CN109289826B - Black nano-titanium oxide with high distortion structure and preparation method thereof - Google Patents
Black nano-titanium oxide with high distortion structure and preparation method thereof Download PDFInfo
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Abstract
高畸变结构黑色纳米氧化钛及其制备方法，物相为金红石相，具有高畸变内核结构；方法为：(1)氧化钛粉体原料置于填装有磨球的旋转高压管式炉内；(2)旋转高压管式炉持续通入混合气体或者为常压惰性气体状态；(3)启动旋转高压管式炉的电机对原料进行球磨，同时升温至300～650℃保温3～120h；(4)停止加热和球磨，温度降至60℃以下后取出。本发明的方法原料廉价易得，采用普通设备，工艺简单，具有大规模工业化生产前景，所制备的产品具有非晶外壳和高畸变内核结构，具有优异的性能。
The high-distortion structure black nano-titanium oxide and its preparation method have a rutile phase and a high-distortion core structure; the method is as follows: (1) the titanium oxide powder raw material is placed in a rotating high-pressure tube furnace filled with grinding balls; (2) The rotary high-pressure tube furnace is continuously fed with mixed gas or in the state of normal pressure inert gas; (3) The motor of the rotary high-pressure tube furnace is started to ball mill the raw materials, and at the same time, the temperature is raised to 300～650℃ and kept for 3～120h; ( 4) Stop heating and ball milling, and take it out after the temperature drops below 60°C. The method of the invention has cheap and easy-to-obtain raw materials, adopts common equipment, simple process, and has the prospect of large-scale industrial production. The prepared product has an amorphous shell and a high-distortion core structure, and has excellent performance.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to black nano titanium oxide with a high distortion structure and a preparation method thereof.
Background
Along with the rapid development and progress of economy in China, the consumption of energy is also larger and larger, but the clear contradiction is formed between the consumption of the traditional energy and the environmental pollution caused by the traditional energy in the energy conversion process; how to develop clean, efficient and renewable novel energy becomes one of important factors for restricting the sustainable development of the society in China; titanium oxide is used as a semiconductor material, has the advantages of stable chemical property, no toxicity, no harm, good photoelectric property, low production cost and the like, and is widely applied to the fields of solar cells, degradation of organic pollutants, catalytic hydrogen production and the like; however, the forbidden band width of titanium oxide is larger than 3.0eV, and according to the semiconductor photocatalysis principle, the titanium oxide can only exert the photocatalysis characteristic by absorbing the ultraviolet light which accounts for less than 5% of the solar spectrum, so that the titanium oxide photocatalysis efficiency is generally low.
In order to improve the photocatalytic efficiency of titanium oxide, the titanium oxide is properly doped to reduce the forbidden band width of the titanium oxide, so that the response range of the titanium oxide to visible light is expanded, and the titanium oxide is a common effective mode; titanium oxide autodoping is carried out by subjecting the surface of titanium oxide to hydrotreating so as to form a large amount of Ti on the surface3+And with Ti3+Replacing original Ti4+Thereby forming disorder and autodoping on the surface, and changing the appearance color from white of common titanium oxide to black; the surface disorder can generate intermediate states of various energy levels, and the energy levels of the intermediate states are continuously distributed and overlapped with the conduction band valence band edge, so that the forbidden bandwidth of titanium oxide is reduced, and the utilization rate of the titanium oxide to visible light is improved; since the preparation of black nano titanium oxide with high visible light response by a high-temperature hydrogen reduction method is firstly reported in Science by Chen X.B. and the like in 2011, the main way for obtaining black titanium oxide is mainly the high-temperature hydrogen reduction method, and some new methods are as follows: plasma hydrogenation, aluminum reduction, two-step non-metal doping, and the like; although the methods can prepare the black nano titanium oxide, the method is limited by the disadvantages of large energy consumption, high cost, complex production process, low yield, difficult quality guarantee and the like, and cannot realize the industrial production of the black nano titanium oxide.
In summary, how to further improve the photocatalytic performance of black nano titanium oxide on the basis of the prior art and how to find a simpler and cheaper production process for preparing black nano titanium oxide becomes a main problem in the current research on black nano titanium oxide.
Disclosure of Invention
Aiming at the problems of the existing preparation technology of the high-catalytic-performance nano titanium oxide, the invention provides the high-distortion-structure black nano titanium oxide and the preparation method thereof.
The phase of one of the high-distortion structure black nano titanium oxide is rutile phase, the particle size is 50-200 nm, the appearance is black, and the high-distortion structure black nano titanium oxide has a high-distortion core structure.
