CN114477278A - Method for preparing black titanium oxide nanosheets by using simple ball milling technology - Google Patents
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 160
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000002135 nanosheet Substances 0.000 title claims abstract description 55
- 238000000498 ball milling Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000005516 engineering process Methods 0.000 title claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000007547 defect Effects 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- -1 oxygen ion Chemical class 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000713 high-energy ball milling Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
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- 239000012153 distilled water Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
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- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 12
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 230000001699 photocatalysis Effects 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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Abstract
The invention provides a method for preparing black titanium oxide nanosheets by using a simple ball milling technology, which sequentially comprises the steps of preparing a fluorine-containing titanium oxide precursor solution, preparing flaky titanium oxide powder by using a hydrothermal method, obtaining high-defect black titanium oxide nanosheets by using the ball milling technology and the like. The crystal structure of the titanium oxide prepared by the invention is rutile phase. The prepared black titanium oxide nano sheet has higher light energy utilization rate in a visible light region and an ultraviolet light region, the sheet structure provides a high specific surface, and the exposed high-activity surface is beneficial to improving the photoelectric activity of titanium oxide and is expected to expand the application efficiency of the titanium oxide photoelectric semiconductor.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a method for preparing black titanium oxide nanosheets by using a simple ball milling technology.
Background
The photoelectric property is one of the unique properties of the nano semiconductor, and has wide application prospect in the fields of photocatalysis, photovoltaics, photoelectric protection and the like. Currently, wide bandgap n-type semiconductors such as titanium oxide, zinc oxide, cadmium sulfide, molybdenum sulfide, and the like are widely studied. Among them, titanium dioxide is highly valued by researchers because of its low production cost, non-toxicity, no photo-corrosion after illumination, good chemical stability and high activity. However, the forbidden band width of titanium dioxide is 3.2eV, and only the ultraviolet light part in a natural light source can be absorbed. On the other hand, the titanium oxide photogenerated electron hole recombination leads to low quantum yield and slow reaction rate, and limits the application and development of the titanium oxide photogenerated electron hole recombination.
A great deal of laboratory researches have been carried out to move the energy level of a semiconductor, enable the light excitation position to approach the surface, reduce the charge separation space, increase the surface area and the like by means of doping, structure regulation and the like so as to improve the quantum yield and the photoelectrochemical property of the titanium dioxide.
Experiments and theories jointly show that the {001} crystal face in the titanium oxide has higher photoelectrochemical activity than the {101} crystal face. The {001} crystal plane has a more efficient dissociative adsorption of reactant molecules than the thermodynamically stable {101} plane, mainly due to the lower number of atoms coordinated thereto among the atoms to which the {001} plane is exposed, the presence of 5-coordinated Ti atoms and unsaturated coordinated O atoms, and the larger bond angle between Ti-O-Ti, resulting in more reactive sites on the {001} crystal plane. The average surface energies of the 001, 100 and 101 crystal planes for the most widely used anatase titanium oxide are 0.90J/m, respectively2、0.53J/m2And 0.44J/m2。
The titanium oxide single crystal is mainly composed of a {101} plane which is a high thermodynamic stability plane, and a {001} plane and a {100} plane which have higher surface energies have a very small crystal face ratio as the titanium oxide crystal grows. Therefore, the preparation of high purity, exposed flake anatase phase titanium oxide having a large number of high active planes {001} or {100} planes by means of a fluoride ion additive method has been widely studied in terms of the synthesis preparation of titanium oxide, which has also been subjected to many theoretical supports and experimental verifications in terms of the improvement of photoelectric efficiency.
The narrow band gap black titanium oxide nanomaterials exhibit good photoelectric activity due to their broad spectral absorption range. At present, a great deal of research is carried out on the synthesis of black titanium oxide, trivalent titanium or oxygen ion vacancies are formed in a titanium oxide crystal lattice, disordered crystal and amorphous layer structures are formed, and the color of the titanium oxide is changed correspondingly.
Chinese patent CN2018111821255 discloses a preparation method of black nano titanium oxide with a high distortion structure, which adopts titanium oxide powder as a raw material, utilizes a rotary ball milling high-pressure tube furnace, and utilizes inert gas to heat titanium oxide while carrying out high-speed ball milling to obtain the black nano titanium oxide with the high distortion structure.
Chinese patent CN2013101536488 discloses a method for preparing black titanium oxide by using a dual-temperature-zone reduction method, in which titanium oxide powder and high-activity metal are respectively placed in a negative-pressure closed system of a dual-temperature zone for heat treatment to obtain black titanium oxide powder.
