CN112875747A - Preparation of black nano TiO by Mg thermal reduction2Method (2) - Google Patents

Preparation of black nano TiO by Mg thermal reduction2Method (2) Download PDF

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CN112875747A
CN112875747A CN202110082990.8A CN202110082990A CN112875747A CN 112875747 A CN112875747 A CN 112875747A CN 202110082990 A CN202110082990 A CN 202110082990A CN 112875747 A CN112875747 A CN 112875747A
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nano tio
black nano
thermal reduction
tio
sample
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王向东
阴倩倩
潘程
高敏
李骁勇
贾怡红
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Xian Jiaotong University
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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
    • C01G23/08—Drying; Calcining ; After treatment of titanium oxide
    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention belongs to the technical field of preparation of inorganic functional materials, and discloses a method for preparing black nano TiO by Mg thermal reduction2The method is characterized by comprising the following steps: 1) mixing magnesium powder and white nanometer TiO2Mixing at room temperature, adding absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A; 2) drying the mixture A, and placing the mixture A in an atmosphere furnace for calcination reaction to obtain a sample B; 3) taking out the sample B, adding an acid solution for soaking, carrying out suction filtration, washing and drying to obtain black nano TiO2. The invention prepares black nano TiO by thermal reduction2The cost of using the metal Mg powder is low, and the large-scale production is facilitated; the invention has simple temperature rising device, simple preparation flow and easy batch production, and the prepared black nano TiO is2The absorption spectrum is extended to the visible and infrared regions, and the light absorption performance is remarkably enhanced.

Description

Preparation of black nano TiO by Mg thermal reduction2Method (2)
Technical Field
The present invention belongs to the preparation technology of inorganic functional materialThe field, in particular to a method for preparing black nano TiO by Mg thermal reduction2The method of (1).
Background
In recent years, in order to meet global problems such as energy crisis and environmental pollution caused by the depletion of fossil fuels, there is an increasing demand for new energy. Hydrogen energy, because it is clean, renewable, is considered one of the most promising and research-valued energy sources. Wherein the nano TiO is used by sunlight2The application of photocatalytic hydrogen production has attracted a wide range of attention. However, nano TiO2The industrial application has limitations, mainly due to: 1) nano TiO22The forbidden band width is large, only ultraviolet light can excite electron transition in sunlight, the ultraviolet light accounts for less than 5% of the sunlight, and the solar energy utilization rate is low; 2) nano TiO generated by light excitation2Surface photo-generated electrons and holes are easy to recombine, and the light quantum efficiency is low. As such, a great deal of research work has been conducted to design black nano TiO2To solve the above problems.
To improve TiO2The visible light absorption performance of the material, in the prior art, sodium borohydride is used for preparing black nano TiO in Liuchuntao and the like2So that the material has higher stability and can effectively remove organic pollutants[1]. Preparation of black nano TiO by using sodium borohydride, such as manine2Subsequent high-temperature treatment is carried out to prepare the double-shell titanium dioxide catalyst, so that the visible light absorption performance of the material is greatly improved, and the material has better catalytic hydrogen production performance[2]. Preparation of black TiO by double-temperature zone aluminothermic reduction method2 [3]Obviously improve TiO2The visible light absorption properties of the material.
In the method, sodium borohydride is harmful to human bodies when being inhaled or contacted with the skin, extremely combustible gas is released when the sodium borohydride meets water, and the cost is high, so that the technology is difficult to be applied on a large scale in industry. The aluminothermic reduction needs double-temperature-zone equipment, the reaction temperature is higher, and the cost is high.
Cited documents:
[1] the preparation method of the black titanium dioxide visible light photocatalyst comprises the following steps of performing Schenberg, Zhang Lin, Zhang Yan, Zhongwei, Liuchuntang: CN104437449A,2015-03-25.
[2] Xulingling, Cao 29740, celluloid, Weibo, Maning, double-shell titanium dioxide catalyst with high photocatalytic hydrogen production performance and preparation method [ P ]. Heilongjiang: CN105771948A,2016-07-20.
