CN112758980A - TiO 22Nano material, preparation method and application thereof - Google Patents

TiO 22Nano material, preparation method and application thereof Download PDF

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CN112758980A
CN112758980A CN201911076127.0A CN201911076127A CN112758980A CN 112758980 A CN112758980 A CN 112758980A CN 201911076127 A CN201911076127 A CN 201911076127A CN 112758980 A CN112758980 A CN 112758980A
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tio
mixed material
hydrochloric acid
titanium chloride
concentration
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朴玲钰
伏兵
吴志娇
曹爽
郭凯
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National Center for Nanosccience and Technology China
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Abstract

The invention relates to a TiO compound2Nanomaterials, methods of preparation and uses thereof. The TiO is2The preparation method of the nano material comprises the following steps: (1) mixing water, a hydrochloric acid solution and a titanium chloride aqueous solution to obtain a mixed material; (2) mixing the mixed material with hydrogen peroxide to obtain a reaction precursor; (3) carrying out hydrothermal reaction on the reaction precursor to obtain TiO2And (3) nano materials. The TiO of the invention2The nano material is rutile type, has uniform size, good monodispersity, good crystallinity and high product purity, has higher photocatalytic activity under ultraviolet light and sunlight, and can effectively degrade organic dye and photolyze water to produce hydrogen. Operation of the preparation method of the inventionSimple, environment-friendly, mild reaction conditions, low energy consumption and more beneficial to practical application.

Description

TiO 22Nano material, preparation method and application thereof
Technical Field
The invention belongs to the field of medicineThe technical field of preparation of organic nano materials, in particular to TiO2Nanomaterials, methods of preparation and uses thereof.
Background
Nano TiO 22Is the hot spot of research today and is known as "the most promising material in the 21 st century" together with other nanomaterials. Nano TiO 22Has strong capability of absorbing and scattering ultraviolet rays, thereby being an excellent ultraviolet screening agent and being used in the fields of sunscreen skin care products, coatings and the like. Nano TiO 22The photocatalyst has high photocatalytic activity and has important application value in the fields of environmental pollutant degradation, antibiosis, self-cleaning and the like. Nano TiO 22The material also has photoelectric conversion performance, can be used as a photoelectric cell material, and shows great application potential in the aspect of solar energy conversion.
TiO of different crystal forms2Nanoparticles exhibit unique physical and chemical properties. In comparison with anatase, one is dealing with rutile TiO2The studies of (a) are rare. The reason is as follows: at present, rutile nano TiO synthesized by common hydrothermal method2The particles have irregular appearance, uneven size, poor dispersibility and serious agglomeration, which greatly reduces the nano TiO2Stability and photocatalytic activity. Researchers have adopted surface modification to improve rutile nano TiO2The dispersibility and stability of the particles are complex to operate and the effect is little. Therefore, the rutile TiO with uniform stability and good monodispersity is prepared2Single crystal materials are of great significance.
CN108455665A discloses a method for preparing rutile type nano titanium dioxide by continuous reaction, which belongs to the field of inorganic nano materials. The method comprises the following steps: (1) reacting a titanium tetrachloride solution with a sodium hydroxide solution in a continuous neutralization tank to generate white slurry, and flowing into a neutralization storage tank; (2) then the mixture enters a peptizing tank in batches, rutile phase titanium dioxide slurry is prepared through peptizing reaction, and rutile type nano titanium dioxide powder is obtained through plate-frame filtration, washing, drying and grinding; (3) and (3) enabling the rutile phase titanium dioxide slurry of the current batch to flow into a plate frame, namely putting the white slurry of the next batch into a peptizing tank, and repeating the operation in the step (2) to continuously prepare the rutile type nano titanium dioxide powder. However, the scheme has a somewhat complicated flow, and the crystallinity of the obtained product is somewhat poor.