Chinese patent CN202110271040X discloses a preparation method of a black titanium dioxide B nanosheet with high oxygen vacancy defect, which utilizes a hydrothermal technology to obtain a white titanium dioxide B nanosheet, and then obtains the high oxygen vacancy defect through thermal decomposition of ethylene glycol molecules adsorbed on the surface.
Chinese patent CN2020103016986 discloses a method for obtaining black titanium dioxide by oxidizing and drying titanium hydride raw material powder and calcining at high temperature in argon atmosphere.
The above-mentioned technology adopts reducing substance or inert atmosphere to heat titanium oxide, and in the course of heat treatment the reduction of titanium oxide can be implemented so as to obtain the black titanium oxide nano particles with oxygen vacancy defect.
Chinese patent CN2020104836836 discloses a preparation method of black titanium dioxide, which prepares black titanium oxide powder by mixing titanium alkoxide with titanium powder and performing hydrothermal treatment. The technology reduces titanium dioxide by titanium powder, but the oxidation degree of the titanium powder in the hydrothermal process limits the purity of the product.
Chinese patent CN2020100834225 discloses a preparation method of porous titanium dioxide nanosheets, and the technology utilizes a mixture of hexafluorotitanic acid and titanium alkoxide as a titanium source to prepare the porous titanium dioxide nanosheets with exposed {001} crystal faces by utilizing solvothermal reaction.
Chinese patent CN2020107485954 discloses a bicrystal phase titanium oxide nanosheet obtained by using tetrabutyl titanate as a titanium source and adopting crystal potassium hydroxide hydrothermal and hydrofluoric acid secondary hydrothermal technologies.
The Chinese patent CN202011582448.0 utilizes sol-gel-hydrothermal preparation and secondary roasting of pore-forming agent to obtain two-dimensional porous titanium oxide nano-sheet.
In fact, titanium oxide nanoplates, due to their high active surface exposure and high specific surface area, are more susceptible to achieving high defect rates by reduction or other techniques when preparing black titanium oxide. However, the prior art is rarely concerned with titanium oxide products having the advantages of both high defect and high activity applications.
The method for preparing the black titanium oxide nanosheets with high defects and high activity by using the high-activity nanosheets obtained by the hydrothermal technology and the simple ball milling technology is not involved in the prior art.
Disclosure of Invention
The invention aims to provide a method for preparing a black titanium oxide nanosheet by using a simple ball milling technology, so as to obtain a titanium oxide nanosheet structure with an exposed high-activity surface and a black titanium oxide nano aggregate with high defects, thereby improving the photoelectric efficiency of a titanium oxide semiconductor.
The technical scheme adopted by the invention is as follows:
a method for preparing black titanium oxide nanosheets by using a simple ball milling technology is characterized by comprising the following steps:
preparing a fluorine-containing titanium oxide precursor solution;
respectively measuring 20-30 parts of analytically pure butyl titanate and 5-10 parts of hydrofluoric acid solution with the concentration of 40% according to the volume parts, mixing, and placing in an ultrasonic cleaner for ultrasonic dispersion to obtain a fluorine-containing titanium oxide precursor solution;
step two, preparing the flaky titanium oxide nano powder by a hydrothermal method:
transferring the fluorine-containing titanium oxide precursor solution obtained in the step one to a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, reacting for 20-30 hours, taking out, and naturally cooling;
after the reaction kettle is completely cooled, opening the reaction kettle, removing supernatant liquor, and performing centrifugal separation on the lower layer sol by using absolute ethyl alcohol and deionized water respectively;
washing with sodium hydroxide solution of 0.1mol/L concentration to eliminate fluoric ion on the surface of the powder while washing with distilled water to obtain neutral centrifugally deposited matter;
finally, placing the centrifuged precipitate in an oven for drying to prepare flaky titanium oxide nano powder, namely the flaky anatase phase nano titanium oxide with high exposed surface;
step three, obtaining black titanium oxide nanosheets by using a ball milling technology:
and (3) placing the flaky titanium oxide nano powder obtained in the step two into a ball milling tank, and carrying out ball milling for 2-12 hours under the condition of high-energy ball milling to obtain black titanium oxide nano sheets.
Further, in the ball milling process, the reaction equation is as follows:
wherein, the mouth is oxygen ion vacancy, x is defect proportion, (g) represents oxygen, because of oxygen ion vacancy, sigma represents oxygen ion vacancy number, and the molecular formula expression is TiO2-σ；
The equilibrium of the defects of the above reaction is:
in the formula
Represents an oxygen atom at an oxygen position in the crystal lattice; vORepresents an oxygen ion vacancy; · denotes carrying two positive charges; e' represents an electron, O2(g) Representing oxygen molecules.
