secondary calcination is to calcine for 10min at the temperature of 320-420 ℃ to obtain the titanium dioxide hollow spherical shell. The titanium dioxide prepared by the method is anatase type, has a hollow shell structure, good sphericity and uniform particle size, has a diameter of between 100 and 400nm, and has wide application prospects in the fields of photoelectrochemistry application such as catalysis, batteries, gas storage and separation.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to an anatase type titanium dioxide hollow spherical shell with a good spherical shape and a preparation method thereof.
Background
The core-shell structure is a nanoscale ordered assembly structure formed by coating one nano material with another nano material through chemical bonds or other acting forces. The core-shell structure integrates the properties of an inner material and an outer material due to the unique structural characteristics of the core-shell structure, mutually supplements the respective defects, and has wide application prospects in the aspects of catalysis, batteries, gas storage and separation.
Due to the nanometer TiO2The specific surface area of the catalyst is large, and the surface has more empty bonds, so that the catalyst is easy to agglomerate in the preparation and application processes, the catalytic efficiency is low, and the excellent performance of the catalyst cannot be fully exerted. Therefore, the research on the titanium dioxide-based core-shell structure nano material is paid attention by the majority of researchers.
At present, the titanium dioxide-based core-shell structure nano material still has more key scientific and technical problems, and the industrial application of the nano material is restricted. The preparation cost of most titanium dioxide-based core-shell structure nano materials is high, the process is complex, the large-scale production is difficult, the cost is reduced, and the process flow is simplified to form the primary task; the core-shell structure synthesized by the titanium dioxide and the materials has the best performance, and the proper proportion of the materials in the core-shell structure needs to be considered.
Researchers have prepared organic-titanium dioxide core-shell structures using nanocarbon spheres or glucose as cores (e.g., CN101905153A, CN101890350A, and CN101857267A) and butyl titanate as a precursor solution, and then removed the organic core by calcination to obtain hollow TiO2And (4) shell layer. However, the size of the carbon nanospheres is not uniform enough, and the sphericity is not perfect enough, so that the coated and calcined TiO is prepared2Shell structures are different in size; in addition, the nano carbon spheres have poor dispersibility and are easy to agglomerate, long-time ultrasonic dispersion is needed before wrapping, and if the side shell layers are seriously adhered, the functional application of the material is influenced. In recent years, colloidal microspheres prepared by a microemulsion method have good dispersity and narrow particle size distribution, and are wrapped by TiO by taking the colloidal microspheres as cores2Methods for preparing hollow spherical shells have been tried (CN105502485A and CN101077792A), but the conditions of the obtained core-shell structure are controlled more rigorously, and especially in the process of calcination, the complete spherical shell structure is seriously damaged, which often causes collapse and produces broken hemispheres.
Up to now, anatase TiO in good spherical form has been prepared in large quantities2Hollow spherical shell has no literature reportAnd (4) carrying out the following steps.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an anatase type titanium dioxide hollow spherical shell with a good spherical shape and a preparation method thereof.
The invention is realized by the following technical scheme:
a preparation method of a spherical perfect anatase titanium dioxide hollow spherical shell comprises the following steps:
step 2, wrapping TiO2Shell layer structure: dispersing the obtained modified PS colloidal microsphere emulsion in a mixed solution of ethanol and acetonitrile, and recording as solution A; dissolving butyl titanate in a mixed solution of ethanol and acetonitrile, and marking as a solution B; slowly injecting the solution B into the solution A under the condition of stirring, and stirring for reaction to obtain PS @ TiO2The dispersion liquid of the microspheres is washed, dried and ground into PS @ TiO2Powder;
step 3, PS @ TiO2And (3) carrying out twice calcination treatment on the powder: the primary calcination is carried out for 2h at the temperature of 450-550 ℃; the secondary calcination is to calcine for 10min at the temperature of 320-420 ℃ to obtain the titanium dioxide hollow spherical shell.
