CN109704400B - Method for preparing black titanium dioxide block in oxygen or air atmosphere - Google Patents
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Abstract
The invention relates to a method for preparing black titanium dioxide blocks in oxygen or air atmosphere, wherein the black titanium dioxide blocks contain Ti3+In the titanium element, Ti3+The content is more than or equal to 1 percent, and preferably 20 to 30 percent.
Description
Technical Field
The invention discloses a method for preparing black titanium dioxide in oxygen or air atmosphere, in particular relates to a method for preparing a black titanium dioxide block by an open gas suspension laser heating technology, and belongs to the technical field of inorganic material preparation.
Background
Titanium dioxide as a photocatalyst has the advantages of good chemical property stability, low cost, high catalytic activity, no toxicity and the like, and is widely researched and applied in the fields of environment and energy. However, the titanium dioxide has a large forbidden band width (3.2 ev for anatase phase and 3.0ev for rutile phase), can only absorb ultraviolet light which accounts for less than 5% of the total energy of sunlight, and has a narrow photoresponse range, while visible light (44%) and infrared light (49%) are mainly used in the solar spectrum, and the absorption utilization rate of the titanium dioxide to the sunlight is extremely low. Therefore, the band structure of the titanium dioxide is widened, the absorption in visible light and infrared light areas is improved, and the method has very important significance for improving the catalytic performance of the titanium dioxide.
In order to improve the utilization of the titanium dioxide to sunlight, the existing methods for modifying the titanium dioxide comprise non-metal element doping, transition or rare earth metal ion doping, noble metal deposition, semiconductor compounding, dye sensitization and the like. Although the spectral response of the titanium dioxide is expanded to a certain extent by the method, the method has the defects of limited expansion range and insufficient improvement of light absorption. In 2011, Xiaobo et al first passed at 200 ℃ H2For white TiO at a pressure of 20.0bar2After 5 days of the hydrogenation treatment, black titanium dioxide was obtained, which was characterized in that the light absorption range was extended to the infrared region, significantly changing the structure, chemical, electronic and optical properties of titanium dioxide, and thus, black titanium dioxide has attracted great attention in the field of photocatalysis. The current method for preparing black titanium dioxide is as follows: hydrogen heat treatment, high temperature high pressure or normal pressure hydrogenation, anodic oxidation, plasma assisted hydrogenation and chemical reduction including aluminum reduction, zinc reduction, magnesium reduction, NaBH4Reduction, NaH reduction, and the like. The yellow rich topic group adopts a dual-temperature zone reduction method to prepare black titanium dioxide, white titanium dioxide and metal aluminum are placed into a closed tube furnace to be vacuumized to 0.1Pa, and then are respectively heated to 300-800 ℃ and 800 ℃. And reacting for 8 hours to obtain black titanium dioxide with an amorphous layer on the surface. The anodic oxidation method has been reported to be titanium dioxide in the presence of NH4F (0.25 wt.%) and H2Anodic oxidation was carried out at 60V for 10 hours in O (2 vol%) in ethylene glycol. A second anodization is performed after the nanotubes are stripped. Sintering at 450 deg.C for 1 hr in ambient atmosphere and removing anode TiO2After the layer, black titanium dioxide having a large visible light absorption was obtained. Wan plasma uses ion-assisted hydrogenation to put titanium dioxide into a sealed tube furnace under the conditions of 100Pa of hydrogen pressure, 200W of plasma radio-frequency power and 500 DEG CHeating for 8h to prepare black titanium dioxide.
In summary, the existing methods for preparing black titanium dioxide mostly require high temperature and high pressure and are realized in a reducing atmosphere. In addition, in order to obtain reducing atmosphere, metal aluminum, hydrogen and other auxiliary agents are added, subsequent processing and purification are needed, and unsafe factors such as flammability, explosiveness and the like exist. Based on the above facts, there is a need to explore and develop a simple, direct and relatively safe method for preparing black titanium dioxide.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing a black titanium dioxide block by laser heating under the atmosphere of oxygen or air at normal pressure. The method is simple to operate, and the black titanium dioxide is directly synthesized in oxygen or air at normal pressure. The obtained titanium dioxide widens the photoresponse range and greatly improves the absorption of visible light and infrared light.