The phase of the two high distortion structure black nano titanium oxide is rutile phase, the grain diameter is 50-200 nm, the appearance is black, and the two high distortion structure black nano titanium oxide has a high distortion core structure and an amorphous shell.
The purity of the two black nano titanium oxides with high distortion structures is more than 99.9 percent.
One of the preparation methods of the black nano titanium oxide with the high distortion structure is carried out according to the following steps:
1. titanium oxide powder is used as a raw material and is placed in a rotary high-pressure tube furnace filled with grinding balls; the titanium oxide powder is anatase phase titanium oxide powder, rutile phase titanium oxide powder or a mixture of the anatase phase titanium oxide powder and the rutile phase titanium oxide powder;
2. vacuumizing the rotary high-pressure tube furnace to be below-0.08 MPa, continuously introducing inert gas to normal pressure, repeatedly exhausting air for at least three times, and finally controlling the state of the inert gas in the rotary high-pressure tube furnace to be in a normal-pressure inert gas state; the inert gas is argon;
3. starting a motor of the rotary high-pressure tube furnace to ball mill the raw materials, and controlling the rotating speed of the ball mill to be 80-2000 rpm; simultaneously heating the materials in the rotary high-pressure tube furnace to 300-650 ℃, and preserving heat for 3-120 h;
4. and stopping heating and ball milling after the heat preservation is finished, taking out the materials in the rotary high-pressure tube furnace when the temperature in the rotary high-pressure tube furnace is reduced to be below 60 ℃, and separating out grinding balls to obtain the black nano titanium oxide with the high distortion structure.
The second preparation method of the black nano titanium oxide with the high distortion structure of the invention is carried out according to the following steps:
1. titanium oxide powder is used as a raw material and is placed in a rotary high-pressure tube furnace filled with grinding balls; the titanium oxide powder is anatase phase titanium oxide powder, rutile phase titanium oxide powder or a mixture of the anatase phase titanium oxide powder and the rutile phase titanium oxide powder;
2. continuously introducing mixed gas into the rotary high-pressure tube furnace, discharging air in the rotary high-pressure tube furnace, and adjusting an exhaust valve of the rotary high-pressure tube furnace to keep the internal gauge pressure of the rotary high-pressure tube furnace at 0.5-3.5 MPa; the mixed gas is a hydrogen and argon mixed gas, a hydrogen and nitrogen mixed gas or a hydrogen and helium mixed gas, wherein the volume percentage of the hydrogen is 30-80%;
3. starting a motor of a rotary high-pressure tube furnace to ball mill the raw materials under the condition of continuously introducing mixed gas, and controlling the rotating speed during ball milling to be 80-2000 rpm; simultaneously heating the materials in the rotary high-pressure tube furnace to 300-650 ℃, and preserving heat for 3-120 h;
4. and stopping heating and ball milling after the heat preservation is finished, stopping introducing the mixed gas when the temperature in the rotary high-pressure tube furnace is reduced to be below 60 ℃, reducing the gauge pressure in the rotary high-pressure tube furnace to be normal pressure, taking out the material in the rotary high-pressure tube furnace, and separating out grinding balls to obtain the black nano titanium oxide with the high distortion structure.
In the two methods, the titanium oxide powder has the particle size of 30-100 nm and the purity of more than 99.99 percent.
In the two methods, the grinding ball is a GCr15 bearing steel ball with the diameter of 6-10 mm.
In the step 1 of the two methods, the total volume of the grinding balls and the raw materials in the rotary high-pressure tube furnace accounts for 1/2-1/10 of the total volume of a furnace chamber of the rotary high-pressure tube furnace.
In the step 1 of the two methods, the mass ratio of the grinding balls in the rotary high-pressure tube furnace to the raw materials is (10-80): 1.
In step 3 of the two methods, the temperature rise speed is controlled to be 6-12 ℃/min during temperature rise.
The principle of the invention is as follows: under the inert atmosphere and the heating condition, the grinding balls are subjected to one-dimensional collision in a rotary high-pressure tube furnace, so that titanium oxide powder particles mixed among the grinding balls are continuously ground and refined, and the microstructure of particles is caused to be distorted; with the prolonging of the grinding time, the distortion quantity in the particles is continuously accumulated, and a high distortion crystal lattice structure is finally formed, wherein the high distortion structure means that the microstructure of the titanium oxide powder particles is highly distorted; when the grinding ball is in an anaerobic atmosphere and the atmosphere contains sufficient hydrogen, the hydrogen can reduce oxygen in the lattice structure on the surface of titanium oxide powder particles and form oxygen vacancies in situ, and when the number of the oxygen vacancies is accumulated to a certain degree, the original ordered lattice structure on the surface becomes disordered to form an amorphous shell, wherein the amorphous shell refers to the high disorder of the lattice structure on the surface of the titanium oxide powder particles.