Preferably, in step 1, the ratio of styrene to α -methacrylic acid to water is: (7-14) mL: (0.5-1) mL: (90-180) mL.
Preferably, in step 1, the ratio of potassium persulfate to styrene is 17 g: (7-14) mL.
Preferably, in step 1, the styrene used is purified by the following steps: washing styrene with sodium hydroxide solution, washing with ultrapure water until the solution is neutral, adding solid anhydrous calcium chloride, and removing water.
Preferably, in step 2, after the solution B is injected into the solution a, the ratio of the modified PS colloidal microspheres to butyl titanate is (3-6) g: (0.5-3) mL.
Preferably, in step 2, after the solution B is slowly injected into the solution A, the reaction is carried out at 20 to 40 ℃ for 1 to 30 hours.
Preferably, in step 2, the dropping speed of the solution B for slowly injecting the solution A is controlled to be 30-60 drops/min, 5mL of solution is added every 5-10min, stirring is kept during the period, and stirring is kept during the period.
Preferably, in step 2, the washing is specifically: adding detergent, ultrasonic dispersing for 20-30min, and centrifuging; the centrifugal speed is 7000 plus 10000r/min, and the centrifugal time is 20-30 min.
Preferably, the primary calcination is to heat up to 480-520 ℃ in a tubular furnace at a heating rate of 1-5 ℃/min; the secondary calcination is to heat up to 320-420 ℃ in a muffle furnace at a heating rate of 1-5 ℃/min.
The anatase titanium dioxide hollow spherical shell with perfect spherical shape is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
the method comprises the steps of firstly adopting a soap-free liquid polymerization method, taking styrene as a raw material, adding alpha-methacrylic acid for modification and enhancing hydrophilicity, and adding an initiator potassium persulfate to prepare Polystyrene (PS) colloidal microspheres with uniform particle sizes; then TiO is realized by a mixed solvent method2And (3) wrapping PS to form a core-shell structure, then calcining twice, carbonizing the PS after primary calcining to form folds in the microspheres, oxidizing carbon into carbon dioxide gas to overflow after secondary calcining, and meanwhile, opening the shell, so that the folding phenomenon is obviously improved, and the large-scale spherical intact anatase type titanium dioxide core-shell powder material is obtained. The titanium dioxide prepared by the method is anatase type, has a hollow shell structure, good sphericity and uniform particle size, has the diameter of between 100 and 400nm, and has wide application prospect in the fields of photoelectrochemistry application such as catalysis, batteries, gas storage and separation. The preparation method is simple and has strong repeatability, and not only solves the problems that the carbon nanospheres are different in size and not perfect in sphericity, but also the coated and calcined TiO is prepared2The technical problem of uneven shell structure is solved, and the problems of poor dispersibility, easy agglomeration and long-time ultra-high requirement before coating of the carbon spheres are solvedSound dispersion, serious adhesion between shell layers, influence on functional application of materials and the like. The process operation process is simple and feasible, and is stable and repeatable.
Furthermore, the addition of the reaction precursor butyl titanate is controlled to realize TiO2The shell thickness can be controlled.
TiO prepared by the invention2The spherical shell is in an anatase type, has a hollow shell structure, is good in sphericity, complete in spherical structure and uniform in size, and is obviously reduced in breakage. Titanium dioxide (TiO)2) Is a semiconductor material with wide application value. In particular TiO of uniform, integral shell structure2The nano material has better permeability, larger specific surface area and smaller density, and the gaps among the shells enable light rays to be reflected repeatedly, thereby improving the TiO content2Light utilization efficiency of materials, which promote TiO2The material is applied to the fields of modern science and technology such as photocatalysis, macromolecule slow release, solar cells, lithium ion batteries and the like. Preparation of Shell-structured TiO2Nanomaterials have become a research hotspot receiving great attention.
