CN111573721B - Preparation method of black titanium dioxide - Google Patents
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- CN111573721B CN111573721B CN202010436466.1A CN202010436466A CN111573721B CN 111573721 B CN111573721 B CN 111573721B CN 202010436466 A CN202010436466 A CN 202010436466A CN 111573721 B CN111573721 B CN 111573721B
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Abstract
The invention relates to a preparation method of black titanium dioxide, belonging to the technical field of inorganic materials. The preparation method of the black titanium dioxide comprises the following steps: A. uniformly mixing titanium dioxide and aluminum powder to obtain a mixed raw material; B. covering the surface of the mixed raw material with a metal sheet with the melting temperature of more than 660 ℃, and covering the metal sheet with molten liquid boron trioxide; C. roasting at 450-650 deg.c for 50-180 min to obtain black TiO 2 (ii) a D. Mixing the black TiO obtained in the step C 2 Acid washing to obtain pure black TiO 2 . The invention realizes the preparation under normal pressure at lower temperature, has lower preparation cost and is suitable for large-scale preparation of the black TiO 2 Provides a feasible process route. The raw material loss is less, ethanol is not needed, and the cost is low.
Description
Technical Field
The invention relates to a preparation method of black titanium dioxide, belonging to the technical field of inorganic materials.
Background
TiO 2 As an important photocatalyst, the photocatalyst is widely used for hydrogen production, environmental pollutant removal and photochemical preparationSensors, etc. TiO 2 2 The photocatalyst has four common crystal phases of anatase, brookite, rutile and monoclinic, wherein the rutile and anatase have better photocatalytic activities and are widely researched. And TiO 2 2 The forbidden band width is about 3.2eV, and the forbidden band width is wide, so that the ultraviolet light can only absorb ultraviolet light, and the ultraviolet light only accounts for 4-6% of natural light.
At present, scientists in various countries aim to promote TiO 2 The light absorption properties of (a) are studied in large numbers, and doping is currently being studied in large numbers. Such as conventional metal doping (Fe, co, cr, ni, mo, etc.), noble metal doping (e.g., au, ag, pt, etc.), non-metallic elements (e.g., N, C, F, S), co-doped metal and non-metallic elements (e.g., mo + C, fe + N, mo + S, co + N/S). In addition, crystal phase, morphology, structure, porosity, etc. are also important factors affecting photocatalytic activity.
Black titanium dioxide (TiO) is discovered by adopting a hydrogenation method from 2011 old wavelet professor 2 ) The original TiO material has been overcome since it can enhance visible light absorption and reduce the recombination of photogenerated charge carriers 2 Ability to be limited, black titanium dioxide (TiO) 2 ) Has been one of the most intensively studied photocatalysts. Black TiO 2 The sample actually showed lower photoactivity. All this leads to some conceptual conflicts with role-play.
The preparation of black TiO has been developed 2 The nanometer titanium dioxide is hydrogenated to synthesize black titanium dioxide with a disordered surface structure in 2011 by more process routes such as aged waves and the like, the displayed band gap is low (1.54 eV), and visible light and even a near infrared region can be absorbed. From then on, black TiO 2 Become an area of activity research that has met with tremendous success in a number of applications, including photocatalytic contaminant degradation, hydrogen production by water splitting, photocatalytic reduction of carbon dioxide, dye sensitization, solar cells, lithium batteries, and other photoelectrochemical applications.
In addition to hydrogen reduction, there are chemical reduction methods including Al reduction, mg reduction, naBH 4 Reduction, naH reduction and the like. Wherein wang et al utilize in a dual zone vacuum furnace that is evacuatedMolten aluminum was prepared with black nanoparticle TiO 2 . However, the process needs to be carried out for 6 hours under the conditions of 0.5Pa of vacuum and 800 ℃. The above methods all need to be prepared under vacuum conditions for a long time, the conditions are very harsh, the preparation cost is high, and large-scale preparation is difficult.
