CN109796043B - Titanium oxide quantum dot material and macro preparation method and application thereof - Google Patents
Titanium oxide quantum dot material and macro preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a titanium oxide quantum dot material, a macro preparation method and application thereof, and relates to the field of materials. The material is prepared according to the following method: mixing and stirring a titanium element compound, a surfactant and an acid solution to obtain a first solution; mixing hydrogen peroxide and water to obtain a second solution; slowly dripping the second solution into the first solution to obtain a titanium oxide quantum dot colloid; and drying the obtained colloid to obtain titanium oxide quantum dot powder. The titanium oxide quantum dot powder provided by the invention is simple in preparation method, low in cost, capable of being prepared in large quantities, free of secondary pollution such as waste water and the like in the preparation process, and suitable for industrial production and the like. The prepared titanium oxide quantum dot material can be used in the fields of photocatalytic degradation, pigments, coatings, cosmetics and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a titanium oxide quantum dot material and a macro preparation method and application thereof.
Background
Titanium oxide is an important industrial raw material and is widely applied to the industries of printing ink, rubber, papermaking, chemical fiber, watercolor and the like. Meanwhile, titanium oxide is also a high-efficiency catalyst of the optical coating pigment, and can be used as an environment-friendly cleaning agent. In addition, because it has no toxicity and no harm to human body, it is also widely used in producing cosmetics such as sunscreen cream. The practical value of titanium oxide is being widely explored and its preparation and use is receiving increasing attention.
At present, the industrial preparation method of the nano titanium oxide mainly comprises a gas phase method and a liquid phase method. The vapor phase method specifically includes a titanium tetrachloride vapor phase method, a titanium alkoxide vapor phase deposition method, and a titanium alkoxide vapor phase hydrolysis method; the liquid phase method specifically includes a liquid phase deposition method, a sol-gel method, an alkoxide hydrolysis method, a hydrothermal method, a hydrolysis method, a microemulsion method, a microwave synthesis method, and the like. The existing preparation method of the titanium oxide material generally has the problems of low yield, high raw material cost, more process flows, generation of wastewater in the preparation process and other secondary pollution, and the development of the titanium oxide material is seriously hindered.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a titanium oxide quantum dot material, a macro preparation method and application thereof, so as to at least partially solve the technical problems.
(II) technical scheme
According to one aspect of the present invention, there is provided a macro preparation method of a titanium oxide quantum dot material, comprising:
a) mixing a titanium element compound, a surfactant and an acid solution to obtain a first solution; mixing hydrogen peroxide and water to obtain a second solution;
b) dropwise adding the second solution into the first solution to obtain a titanium oxide quantum dot colloid;
c) and drying the colloid to obtain titanium oxide quantum dot powder.
In further embodiments, the titanium atom compound comprises at least one of: titanium tert-butoxide, titanium trichloride, titanium tetrachloride, ammonium titanyl oxalate, tetraisobutyl titanate, tetra-n-butyl titanate, titanium isopropoxide and titanium sulfate.
In further embodiments, the surfactant comprises at least one of: lignosulfonate, heavy alkylbenzene sulfonate, alkyl sulfonate, hexadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, disodium ethylene diamine tetraacetate, lauroyl glutamic acid, sodium octadecyl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate.
In a further embodiment, the mixing amount ratio of the titanium element compound, the surfactant and the acid solution is 0.01-20 g: 0-10 g: 100 mL.
In further embodiments, the acid solution comprises at least one of: hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, and citric acid; and the pH value of the acid solution is 1-5.
In a further embodiment, the volume ratio of hydrogen peroxide to water in the second solution is between 0: 100 and 50: 100.
In a further embodiment, the second solution is added dropwise to the first solution at a rate of 0.1 to 50 drops/second, the temperature of the first solution is controlled at 5 to 100 ℃, and the first solution is stirred.
In further embodiments, the drying is freeze drying, heat drying or spray drying, and the drying is at a temperature of-50 to 150 ℃ for 1 to 72 hours.
According to still another aspect of the present invention, there is provided a titanium oxide quantum dot material prepared according to the above preparation method.
According to still another aspect of the present invention, there is provided a use of the above titanium oxide quantum dot material in the fields of photocatalytic degradation, pigments, coatings and cosmetics.