CN1172856C discloses a method for producing rutile type nano titanium dioxide by a metastable chlorination method and the rutile type nano titanium dioxide obtained thereby. The method comprises the following steps: (1) and (3) hydrolysis reaction: hydrolyzing a titanium tetrachloride raw material in the presence of an alkali selected from ammonium hydroxide, sodium hydroxide or potassium hydroxide to obtain a mixed liquid containing a white precipitate; (2) sol-gel reaction: adding an acidic substance into the mixed liquid obtained in the step (1) to dissolve the white precipitate to form a uniform reaction solution, and then heating at 50-150 ℃ to slowly evaporate the liquid to form sol-gel, wherein the acidic substance is selected from hydrochloric acid, ammonium sulfide, sulfurous acid, stannous chloride, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium nitrite or sodium hydrosulfite; (3) filtering and washing: filtering and repeatedly washing the product obtained in the step (2) with water until the pH value is 6-8; (4) and (3) drying: drying the product obtained in the step (3) at the temperature of-30 ℃ and under the vacuum degree of 5-15 mmHg to obtain a metastable titanium dioxide precursor of a self-forming particle system; (5) high-temperature calcination: and (4) calcining the precursor obtained in the step (4) at the temperature of 200-1000 ℃ for 5 minutes to 6 hours. However, the synthesis steps of the scheme are somewhat complicated, and the dispersibility of the sample calcined at high temperature in a water phase is reduced, so that the economic benefit and performance of the product in practical application are lost.
Therefore, there is a need in the art to develop a new rutile TiO2Preparation method of nano material and rutile TiO obtained by using method2The nano material has regular appearance, uniformity and stability, good crystallinity and high photocatalytic activity, and is beneficial to practical application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide TiO2Nanomaterials, methods of preparation and uses thereof. The TiO is2The nano material has the advantages of regular shape, uniformity, stability, good monodispersity, good crystallinity, high product purity, high photocatalytic activity under sunlight and ultraviolet light and the like; and the preparation method is simple and environment-friendly,mild reaction conditions, low energy consumption and low cost, and is more beneficial to practical application.
One of the objects of the present invention is to provide a TiO compound2A method for preparing a nanomaterial, the method comprising the steps of:
(1) mixing water, a hydrochloric acid solution and a titanium chloride aqueous solution to obtain a mixed material;
(2) mixing the mixed material with hydrogen peroxide to obtain a reaction precursor;
(3) carrying out hydrothermal reaction on the reaction precursor to obtain TiO2And (3) nano materials.
The invention takes titanium chloride as a titanium source, hydrochloric acid and hydrogen peroxide as additives to form a precursor, and utilizes a hydrothermal method to synthesize stable TiO in one step2Nanomaterial of said TiO2The nano material is rutile type, and the method has the advantages of simple preparation method, environmental friendliness, mild reaction conditions, low energy consumption, low cost, more contribution to practical application and the like.
TiO obtained by the invention2The nano material has higher catalytic activity under sunlight and ultraviolet light, and can effectively degrade organic dye and photolyze water to produce hydrogen.
Preferably, the concentration of hydrochloric acid in the mixed material in the step (1) is 1-6 mol/L, such as 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L or 5.5 mol/L.
The concentration of the hydrochloric acid is 1-6 mol/L, the concentration is too high, and the product is easy to agglomerate; if the concentration is too low, the product is impure and has poor crystallinity.
Preferably, in the mixed material in the step (1), the concentration of the titanium chloride is 0.1-1.0 mol/L, such as 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L or 0.9 mol/L.
Preferably, the hydrochloric acid solution in the step (1) is concentrated hydrochloric acid with a mass fraction of 36% to 38%, such as 36.2%, 36.5%, 36.8%, 37%, 37.2%, 37.5%, 37.8%, and the like.
Preferably, the titanium chloride aqueous solution in the step (1) is a titanium trichloride aqueous solution and/or a titanium tetrachloride aqueous solution, preferably a titanium tetrachloride aqueous solution of 1-6 mol/L, such as 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L or 5.5 mol/L.
Preferably, the temperature of the mixing process in step (1) is <4 ℃, preferably the mixing is performed in an ice-water bath below 4 ℃, such as 0 ℃, 1 ℃, 2 ℃ or 3 ℃, and the like.