In one aspect, the invention provides a black titanium dioxide block, wherein the black titanium dioxide block contains Ti3+In the titanium element, Ti3+The content is more than or equal to 1 percent, and preferably 20 to 30 percent (wherein, the content means Ti3+Atomic ratio to the total amount of titanium element).
In the present disclosure, the black titanium dioxide block contains Ti3+Not less than 1 percent and oxygen vacancy not less than 1 percent, causes the width of the forbidden band to be reduced, enhances the absorption of visible light and near infrared light, has obvious photo-thermal effect in a near infrared light area, and is potentially applied to photo-thermal treatment.
Preferably, the black titanium dioxide block is a black titanium dioxide ball with a diameter of 2-4 mm.
Preferably, the forbidden band width of the black titanium dioxide block is 2.61 eV.
Preferably, the black titanium dioxide block has a large oxygen vacancy content of 1% or more (wherein the content means "atomic ratio of oxygen vacancy to total amount of O atom"), preferably 20 to 30%.
Preferably, the black titanium dioxide bulk has significantly enhanced absorption in the visible and near infrared regions.
Preferably, the temperature of the black titanium dioxide block can rise to 119 ℃ under the irradiation of near infrared light of 808 nm.
In another aspect, the present invention also provides a method for preparing the black titanium dioxide block in an oxygen or air atmosphere, comprising the steps of:
(1) white TiO is mixed2Pressing the raw materials into tablets and calcining;
(2) cutting the calcined sample into 25-125 mg small pieces, placing the small pieces in an air suspension furnace, introducing oxygen or air to enable the small pieces to be suspended, turning on laser and increasing power to heat the sample to a molten state, and then rapidly cooling the sample to obtain the black titanium dioxide block;
the speed of the rapid cooling is more than or equal to 200 ℃/second.
In this disclosure, white TiO is first treated2The method comprises the steps of pressing raw materials into a tablet, calcining, cutting into small 25-125 mg blocks, placing the small 25-125 mg blocks into a nozzle of an air suspension furnace, introducing oxygen or air to enable the small blocks to be suspended, turning on a laser, slowly increasing laser power, heating to enable a sample to be in a molten state, adjusting gas flow to enable the molten sample to be in the suspended state, turning off the laser after a melt is suspended stably, cooling quickly, and solidifying the sample to obtain pure black titanium dioxide and a whole black titanium dioxide block. Wherein, the material which is kept in the whole process of melting and rapid cooling through gas (oxygen, air or nitrogen) is always in a suspension container-free state to avoid contacting with the wall of the container, the cooling rate is not lower than 200 ℃/s (200-500 ℃/s), the laser heating high-temperature melting causes the movement speed of atomic ion electron oxygen vacancy and the like to be intensified, the oxygen partial pressure in the melt is higher than the surrounding environment, the oxygen atom in the sample in the melting state can escape to cause Ti3+And the occurrence of oxygen vacancies, and the rapid cooling process results in Ti3+And oxygen vacancy is fixed in the original state of moving in the melt, and the oxygen can not diffuse in time to form a solid state, so that pure black titanium dioxide which is a whole black titanium dioxide block is prepared.
Preferably, theWhite TiO 22The raw material includes crystalline phase titanium dioxide or amorphous phase titanium dioxide.
Preferably, the tablet pressing mode is dry pressing, the pressure of the dry pressing is 2-5 MPa, and the pressure maintaining time is 1-2 minutes.
Preferably, the calcining temperature is 1100-1300 ℃ and the calcining time is 2-8 hours.