The invention has the advantages and positive effects that:
1. the used raw material is anatase phase titanium oxide powder sold in the market, and is cheap and easy to obtain;
2. the equipment is a common rotary high-pressure tube furnace, and the performance is stable;
3. the preparation process is simple and easy to operate, and has a large-scale industrial production prospect;
4. the prepared black nano titanium oxide has an amorphous shell and a high-distortion core structure, the capacity of degrading organic dye rhodamine-B is 2-3 times of that of common titanium oxide serving as a raw material, and in addition, the black nano titanium oxide has good effects in the aspects of antibiosis, formaldehyde removal and the like.
Drawings
FIG. 1 is a photograph showing the appearance of black nano-titanium oxide having a high distortion structure obtained in example 1 of the present invention;
FIG. 2 is a transmission electron micrograph of the black nano-titanium oxide with a high distortion structure obtained in example 1 of the present invention; in the figure, (a) is hypo-magnification and (b) is hyper-magnification;
FIG. 3 is an X-ray diffraction chart of the black nano titanium oxide of high distortion structure obtained in example 1 of the present invention and the raw material; in the figure, the upper part is black nano titanium oxide with a high distortion structure, and the lower part is raw material;
FIG. 4 is a graph showing the diffuse reflection of ultraviolet rays of the black nano titanium oxide with a high distortion structure and the raw material obtained in example 1 of the present invention; in the figure, a tangle-solidup is black nano titanium oxide with a high distortion structure, and ● is used as a raw material;
FIG. 5 is the electron paramagnetic resonance spectrum of the black nano titanium oxide with high distortion structure and the raw material obtained in example 1 of the present invention; in the figure, a tangle-solidup is black nano titanium oxide with a high distortion structure, and ● is used as a raw material;
FIG. 6 is a graph of absorption intensity versus time for a high distortion structure black nano titanium oxide obtained in example 1 of the present invention and a degradation rhodamine-B solution test of the raw material; in the figure, the tangle-solidup is black nano titanium oxide with a high distortion structure, ● is used as a raw material, and ■ is no titanium oxide.
Detailed Description
How the present invention is implemented is described in detail and fully below with reference to specific embodiments.
The black nano titanium oxide product with the high distortion structure prepared in the embodiment of the invention is characterized by the following means: TECNNAI G produced by FEI corporation of America was used2Observing the microscopic morphology of the product by using a 20-type transmission electron microscope; the product phase is characterized by adopting an X-ray diffractometer of X' Pert Pro PW3040/60 type manufactured by Panalytical company in the Netherlands; the spectrum absorption condition of the product is tested by using a CARY 100 type ultraviolet-visible diffuse reflection spectrometer produced by Agilent in America.
The rotary high-pressure tube furnace used in the embodiment of the invention is a KJ-T2400-S1200DIC type rotary high-pressure tube furnace of Zhengzhou Kejia electric furnace Co., Ltd, Henan, or a GG-T1000 type rotary high-pressure tube furnace of Shenyang Yinggu environmental protection technology Co., Ltd.
The anatase phase titanium oxide powder adopted in the embodiment of the invention is a product of Shandong Linyi Youx chemical technology Co., Ltd or a product of Jiangsu Nanjing titanium white chemical Co., Ltd.
The rutile phase titanium oxide powder adopted in the embodiment of the invention is R-902 micron rutile phase titanium oxide powder of DuPont company in the United states.
The grinding ball adopted in the embodiment of the invention is a GCr15 bearing steel ball produced by Shandong Taian new stainless steel ball factory.
In the embodiment of the invention, the grinding balls are separated by screening with a sieve with the aperture of 3-5 mm.
In the embodiment of the invention, the purity of the product is slightly reduced due to furnace chamber pollution.
In the embodiment of the invention, the flow rate of the mixed gas is controlled to be 500-5000 mL/min when the mixed gas is continuously introduced.
When the mixed gas introduced into the reactor is the mixed gas of hydrogen and nitrogen, the mode of simultaneously introducing the hydrogen and the nitrogen is adopted, or the mode of introducing ammonia gas for pyrolysis to form the mixed gas of the hydrogen and the nitrogen is adopted.