Preferably, H in the hydrogen peroxide in the step (2)2O2The molar ratio of the titanium chloride to the titanium chloride in the mixed material is (0.025 to 1.2):1, for example, 0.03:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1 or 1.1: 1.
H in hydrogen peroxide2O2The molar ratio of the titanium chloride to the titanium chloride in the mixed material is (0.025-1.2): 1, and the molar ratio is too large, so that the product properties are not greatly influenced, but the raw materials are wasted; the molar ratio is too small, and the product is easy to agglomerate.
Preferably, the hydrogen peroxide in the step (2) is 20-30% by mass, such as 22%, 24%, 25%, 26%, 28% or 29%.
Preferably, the mixing process of the mixed material and hydrogen peroxide in the step (2) is as follows: and (4) dropwise adding hydrogen peroxide into the mixed material.
Preferably, the hydrothermal reaction in step (3) is carried out at a temperature of 100 to 220 ℃, for example, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ or 210 ℃.
The temperature of the hydrothermal reaction is 100-220 ℃, the temperature of the hydrothermal reaction is too high, and the product is easy to agglomerate; the hydrothermal reaction temperature is too low, and the crystallinity of the product is poor.
Preferably, the hydrothermal reaction time in the step (3) is 6-20 h, such as 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h or 19 h.
Preferably, after the hydrothermal reaction in step (3), a washing and drying process is further included.
Preferably, the washing is 2-3 times by respectively washing with ethanol and water.
Preferably, the drying is room temperature drying, 60 to 80 ℃ (e.g. 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃ or 78 ℃) air blast drying or-75 to-50 ℃ (e.g. -72 ℃, -70 ℃, -68 ℃, -65 ℃, -62 ℃, -60 ℃ or-55 ℃) freeze drying.
As a preferred technical scheme, the TiO is2A method for preparing a nanomaterial, the method comprising the steps of:
(1) mixing water, concentrated hydrochloric acid with the mass fraction of 36% -38% and a titanium chloride aqueous solution in an ice-water bath at the temperature of below 4 ℃ to obtain a mixed material, wherein the hydrochloric acid concentration is 1-6 mol/L, and the titanium chloride concentration is 0.1-1.0 mol/L;
(2) dropwise adding 20-30% of hydrogen peroxide in the mixed material, wherein H is contained in the hydrogen peroxide2O2The molar ratio of the titanium chloride to the titanium chloride in the mixed material is (0.025-1.2): 1, and a reaction precursor is obtained;
(3) carrying out hydrothermal reaction on the reaction precursor at the temperature of 100-220 ℃ for 6-20 h, washing and drying to obtain TiO2And (3) nano materials.
Preferably, the concentration of the hydrochloric acid is 1.0-6.0 mol/L, the concentration of the titanium chloride is 0.1-1.0 mol/L, and the obtained TiO2More than or equal to 90 wt% of the crystal form of the nano material is rutile, and the rest is brookite, wherein the TiO is2The morphology of nanomaterials includes rod-like, spherical and cubic particles.
In the invention, under the acidic condition, chloride ions play a crucial role in the formation of rutile, so when the concentration of hydrochloric acid and the concentration of titanium chloride are proper, pure rutile nanocrystals are formed. Brookite is a thermodynamically unstable phase, formed as a by-product at the critical point of pure rutile formation.
In the invention, the concentration of hydrochloric acid is 2.5-3.5 mol/L, the concentration of titanium chloride is 0.2-0.5 mol/L, and the obtained TiO290-95 wt% of the crystal form of the nano material is rutile, and the balance is brookite.
In the present invention, other concentration ranges than the above range are exemplified by: the concentration of the hydrochloric acid is 1.0-6.0 mol/L, and the concentration of the titanium chloride is 0.5-1.0 mol/L; the concentration of the hydrochloric acid is 1.0-2.5 mol/L, and chlorineThe titanium concentration is 0.1-0.5 mol/L; the concentration of the hydrochloric acid is 2.5-3.5 mol/L, and the concentration of the titanium chloride is 0.1-0.2 mol/L; the concentration of the hydrochloric acid is 3.5-6.0 mol/L, the concentration of the titanium chloride is 0.1-0.5 mol/L, and the obtained TiO2The crystal form of the nano material is pure rutile, and the TiO is2The shape of the nano material is rod-shaped.