[3]Z.Wang,C.Yang,T.Lin,et al.Energy Environ.Sci.,2013,6:3007.
Disclosure of Invention
The invention aims to solve the technical problems that sodium borohydride is harmful to human bodies due to inhalation or skin contact, easily combustible gas is released when water is encountered, the cost is high, double-temperature-zone equipment is required for Al thermal reduction, the reaction temperature is high, and the cost is high in the prior art, and provides a method for preparing black nano TiO by Mg thermal reduction2The preparation method of (1).
The technical scheme of the invention is as follows: the invention provides a method for preparing black nano TiO by Mg thermal reduction2The preparation method comprises the following steps:
1) mixing magnesium powder and white nanometer TiO2Mixing at room temperature, adding organic solvent for grinding, uniformly distributing the grinding materials on a grinding tool, mixing uniformly easily, cooling and lubricating, and grinding and mixing uniformly to obtain a mixture A;
2) drying the mixture A, removing the organic solvent, and placing the mixture A in an atmosphere furnace for calcination reaction to obtain a sample B;
3) taking out the sample B, adding a hydrochloric acid solution for soaking, removing magnesium powder, performing suction filtration, washing, drying, and removing a solvent and water to obtain black nano TiO2。
In the technical scheme of the invention, in the step 1), the organic solvent is selected from one of absolute ethyl alcohol and ethyl acetate.
In the technical scheme of the invention, in the step 3), the acid solution is selected from one of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, the soaking time is 6-8 h, the soaking is repeated for 3-6 times, and the washing is performed by filtering and washing with deionized water and repeated for 3-6 times.
In the technical scheme of the invention, the initial pH of the acid solution is less than 0.
In the inventionIn the technical scheme, in the step 1), the magnesium powder and the white nano TiO2The mass ratio of the substances is (0.5-3): 1.
in the technical scheme of the invention, in the step 1), the particle size of the magnesium powder is 100-200 meshes, and the white nano TiO is2The particle size is 10-20 nm.
In the technical scheme of the invention, in the step 1), the absolute ethyl alcohol and the white nano TiO are mixed2The mass ratio of (5-15): 1.
in the technical scheme of the invention, in the step 2) and the step 3), the drying temperature is 60-100 ℃, and the drying time is 4-8 h.
In the technical scheme of the invention, in the step 2), the atmosphere in the atmosphere furnace is argon or nitrogen, the heating rate and the cooling rate are 3-10 ℃/min, the calcining temperature in the atmosphere is 400-600 ℃, and the temperature is kept for 3-5 h at the calcining temperature.
In the technical scheme of the invention, in the step 3), the mass concentration of the dilute hydrochloric acid solution is 5-8%, the mass concentration of the dilute sulfuric acid is 6-10%, and the mass concentration of the dilute nitric acid is 8-12%.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention prepares black nano TiO by thermal reduction2The metal Mg powder has relatively low price and low cost, and is beneficial to large-scale production.
2. The invention utilizes Mg metal powder to thermally reduce TiO2The preparation is easy, the temperature rising device is simple and convenient, the preparation flow is simple, and the batch production is easy.
3. The black TiO prepared by the invention2The absorption spectrum is extended to the visible and infrared regions, and the light absorption performance is remarkably enhanced.
Drawings
FIG. 1 shows that the invention obtains black nano TiO by Mg thermal reduction2The preparation process schematic diagram of (1);
FIG. 2 is a graph showing the preparation of black TiO according to the present invention at different calcination temperatures in examples 4 to 72XRD pattern of (a);
FIG. 3 shows a commercial white nano TiO2And example 6, example 8 and example 9 of the present invention are differentPreparation of black nano TiO by magnesium content2A UV-Vis diffuse reflectance spectrum of the sample;
FIG. 4 shows a commercial white nano TiO2And the invention prepares black nanometer TiO with different magnesium contents2Photo picture of sample and preparation of black nano TiO by the invention2A TEM image of the sample; wherein, the picture a is white nano TiO2B is the black nano TiO prepared in example 82Photograph of sample, FIG. c is the black nano TiO made in example 92Photographs of samples, FIGS. d and e are black nano TiO made in example 92TEM images of the samples.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
It should be noted that the following embodiments are provided for the purpose of teaching those skilled in the art the present invention and are not to be limited thereby, and all equivalent changes and modifications made in accordance with the spirit of the present invention are intended to be included therein.
Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings, and it will be apparent to those skilled in the art from this detailed description that the present invention can be practiced. Features from different embodiments may be combined to yield new embodiments, or certain features may be substituted for certain embodiments to yield yet further preferred embodiments, without departing from the principles of the present invention.
The invention is proved to be feasible by experiments to prepare the black nano TiO2Is characterized in that: anatase type has a crystal grain diameter of about 12.0nm and absorbs in the visible light region.
As shown in figure 1, the invention obtains black nano TiO by Mg thermal reduction2The preparation process of (1) is shown in the schematic diagram, and concretely, in the following examples, Mg is subjected to thermal reduction to prepare black nano TiO2The method comprises the following steps:
1) according to the mass ratio of (0.5-3): 1 respectively taking magnesium powder (100-200 meshes) and whiteNano TiO22(the particle size is 10-20 nm) is mixed at room temperature, absolute ethyl alcohol is added for uniform grinding and mixing to obtain a mixture A, wherein the absolute ethyl alcohol and the commercial nano TiO are adopted2The mass ratio of (5-15) to (1);
2) putting the mixture A into a constant-temperature drying oven for drying at the temperature of 60-100 ℃ for 4-8 h, and removing the solvent;
3) putting the dried substance into a crucible, placing the crucible into an atmosphere furnace for reaction, keeping the atmosphere of argon or nitrogen in the atmosphere furnace, wherein the heating rate and the cooling rate are 3-10 ℃/min, the calcining temperature in the atmosphere is 400-600 ℃, and the calcining temperature is kept for 3-5 h to obtain a sample B;
4) taking out the sample B, adding a dilute hydrochloric acid solution with the mass concentration of 5-8%, soaking for 6-8 hours, repeating for 3-6 times, then adopting deionized water, performing suction filtration and washing, and repeating for 3-6 times;
5) putting the washed sample B into a constant-temperature drying oven for drying at the temperature of 60-100 ℃ for 4-6 h, and removing the solvent and the water to obtain the black nano TiO2。
White nano TiO used in the following examples2Is commercial nano TiO2。
Example 1
This example illustrates the thermal reduction of Mg to prepare black nano TiO2The method comprises the following steps:
1) taking an agate mortar at room temperature, and respectively taking 0.08g of magnesium powder and 0.50g of commercial nano TiO2Mixing, adding 4.00ml of absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A;
2) putting the mixture A into a constant-temperature drying oven, drying for 4h at 80 ℃, and removing the solvent;
3) putting the dried substance into a crucible, putting the crucible into an argon atmosphere furnace, and calcining for 4 hours at 500 ℃ at the heating rate and the cooling rate of 5 ℃/min to obtain a sample B;
4) taking out the sample B, adding a hydrochloric acid solution with the mass concentration of 8%, soaking for 6h, repeating for 3 times, performing suction filtration by using deionized water, and washing for 4 times;
5) the washed sampleB is put into a constant temperature drying oven and dried for 4 hours at the temperature of 80 ℃ to obtain black nano TiO2And (5) producing the product.
The prepared black nano TiO is obtained by Mg thermal reduction2The product is characterized in that: anatase type has a crystal grain diameter of about 12.0nm and absorbs in the visible light region.
Example 2
This example illustrates the thermal reduction of Mg to prepare black nano TiO2The method comprises the following steps:
1) at room temperature, an agate mortar is taken, 0.15g of magnesium powder and 0.50g of commercial nano TiO are respectively taken2Mixing, adding 5.00ml of absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A;
2) putting the mixture A into a constant-temperature drying oven, drying for 4h at 90 ℃, and removing the solvent;
3) putting the dried substance into a crucible, putting the crucible into an argon atmosphere furnace, and calcining for 4 hours at 600 ℃ with the heating rate and the cooling rate of 5 ℃/min to obtain a sample B;
4) taking out the sample B, adding a hydrochloric acid solution with the mass concentration of 8%, soaking for 6h, repeating for 4 times, carrying out suction filtration by using deionized water, and washing for 4 times;
5) drying in a constant temperature drying oven at 70 deg.C for 6 hr to obtain black nanometer TiO2And (5) producing the product.