Preferably, the pressure of the oxygen or air introduced into the gas suspension furnace is 0.2-1.5 MPa.
Preferably, the power of the laser is 60-90W, and the heating time is 30-120 seconds; the temperature of the laser heated melt is higher than that of TiO2Melting point (1850 ℃); preferably, the wavelength of the laser is 800-1100 nm. The specific laser parameters of the invention are 800-1100 nm in the near infrared region, and the power of the continuous wave carbon dioxide laser is 60-90W. The use of the laser with the near infrared region of 800-1100 nm has no harm or little harm to human tissues, so the operation is safer.
Preferably, the rapid cooling rate is 200 to 500 ℃/s, preferably 300 to 500 ℃/s. Wherein, the high cooling speed is beneficial to the formation of trivalent titanium and oxygen vacancy in the black titanium dioxide.
The invention has the beneficial effects that:
(1) the invention is prepared in the normal pressure atmosphere (oxidation environment) in the presence of oxygen, does not need reducing atmosphere such as hydrogen and the like, reduces the risk of experiment and has simple preparation. In the preparation process of the black titanium dioxide, the valence of titanium ions is changed and oxygen vacancies are introduced through the processes of laser heating melting and rapid cooling in gas suspension, so that the change of the forbidden bandwidth is caused, and the absorption of visible light and infrared light regions is greatly increased;
(2) compared with the original methods for preparing black titanium dioxide, such as a hydrogenation method, plasma-assisted hydrogenation, an aluminothermic reduction method and the like, the method is simple to operate, short in reaction time, capable of preparing black titanium dioxide in only 30-120 seconds and considerable in yield;
(3) the black titanium dioxide prepared by the method avoids introducing external (auxiliary) additives, does not need purification steps, is suspended by gas in the sintering process to avoid contacting with the wall of a container, and has no impurity pollution, so that a pure black titanium dioxide block is prepared;
(4) the black titanium dioxide prepared by the invention is prepared in an open gas suspension furnace, the whole preparation process is under normal pressure, special pressurizing equipment and an air extractor are not needed, and the requirement on equipment is low;
(5) the black titanium dioxide block prepared by adopting a container-free preparation technology greatly improves the absorption of the black titanium dioxide block in visible light and infrared light regions, changes an energy band structure, and has potential application values in the fields of dye-sensitized solar cells, visible light hydrogen production, environmental management and the like;
(6) the invention can achieve extremely fast cooling speed only by improving the cooling environment, and can achieve the cooling rate higher than 300 ℃/s even without any measures, thereby being capable of preparing the block material which can not be prepared by the conventional method. For example, a circulating cooling water tank is adopted for cooling (the circulating water cools the surrounding gas, and the gas cools the suspended black titanium dioxide block), and the cooling speed is as high as-500 ℃/s;
(7) the titanium dioxide is prepared by adopting an air suspension method, for example, in an air environment, black titanium dioxide with different trivalent titanium and oxygen vacancy contents can be obtained only by changing different suspension gases such as oxygen, air or nitrogen;
(8) the method for preparing the silicon nitride by adopting the gas suspension method has the characteristics that the sample is heated and melted in the suspension state, the purity of the sample is ensured, and the metastable state of atoms and the like in the melt is kept as much as possible due to quick cooling, so that the silicon nitride can not return to the due equilibrium state; because the laser heating is adopted, the method is characterized in that the laser is turned off, the temperature of the sample can be instantly reduced to the room temperature from high temperature, and the cooling rate can reach 200-500 ℃/second or even higher according to different external conditions.