The following are preferred embodiments of the present invention.
Example 1
Titanium oxide powder with the particle size of 50nm and the purity of 99.99 percent is used as a raw material and is placed in a rotary high-pressure tube furnace filled with grinding balls; the titanium oxide powder is anatase phase titanium oxide powder; the grinding ball is a GCr15 bearing steel ball with the diameter of 10 mm; 1/2 the total volume of the grinding balls and the raw materials accounts for the total volume of the furnace chamber of the rotary high-pressure tube furnace; the mass ratio of the grinding balls to the raw materials is 50: 1;
continuously introducing mixed gas into the rotary high-pressure tube furnace, discharging air in the rotary high-pressure tube furnace, adjusting an exhaust valve of the rotary high-pressure tube furnace to keep the internal gauge pressure of the rotary high-pressure tube furnace at 0.5MPa, and continuously introducing the mixed gas at the flow rate of 500 mL/min; the mixed gas is hydrogen and argon mixed gas, wherein the volume percentage of hydrogen is 50%;
starting a motor of the rotary high-pressure tube furnace to ball mill the raw materials, and controlling the rotating speed of the ball mill to be 1000 rpm; simultaneously heating the materials in the rotary high-pressure tube furnace to 500 ℃ and preserving the heat for 20 h; controlling the temperature rise speed to be 8 ℃/min during temperature rise;
stopping heating and ball milling after the heat preservation is finished, stopping introducing the mixed gas when the temperature in the rotary high-pressure tube furnace is reduced to be below 60 ℃, reducing the gauge pressure in the rotary high-pressure tube furnace to be normal pressure, taking out the material in the rotary high-pressure tube furnace, and screening out grinding balls to obtain black nano titanium oxide with a high distortion structure;
the phase of the black nano titanium oxide with the high distortion structure is rutile phase, the grain diameter is 10nm, andthe product has an amorphous shell and a high-distortion core structure, and the purity is over 99.9 percent; the appearance photograph is shown in FIG. 1, and the appearance is black; the high power and low power electron microscope micrographs are shown in figure 2, the X-ray diffraction of the product and the raw material is shown in figure 3, and the phase of the product is rutile phase; the ultraviolet diffuse reflection curves of the product and the raw materials are shown in figure 4, and the product has stronger absorption capacity in a visible spectrum region; the electron paramagnetic resonance spectrum of the product and the raw materials is shown in FIG. 5, and the product has Ti at the magnetic field strength of 3103Gauss3+A resonance peak;
the degradation test of the rhodamine-B solution is carried out by comparing the product with the raw material, and the test scheme is as follows:
respectively placing 100mL of rhodamine-B solution with the concentration of 10mg/L into two 150mL quartz cups, and carrying out ultrasonic cleaning by using a TitanSonic ultrasonic cleaning machine, wherein the frequency is 40kHz, and the time is at least 1 min; the absorbance C of the solution at this time was measured by an ultraviolet-visible spectrophotometer0；
Respectively adding 20mg of raw material products into two quartz cups, and respectively marking the cup bodies as A and B;
placing the two quartz cups under 30W xenon light, timing, sampling every 1 hr, measuring absorbance with ultraviolet-visible spectrophotometer, and recording as CA1、CA2、…CA5、CB1、CB2、…CB5Pouring all the sample solution after each test into the original quartz cup;
an absorption intensity-time curve is drawn according to the absorbance data as shown in fig. 6, and the photocatalytic degradation capacity of the product is at least 2-3 times that of the raw material.
Example 2
The method is the same as example 1, except that:
(1) the raw material is rutile phase titanium oxide powder with the particle size of 30 nm; the diameter of the grinding ball is 6 mm; 1/10 the total volume of the grinding balls and the raw materials accounts for the total volume of the furnace chamber of the rotary high-pressure tube furnace; the mass ratio of the grinding balls to the raw materials is 80: 1;
(2) adjusting an exhaust valve of the rotary high-pressure tube furnace to keep the internal gauge pressure at 1.5MPa and the flow rate of the mixed gas at 2000 mL/min; the mixed gas is hydrogen and nitrogen mixed gas, wherein the volume percentage of hydrogen is 30 percent;
(3) the ball milling speed is 2000 rpm; keeping the temperature at 650 ℃ for 3 h; the temperature rising speed is 12 ℃/min;
(4) the grain diameter of the black nano titanium oxide with the high distortion structure is 20 nm.