The prepared black nano TiO is obtained by Mg thermal reduction2The product is characterized in that: anatase type has a crystal grain diameter of about 13.0nm and absorbs in the visible light region.
Example 3
This example illustrates the thermal reduction of Mg to prepare black nano TiO2The method comprises the following steps:
1) taking an agate mortar at room temperature, and respectively taking 0.23g of magnesium powder and 0.50g of commercial nano TiO2Mixing, adding 8.00ml of absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A;
2) putting the mixture A into a constant-temperature drying oven, drying for 4h at 100 ℃, and removing the solvent;
3) putting the dried substance into a crucible, putting the crucible into an argon atmosphere furnace, and calcining for 4 hours at 550 ℃ with the heating rate and the cooling rate of 5 ℃/min to obtain a sample B;
4) taking out the sample B, adding a hydrochloric acid solution with the mass concentration of 8%, soaking for 6h, repeating for 3 times, performing suction filtration by using deionized water, and washing for 4 times;
5) putting the washed sample B into a constant-temperature drying box, and drying for 6h at 80 ℃ to obtain black nano TiO2And (5) producing the product.
The prepared black nano TiO is obtained by Mg thermal reduction2The product is characterized in that: anatase type has a crystal grain diameter of about 12.0nm and absorbs in the visible light region.
Example 4
This example illustrates the thermal reduction of Mg to prepare black nano TiO2The method comprises the following steps:
1) taking an agate mortar at room temperature, and respectively taking 0.30g of magnesium powder and 0.50g of commercial nano TiO2Mixing, adding 8.00ml of absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A;
2) putting the mixture A into a constant-temperature drying oven, drying for 4h at 100 ℃, and removing the solvent;
3) putting the dried substance into a crucible, putting the crucible into an argon atmosphere furnace, and carrying out calcination reaction at 400 ℃, wherein the calcination time is 4h, and the heating rate and the cooling rate are 5 ℃/min, so as to obtain a sample B;
4) taking out the sample B, adding a hydrochloric acid solution with the mass concentration of 8%, soaking for 6h, repeating for 3 times, performing suction filtration by using deionized water, and washing for 4 times;
5) putting the washed sample B into a constant-temperature drying box, and drying for 6h at 80 ℃ to obtain black nano TiO2And (5) producing the product.
The prepared black nano TiO is obtained by Mg thermal reduction2The product is characterized in that: anatase type has a crystal grain diameter of about 13.0nm and absorbs in the visible light region.
Example 5
This example illustrates the thermal reduction of Mg to prepare black nano TiO2The method comprises the following steps:
1) taking an agate mortar at room temperature, and respectively taking 0.30g of magnesium powder and 0.50g of commercial nano TiO2Mixing, adding 8.00ml of absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A;
2) putting the mixture A into a constant-temperature drying oven, drying for 4h at 100 ℃, and removing the solvent;
3) putting the dried substance into a crucible, putting the crucible into an argon atmosphere furnace, and carrying out calcination reaction at 450 ℃, wherein the calcination time is 4h, and the heating rate and the cooling rate are 5 ℃/min, so as to obtain a sample B;
4) taking out the sample B, adding a hydrochloric acid solution with the mass concentration of 8%, soaking for 6h, repeating for 3 times, performing suction filtration by using deionized water, and washing for 4 times;
5) putting the washed sample B into a constant-temperature drying box, and drying for 6h at 80 ℃ to obtain black nano TiO2And (5) producing the product.
The prepared black nano TiO is obtained by Mg thermal reduction2The product is characterized in that: anatase type has a crystal grain diameter of about 10.0nm and absorbs in the visible light region.