In a further preferable embodiment, the hydrothermal reaction is carried out for 24 hours and the high-energy ball milling time is 12 hours, wherein the butyl titanate is 25 parts, and the hydrofluoric acid solution is 6 parts.
Further, black titanium oxide nanosheets, Ti, obtained by ball milling3+And Ti4+The content ratio is 0.45, and the forbidden band width is 2.25 eV. The black titanium oxide nanosheet has high oxygen defect content, and a titanium oxide sample obtained by ball milling has fine granularity and strong surface adsorption capacity. High energyThe ball milling time is prolonged, the defect concentration of the titanium oxide nano-sheet is increased, the color is gradually deepened from gray to black, and Ti is obtained after ball milling3+Defect, Ti3+The existence of the titanium dioxide enables the forbidden bandwidth of the titanium dioxide to be reduced, and the titanium dioxide can better absorb visible light, so that the titanium dioxide is changed into gray or black from white, is an aggregate of titanium dioxide nanosheets, and the crystal structure is changed into a rutile crystal form.
Further, in the second step, the fluorine-containing titanium oxide precursor solution is transferred to a hydrothermal reaction kettle, and the hydrothermal reaction kettle is placed in a 190 ℃ oven for hydrothermal reaction.
Further, in the second step, the number of times of centrifugal separation using absolute ethanol and deionized water is three.
Further, in the second step, the centrifuged precipitate is placed in an oven at 60 ℃ for drying, and the flaky titanium oxide nano powder is prepared.
Further, in the third step, the titanium oxide nano powder is put into a ball milling tank for high-energy ball milling, the ball-material ratio is 32:3, and the rotating speed is 1080 r/min.
Compared with the prior art, the invention has the following beneficial effects:
the invention obtains the flaky anatase phase nano titanium oxide with high exposed surface by the hydrothermal technology, and introduces a large amount of oxygen vacancies and Ti by the ball milling technology3+Defect due to Ti3+The existence of the titanium oxide enables the forbidden bandwidth of the titanium oxide to be reduced, so that the visible light can be better absorbed, the titanium oxide is changed from white to black, the ball-milled powder is an aggregate of titanium oxide nano-sheets, and the crystal structure is changed into a rutile crystal form, so that the black titanium oxide nano-sheets prepared by the technical scheme have high surface activity and wide light absorption range, and are expected to have higher photoelectric application efficiency;
the method provided by the invention has the advantages of simple process, low manufacturing cost and strong practicability.
Drawings
In FIG. 1, a is an X-ray diffraction pattern (XRD) of hydrothermal anatase phase titanium oxide nanosheets, and b is an X-ray diffraction pattern (XRD) of high-energy ball-milled black titanium oxide nanosheets;
in fig. 2, a and b are Scanning Electron Microscope (SEM) photographs of the hydrothermal anatase-phase titanium oxide nanosheets and the high-energy ball-milled black titanium oxide nanosheets, respectively.
Detailed Description
The drawings are for illustration only; for a better understanding of the present embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; some well-known structures in the drawings and descriptions thereof may be omitted for those skilled in the art.
The technical solutions in the embodiments of the present disclosure will be clearly and completely described below with reference to the drawings in the embodiments of the present disclosure. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present specification without any creative effort shall fall within the protection scope of the present specification.
Example 1
A preparation method of a black titanium oxide nanosheet with high activity and high defect comprises the following steps:
step one, preparing a fluorine-containing titanium oxide precursor solution:
respectively measuring 25 parts of analytically pure butyl titanate and 6 parts of hydrofluoric acid solution with the concentration of 40% according to the volume parts, mixing, and placing in an ultrasonic cleaner for ultrasonic dispersion to obtain a fluorine-containing titanium oxide precursor solution;
step two, preparing the flaky titanium oxide nano powder by a hydrothermal method:
transferring the fluorine-containing titanium oxide precursor solution obtained in the step one to a hydrothermal reaction kettle, reacting for 24 hours, taking out, and naturally cooling; wherein, the hydrothermal reaction kettle is arranged in an oven at 190 ℃;
after the reaction kettle is completely cooled, opening the reaction kettle, removing supernatant liquor, and performing centrifugal separation on the lower layer sol by using absolute ethyl alcohol and deionized water for three times respectively; washing with sodium hydroxide solution of 0.1mol/L concentration to eliminate fluoric ion on the surface of the powder while washing with distilled water to obtain neutral centrifugally deposited matter;
finally, placing the centrifuged precipitate in a drying oven at 60 ℃ for drying to prepare flaky titanium oxide nano powder;
step three, obtaining black titanium oxide nanosheets by using a ball milling technology:
placing the flaky titanium oxide nano powder obtained in the step two into a ball milling tank, setting the ball-to-material ratio to be 32:3, setting the rotating speed to be 1080r/min, and setting the high-energy ball milling time to be 12h to obtain black titanium oxide nano sheets;
example 2
Step one, in the step of preparing a fluorine-containing titanium oxide precursor solution, 25 parts of butyl titanate and 6 parts of a hydrofluoric acid solution with the concentration of 40% are measured;
step two, in the step of preparing the flaky titanium oxide nano powder by a hydrothermal method, the hydrothermal reaction time is 24 hours;
step three, in the step of obtaining the black titanium oxide nanosheets by utilizing the ball milling technology, the ball milling time is 10 hours;
the rest is the same as in example 1.