Preferably, the TiO is2The crystal form of the nano material is pure rutile, the shape is rod-shaped, and the sizes of the long axis and the short axis of the nano material are both less than 100 nm.
Preferably, the diameter of the sphere is 35-45 nm, such as 36nm, 37nm, 38nm, 40nm, 42nm or 44 nm.
Preferably, the cubic particles have a size of 25 to 45nm, such as 26nm, 27nm, 28nm, 30nm, 32nm, 34nm, 35nm, 36nm, 38nm, 40nm, 42nm, 44nm, or the like.
The second object of the present invention is to provide a TiO compound2Nanomaterial of said TiO2The nanomaterial is obtained by the preparation method described in one of the purposes.
TiO of the invention2The nano material has the advantages of regular shape, uniformity, stability, good monodispersity, good crystallinity, high product purity, high photocatalytic activity under sunlight and ultraviolet light and the like.
Preferably, the TiO is2The crystalline form of the nanomaterial comprises rutile, preferably pure rutile TiO2。
It is a further object of the present invention to provide a TiO as described in the second object2Use of nanomaterials, said TiO2The nano material is used in any one or combination of at least two of the fields of photocatalysis, solar cells, self-cleaning materials and sterilization and bacteriostasis.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention develops a new TiO2Preparation method of nano material and TiO obtained by using method2The nano material is rutile type, has regular shape, uniformity, stability, good monodispersity, good crystallinity and high product purity, and can be used in sunlight and ultravioletHas the advantages of high photocatalytic activity under light and the like.
(2) The preparation method disclosed by the invention is simple to operate, environment-friendly, mild in reaction condition, low in energy consumption and low in cost, and is more beneficial to practical application.
Drawings
FIG. 1 shows TiO prepared in example 1 of the present invention2SEM images of nanomaterials;
FIG. 2 shows TiO prepared in example 1 of the present invention2XRD pattern of the nano material;
FIG. 3 shows TiO prepared in example 1 of the present invention2A curve graph of the change of the gas generation amount along with time in the process of preparing hydrogen by decomposing water by photocatalysis of the nano material under ultraviolet light;
FIG. 4 shows TiO prepared in example 1 of the present invention2Nano material (A) and rutile type TiO with particle size of 25nm purchased from alatin2And (3) degrading the rhodamine B photocatalysis effect contrast diagram by the particles (B) under ultraviolet light.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
(1) Adding 4mL of concentrated hydrochloric acid solution into 7mL of deionized water, uniformly stirring to form a dilute hydrochloric acid solution, and dropwise adding 1mL of 3mol/L TiCl while stirring4Continuously stirring the solution uniformly to obtain a mixed material, wherein the concentration of hydrochloric acid (HCl) in the mixed material is 4.02mol/L, and TiCl4The concentration is 0.25 mol/L;
(2) dropwise adding 0.1mL of 30 wt% commercially available hydrogen peroxide into the mixed material obtained in the step (1) while stirring, and continuously stirring uniformly to obtain an orange precursor;
(3) transferring the precursor in the step (2) into a 100mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 8h to obtain white emulsion;
(4) after the reaction is finished, washing the white emulsion obtained in the step (3) with ethanol for 3 times, then washing with water for 3 times, drying by air blowing at 80 ℃,to obtain TiO2Nanomaterial of said TiO2The nano material is rutile type, and has regular appearance, uniform size, stable property and good monodispersity.