Example 6
This example illustrates the thermal reduction of Mg to prepare black nano TiO2The method comprises the following steps:
1) taking an agate mortar at room temperature, and respectively taking 0.30g of magnesium powder and 0.50g of commercial nano TiO2Mixing, adding 8.00ml of absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A;
2) putting the mixture A into a constant-temperature drying oven, drying for 4h at 100 ℃, and removing the solvent;
3) putting the dried substance into a crucible, putting the crucible into an argon atmosphere furnace, and carrying out calcination reaction at 500 ℃, wherein the calcination time is 4h, and the heating rate and the cooling rate are 5 ℃/min, so as to obtain a sample B;
4) taking out the sample B, adding a hydrochloric acid solution with the mass concentration of 8%, soaking for 6h, repeating for 3 times, performing suction filtration by using deionized water, and washing for 4 times;
5) putting the washed sample B into a constant-temperature drying box, and drying for 6h at 80 ℃ to obtain black nano TiO2And (5) producing the product.
The prepared black nano TiO is obtained by Mg thermal reduction2The product is characterized in that: anatase type has a crystal grain diameter of about 18.0nm and absorbs in the visible light region.
Example 7
This example describes the thermal reduction of Mg to produce BlackNano TiO22The method comprises the following steps:
1) taking an agate mortar at room temperature, and respectively taking 0.30g of magnesium powder and 0.50g of commercial nano TiO2Mixing, adding 8.00ml of absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A;
2) putting the mixture A into a constant-temperature drying oven, drying for 4h at 100 ℃, and removing the solvent;
3) putting the dried substance into a crucible, putting the crucible into an argon atmosphere furnace, and carrying out calcination reaction at 600 ℃, wherein the calcination time is 4h, and the heating rate and the cooling rate are 5 ℃/min, so as to obtain a sample B;
4) taking out the sample B, adding a hydrochloric acid solution with the mass concentration of 8%, soaking for 6h, repeating for 3 times, performing suction filtration by using deionized water, and washing for 4 times;
5) putting the washed sample B into a constant-temperature drying box, and drying for 6h at 80 ℃ to obtain black nano TiO2And (5) producing the product.
The prepared black nano TiO is obtained by Mg thermal reduction2The product is characterized in that: anatase type has a crystal grain diameter of about 19.0nm and absorbs in the visible light region.
Example 8
This example illustrates the thermal reduction of Mg to prepare black nano TiO2The method comprises the following steps:
1) at room temperature, an agate mortar is taken, 0.15g of magnesium powder and 0.50g of commercial nano TiO are respectively taken2Mixing, adding 8.00ml of absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A;
2) putting the mixture A into a constant-temperature drying oven, drying for 4h at 100 ℃, and removing the solvent;
3) putting the dried substance into a crucible, putting the crucible into an argon atmosphere furnace, and carrying out calcination reaction at 500 ℃, wherein the calcination time is 4h, and the heating rate and the cooling rate are 5 ℃/min, so as to obtain a sample B;
4) taking out the sample B, adding a hydrochloric acid solution with the mass concentration of 8%, soaking for 6h, repeating for 3 times, performing suction filtration by using deionized water, and washing for 4 times;
5) putting the washed sample B into a constant-temperature drying box, and drying for 6h at 80 ℃ to obtain black nano TiO2And (5) producing the product.
The prepared black nano TiO is obtained by Mg thermal reduction2The product is characterized in that: anatase type has a crystal grain diameter of about 11.0nm and absorbs in the visible light region.
Example 9
This example illustrates the thermal reduction of Mg to prepare black nano TiO2The method comprises the following steps:
1) taking an agate mortar at room temperature, and respectively taking 0.45g of magnesium powder and 0.50g of commercial nano TiO2Mixing, adding 8.00ml of absolute ethyl alcohol, grinding and uniformly mixing to obtain a mixture A;
2) putting the mixture A into a constant-temperature drying oven, drying for 4h at 100 ℃, and removing the solvent;
3) putting the dried substance into a crucible, putting the crucible into an argon atmosphere furnace, and carrying out calcination reaction at 500 ℃, wherein the calcination time is 4h, and the heating rate and the cooling rate are 5 ℃/min, so as to obtain a sample B;
4) taking out the sample B, adding a hydrochloric acid solution with the mass concentration of 8%, soaking for 6h, repeating for 3 times, performing suction filtration by using deionized water, and washing for 4 times;
5) putting the washed sample B into a constant-temperature drying box, and drying for 6h at 80 ℃ to obtain black nano TiO2And (5) producing the product.