Drawings
In FIG. 1, (a) shows the change of state of the black titanium dioxide prepared in example 1 before and after the black titanium dioxide is heated by the aerosol laser, and (b) shows the black titanium dioxide spheres prepared in example 1;
FIG. 2 is a graph comparing a white titanium dioxide raw powder (left) to a powder milled through a 200 mesh screen using black titanium dioxide pellets of example 1 (right);
FIG. 3 shows the black titanium dioxide powder prepared in example 1 and the original white titanium dioxide (TiO)2) X-ray diffraction pattern of (a);
FIG. 4 shows black titanium dioxide powder and white titanium dioxide raw material powder (TiO) prepared in example 12) Ultraviolet-visible-near infrared diffuse reflectance spectrum of (a);
FIG. 5 shows black titanium dioxide powder and white titanium dioxide raw material powder (TiO) prepared in example 12) The forbidden band width spectrogram;
FIG. 6 is an X-ray photoelectron spectrum of Ti element of black titanium dioxide prepared in example 1;
FIG. 7 is an X-ray photoelectron spectrum of the O element of the black titanium dioxide prepared in example 1;
FIG. 8 shows black titanium dioxide powder (B-TiO) prepared in example 12) With white titanium dioxide raw material powder (TiO)2) Graph of temperature change after 808nm laser irradiation.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The invention changes the energy band and the photoresponse range of the titanium dioxide material to obtain black TiO2The absorption in visible light and infrared light regions is greatly improved.
In one embodiment of the invention, the diameter of the black titanium dioxide sphere can be 2-4 mm, the forbidden band width is 2.61ev, and the absorption in visible light and infrared light regions is greatly enhanced.
In the invention, the grain size of the black titanium dioxide is calculated according to a Sheller formula (formula 1) to obtain the grain size of 45-55 nm:
in the invention, the black titanium dioxide block is prepared by simple steps without auxiliary additives, can be prepared under normal pressure and has low raw material cost. The following exemplarily illustrates a method for preparing a black titanium dioxide bulk.
White TiO is mixed2The raw materials are pressed into tablets and put into a muffle furnace or a resistance wire furnace for calcination (presintering). White TiO 22The starting material is simply titanium dioxide in any form, including crystalline or amorphous. Wherein, the mode of pressing into tablets can be dry pressing, the pressure of the dry pressing can be 2-5 MPa, and the pressure maintaining time can be 1-2 minutes. The calcination temperature can be 1100-1300 ℃ and the calcination time can be 2-8 hours.
And placing the pre-sintered sample in an open type gas suspension device, introducing oxygen or air (suspending the sample so as to facilitate container-free laser firing), heating to a molten state by laser, and rapidly cooling to obtain a black titanium dioxide block. Wherein, the laser heating power can be 60-90W, and the heating time can be 30-120 seconds. The highest temperature of the laser heating melt can reach 2500 ℃, and the preferred laser wavelength is 800-1100 nm. The rapid cooling rate can be 200-500 ℃/s.
The black titanium dioxide prepared by the method has high purity, is a block material, reduces the dependence of the formation of the black titanium dioxide on the atmosphere, and creatively utilizes the high cooling speed to be beneficial to the formation of trivalent titanium and oxygen vacancy in the black titanium dioxide.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. In the following examples, unless otherwise specified, the starting materials used include: white TiO 22Raw material (e.g., white titanium dioxide having a purity of 4N, produced by Kabushiki Kaisha high purity chemical research institute).
Example 1
The method for preparing the black titanium dioxide in the oxygen atmosphere comprises the following specific steps:
(1) 2g of white TiO are taken2Pressing the raw materials into tablets, and putting the tablets into a muffle furnace for calcining to obtain ceramic plates; white TiO 22The raw material is rutile phase; the pressing and tabletting mode is dry pressing, the pressure of the dry pressing is 2-5 MPa, and the pressure maintaining time is 1-2 minutes; calcining at 1100-1300 ℃ for 2-8 hours;
(2) cutting the calcined sample into 25-125 mg small pieces, placing the small pieces in an air suspension furnace, introducing oxygen (0.6MPa), turning on laser, increasing power, heating the sample to a molten state, and then rapidly cooling the sample, wherein the laser heating power is 70W, the heating time is 100 seconds, and the temperature of the laser heating melt reaches-2500 ℃; the laser wavelength is 1064 nm; and obtaining the black titanium dioxide balls with the diameter of 2-4 mm. Wherein, the circulating cooling water tank is adopted for cooling (the circulating water cools the surrounding gas, and the gas cools the suspended black titanium dioxide block), so that the cooling rate is 300 ℃/s. The obtained black titanium dioxide block contains Ti3+And oxygen vacancies in an amount of 21.5% (see FIG. 6) and 26.95% (see FIG. 7) of the Ti ions.