Drawings
FIG. 1 is an XRD pattern of titanium dioxide powder obtained by the secondary calcination in example 1;
FIG. 2 is an SEM photograph of a titanium dioxide powder obtained by primary calcination in example 1;
FIGS. 3 and 4 are SEM images of titanium dioxide powders obtained by the secondary calcination in example 1;
FIG. 5 is an SEM photograph of a titanium dioxide powder obtained by the secondary calcination in example 3;
FIG. 6 is an EDS chart of titanium dioxide powder obtained by the secondary calcination in example 3;
FIG. 7 is a two-dimensional area scan EDS chart of the titanium dioxide powder obtained by the secondary calcination in example 3.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method of the anatase titanium dioxide hollow spherical shell with perfect spherical shape comprises the following steps:
1) purifying styrene, namely taking a purified styrene solution, adding alpha-methacrylic acid and deionized water into a three-neck round-bottom flask, magnetically stirring for more than 30min to mix the solution, and additionally preparing a potassium persulfate solution; the proportions of styrene, alpha-methacrylic acid and deionized water are: (7-14) mL: (0.5-1) mL: (90-180) mL; the concentration of the potassium persulfate solution was 1.7 g/mL.
2) Preparing PS colloidal microsphere emulsion: connecting a condensing device, putting into an oil bath kettle at 80 ℃, magnetically stirring for 30-60min, injecting the potassium persulfate solution obtained in the step 1) into the system, and reacting for 7-9h at the constant temperature of 75-90 ℃ to obtain PS colloidal microsphere emulsion; the ratio of potassium persulfate to styrene was 1.7 g: (7-14) mL.
3) One third of the obtained PS colloidal microsphere emulsion is dispersed in a mixed solution of ethanol and acetonitrile to be marked as solution A, and butyl titanate (TBOT) is dissolved in the mixed solution of the ethanol and the acetonitrile to be marked as solution B; in the solution A, the proportion of the PS colloidal microsphere emulsion, ethanol and acetonitrile is as follows: 20mL of: 80mL of: 20 mL; in the solution B, the ratio of the butyl titanate, the ethanol and the acetonitrile is as follows: (0.5-3) mL: 16mL of: 4 mL.
4) Method for preparing PS @ TiO with core-shell structure by mixed solvent method2: slowly injecting the solution B into the solution A, wherein the ratio of the modified PS colloidal microspheres to the butyl titanate is (3-6) g: (0.5-3) mL, rapidly stirring by magnetic force at 20-40 ℃, and obtaining PS @ TiO after a period of time2The dispersion liquid is washed, ultrasonically dispersed, dried and ground into PS @ TiO2And (3) powder.
5) High-temperature treatment: PS @ TiO 22Calcining the powder twice to obtain anatase TiO with perfect spherical shape2A core-shell powder material.
In the step 1), the styrene purification means that purchased styrene is washed twice by using a 10% sodium hydroxide solution and is washed for more than three times by using ultrapure water until the solution is neutral so as to remove a polymerization inhibitor, a small amount of solid anhydrous calcium chloride is added, water is removed, and the solution is sealed and stored in a refrigerating chamber of a refrigerator for later use. The stirring speed of the magnetic stirring was 400 r/min.
In the step 2), the heating magnetic stirring speed is 300 r/min.
In the step 4), the dripping speed of the slow injection is controlled at 60 drops/min, 5mL of the solution is added every 5min, and stirring is kept during the period; the period of time ranges from 1 to 30 hours; the rapid magnetic stirring is 500 r/min; the washing and ultrasonic operation refers to deionized water washing for 3 times, absolute ethyl alcohol washing for 3 times, ultrasonic dispersion for 20-30min in washing and centrifugal gaps, centrifugal rotation speed of 7000 once 10000r/min, and centrifugal time of 20-30 min.