The prepared black nano TiO is obtained by Mg thermal reduction2The product is characterized in that: anatase type has a crystal grain diameter of about 10.0nm and absorbs in the visible light region.
FIG. 2 is a graph showing the preparation of black TiO according to the present invention at different calcination temperatures in examples 4 to 72XRD pattern of (a); as can be seen from FIG. 2, reduction with Mg (magnesium powder and white nano TiO)2The mass ratio of the substances is 2:1), and the black nano TiO is prepared by calcining at 400, 450, 500 and 600 ℃ respectively in argon atmosphere2X-ray diffraction pattern of the photocatalyst. The XRD curves of the samples prepared by calcination at 400, 450 and 500 ℃ all showed diffraction peaks at 25.4 °, 37.8 °, 47.5 °, 54.3 °, 62.4 °, 70.6 ° and 75.9 ° respectively, which are anatase-phase mesoporous TiO peaks respectively, according to the analysis of the curves in the figure2The characteristic peaks of the (101), (004), (200), (105), (204), (116) and (215) crystal planes of (A), and no other derivatives appearThe peak injection shows that the samples prepared by calcining at the temperature of 400, 450 and 500 ℃ are only anatase phase TiO2No brookite and rutile mesoporous TiO2A nanostructure. The XRD curves of the samples prepared by calcining at the temperature of 600 ℃ all have stronger diffraction peaks at 27 degrees 2 theta, which indicates that the anatase phase begins to be converted into the rutile phase, and TiO in the product2The rutile phase content is higher. This indicates that at 600 c the anatase phase begins to transform to the rutile phase.
FIG. 3 is a white nano TiO2And example 6 of the invention (magnesium powder and white nano TiO)2Mass ratio 2:1), example 8 (magnesium powder and white nano TiO)2The mass ratio of 1:1) and example 9 (magnesium powder and white nano TiO)2The mass ratio of the materials is 3:1) the preparation of the black nano TiO with different magnesium contents2The UV-Vis diffuse reflectance spectrum of the sample, and the UV-Vis curve is used for analyzing the light response range of the sample. All TiO can be seen from FIG. 32The sample has strong absorption in the ultraviolet region of 200-400nm, and the difference is not large, which shows that the modified black nano TiO2The response of the sample to uv light remains substantially unchanged. The absorption intensities of the four samples all showed a decreasing trend in the visible region range of 400-800nm, but at different degrees. With black nano TiO2Compared with the sample, the light absorption intensity of the white commercial TiO2 sample is reduced most obviously, the light absorption intensity is reduced sharply at 390nm, and the absorption intensity in the visible light region is almost zero. The three black nano TiO prepared by the invention2The sample has a certain degree of absorption in a visible light area, and the degree of curve decline of the sample is reduced along with the increase of the content of the metal reducing agent, which shows that the color of the sample is deepened along with the addition of the reducing agent, and the absorption capacity to visible light is stronger.