Example 3
The method is the same as example 1, except that:
(1) the raw material is a mixture of anatase phase titanium oxide powder and rutile phase titanium oxide powder with the same mass, and the particle size is 60 nm; 1/5 the total volume of the grinding balls and the raw materials accounts for the total volume of the furnace chamber of the rotary high-pressure tube furnace; the mass ratio of the grinding balls to the raw materials is 40: 1;
(2) adjusting an exhaust valve of the rotary high-pressure tube furnace to keep the internal gauge pressure at 3.5MPa and the flow rate of mixed gas at 5000 mL/min; the mixed gas is hydrogen-helium mixed gas, wherein the volume percentage of hydrogen is 80%;
(3) the ball milling rotating speed is 900 rpm; keeping the temperature at 600 ℃ for 10 h; the temperature rising speed is 10 ℃/min;
(4) the grain diameter of the black nano titanium oxide with the high distortion structure is 18 nm.
Example 4
The method is the same as example 1, except that:
(1) the raw material is rutile phase titanium oxide powder with the particle size of 45 nm; the diameter of the grinding ball is 8 mm;
(2) introducing high-purity ammonia gas into the rotary high-pressure tube furnace, wherein the purity of the ammonia gas is 99.99%, and the mixed gas is hydrogen-nitrogen mixed gas formed after the high-purity ammonia gas is decomposed;
(3) adjusting an exhaust valve of the rotary high-pressure tube furnace to keep the internal gauge pressure at 2.0MPa, wherein the flow rate of ammonia gas is 1L/min;
(4) the grain diameter of the black nano titanium oxide with the high distortion structure is 15 nm.
Example 5
Anatase phase titanium oxide powder with the particle size of 80nm and the purity of 99.99 percent is used as a raw material and is placed in a rotary high-pressure tube furnace filled with grinding balls; the grinding ball is a GCr15 bearing steel ball with the diameter of 6 mm; 1/2 the total volume of the grinding balls and the raw materials accounts for the total volume of the furnace chamber of the rotary high-pressure tube furnace; the mass ratio of the grinding balls to the raw materials is 10: 1;
vacuumizing the rotary high-pressure tube furnace to be below-0.08 MPa, continuously introducing argon to normal pressure, repeatedly exhausting air for at least three times, and finally controlling the inside of the rotary high-pressure tube to be in a normal-pressure argon state;
starting a motor of the rotary high-pressure tube furnace to ball mill the raw materials, and controlling the rotating speed of the ball mill to be 80 rpm; simultaneously heating the materials in the rotary high-pressure tube furnace to 300 ℃ and preserving the heat for 120 h; controlling the temperature rise speed to be 6 ℃/min;
and stopping heating and ball milling after the heat preservation is finished, taking out the materials in the rotary high-pressure tube furnace when the temperature in the rotary high-pressure tube furnace is reduced to be below 60 ℃, and separating out grinding balls to obtain the black nano titanium oxide with the high distortion structure, wherein the phase of the black nano titanium oxide is a rutile phase, and the black nano titanium oxide has a high distortion core structure, the purity is more than 99.9 percent, and the particle size is 15 nm.
Example 6
The method is the same as example 5, except that:
(1) the raw material is rutile phase titanium oxide powder with the particle size of 100 nm; the diameter of the grinding ball is 10 mm; 1/10 the total volume of the grinding balls and the raw materials accounts for the total volume of the furnace chamber of the rotary high-pressure tube furnace; the mass ratio of the grinding balls to the raw materials is 60: 1;
(2) the ball milling speed is 1500 rpm; keeping the temperature at 400 ℃ for 10 h; the temperature rising speed is 9 ℃/min;
(3) the phase of the black nano titanium oxide with the high distortion structure is rutile phase, and the particle size is 20 nm.