The firing systems of the two times of calcination in the step 5) are respectively as follows: calcining for 2h in a tubular furnace at 480-520 ℃ with the heating rate of 1-5 ℃/min; then calcining the mixture in a muffle furnace at the temperature of 320 ℃ and 420 ℃ for 10min, wherein the heating rate is 1-5 ℃/min.
Example 1
An anatase titanium dioxide core-shell material with good spherical shape comprises the following steps:
1) purifying styrene, washing twice with 10% sodium hydroxide solution, washing three times with ultrapure water until the solution is neutral to remove a polymerization inhibitor, adding a small amount of solid anhydrous calcium chloride, removing water, sealing and storing in a refrigerator cold storage chamber, taking 7mL of the purified styrene solution, adding 0.5mL of alpha-methacrylic acid and 90mL of deionized water into a three-neck round-bottom flask, magnetically stirring for 30min at the rotation speed of 400r/min to uniformly mix the solution, and additionally preparing 10mL of 1.7g/mL of potassium persulfate solution;
2) preparing PS colloidal microsphere emulsion: connecting a condensing device, putting the condensation device into a 75 ℃ oil bath pot, magnetically stirring the condensation device for 30min at 300r/min, injecting the potassium persulfate solution obtained in the step 1) into the system, reacting for 7h at the constant temperature of 75 ℃ to obtain PS microsphere dispersion, and centrifuging and washing;
3) one third of the obtained PS emulsion is dispersed in a mixed solution of 80mL of ethanol and 20mL of acetonitrile and is marked as solution A, and 0.5mL of butyl titanate (TBOT) is dissolved in a mixed solution of 16mL of ethanol and 4mL of acetonitrile and is marked as solution B;
4) method for preparing PS @ TiO with core-shell structure by mixed solvent method2: slowly injecting the solution B into the solution A, controlling the dropping speed at 30 drops/min, adding 5mL of solution per drop at an interval of 5min, keeping stirring during the period, quickly and magnetically stirring for 500r/min at the temperature of 20 ℃, and obtaining PS @ TiO after 1h2Cleaning the dispersion with deionized water for 3 times, cleaning with anhydrous ethanol for 3 times, and centrifugingSound dispersion is carried out for 20min, the centrifugal rotation speed is 7000r/min, and the centrifugal time is 20 min. Drying and grinding into powder;
5) high-temperature treatment: calcining for 2h in a tubular furnace at 480 ℃ with the heating rate of 1 ℃/min; then calcined in a muffle furnace at 320 ℃ for 10min, with a heating rate of 1 ℃/min. Calcining twice to obtain anatase TiO with perfect spherical shape2A core-shell powder material.
Example 2
An anatase titanium dioxide core-shell material with good spherical shape comprises the following steps:
1) purifying styrene, washing twice with 10% sodium hydroxide solution, washing three times with ultrapure water until the solution is neutral to remove a polymerization inhibitor, adding a small amount of solid anhydrous calcium chloride, removing water, sealing and storing in a refrigerator cold storage chamber, taking 11mL of the purified styrene solution, adding 0.8mL of alpha-methacrylic acid, 120mL of deionized water, and stirring for 30min by magnetic force at 400r/min, mixing the solutions, and preparing 10mL of 1.7g/mL of potassium persulfate solution;
2) preparing PS colloidal microsphere emulsion: connecting a condensing device, putting the condensation device into an oil bath kettle at 80 ℃, magnetically stirring for 40min at 300r/min, injecting the potassium persulfate solution obtained in the step 1) into the system, reacting for 8h at the constant temperature of 80 ℃ to obtain PS microsphere dispersion, and centrifuging and washing;
3) one third of the obtained PS emulsion is dispersed in a mixed solution of 80mL of ethanol and 20mL of acetonitrile and is marked as solution A, and 2mL of butyl titanate (TBOT) is dissolved in a mixed solution of 16mL of ethanol and 4mL of acetonitrile and is marked as solution B;
4) method for preparing PS @ TiO with core-shell structure by mixed solvent method2: slowly injecting the solution B into the solution A, controlling the dropping speed at 40 drops/min, adding 5mL of solution per drop at an interval of 8min, keeping stirring during the period, quickly and magnetically stirring at 30 ℃ for 500r/min, and obtaining PS @ TiO after 5h2The dispersion liquid is washed by deionized water for 3 times, washed by absolute ethyl alcohol for 3 times, ultrasonically dispersed for 25min in a washing and centrifuging gap, and the centrifuging speed is 8000r/min and the centrifuging time is 25 min. Drying and grinding into powder;
5) high-temperature treatment: calcining for 2h at 500 ℃ in a tubular furnace at the heating rate of 2 ℃/min; then calcining the mixture in a muffle furnace at 370 ℃ for 10min at the heating rateThe rate is 2 ℃/min. Calcining twice to obtain anatase TiO with perfect spherical shape2A core-shell powder material.