(III) advantageous effects
The titanium oxide quantum dot material colloid provided by the invention is a mixture of a nano material and a liquid phase, and the operations of solid-liquid separation, washing and the like are not needed when the material is prepared; the titanium oxide quantum dot material powder is obtained by drying titanium oxide quantum dot material colloid, and water and acid solution generated in the drying process can be recycled; therefore, the titanium oxide quantum dot material provided by the invention is simple in preparation method, low in cost, capable of being prepared in large quantities, free of secondary pollution such as waste water and the like in the preparation process, and good in economic benefit and environmental protection benefit. In addition, the titanium oxide quantum dot material provided by the invention has a huge application prospect, and is very suitable for being applied to the fields of photocatalytic degradation, pigments, coatings, cosmetics and the like.
Drawings
FIG. 1 is an XRD spectrum of a titanium oxide quantum dot material provided in example 1 of the present invention;
FIG. 2 is a transmission electron micrograph of a titanium oxide quantum dot material provided in example 1 of the present invention;
FIG. 3 is a graph of the UV-visible transmittance of a titanium oxide quantum dot material provided in example 1 of the present invention;
fig. 4 is a photograph of an actual image of 100g of the titanium oxide quantum dot material provided in example 1 of the present invention.
Detailed Description
The invention provides a titanium oxide quantum dot material, a macro preparation method and application thereof, and the technical scheme in the embodiment of the invention is clearly and completely described below. 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.
The invention provides a macroscopic quantity preparation method of a titanium oxide quantum dot material, which comprises the following steps:
a) mixing a titanium element compound, a surfactant and an acid solution to obtain a first solution; mixing hydrogen peroxide and water to obtain a second solution;
b) dropwise adding the second solution into the first solution to obtain a titanium oxide quantum dot colloid;
c) and drying the colloid to obtain titanium oxide quantum dot powder.
In the present invention, when the first solution is prepared, the acid solution is a concentrated acid or an aqueous solution thereof; and the concentrated acid includes but is not limited to one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and citric acid, preferably one or more of hydrochloric acid, nitric acid, acetic acid, oxalic acid and citric acid, and more preferably one or more of hydrochloric acid, acetic acid, oxalic acid and citric acid; the pH value of the acid solution is preferably 1-5, more preferably 2-5, and particularly 4.5. The titanium compound includes but is not limited to one or more of titanium tert-butoxide, titanium trichloride, titanium tetrachloride, titanyl ammonium oxalate, tetraisobutyl titanate, tetra-n-butyl titanate, titanium isopropoxide and titanium sulfate, preferably one or more of titanium tert-butoxide, titanium tetrachloride, titanyl ammonium oxalate, tetraisobutyl titanate, tetra-n-butyl titanate, titanium isopropoxide and titanium sulfate, more preferably one or more of titanium tert-butoxide, titanyl ammonium oxalate, tetraisobutyl titanate, tetra-n-butyl titanate, titanium isopropoxide and titanium sulfate; the surfactant includes, but is not limited to, lignosulfonate, heavy alkylbenzene sulfonate, alkylsulfonate, cetyl trimethyl ammonium bromide, sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, disodium ethylenediaminetetraacetate, lauroyl glutamic acid, sodium stearyl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate, preferably one or more of lignosulfonate, alkylsulfonate, cetyl trimethyl ammonium bromide, sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, disodium ethylenediaminetetraacetate, lauroyl glutamic acid, sodium stearyl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate, more preferably lignosulfonate, alkylsulfonate, hexadecyltrimethyl ammonium bromide, sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, disodium ethylenediaminetetraacetate, sodium lauryl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate, and more preferably lignosulfonate, alkylsulfonate, hexadecyltrimethyl ammonium bromide, sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, disodium ethylenediaminetetraacetate, sodium lauryl sulfate, sodium polyoxyethylene ether, One or more of lauroyl glutamic acid and sodium stearyl sulfate; in the present invention, the amount ratio of the titanium-containing compound, the surfactant and the acid solution is preferably (0.01-20) g to (0-10) g to 100mL, more preferably (0.1-10) g to (0-10) g to 100mL, and specifically may be 1: 0.5: 10.