Example 7
The method is the same as example 5, except that:
(1) the raw material is a mixture of anatase phase titanium oxide powder and rutile phase titanium oxide powder with equal mass, and the particle size is 70 nm; the diameter of the grinding ball is 10 mm; 1/3 the total volume of the grinding balls and the raw materials accounts for the total volume of the furnace chamber of the rotary high-pressure tube furnace; the mass ratio of the grinding balls to the raw materials is 80: 1;
(2) the ball milling rotating speed is 1200 rpm; keeping the temperature at 450 ℃ for 6 h; the temperature rising speed is 11 ℃/min;
(4) the phase of the black nano titanium oxide with the high distortion structure is rutile phase, and the grain size is 15 nm.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A preparation method of black nano titanium oxide with a high distortion structure is characterized by comprising the following steps:
(1) titanium oxide powder is used as a raw material and is placed in a rotary high-pressure tube furnace filled with grinding balls; the titanium oxide powder is anatase phase titanium oxide powder, rutile phase titanium oxide powder or a mixture of the anatase phase titanium oxide powder and the rutile phase titanium oxide powder; the titanium oxide powder has a particle size of 30-100 nm and a purity of more than 99.99%;
(2) vacuumizing the rotary high-pressure tube furnace to be below-0.08 MPa, continuously introducing inert gas to normal pressure, repeatedly exhausting air for at least three times, and finally controlling the state of the inert gas in the rotary high-pressure tube furnace to be in a normal-pressure inert gas state; the inert gas is argon;
(3) starting a motor of the rotary high-pressure tube furnace to ball mill the raw materials, and controlling the rotating speed of the ball mill to be 80-2000 rpm; simultaneously heating the materials in the rotary high-pressure tube furnace to 300-650 ℃, and preserving heat for 3-120 h; controlling the temperature rise speed to be 6-12 ℃/min during temperature rise;
(4) and stopping heating and ball milling after the heat preservation is finished, taking out the materials in the rotary high-pressure tube furnace when the temperature in the rotary high-pressure tube furnace is reduced to be below 60 ℃, and separating out grinding balls to obtain the black nano titanium oxide with the high distortion structure, wherein the phase of the black nano titanium oxide is a rutile phase, the particle size of the black nano titanium oxide is 50-200 nm, the appearance of the black nano titanium oxide is black, and the black nano titanium oxide has a high distortion inner core structure.
2. A preparation method of black nano titanium oxide with a high distortion structure is characterized by comprising the following steps:
(1) titanium oxide powder is used as a raw material and is placed in a rotary high-pressure tube furnace filled with grinding balls; the titanium oxide powder is anatase phase titanium oxide powder, rutile phase titanium oxide powder or a mixture of the anatase phase titanium oxide powder and the rutile phase titanium oxide powder; the titanium oxide powder has a particle size of 30-100 nm and a purity of more than 99.99%;
(2) continuously introducing mixed gas into the rotary high-pressure tube furnace, discharging air in the rotary high-pressure tube furnace, and adjusting an exhaust valve of the rotary high-pressure tube furnace to keep the internal gauge pressure of the rotary high-pressure tube furnace at 0.5-3.5 MPa; the mixed gas is a hydrogen and argon mixed gas, a hydrogen and nitrogen mixed gas or a hydrogen and helium mixed gas, wherein the volume percentage of the hydrogen is 30-80%;
(3) starting a motor of a rotary high-pressure tube furnace to ball mill the raw materials under the condition of continuously introducing mixed gas, and controlling the rotating speed during ball milling to be 80-2000 rpm; simultaneously heating the materials in the rotary high-pressure tube furnace to 300-650 ℃, and preserving heat for 3-120 h; controlling the temperature rise speed to be 6-12 ℃/min during temperature rise;
(4) and stopping heating and ball milling after the heat preservation is finished, stopping introducing the mixed gas when the temperature in the rotary high-pressure tube furnace is reduced to be below 60 ℃, reducing the gauge pressure in the rotary high-pressure tube furnace to be normal pressure, taking out the materials in the rotary high-pressure tube furnace, and separating out grinding balls to obtain the black nano titanium oxide with the high distortion structure, wherein the phase of the black nano titanium oxide is a rutile phase, the particle size of the black nano titanium oxide is 50-200 nm, the appearance of the black nano titanium oxide is black, and the black nano titanium oxide has an amorphous shell and a high distortion core structure.
3. The method for preparing black nano titanium oxide with high distortion structure according to claim 1 or 2, wherein the purity of the black nano titanium oxide with high distortion structure is more than 99.9%.
4. The preparation method of the black nanometer titanium oxide with the high distortion structure according to claim 1 or 2, wherein the grinding ball is a GCr15 bearing steel ball with a diameter of 6-10 mm.
5. The method for preparing black nano titanium oxide with high distortion structure according to claim 1 or 2, wherein in the step (1), the total volume of the grinding balls and the raw materials in the rotary high-pressure tube furnace accounts for 1/2-1/3 of the total volume of the furnace chamber of the rotary high-pressure tube furnace.
6. The method for preparing black nano titanium oxide with a high distortion structure according to claim 1 or 2, wherein in the step (1), the mass ratio of the grinding ball to the raw material in the rotary high-pressure tube furnace is (10-80): 1.
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