FIG. 1 shows TiO prepared in this example2SEM image of the nanomaterial, from which it can be seen that TiO obtained in this example2The nano material has regular appearance, uniform size and good monodispersity;
FIG. 2 shows TiO prepared in this example2XRD pattern of the nanomaterial, as can be seen from the figure, TiO obtained in this example2The nano material is in a rutile type, does not have other crystal forms, and has high purity;
FIG. 3 shows TiO prepared in this example2The curve of the change of the gas generation amount with time in the process of preparing hydrogen by decomposing water through photocatalysis of the nano material under ultraviolet light can be seen from the figure, and the rutile TiO prepared by the embodiment2The nano material can stably decompose water under ultraviolet light to generate hydrogen.
Example 2
(1) Adding 4mL of concentrated hydrochloric acid solution into 19mL of deionized water, uniformly stirring to form dilute hydrochloric acid solution, and dropwise adding 1mL of 3mol/L TiCl while stirring4Continuously stirring the solution uniformly to obtain a mixed material, wherein the concentration of hydrochloric acid in the mixed material is 2.0mol/L, and TiCl is used for preparing the mixed material4The concentration is 0.13 mol/L;
(2) dropwise adding 0.05mL of 30 wt% commercially available hydrogen peroxide into the mixed material obtained in the step (1) while stirring, and continuously stirring uniformly to obtain an orange precursor;
(3) transferring the precursor in the step (2) into a 100mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 220 ℃ for 8h to obtain white emulsion;
(4) after the reaction is finished, washing the white emulsion obtained in the step (3) with ethanol for 3 times, then washing with water for 3 times, and drying by blowing air at 80 ℃ to obtain TiO2Nanomaterial of said TiO2The nano material is rutile type, and has regular appearance, uniform size, stable property and good monodispersity.
Example 3
(1) Will be 5mAdding L concentrated hydrochloric acid solution into 6mL deionized water, stirring uniformly to form dilute hydrochloric acid solution, and dropwise adding 1mL of 3mol/L TiCl while stirring4Continuously stirring the solution uniformly to obtain a mixed material, wherein the concentration of hydrochloric acid in the mixed material is 5.03mol/L, and TiCl4The concentration is 0.25 mol/L;
(2) dropwise adding 0.1mL of 30 wt% commercially available hydrogen peroxide into the mixed material obtained in the step (1) while stirring, and continuously stirring uniformly to obtain an orange precursor;
(3) transferring the precursor in the step (2) into a 100mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 12h to obtain white emulsion;
(4) after the reaction is finished, washing the white emulsion obtained in the step (3) with ethanol for 3 times, then washing with water for 3 times, and drying by blowing air at 80 ℃ to obtain TiO2Nanomaterial of said TiO2The nano material is in a rutile type.
Example 4
(1) Adding 16mL of concentrated hydrochloric acid solution into 24mL of deionized water, uniformly stirring to form dilute hydrochloric acid solution, and dropwise adding 8mL of 3mol/L TiCl while stirring4Continuously stirring the solution uniformly to obtain a mixed material, wherein the concentration of hydrochloric acid in the mixed material is 4.02mol/L, and TiCl4The concentration is 0.25 mol/L;
(2) dropwise adding 0.6mL of 30 wt% commercially available hydrogen peroxide into the mixed material obtained in the step (1) while stirring, and continuously stirring uniformly to obtain an orange precursor;
(3) transferring the precursor in the step (2) into a 100mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 8h to obtain white emulsion;
(4) after the reaction is finished, ultrasonically dispersing the white emulsion obtained in the step (3), washing the white emulsion for 3 times by using ethanol, then washing the white emulsion for 3 times, and drying the white emulsion by blowing air at the temperature of 80 ℃ to obtain TiO2Nanomaterial of said TiO2The nano material is rutile type, and has regular appearance, uniform size, stable property and good monodispersity.
Example 5
The difference from the example 1 is that hydrochloric acid is contained in the mixed material in the step (1)The concentration is 1.0mol/L, TiO is obtained2Nanomaterial of said TiO2The nano material is pure rutile type, but the dispersibility thereof is deteriorated.
Example 6
The difference from example 1 is that in the mixed material in the step (1), the hydrochloric acid concentration is 6.0mol/L to obtain TiO2Nanomaterial of said TiO2The nano material is pure rutile type, but the dispersibility thereof is deteriorated.