Example 3
An anatase titanium dioxide core-shell material with good spherical shape comprises the following steps:
1) purifying styrene, washing twice with 10% sodium hydroxide solution, washing three times with ultrapure water until the solution is neutral to remove a polymerization inhibitor, adding a small amount of solid anhydrous calcium chloride, removing water, sealing and storing in a refrigerator cold storage chamber, taking 14mL of the purified styrene solution, adding 1.0mL of alpha-methacrylic acid, 180mL of deionized water, and magnetically stirring for 30min at 400r/min to mix the solutions, and preparing 10mL of 1.7g/mL of potassium persulfate solution;
2) preparing PS colloidal microsphere emulsion: connecting a condensing device, putting the condensation device into a 90 ℃ oil bath kettle, magnetically stirring for 60min at 300r/min, injecting the potassium persulfate solution obtained in the step 1) into the system, reacting for 9h at the constant temperature of 90 ℃ to obtain PS microsphere dispersion, and centrifuging and washing;
3) one third of the obtained PS emulsion is dispersed in a mixed solution of 80mL of ethanol and 20mL of acetonitrile and is marked as solution A, and 3mL of butyl titanate (TBOT) is dissolved in a mixed solution of 16mL of ethanol and 4mL of acetonitrile and is marked as solution B;
4) method for preparing PS @ TiO with core-shell structure by mixed solvent method2: slowly injecting the solution B into the solution A, controlling the dropping speed at 60 drops/min, keeping stirring at the interval of 10min every 5mL, rapidly and magnetically stirring at 40 ℃ for 500r/min, and obtaining PS @ TiO after 5h2The dispersion liquid is washed by deionized water for 3 times, washed by absolute ethyl alcohol for 3 times, ultrasonically dispersed for 30min in a washing and centrifuging gap, and centrifuged at a rotating speed of 10000r/min for 30 min. Drying and grinding into powder;
5) high-temperature treatment: calcining for 2h at 520 ℃ in a tubular furnace, wherein the heating rate is 5 ℃/min; followed by calcination in a muffle furnace at 420 ℃ for 10min, with a temperature rise rate of 5 ℃/min. Calcining twice to obtain anatase TiO with perfect spherical shape2A core-shell powder material.
XRD analysis of the sample obtained in example 1 is shown in FIG. 1, TiO2In the anatase modification and in addition to TiO2And no impurity peak appears outside the characteristic peak, which indicates that the sample prepared by the method is pure.
The scanning electron micrograph of the sample after the primary calcination of example 1 is shown in fig. 2, and it can be seen from the micrograph that the spherical shell has a rough, wrinkled, uneven and severe aggregation surface, and the nucleus PS is reduced to carbon. EXAMPLE 1 Secondary calcination of the anatase TiO form2As shown in FIGS. 3 and 4, the thickness of the shell layer of the powder sample is about 10nm, and it can be clearly seen that the powder sample is a hollow spherical shell, the structure is uniform and complete, and the powder sample has few broken parts. The explanation shows that after the secondary low-temperature calcination in the muffle furnace, the carbon is oxidized into carbon dioxide gas to overflow, and meanwhile, the shell is expanded, and the phenomenon of wrinkles is obviously improved.
