CN112142104A - Preparation of nano black TiO by aerosol method2Method (2) - Google Patents

Preparation of nano black TiO by aerosol method2Method (2) Download PDF

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CN112142104A
CN112142104A CN202011088134.5A CN202011088134A CN112142104A CN 112142104 A CN112142104 A CN 112142104A CN 202011088134 A CN202011088134 A CN 202011088134A CN 112142104 A CN112142104 A CN 112142104A
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aerosol
precursor solution
titanium
black tio
tio
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Inventor
姜兴茂
季凯
张睿
许梓欣
许钰清
姜建霖
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Wuhan Institute of Technology
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Wuhan Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/07—Producing by vapour phase processes, e.g. halide oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Abstract

The invention discloses a method for preparing nano black TiO by aerosol method2The method comprises the following steps: 1) dissolving a titanium source in an organic solvent, and uniformly mixing to form a homogeneous solution or a colloidal solution to obtain a precursor solution; 2) atomizing the obtained precursor solution by using an atomizer to form aerosol liquid drops; 3) introducing the formed aerosol droplets into a tubular furnace for calcination to obtain the black TiO2And (3) nano powder. The invention firstly proposes that the black TiO is prepared by adopting an aerosol method2Preparing precursor solution by using a titanium source and an organic solvent, atomizing the precursor solution to form small droplets, directly calcining the droplets without additionally introducing other reduction conditions to obtain black TiO2A nanoparticle; the related preparation method is simple, convenient to operate, good in repeatability and suitable for popularization and application.