Example 7
The difference from example 1 is that in the mixed material in the step (1), the hydrochloric acid concentration is 0.5mol/L, and TiO is obtained2Nanomaterial of said TiO2The content of rutile in the nano material is 40-50%, and the rest is anatase, so that the dispersibility is poor.
Example 8
The difference from the example 1 is that in the mixed material in the step (1), the hydrochloric acid concentration is 8mol/L, and TiO is obtained2Nanomaterial of said TiO2The nano material is pure rutile type, but the agglomeration is serious.
Example 9
The difference from the example 1 is that in the mixed material in the step (1), TiCl4The concentration is 0.05mol/L, TiO is obtained2Nanomaterial of said TiO2The nano material is pure rutile type, but the size is larger.
Example 10
The difference from the example 1 is that in the mixed material in the step (1), TiCl4The concentration is 2mol/L, TiO is obtained2Nanomaterial of said TiO2The nano material is pure rutile type, but the agglomeration is serious.
Example 11
The difference from the example 1 is that the hydrogen peroxide in the step (2) is H2O2The molar ratio of the titanium chloride to the titanium chloride in the mixed material is 0.01:1 to obtain TiO2Nanomaterial of said TiO2The nano material is pure rutile type, but the agglomeration is serious.
Example 12
The difference from example 1 is the steps(2) H in the hydrogen peroxide2O2The mass ratio of the titanium chloride to the titanium chloride in the mixed material is 2:1 to obtain TiO2Nanomaterial of said TiO2The nano material is pure rutile type.
Example 13
The difference from example 1 is that the temperature of the hydrothermal reaction in step (3) is 80 ℃ to obtain TiO2Nanomaterial of said TiO2The nano material contains rutile and anatase, and has poor crystallinity and dispersibility.
Example 14
The difference from example 1 is that the temperature of the hydrothermal reaction in step (3) is 240 ℃ to obtain TiO2Nanomaterial of said TiO2The nano material is pure rutile, but the size of the nano material is overlarge and the dispersibility of the nano material is poor.
Comparative example 1
The difference from example 1 is that TiCl is used in step (1)4Replacing with an equimolar amount of titanate to obtain TiO2Nanomaterial of said TiO2The nano material is pure rutile, but the size of the nano material is increased, and the dispersibility of the nano material is poor.
Comparative example 2
The difference from example 1 is that the hydrochloric acid in step (1) is replaced by nitric acid to obtain TiO2Nanomaterial of said TiO2The nano material contains rutile and anatase, and has poor crystallinity and dispersibility.
Comparative example 3
The difference from example 1 is that TiO was obtained without carrying out step (2), i.e., without adding hydrogen peroxide2Nanomaterial of said TiO2The nano material is pure rutile type, but the agglomeration is serious.
Comparative example 4
Rutile TiO with particle size of 25nm from Allantin2And (3) granules.
FIG. 4 shows TiO prepared in example 12The comparison graph of the photocatalytic effect of the nano material (A) and the comparative example (B) for degrading rhodamine B under ultraviolet light shows that the rutile TiO prepared in the embodiment 3 of the invention2The nanometer material has higher activity in photodegradation of rhodamine BHigh, compared to 25nm particle size rutile TiO available from Aladdin2The particle performance is excellent.