Patent application No. 2017101203100 discloses a preparation method of a magneli phase low-valence titanium oxide material. Titanium dioxide, aluminum powder and absolute ethyl alcohol are mixed according to the mass volume ratio of 0.4-0.8g: 0.5-0.8 mL of the mixture is mixed evenly, and then the mixed raw materials are put into a crucible to be compacted. The boron oxide with low melting point is melted and covered on the surface of the raw material, and the boron oxide with low melting point plays a role in isolating air. However, the preparation temperature is higher, the loss of raw materials is large, B 2 O 3 The recycling of (2) is difficult. And prepared as Magneli phase low valence titanium oxide, black TiO 2 The material and the magneli phase low-valence titanium oxide are two completely different materials and have different application fields. Black TiO 2 Materials and white anatase TiO 2 Has the same crystal structure, and white TiO is designed by the process of the invention 2 The surface forms oxygen vacancy and a layer of disordered structure, so that the color is changed into black, therefore, the surface is called black TiO 2 . While the Magnesli phase of low valence titanium oxide and white anatase TiO 2 Having a completely different crystal structure and having the formula Ti n O 2n-1 (4<n<10): such as Ti 4 O 7 ，Ti 5 O 9 Etc., non-stoichiometric amounts of titanium suboxides.
Disclosure of Invention
The first problem to be solved by the present invention is to provide a method for producing black titanium dioxide.
To solve the first technical problem of the present invention, the method for producing black titanium dioxide is characterized by comprising:
A. uniformly mixing titanium dioxide and aluminum powder to obtain a mixed raw material;
B. covering the surface of the mixed raw material with a metal sheet with the melting temperature of more than 660 ℃, and covering the molten liquid boron trioxide on the metal sheet with the melting temperature of more than 660 ℃;
C. then roasting at 450-650 deg.C for 50-180 min to obtain black TiO 2 ；
D. Mixing the black TiO obtained in the step C 2 Acid washing to obtain pure black TiO 2 。
Preferably, the aluminum powder: the weight ratio of the titanium dioxide is 0.2-0.6.
Preferably, the aluminum powder: the weight ratio of the titanium dioxide is 0.2-0.4.
Preferably, the titanium dioxide is at least one of anatase, brookite or rutile crystal forms.
Preferably, the thickness of the diboron trioxide is 1-2 cm.
Preferably, the acid washing in the step D adopts at least one of hydrochloric acid, sulfuric acid or nitric acid.
Preferably, the acid is hydrochloric acid.
Preferably, the concentration of the hydrochloric acid is 2mol/L to 4mol/L.
Preferably, the particle size of the titanium dioxide is as follows: 50-300 nm.
Preferably, the particle size of the aluminum powder is as follows: 200-600 nm.
Preferably, the material of the metal sheet is at least one of aluminum, copper, iron, nickel, manganese, chromium and cobalt.
Has the beneficial effects that:
1. the invention realizes the preparation under the normal pressure condition at lower temperature, has lower preparation cost and is suitable for preparing the black TiO on a large scale 2 Provides a feasible process route.
2. The invention has less raw material loss.
3. The invention does not need ethanol and has low cost.
4. The black TiO prepared by the invention 2 The surface has partial oxygen vacancy and a layer of disordered structure, and has good visible light and near infrared light absorption performance.
5. The invention controls the roasting temperature and time to only allow TiO 2 Oxygen vacancies and disordered structures are generated on the surface and TiO is to be prevented 2 Over-reduction to form MagnThe eili phase titanium suboxide has very strict control on temperature and time, and the roasting temperature and time must be controlled cooperatively to obtain the ideal result.
Drawings
FIG. 1 a shows a black TiO prepared according to the present invention 2 B is a Raman spectrogram;
FIG. 2 is a graph of the UV-VIS absorption spectrum of black titanium dioxide prepared in accordance with the present invention;
FIG. 3 TEM analysis of black titanium dioxide prepared by the present invention; A-TiO in the figure 2 Denotes Anatase TiO 2 Starting material, i.e. anatase phase TiO 2 ；
FIG. 4 SEM and EDS analysis of black titanium dioxide prepared by the present invention.
Detailed Description
In order to solve the first technical problem of the present invention, the method for preparing black titanium dioxide is characterized by comprising:
A. uniformly mixing titanium dioxide and aluminum powder to obtain a mixed raw material;
B. covering the surface of the mixed raw material with a metal sheet with the melting temperature of more than 660 ℃, and covering the molten liquid boron trioxide on the metal sheet with the melting temperature of more than 660 ℃;
C. then roasting at 450-650 deg.C for 50-180 min to obtain black TiO 2 ；
D. Mixing the black TiO of step C 2 Acid washing to obtain pure black TiO 2 。
Preferably, the aluminum powder: the weight ratio of the titanium dioxide is 0.2-0.6.