Description

Preparation of nano black TiO by aerosol method2Method (2)
Technical Field
The invention belongs to the technical field of preparation of inorganic functional materials, and particularly relates to a method for preparing nano black TiO by an aerosol method2The method of (1).
Background
Since 1972, Japanese scientists discovered TiO2The electrode has the property of hydrolyzing water, and then TiO2The material has become a hot spot for researchers of photocatalyst materials. Compared with other various materials, the material can remove organic pollutants, photolyze water to produce hydrogen and carry out various photocatalytic reactions, and TiO2Has the unique advantages of rich energy storage, strong oxidizing property, light corrosion resistance and the like. TiO 22The forbidden band energy width of the solar cell is 3.0-3.2 eV, and the solar cell can only absorb the energy of an ultraviolet region, so that the utilization efficiency of solar energy is less than 5%. To promote TiO2Performance of (2) on ordinary TiO by researchers2The materials are doped, coupled and disordered, and the like, so that the performance is improved to a certain extent, but the effect is still unsatisfactory, and secondary pollution is caused. 2011, black TiO2The discovery of (A) brings a new hope to the series of problems, and the dawn et al think that hydrogenation can adjust TiO2The material has wide band gap, and can extend the light absorption range to the infrared light region, thereby effectively improving the quantum efficiency and the light response range. From this, black TiO2The nano material has attracted extensive scientific research interest, and has extensive application research in the fields of lithium battery, super capacitor, energy battery, field emission electrode, etc.
At present, nano-black TiO2The main preparation method mainly comprises the following steps: hydrogenation (high-temperature treatment in a hydrogen gas or hydrogen plasma environment), chemical reduction (aluminum reduction, magnesium reduction, sodium borohydride reduction, sodium hydride reduction), chemical oxidation, electrochemical reduction, anodic oxidation-annealing, ultrasonic excitation, laser modification, and the like. Among the specific preparation methods, the hydrogenation treatment needs a high-pressure environment and a hydrogen atmosphere, and the safety is low; the chemical reduction method needs to introduce a certain amount of reducing agent, so that the purity of the product is not high; other materials have complicated preparation methods, high energy consumption and high yieldThe particles are large and cannot meet the related performance requirements.
Disclosure of Invention
The invention mainly aims to provide a method for preparing nano black TiO by aerosol aiming at the defects of the prior preparation technology2The method comprises the steps of preparing a precursor solution from a titanium source and an organic solvent, atomizing the precursor solution into aerosol droplets, and then evaporating, crystallizing, drying and pyrolyzing the aerosol droplets in a reducing atmosphere to finally form black TiO2Nano powder; the preparation method provided by the invention is simple, and the obtained product has high purity, good monodispersity, high purity of particle spherical shape and stable product performance, and is suitable for industrial production.
In order to achieve the purpose, the invention adopts the technical scheme that:
preparation of nano black TiO by aerosol method2The method comprises the following steps:
1) dissolving a titanium source in an organic solvent, and uniformly mixing to form a homogeneous solution or a colloidal solution to obtain a precursor solution;
2) atomizing the obtained precursor solution by using an atomizer to form aerosol liquid drops;
3) introducing the formed aerosol droplets into a tubular furnace for calcination to obtain the black TiO2And (3) nano powder.
In the scheme, the titanium source can be tetrabutyl titanate, titanium tetrachloride, titanium trichloride, titanium isopropoxide, titanium sulfate, titanyl difluoride, metatitanic acid or nano-scale titanium dioxide and the like.
In the above scheme, the organic solvent may be alcohol such as absolute ethyl alcohol, methanol, benzyl alcohol or isopropanol, or soluble alkane such as hexane, heptane or octane, or a mixture of the above solvents.
In the scheme, the molar ratio of the titanium source to the organic solvent in the precursor solution is 1 (1-1000); preferably 1 (10-500).
In the scheme, the particle size of the aerosol liquid drop is 0.01-200 mu m.
In the above scheme, the atomization mode comprises an ultrasonic atomizer, an air compression atomizer or centrifugal atomization and the like.
In the above scheme, the black TiO2The nano-powder can be collected by a filter.
In the scheme, the calcining temperature is 600-1600 ℃, the time is 0.01-60 s, and the atmosphere is Air and N2Ar, He or other mixed gases.
Preferably, the calcination time in the step 3) is 0.01-10 s.
Preferably, the calcination temperature is 600-1000 ℃.
In the scheme, the obtained nano black TiO2The particle diameter of the particles is 0.001 to 100 μm.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention firstly proposes that the black TiO is prepared by adopting an aerosol method2Preparing precursor solution by using a titanium source and an organic solvent, atomizing the precursor solution, directly calcining the atomized precursor solution without additionally introducing other reduction conditions to obtain black TiO2A nanoparticle; the related preparation method is simple, convenient to operate, good in repeatability and suitable for popularization and application;
2) the invention has wide source of raw materials, relatively mild reaction conditions and can prepare the nano black TiO with different particle sizes and different reduction degrees according to different product requirements2And (3) granules.
3) The black TiO obtained by the invention2The nano particles have high purity and good monodispersity, can show excellent photocatalytic performance and the like, have the photodegradation efficiency of methylene blue, rhodamine B and other fuels of over 95 percent, and can be suitable for the fields of photocatalytic environmental pollutants and the like.
Drawings
FIG. 1 shows the black TiO nanoparticles obtained in example 12A graph of the ultraviolet-visible absorption spectrum of the particles;
FIG. 2 shows the black TiO nanoparticles obtained in example 12XRD pattern of the particles;
FIG. 3 shows the black TiO nanoparticles obtained in example 12TEM images of the particles;
FIG. 4 shows the black TiO nanoparticles obtained in example 22XRD pattern of the particles;
FIG. 5 nanometer black TiO obtained in example 22TEM images of the particles;
FIG. 6 nanometer black TiO obtained in example 32XRD pattern of the particles;
FIG. 7 nanometer black TiO obtained in example 32TEM images of the particles.
FIG. 8 is a graph showing the comparison of the performance of the black titanium dioxide obtained by the present invention and the performance of the common white titanium dioxide for degrading tetracycline.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Preparation of nano black TiO by aerosol method2The method comprises the following steps:
respectively weighing 10g of n-butyl titanate and 100g of absolute ethyl alcohol, pouring the n-butyl titanate and the absolute ethyl alcohol into a beaker, and uniformly mixing the n-butyl titanate and the absolute ethyl alcohol by ultrasonic waves to obtain a homogeneous precursor solution; with N2Is used as carrier gas, the pressure of the carrier gas is controlled to be 0.1Mpa, the precursor solution is atomized into aerosol liquid drops with the diameter of 2 mu m by an atomizer, and then the aerosol liquid drops are sent into a 600 ℃ tube furnace for reaction for 3 to 4 seconds; collecting the obtained sample powder to obtain black TiO2And (3) nanoparticles.
The product obtained in this example was analyzed by X-ray diffraction, and the results are shown in FIG. 1. As can be seen from FIG. 1, the product obtained was anatase TiO2。
The transmission electron micrograph of the product obtained in the example is shown in FIG. 2, and it can be seen that the obtained product is spherical and has a particle size of 100nm to 150 nm.
The UV-VIS absorption spectrum of the product obtained in this example is shown in FIG. 3, which shows that the product is compatible with conventional TiO2In contrast, the material has certain ultraviolet absorption at 400-800nm, which shows that the material can effectively expand the photoresponse range to the visible light range.
Example 2
Aerosol methodPreparing nano black TiO2The method comprises the following steps:
respectively weighing 5g of titanium tetrachloride and 100g of absolute ethyl alcohol, pouring the titanium tetrachloride and the absolute ethyl alcohol into a beaker, and uniformly mixing by ultrasonic waves to obtain a homogeneous precursor solution; with N2As carrier gas, controlling the pressure of the carrier gas at 0.3Mpa, atomizing the precursor solution into aerosol droplets by an atomizer, then sending into a 700 ℃ tubular furnace, collecting the obtained sample powder with the reaction time of 0.9-1s, and obtaining black TiO2And (3) nanoparticles.
The XRD pattern and TEM of the product obtained in this example are shown in FIGS. 4 and 5, respectively. The results show that the product obtained is spherical TiO2And (3) granules.
Example 3
Preparation of nano black TiO by aerosol method2The method comprises the following steps:
respectively weighing 10g of n-butyl titanate and 100g of n-hexane, pouring into a beaker, and uniformly mixing by ultrasonic waves to obtain a homogeneous precursor solution; with N2Is used as carrier gas, the pressure of the carrier gas is controlled to be 0.2Mpa, the precursor solution is atomized into aerosol droplets through an atomizer, and then the aerosol droplets are sent into a 800 ℃ tubular furnace for reaction for 1 to 2 seconds; collecting sample powder to obtain black TiO2And (3) nanoparticles.
The XRD pattern and TEM of the product obtained in this example are shown in FIGS. 6 and 7, respectively. The results show that the product obtained is spherical TiO2And (3) granules.
Application example
The black titanium dioxide and common white titanium dioxide obtained by the invention are applied to degrading tetracycline, and the specific steps comprise: 350ppm of tetracycline is used as degradation solution, degradation reaction is carried out under an ultraviolet lamp of 200W, and as can be seen from an ultraviolet diagram (figure 8), compared with the standard solution, the degradation efficiency of common white titanium dioxide to tetracycline is basically zero, and no degradation reaction occurs; the black titanium dioxide obtained by the invention has obvious change of ultraviolet absorption peak, which proves that tetracycline is degraded into other products.
Comparative example
Preparation of nano TiO by aerosol method2The method comprises the following stepsThe method comprises the following steps:
respectively weighing 5g of titanium tetrachloride and 50g of absolute ethyl alcohol, pouring the titanium tetrachloride and the absolute ethyl alcohol into a beaker, and uniformly mixing by ultrasonic waves to obtain a homogeneous precursor solution; with N2The precursor solution is atomized into aerosol droplets by an atomizer, and then sent into a 400 ℃ tubular furnace, wherein the reaction time is 5 s; the obtained sample powder was collected, and the obtained product was not black titanium dioxide but conventional anatase white titanium dioxide.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims (10)