In the present invention, the volume ratio of the hydrogen peroxide to the water in preparing the second solution is preferably (0 to 50) to 100, more preferably (0 to 30) to 70, and particularly may be 30 to 70. The second solution is dripped into the first solution, and the dripping speed is preferably 0.1-50 drops/second, more preferably 0.2-10 drops/second, and specifically can be 3 drops/10 seconds, 1 drop/second, 2 drops/second, 3 drops/second, 4 drops/second, 5 drops/second, 6 drops/second, 7 drops/second, 8 drops/second, 9 drops/second or 10 drops/second; when the second solution is dripped, the temperature of the first solution is preferably controlled to be 5-100 ℃, and specifically can be 20 ℃, 40 ℃, 60 ℃, 80 ℃ or 95 ℃; when the second solution is added dropwise, the first solution is preferably stirred.
In the present invention, the provided titanium oxide quantum dot colloidal material may be dried into a solid powder. The drying method is preferably one of freeze drying, heat drying and spray drying. The drying temperature is preferably-50-150 ℃, more preferably 0-120 ℃, and particularly can be 80 ℃. The drying time is preferably 1-72 h, more preferably 8-36 h, and particularly 15 h.
The titanium oxide quantum dot material colloid provided by the invention is a mixture of a nano material and a liquid phase, and the operations of solid-liquid separation, washing and the like are not needed when the material is prepared; the titanium oxide quantum dot material powder is obtained by drying titanium oxide quantum dot material colloid, and water and acid solution generated in the drying process can be recycled; therefore, the titanium oxide quantum dot material provided by the invention is simple in preparation method, low in cost, capable of being prepared in large quantities, free of secondary pollution such as waste water and the like in the preparation process, and good in economic benefit and environmental protection benefit. The titanium oxide quantum dot material provided by the invention has a huge application prospect, and is very suitable for being applied to the fields of photocatalytic degradation, pigments, coatings, cosmetics and the like.
The invention also provides a titanium oxide quantum dot material, which is prepared by the preparation method. And the titanium oxide quantum dot material is applied to the fields of photocatalytic degradation, pigments, coatings and cosmetics.
For greater clarity, further details are provided below by way of the following exemplary embodiments.
Example 1
Weighing 0.5g of tetrabutyl titanate, 0.2g of disodium ethylene diamine tetraacetate and 0.5g of citric acid, adding the weighed materials into a beaker which is filled with 50mL of deionized water and has the volume of 100mL, and stirring the mixture for 15 minutes by using a magnetic stirrer;
measuring 15mL of deionized water by using a measuring cylinder which is purchased from the market and has a measuring range of 50 mL;
and transferring the deionized water into a dropping funnel with the volume of 25mL, fixing the dropping funnel above the 100mL beaker by using an iron support, controlling the dropping speed to be 2 drops/second, dropwise adding the deionized water into the 100mL beaker, and continuously keeping the temperature of the solution at 40 ℃ during the dropwise adding process and continuously stirring. Finally, a milky white colloid was obtained. And finally, drying the colloid in a constant-temperature vacuum drying oven at 60 ℃ to obtain a white powder sample.
Detecting the obtained sample with X-ray diffractometer (model: PhilipsX' Pert PRO SUPER) to obtain X-ray diffraction pattern shown in figure 1, and determining the sample as Ti5O9. As can be seen from fig. 1: ti prepared in example 15O9The nano material is in an amorphous structure.
The obtained sample was examined with a transmission electron microscope (model: JEM-2100F) to obtain a transmission electron microscope photograph as shown in FIG. 2, and FIG. 2 is a transmission electron microscope photograph of the titanium oxide quantum dot material provided in example 1 of the present invention. As can be seen from fig. 2: the titanium oxide nano material prepared by the method is quantum dot in appearance and about 5 nm in size.
The sample was examined with an ultraviolet-visible spectrophotometer (model: DUV-3700) to obtain an ultraviolet-visible transmittance spectrum as shown in FIG. 3. As can be seen in fig. 3: the titanium oxide quantum dot material prepared by the embodiment can block over 75% of ultraviolet light.
FIG. 4 is a photograph showing 100g of a titanium oxide quantum dot powder provided in example 1 of the present invention.
Example 2
Weighing 0.35g of ammonium titanyl oxalate, 0.2g of polyvinylpyrrolidone and 0.45g of oxalic acid, adding the mixture into a beaker which is filled with 60mL of deionized water and has the volume of 100mL, and stirring the mixture for 15 minutes by using a magnetic stirrer;
measuring 2.5mL of 30% hydrogen peroxide aqueous solution by using a measuring cylinder which is purchased from the market and has the measuring range of 50 mL;
the aqueous hydrogen peroxide solution was transferred to a dropping funnel having a volume of 25mL, the dropping funnel was fixed above the 100mL beaker by an iron stand, the dropping speed was controlled to 1.5 drops/sec, the aqueous hydrogen peroxide solution was added dropwise to the 100mL beaker, and the solution temperature was kept at 30 ℃ during the dropwise addition while continuing to stir. Finally, a milky white colloid was obtained.