Preferably, the aluminum powder: the weight ratio of the titanium dioxide is 0.2-0.4.
Preferably, the titanium dioxide is at least one of anatase, brookite or rutile crystal forms.
Preferably, the thickness of the diboron trioxide is 1-2 cm.
Preferably, the acid washing in the step D adopts at least one of hydrochloric acid, sulfuric acid or nitric acid.
Preferably, the acid is hydrochloric acid.
Preferably, the concentration of the hydrochloric acid is 2mol/L to 4mol/L.
Preferably, the particle size of the titanium dioxide is as follows: 50-300 nm.
Preferably, the particle size of the aluminum powder is: 200-600 nm.
Preferably, the material of the metal sheet is at least one of aluminum, copper, iron, nickel, manganese, chromium and cobalt.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the invention to the embodiments described.
Example 1
EXAMPLE 1 preparation of Black TiO 2 The material comprises the following steps:
s101, uniformly mixing raw materials of aluminum powder and anatase titanium dioxide in a mortar, wherein the mass percentage of the raw materials is 0.6;
s102, filling the uniformly mixed raw materials into a corundum crucible, preparing an aluminum sheet on the surface of the raw materials according to the size of the crucible, covering the surface of the mixed raw materials, wherein the aluminum sheet is mainly used for melting B 2 O 3 The raw material is corroded, and the loss of the raw material is reduced. Then covering a layer of molten B on the aluminum sheet 2 O 3 For isolating air.
S103, placing the prepared raw materials into a box-type resistance furnace for roasting at 650 ℃ for 60min, and naturally cooling in an air atmosphere;
s104, acid washing the prepared material in hydrochloric acid with the concentration of 4mol/L for 60min, and stirring at the speed of 60 r/min.
Example 1A black TiO was obtained 2 . The main phase of the anatase titanium dioxide is almost consistent with that of the anatase titanium dioxide, but the peak is shifted and broadened to the right, a layer of disordered structure is formed on the surface of the particles, the color is changed from white to black, and the anatase titanium dioxide has good visible light and even near infrared light absorption performance, and is shown in figures 1-4.
Example 2
EXAMPLE 2 preparation of Black TiO 2 The material comprises the following steps:
s101, uniformly mixing the raw material aluminum powder and anatase titanium dioxide in a mortar, wherein the mass percentage of the raw material aluminum powder to the anatase titanium dioxide is 0.4;
s102, the uniformly mixed raw materials are put into a corundum crucible, and an aluminum sheet is prepared on the surface of the raw materials according to the size of the crucible and covers the surface of the mixed raw materials.
S103, placing the prepared raw materials into a box-type resistance furnace for roasting at 550 ℃ for 120min, and naturally cooling in an air atmosphere;
s104, acid washing the prepared material in hydrochloric acid with the concentration of 4mol/L for 60min, and stirring at the speed of 60 r/min.
Example 2A black TiO was obtained 2 . The main phase of the anatase titanium dioxide is almost consistent with that of anatase titanium dioxide, but the peak is shifted and broadened to the right, a layer of disordered structure is formed on the surface of particles, the color is changed from white to black, and the anatase titanium dioxide has good visible light even near-infrared light absorption performance.
Example 3
EXAMPLE 3 preparation of Black TiO 2 The material comprises the following steps:
s101, uniformly mixing the raw material aluminum powder and anatase titanium dioxide in a mortar according to the mass percentage of 0.2;
s102, the uniformly mixed raw materials are put into a corundum crucible, and an aluminum sheet is prepared on the surface of the raw materials according to the size of the crucible and covers the surface of the mixed raw materials.
S103, placing the prepared raw materials into a box-type resistance furnace for roasting at 550 ℃ for 180min, and naturally cooling in an air atmosphere;
s104, acid washing the prepared material in hydrochloric acid with the concentration of 4mol/L for 60min, and stirring at the speed of 60 r/min.