1. Preparation of nano black TiO by aerosol method2The method is characterized by comprising the following steps:
1) dissolving a titanium source in an organic solvent, and uniformly mixing to form a homogeneous solution or a colloidal solution to obtain a precursor solution;
2) atomizing the obtained precursor solution by using an atomizer to form aerosol liquid drops;
3) introducing the formed aerosol droplets into a tubular furnace for calcination to obtain the black TiO2And (3) nano powder.
2. The method of claim 1, wherein the titanium source is tetrabutyl titanate, titanium tetrachloride, titanium trichloride, titanium isopropoxide, titanium sulfate, titanyl difluorosulfate, metatitanic acid, or nanoscale titanium dioxide.
3. The method of claim 1, wherein the organic solvent is an organic alcohol solvent, a soluble alkane solvent, or a mixture thereof.
4. The method according to claim 3, wherein the organic alcohol solvent is one or more of absolute ethyl alcohol, methanol, benzyl alcohol and isopropanol; the soluble alkane solvent is one or more of hexane, heptane and octane.
5. The method according to claim 1, wherein the molar ratio of the titanium source to the organic solvent in the precursor solution is 1 (1-1000).
6. The method according to claim 1, wherein the molar ratio of the titanium source to the organic solvent in the precursor solution is 1 (10-500).
7. The method according to claim 1, wherein the aerosol droplets have a particle size of 0.01 to 200 μm.
8. The method according to claim 1, wherein the calcination temperature is 600 to 1600 ℃ and the calcination time is 0.01 to 60 s.
9. The method of claim 1, wherein the calcination time is 0.01 to 10 seconds.
10. The method of claim 1, wherein the calcining atmosphere is N2Ar or He.
CN202011088134.5A 2020-10-13 2020-10-13 Preparation of nano black TiO by aerosol method2Method (2) Pending CN112142104A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057224A (en) * 2021-10-13 2022-02-18 北京石油化工学院 Preparation method of titanium dioxide, preparation method and application of titanium-based titanium dioxide electrode
CN114885959A (en) * 2022-05-16 2022-08-12 北京爱护纳米技术有限公司 Slow-release nano zinc oxide antibacterial agent and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN107934922A (en) * 2017-12-13 2018-04-20 武汉工程大学 A kind of microwave radiation technology aerosol prepares nanometer TeO2Method
CN109911933A (en) * 2019-03-08 2019-06-21 广东工业大学 A kind of black titanium dioxide nano material and its preparation method and application
CN111960464A (en) * 2020-08-28 2020-11-20 陕西科技大学 Black titanium dioxide light nano material rich in oxygen vacancy defects and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107934922A (en) * 2017-12-13 2018-04-20 武汉工程大学 A kind of microwave radiation technology aerosol prepares nanometer TeO2Method
CN109911933A (en) * 2019-03-08 2019-06-21 广东工业大学 A kind of black titanium dioxide nano material and its preparation method and application
CN111960464A (en) * 2020-08-28 2020-11-20 陕西科技大学 Black titanium dioxide light nano material rich in oxygen vacancy defects and preparation method and application thereof

Non-Patent Citations (1)

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Title
司志琛: "高活性二氧化钛的制备及去除甲基橙的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057224A (en) * 2021-10-13 2022-02-18 北京石油化工学院 Preparation method of titanium dioxide, preparation method and application of titanium-based titanium dioxide electrode
CN114885959A (en) * 2022-05-16 2022-08-12 北京爱护纳米技术有限公司 Slow-release nano zinc oxide antibacterial agent and preparation method thereof

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