Characterization test:
x-ray diffraction testing: the black titanium dioxide is ball-milled into powder and sieved by a 200-mesh sieve, and phase analysis is carried out by adopting a Nippon science Ultima IV X-ray diffractometer, wherein the main parameters are as follows: cu target KαRay, tube voltage 40KV, tube current 40mA, step length 0.02 degree, scanning speed 5 degree/min;
ultraviolet-visible-near infrared diffuse reflection spectrum test: ball-milling black titanium dioxide into powder, sieving the powder by a 200-mesh sieve, testing by using an ultraviolet spectrophotometer (Cary 5000), observing the diffuse reflection spectrum of the material, wherein the scanning range is as follows: 300-1600 nm;
x-ray photoelectron spectroscopy: the ESCALB 250X-ray photoelectron spectrometer is used for testing to prove that Ti in the black titanium dioxide3+And oxygen vacancies and their content;
testing the photo-thermal performance: irradiating black titanium dioxide in dry state with near infrared light of 808nm for 5min at power density0.4W/cm2The temperature of the stent was monitored in real time using an Infrared thermographer (infra imaging thermometer, A325sc, FLIR, USA), data were recorded, and the data were recorded by FLIR R&Software D plots the temperature versus time. The photo-thermal property of black titanium dioxide can be potentially applied to photo-thermal treatment, selects 808nm to be the laser wavelength of photo-thermal experiment, and is mainly because in this wavelength is in human tissue optical window scope, the penetrability to human tissue is the best.
FIG. 1 (a) shows the change of state of black titanium dioxide prepared in example 1 before and after the black titanium dioxide is subjected to air-suspension laser heating, and white pieces are ceramic pieces cut before the black titanium dioxide is subjected to laser heating; the part which is not completely melted after laser irradiation is in an intermediate state, and the part which is irradiated by the laser is cooled to become black, and the part which is not irradiated by the laser is still white; the black pellets on the right side are black titanium dioxide formed by cooling after being completely melted by laser irradiation;
FIG. 1 (b) shows the black titanium dioxide spheres prepared in example 1, in which it can be seen that the black titanium dioxide is in the form of spherical lumps formed by cooling after the black titanium dioxide is completely melted by laser irradiation;
FIG. 2 is a comparison of white titanium dioxide raw powder, which is white powder and is still black after milling black titanium dioxide blocks prepared without a container, with the powder of example 1 in which black titanium dioxide balls were milled through a 200 mesh screen;
FIG. 3 is an X-ray diffraction pattern of the black titanium dioxide powder prepared in example 1 and the original white titanium dioxide, from which it can be seen that the raw material powder contains a small amount of anatase, and the black titanium dioxide after the container-free treatment is entirely changed into rutile phase;
FIG. 4 is a graph showing the ultraviolet-visible-near infrared diffuse reflection spectra of the black titanium dioxide powder and the white titanium dioxide raw powder prepared in example 1, and FIG. 5 is a graph showing the black titanium dioxide powder and the white titanium dioxide raw powder (TiO powder) prepared in example 12) The forbidden band width spectrogram. As can be seen from fig. 4, the absorption of the black titanium dioxide in the visible and near-infrared regions is significantly enhanced, and as can be seen from fig. 5, the forbidden band width of the black titanium dioxide is reduced (to 2.61 ev);
FIG. 6 is an X-ray photoelectron spectrum of Ti element of black titanium dioxide prepared in example 1, and it can be seen that Ti is present3+Appearance of ion (457.9eV, Peak 2), content 21.5%;