FIG. 4 shows white TiO nanoparticles2And the invention prepares black nanometer TiO with different magnesium contents2Photo picture of sample and preparation of black nano TiO by the invention2TEM images of the samples. The picture a is white nano TiO2B is the black nano TiO prepared in example 82Photograph of sample, FIG. c is the black nano TiO made in example 92Photographs of the samples, FIGS. d and e are actualBlack nano TiO2 prepared in example 92TEM images of the samples. As can be seen from fig. a to c, the color of the sample gradually changed from light yellow to black as the content of Mg increased, mainly because the more Mg content, the more thoroughly the sample was reduced, the thicker the surface disordered layer was generated, and the darker the color of the sample was. The dispersion of the sample is reflected in the graph d, from which it can be seen that the sample has a particle size of about 10-15nm and a uniform relative distribution. As can be seen in fig. 4, the sample shows a specific core-shell structure, i.e., a crystalline core with good crystallinity inside and a surface disordered layer outside, and the disordered structure about 2nm thick is marked by a gray line in fig. 4, e.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the scope of the present invention.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. Preparation of black nano TiO by Mg thermal reduction2The method is characterized by comprising the following steps:
1) mixing magnesium powder and white nanometer TiO2Mixing at room temperature, adding an organic solvent, grinding and uniformly mixing to obtain a mixture A;
2) drying the mixture A, and placing the mixture A in an atmosphere furnace for calcination reaction to obtain a sample B;
3) taking out the sample B, adding an acid solution for soaking, carrying out suction filtration, washing and drying to obtain black nano TiO2。
2. The method for preparing black nano TiO by Mg thermal reduction according to claim 12The method of (1), wherein the organic solvent is one selected from the group consisting of absolute ethanol and ethyl acetate.
3. The method for preparing black nano TiO by Mg thermal reduction according to claim 12The method is characterized in that in the step 3), the acid solution is selected from one of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, the soaking time is 6-8 hours, the soaking time is repeated for 3-6 times, and the washing is performed by filtering and washing with deionized water and is repeated for 3-6 times.
4. The method for preparing black nano TiO by Mg thermal reduction according to claim 32The method of (2), wherein the acid solution has an initial pH of less than 0.
5. The method for preparing black nano TiO by Mg thermal reduction according to claim 12The method is characterized in that in the step 1), the magnesium powder and the white nano TiO are mixed2The mass ratio of the substances is (0.5-3): 1.
6. the method for preparing black nano TiO by Mg thermal reduction according to claim 12The method is characterized in that in the step 1), the particle size of the magnesium powder is 100-200 meshes, and white nano TiO is used2The particle size is 10-20 nm.
7. The method for preparing black nano TiO by Mg thermal reduction according to claim 12The method is characterized in that in the step 1), the absolute ethyl alcohol and the white nano TiO are mixed2The mass ratio of (5-15): 1.
8. the method for preparing black nano TiO by Mg thermal reduction according to claim 12The method is characterized in that in the step 2) and the step 3), the drying temperature is 60-100 ℃, and the drying time is 4-8 hours.
9. The method for preparing black nano TiO by Mg thermal reduction according to claim 12Characterized in that, in step 2), gas is usedThe atmosphere in the atmosphere furnace is argon or nitrogen, the heating rate and the cooling rate are 3-10 ℃/min, the calcining temperature in the atmosphere is 400-600 ℃, and the temperature is kept for 3-5 h at the calcining temperature.
10. The method for preparing black nano TiO by Mg thermal reduction according to claim 12The method is characterized in that in the step 3), the mass concentration of the dilute hydrochloric acid solution is 5-8%, the mass concentration of the dilute sulfuric acid is 6-10%, and the mass concentration of the dilute nitric acid is 8-12%.
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Citations (2)

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CN104941614A (en) * 2014-03-24 2015-09-30 中国科学院上海硅酸盐研究所 Method for preparing black titanium dioxide by contact type reduction method
CN111056567A (en) * 2019-12-25 2020-04-24 苏州机数芯微科技有限公司 Preparation method of black rutile phase titanium dioxide

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Publication number Priority date Publication date Assignee Title
CN104941614A (en) * 2014-03-24 2015-09-30 中国科学院上海硅酸盐研究所 Method for preparing black titanium dioxide by contact type reduction method
CN111056567A (en) * 2019-12-25 2020-04-24 苏州机数芯微科技有限公司 Preparation method of black rutile phase titanium dioxide

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MIAOMIAO YE等: "Synthesis of Black TiOx Nanoparticles by Mg Reduction of TiO2 Nanocrystals and their Application for Solar Water Evaporation", 《ADV. ENERGY MATER.》 *
YUXIN LI等: "B-N co-doped black TiO2 synthesized via magnesiothermic reduction for enhanced photocatalytic hydrogen production", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *
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