And (3) performance testing:
the products obtained in the examples and comparative examples were subjected to the following photocatalytic performance tests:
(1) prepared TiO2Platinum nanoparticles with the mass fraction ratio of 1.0 percent on the nano material photo-reduction load are used as a photocatalyst, 0.001g of the photocatalyst is added into 20mL of deionized water, the mixture is uniformly dispersed by ultrasonic waves and transferred into a quartz reactor, a silica gel plug is used for sealing, argon is introduced to remove air dissolved in the reactor and the mixed solution, a high-pressure mercury lamp is used for irradiating the reactor to generate hydrogen, and the type and the quantity of the generated gas are detected by gas chromatography every 1 h. (the test was cumbersome and only the product performance in example 1 was tested as a reference)
(2) 0.01g of TiO was taken2Adding a nano material serving as a photocatalyst into 50mL of 25mg/L rhodamine B aqueous solution, stirring for 1h under a dark condition to enable adsorption-desorption balance between the photocatalyst and a dye to be achieved, irradiating a reactor from the outside by using a high-pressure xenon lamp with the emission wavelength of 350-360 nm, sampling every 15min in the illumination process, centrifuging for 5min at 10000r/min, taking upper-layer clear liquid, and testing in an ultraviolet-visible spectrophotometer, wherein the concentration of the rhodamine B solution corresponds to the absorbance at 553.5 nm;
table 1 shows the comparative data of the photocatalytic degradation rate (%) of rhodamine B degraded by the products obtained in the examples and the comparative examples under the ultraviolet light for 2 h.
TABLE 1
Figure BDA0002262504990000121
Figure BDA0002262504990000131
As can be seen from Table 1, the rutile TiO obtained in the examples of the invention2The single crystal nano rod has high photocatalytic activity and can be degraded under the irradiation of ultraviolet light for 2 hoursThe photocatalytic degradation rate of rhodamine B can reach 99%.
As can be seen from Table 1, the materials obtained in examples 7-8 of the present invention have poor photocatalytic activity compared to example 1, because the hydrochloric acid concentration in example 7 is 0.5mol/L, and the concentration is too low, the product is impure and has poor crystallinity; in example 8, since the concentration of hydrochloric acid was too high, the product was easily agglomerated, and thus the photocatalytic activities of the materials obtained in examples 7 to 8 were inferior to those of the material obtained in example 1.
As can be seen from Table 1, the materials obtained in inventive examples 9 to 10 have a poorer photocatalytic activity than in example 1, since TiCl is present in example 94The concentration is 0.05mol/L, TiCl4The content is too small, and the size is large; TiCl in example 104At a concentration of 2mol/L, TiCl4Too much content causes serious agglomeration, and thus the photocatalytic activity is poor.
As can be seen from Table 1, the photocatalytic activity of the materials obtained in inventive examples 11 to 12 is inferior to that of example 1, since H is present in example 112O2The molar ratio of the titanium chloride to the titanium chloride in the mixed material is 0.01:1, and the product is easy to agglomerate to influence the photocatalytic activity; example 12H2O2The molar ratio of the titanium chloride to the titanium chloride in the mixed material is 2:1, and the excessive molar ratio has little influence on the properties of the product but causes resource waste.
As can be seen from Table 1, the materials obtained in examples 13-14 of the present invention have poor photocatalytic activity compared to example 1, because the hydrothermal reaction temperature in example 13 is 80 ℃, the hydrothermal reaction temperature is too low, and the crystallinity of the product is poor; in example 13, the hydrothermal reaction temperature was 240 ℃, and the product was easily agglomerated due to the excessively high hydrothermal reaction temperature, and thus the photocatalytic activity was poor.
As can be seen from Table 1, comparative examples 1 to 4 according to the invention have a poorer photocatalytic activity than the material obtained in example 1, since in comparative example 1 an organic titanate is used and the TiO obtained is2The size of the nano material is increased, and the dispersibility is deteriorated; comparative example 2 in which hydrochloric acid was replaced with nitric acid, resulting in TiO2The crystallinity and the dispersibility of the nano material are poor; comparative example 3 No Hydrogen peroxide addition, resulting TiO2The agglomeration of the nano material is serious, which affects the photo catalytic activitySex; TiO obtained by the invention2The photocatalytic activity of the nano material is far higher than that of the existing commercially available TiO2And (5) producing the product.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. TiO 22The preparation method of the nano material is characterized by comprising the following steps:
(1) mixing water, a hydrochloric acid solution and a titanium chloride aqueous solution to obtain a mixed material;
(2) mixing the mixed material with hydrogen peroxide to obtain a reaction precursor;
(3) carrying out hydrothermal reaction on the reaction precursor to obtain TiO2And (3) nano materials.