The same identification and detection analyses as in example 1 above were carried out on the obtained sample to confirm that the obtained sample contained Ti of uniform size0.72O2The nano particles, the titanium oxide quantum dot material prepared by the embodiment, can block over 75% of ultraviolet light.
Example 3
Weighing 1.5g of hydrochloric acid, adding the hydrochloric acid into a beaker which is filled with 60mL of deionized water and has the volume of 100mL, wherein the pH value is about 3, weighing 0.6g of titanium isopropoxide, adding the titanium isopropoxide into the acid solution, and stirring the mixture for 15 minutes by using a magnetic stirrer;
measuring 2mL of 30% hydrogen peroxide aqueous solution and 3mL of deionized water by using a measuring cylinder which is purchased from the market and has the measuring range of 50mL, and adding the measured solution and the 3mL of deionized water into a beaker with the volume of 20mL to obtain diluted hydrogen peroxide aqueous solution;
the diluted aqueous hydrogen peroxide solution was transferred to a dropping funnel having a volume of 15mL, the dropping funnel was fixed above the 100mL beaker by an iron stand, the dropping speed was controlled to 0.5 drops/sec, the aqueous hydrogen peroxide solution was added dropwise to the 100mL beaker, and the solution temperature was kept at 30 ℃ during the dropwise addition while continuing to stir. Finally, a milky white colloid was obtained.
The same identification and detection analyses as in example 1 above were carried out on the obtained sample to confirm that the obtained sample contained TiO of uniform size2The nano particles, the titanium oxide quantum dot material prepared by the embodiment, can block over 75% of ultraviolet light.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A macroscopic quantity preparation method of a titanium oxide quantum dot material comprises the following steps:
a) mixing a titanium source compound, a surfactant and an acid solution to obtain a first solution; mixing hydrogen peroxide and water to obtain a second solution;
b) dropwise adding the second solution into the first solution to obtain a titanium oxide quantum dot colloid;
c) drying the colloid to obtain titanium oxide quantum dot powder;
the mixing dosage ratio of the titanium source compound, the surfactant and the acid solution is 0.01-20 g: 0-10 g: 100 mL; the pH value of the acid solution is 1-5; the volume ratio of the hydrogen peroxide to the water in the second solution is between 0: 100 and 50: 100; the addition amounts of the hydrogen peroxide and the surfactant are not 0 at the same time; and when the second solution is dropwise added into the first solution, the speed is 0.2-10 drops/second, the temperature of the first solution is controlled at 20-40 ℃, and the first solution is stirred.
2. The macro production method of titanium oxide quantum dot material according to claim 1, wherein the titanium source compound comprises at least one of: titanium tert-butoxide, titanium trichloride, titanium tetrachloride, ammonium titanyl oxalate, tetraisobutyl titanate, tetra-n-butyl titanate, titanium isopropoxide and titanium sulfate.
3. The macro-preparation method of titanium oxide quantum dot material according to claim 1, wherein the surfactant comprises at least one of: lignosulfonate, heavy alkylbenzene sulfonate, alkyl sulfonate, hexadecyl trimethyl ammonium bromide, polyvinylpyrrolidone, polyvinyl alcohol, ethylene diamine tetraacetic acid, lauroyl glutamic acid, sodium stearyl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate.
4. The macroscopic quantity preparation method of titanium oxide quantum dot material of claim 1, wherein the acid solution comprises at least one of: hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, and citric acid.
5. The macro preparation method of the titanium oxide quantum dot material according to claim 1, wherein the drying is freeze drying, heat drying or spray drying, and the drying temperature is-50 to 150 ℃ and the drying time is 1 to 72 hours.
6. A titanium oxide quantum dot material, which is prepared by the preparation method according to any one of claims 1 to 5; the size of the titanium oxide quantum dot material is 5 nanometers.
7. Use of the titanium oxide quantum dot material according to claim 6 in the fields of photocatalytic degradation, pigments, coatings or cosmetics.
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