Example 3 increasing the ratio of the precursor solution butyl titanate to PS microspheres to obtain anatase TiO2The powder sample is shown in FIG. 5, and the shell thickness is about 20 nm. The hollow spherical shell can be clearly seen, the structure is uniform and complete, and the breakage is less.
Shell-structured TiO prepared in example 32The EDS spectrum is shown in figure 6, the existence of a small amount of C element indicates that residual in-situ synthesized carbon exists after the PS nuclear body is calcined in vacuum, and the elements of Ti and O prove that TiO2Is present. FIG. 7 is a two-dimensional surface scanning EDS energy spectrum showing that hollow TiO is evident2The large area distribution of structure, C, is due to the interference effect of the carbon film on the copper network.
Claims (5)
1. A preparation method of a spherical perfect anatase titanium dioxide hollow spherical shell is characterized by comprising the following steps:
step 1, preparing modified PS colloidal microsphere emulsion: uniformly mixing styrene, alpha-methacrylic acid and water, stirring and reacting at 75-90 ℃ for 30-60min, then injecting an initiator potassium persulfate solution, and reacting at 75-90 ℃ for 7-9h to obtain modified PS colloidal microsphere emulsion;
step 2, wrapping TiO2Shell layer structure: dispersing the obtained modified PS colloidal microsphere emulsion in a mixed solution of ethanol and acetonitrile, and recording as solution A; dissolving butyl titanate in a mixed solution of ethanol and acetonitrile, and marking as a solution B; under the condition of stirring, mixing the solution BSlowly injecting into the solution A, stirring and reacting to obtain PS @ TiO2The dispersion liquid of the microspheres is washed, dried and ground into PS @ TiO2Powder;
step 3, PS @ TiO2And (3) carrying out twice calcination treatment on the powder: the primary calcination is carried out for 2h at the temperature of 450-550 ℃; the secondary calcination is to calcine for 10min at the temperature of 320-420 ℃ to obtain the titanium dioxide hollow spherical shell;
in step 1, the ratio of styrene, alpha-methacrylic acid and water is: (7-14) mL: (0.5-1) mL: (90-180) mL;
in step 1, the ratio of potassium persulfate to styrene was 17 g: (7-14) mL;
in the step 2, after the solution B is injected into the solution A, the ratio of the modified PS colloidal microspheres to the butyl titanate is (3-6) g: (0.5-3) mL;
in the step 2, the solution B is slowly injected into the solution A and reacts for 1 to 30 hours at the temperature of between 20 and 40 ℃.
2. The method for preparing spherical hollow spherical shells of anatase titanium dioxide according to claim 1 wherein in step 1 the styrene used is purified by the following steps: washing styrene with sodium hydroxide solution, washing with ultrapure water until the solution is neutral, adding solid anhydrous calcium chloride, and removing water.
3. The method for preparing spherical intact anatase titanium dioxide hollow spheres according to claim 1 wherein in step 2, the dropping rate of the solution B is slowly injected into the solution A is controlled to be 30-60 drops/min, 5mL of solution is added every 5-10min, and stirring is maintained during the period.
4. The method for preparing spherical hollow spherical shells of anatase titanium dioxide according to claim 1 wherein in step 2, the washing is specifically: adding detergent, ultrasonic dispersing for 20-30min, and centrifuging; the centrifugal speed is 7000 plus 10000r/min, and the centrifugal time is 20-30 min.
5. The method for preparing spherical intact anatase titanium dioxide hollow spheres according to claim 1, wherein the primary calcination is carried out in a tube furnace at a temperature rise rate of 1-5 ℃/min to 480-520 ℃; the secondary calcination is to heat up to 320-420 ℃ in a muffle furnace at a heating rate of 1-5 ℃/min.
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