Example 3A black TiO was obtained 2 . The main phase of the anatase titanium dioxide is almost consistent with that of the anatase titanium dioxide, but the peak is shifted and broadened to the right, a layer of disordered structure is formed on the surface of the particles, and the color is changed from white to blackHas better absorption performance of visible light and even near infrared light.
Comparative example 1
Example preparation of Black TiO 2 The material comprises the following steps:
s101, uniformly mixing raw materials of aluminum powder and anatase titanium dioxide in a mortar, wherein the mass percentage of the raw materials is 0.6;
s102, pressing the uniformly mixed raw materials into a cylindrical sample on an automatic tablet press.
S103, placing the pressed wafer into a corundum crucible, placing the corundum crucible into a box type resistance furnace for roasting, wherein the roasting temperature is 550 ℃, the roasting time is 180min, and naturally cooling the corundum crucible in the air atmosphere;
s104, acid washing the prepared material in hydrochloric acid with the concentration of 4mol/L for 60min, and stirring at the speed of 60 r/min.
The sample prepared in this example was white, and no black TiO could be obtained 2 。
Claims (11)
1. A method for producing black titanium dioxide, characterized by comprising:
A. mixing titanium white powder and aluminum powder uniformly to obtain a mixed raw material,
B. covering the surface of the mixed raw material with a metal sheet with the melting temperature of more than 660 ℃, and covering the metal sheet with the melting temperature of more than 660 ℃ with molten liquid boron trioxide;
C. then roasting at 450-650 ℃ for 50-180 min to obtain black TiO 2 ；
D. Mixing the black TiO of step C 2 Acid washing to obtain pure black TiO 2 。
2. The method for producing black titanium dioxide according to claim 1, wherein the aluminum powder: the weight ratio of the titanium dioxide is 0.2-0.6.
3. The method for producing black titanium dioxide according to claim 2, wherein the aluminum powder: the weight ratio of the titanium dioxide is 0.2-0.4.
4. The method for preparing black titanium dioxide according to claim 1 or 2, wherein the titanium dioxide is at least one of anatase, brookite or rutile.
5. The method for producing black titanium dioxide according to claim 1 or 2, wherein the diboron trioxide is 1 to 2cm thick.
6. The method for producing black titanium dioxide according to claim 1 or 2, wherein the acid washing in the step D is performed with at least one of hydrochloric acid, sulfuric acid, or nitric acid.
7. The method of producing black titanium dioxide according to claim 6, wherein the acid is hydrochloric acid.
8. The method for producing black titanium dioxide according to claim 7, wherein the concentration of the hydrochloric acid is 2 to 4mol/L.
9. The method for preparing black titanium dioxide according to claim 1 or 2, wherein the particle size of the titanium dioxide is as follows: 50-300 nm.
10. The method for producing black titanium dioxide according to claim 1 or 2, wherein the particle diameter of the aluminum powder is: 200-600 nm.
11. The method for producing black titanium dioxide according to claim 1 or 2, wherein the material of the metal sheet is at least one of aluminum, copper, iron, nickel, manganese, chromium, and cobalt.
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| JP2011011954A (en) * | 2009-07-03 | 2011-01-20 | Toho Titanium Co Ltd | Method for producing titanium suboxide |
| CN101983929A (en) * | 2010-11-29 | 2011-03-09 | 四川大学 | Preparation method of low-valence titanium oxide powder |
| 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 |
| CN106830065A (en) * | 2017-03-02 | 2017-06-13 | 攀枝花学院 | The method for preparing Magn é li phase titanium suboxides |
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011011954A (en) * | 2009-07-03 | 2011-01-20 | Toho Titanium Co Ltd | Method for producing titanium suboxide |
| CN101983929A (en) * | 2010-11-29 | 2011-03-09 | 四川大学 | Preparation method of low-valence titanium oxide powder |
| 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 |
| CN106830065A (en) * | 2017-03-02 | 2017-06-13 | 攀枝花学院 | The method for preparing Magn é li phase titanium suboxides |
| 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 |
Non-Patent Citations (1)
| Title |
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| 铝热还原TiO_2制备Magnéli相低价钛氧化物工艺及过程机制研究;李军等;《稀有金属》;20180606(第06期);全文 * |
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