2. The preparation method according to claim 1, wherein the concentration of hydrochloric acid in the mixed material in the step (1) is 1 to 6 mol/L;
preferably, in the mixed material in the step (1), the concentration of titanium chloride is 0.1-1.0 mol/L;
preferably, the hydrochloric acid solution in the step (1) is concentrated hydrochloric acid with the mass fraction of 36-38%.
3. The preparation method according to claim 1 or 2, wherein the aqueous titanium chloride solution in the step (1) is an aqueous titanium trichloride solution and/or an aqueous titanium tetrachloride solution, preferably an aqueous titanium tetrachloride solution of 1 to 6 mol/L;
preferably, the temperature of the mixing process of step (1) is <4 ℃, preferably the mixing is performed in an ice-water bath below 4 ℃.
4. The method according to any one of claims 1 to 3, wherein H in the hydrogen peroxide in the step (2)2O2The molar ratio of the titanium chloride to the titanium chloride in the mixed material is (0.025-1.2): 1;
preferably, the hydrogen peroxide in the step (2) is 20-30% by mass;
preferably, the mixing process of the mixed material and hydrogen peroxide in the step (2) is as follows: and (4) dropwise adding hydrogen peroxide into the mixed material.
5. The method according to any one of claims 1 to 4, wherein the hydrothermal reaction in the step (3) is carried out at a temperature of 100 to 220 ℃;
preferably, the hydrothermal reaction time in the step (3) is 6-20 h;
preferably, after the hydrothermal reaction in step (3), washing and drying processes are also included;
preferably, the washing is respectively washing for 2-3 times by adopting ethanol and water;
preferably, the drying is room temperature drying, 60-80 ℃ forced air drying or-75-50 ℃ freeze drying.
6. Preparation process according to one of claims 1 to 5, characterized in that it comprises the following steps:
(1) mixing water, concentrated hydrochloric acid with the mass fraction of 36% -38% and a titanium chloride aqueous solution in an ice-water bath at the temperature of below 4 ℃ to obtain a mixed material, wherein the hydrochloric acid concentration is 1-6 mol/L, and the titanium chloride concentration is 0.1-1.0 mol/L;
(2) dropwise adding 20-30% of hydrogen peroxide in the mixed material, wherein H is contained in the hydrogen peroxide2O2The molar ratio of the titanium chloride to the titanium chloride in the mixed material is (0.025-1.2) 1, so as to obtain a reaction precursor;
(3) carrying out hydrothermal reaction on the reaction precursor at the temperature of 100-220 ℃ for 6-20 h, washing and drying to obtain TiO2And (3) nano materials.
7. The method according to any one of claims 1 to 6, wherein the hydrochloric acid concentration is 1.0 to 6.0mol/L and the titanium chloride concentration is 0.1 to 1.0mol/L, and the obtained TiO2More than or equal to 90 wt% of the crystal form of the nano material is rutile, and the rest is brookite, wherein the TiO is2The morphology of the nano material comprises rod-shaped, spherical and cubic particles;
preferably, the TiO is2The nano material is pure rutile type, the shape is rod-shaped, and the sizes of the long axis and the short axis are both less than 100 nm;
preferably, the diameter of the sphere is 35-45 nm;
preferably, the size of the cubic particles is 25 to 45 nm.
8. TiO 22Nanomaterial characterized in that the TiO is2The nanomaterial obtained by the production method according to any one of claims 1 to 7.
9. The TiO of claim 82Nanomaterial characterized in that the TiO is2The crystalline form of the nanomaterial comprises rutile, preferably pure rutile TiO2。
10. A TiO as claimed in claim 8 or 92Use of a nanomaterial, characterized in that the TiO is2The nano material is used in any one or combination of at least two of the fields of photocatalysis, solar cells, self-cleaning materials and sterilization and bacteriostasis.
CN201911076127.0A 2019-11-06 2019-11-06 TiO 22Nano material, preparation method and application thereof Pending CN112758980A (en)

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