FIG. 7 is an X-ray photoelectron spectrum of the O element of the black titanium dioxide produced in example 1, and it can be seen that 531.31ev is a peak of oxygen vacancy (peak 1), 529.94ev is a peak of Ti-O bond (peak 2), 529.56ev is a peak of surface adsorption of oxygen (peak 3), and it can be said that a large amount of vacancies are present, the content being 26.95%;
FIG. 8 shows black titanium dioxide powder (B-TiO) prepared in example 12) With white titanium dioxide raw material powder (TiO)2) The temperature change graph after 808nm laser irradiation shows that the black titanium dioxide powder prepared in the example 1 has the photothermal effect, and the temperature can be raised to more than 100 ℃ within 1min and the maximum temperature can be raised to 128 ℃ by 808nm laser irradiation; and white titanium dioxide raw powder (TiO)2) The temperature change was only 2.5 ℃, indicating that the photothermal effect of black titanium dioxide was significant.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (8)
1. A black titanium dioxide block, characterized in that, the black titanium dioxide block contains Ti3+In the titanium element, Ti3+The content is more than or equal to 1 percent, and the black titanium dioxide block contains oxygen vacancies with the content more than or equal to 1 percent; the black titanium dioxide block is a black titanium dioxide ball with the diameter of 2-4 mm; the forbidden band width of the black titanium dioxide block is 2.61 eV;
the method for preparing the black titanium dioxide block comprises the following steps:
(1) white TiO is mixed2The raw material is pressed into tablets and calcined, the white TiO2The raw material is crystalline phase titanium dioxide, and the calcined titanium dioxide isThe burning temperature is 1100-1300 ℃, and the time is 2-8 hours;
(2) cutting the calcined sample into 25-125 mg small pieces, placing the small pieces in an air suspension furnace, introducing oxygen or air to enable the small pieces to be suspended, turning on laser and increasing power to heat the sample to a molten state, and then rapidly cooling the sample to obtain the black titanium dioxide block; the power of the laser is 70-90W, and the heating time is 100-120 seconds; the temperature of the laser heated melt is higher than that of TiO2Melting point; the speed of the rapid cooling is more than or equal to 200 ℃/second.
2. The black titanium dioxide block according to claim 1, wherein Ti is among the titanium elements3+The content is 20-30%.
3. The black titanium dioxide block according to claim 1, wherein the black titanium dioxide block contains oxygen vacancies in an amount of 20 to 30%.
4. The black titanium dioxide block according to claim 1, wherein the compression molding is dry compression molding, the pressure of the dry compression molding is 2 to 5MPa, and the pressure holding time is 1 to 2 minutes.
5. The black titanium dioxide block according to claim 1, wherein the pressure of oxygen or air introduced into the gas suspension furnace is 0.2 to 1.5 MPa.
6. The black titanium dioxide bulk according to claim 1, wherein the laser has a wavelength of 800 to 1100 nm.
7. The black titanium dioxide block according to claim 1, wherein the rapid cooling rate is 200 to 500 ℃/sec.
8. The black titanium dioxide block according to claim 7, wherein the rapid cooling rate is 300 to 500 ℃/sec.
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| CN111847503B (en) * | 2020-06-10 | 2023-02-10 | 宁夏中科欧德科技有限公司 | Preparation method of black titanium dioxide |
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| CN115159567A (en) * | 2022-08-16 | 2022-10-11 | 济南大学 | Defect-induced heteroatom-doped titanium dioxide electrode material and preparation method thereof |
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| CN104817107A (en) * | 2015-03-31 | 2015-08-05 | 吉林大学 | Method for preparing black titanium dioxide B phase and anatase phase nanoparticles |
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