Example 3
Step one, in the step of preparing a fluorine-containing titanium oxide precursor solution, 25 parts of butyl titanate and 6 parts of a hydrofluoric acid solution with the concentration of 40% are measured;
step two, in the step of preparing the flaky titanium oxide nano powder by a hydrothermal method, the hydrothermal reaction time is 24 hours;
step three, in the step of obtaining the black titanium oxide nanosheets by utilizing the ball milling technology, the ball milling time is 8 hours;
the rest of the process was the same as in example 1.
Example 4
Step one, in the step of preparing a fluorine-containing titanium oxide precursor solution, 25 parts of butyl titanate and 6 parts of a hydrofluoric acid solution with the concentration of 40% are measured;
step two, in the step of preparing the flaky titanium oxide nano powder by a hydrothermal method, the hydrothermal reaction time is 24 hours;
step three, in the step of obtaining the black titanium oxide nanosheets by utilizing the ball milling technology, the ball milling time is 6 hours;
the rest is the same as in example 1.
Example 5
Step one, in the step of preparing a fluorine-containing titanium oxide precursor solution, 25 parts of butyl titanate and 6 parts of a hydrofluoric acid solution with the concentration of 40% are measured;
step two, in the step of preparing the flaky titanium oxide nano powder by a hydrothermal method, the hydrothermal reaction time is 24 hours;
step three, in the step of obtaining the black titanium oxide nanosheets by utilizing the ball milling technology, the ball milling time is 4 hours;
the rest is the same as in example 1.
Example 6
Step one, in the step of preparing a fluorine-containing titanium oxide precursor solution, measuring 25 parts of butyl titanate and 6 parts of a 40% hydrofluoric acid solution;
step two, in the step of preparing the flaky titanium oxide nano powder by a hydrothermal method, the hydrothermal reaction time is 24 hours;
step three, in the step of obtaining the black titanium oxide nanosheets by utilizing the ball milling technology, the ball milling time is 2 hours;
the rest is the same as in example 1.
The hydrothermal anatase phase titanium oxide nanosheets and the high-energy ball-milled black titanium oxide nanosheets prepared in example 1 were selected for X-ray diffraction (XRD) analysis, and the results are shown in fig. 1:
it can be seen that: the hydrothermal anatase phase titanium oxide nanosheets are anatase phases, and black titanium oxide nanosheets corresponding to a rutile structure are obtained after the anatase phases are crushed and reconstructed by high-energy ball milling.
Scanning Electron Microscope (SEM) observation was performed on the hydrothermal anatase phase titanium oxide nanosheets and the high-energy ball-milled black titanium oxide nanosheets prepared in example 1, and the results are shown in fig. 2:
it can be seen that the hydrothermal anatase phase titanium oxide is of a sheet structure and relatively uniform in size, and black titanium oxide nanosheets obtained by high-energy ball milling tend to form aggregates due to the existence of a large number of surface defects. But the particle size remains on a smaller scale. The nano particles can be dispersed by means of surface modification and the like subsequently, and the performance of the photoelectric device is improved when the photoelectric performance is applied by means of loading, adding and the like.
Table one: influence of different ball milling time on content of trivalent titanium and photoelectric property of titanium oxide in sample
The above table shows that an increase in the content of trivalent titanium causes an increase in the ultraviolet-visible light absorption wavelength of titanium oxide, an increase in the wavelength indicates an increase in the range of light absorption of titanium oxide, and the absorbance refers to the ability of titanium oxide to absorb light, and thus it was found that an increase in trivalent titanium increases the light absorption range and light absorption ability of titanium oxide and can greatly improve the photoelectric properties of titanium oxide. The black titanium oxide is used as a modified oxide semiconductor material, and has narrower energy level gap and higher conductivity. In general, a large number of intermediate band gaps exist in the black titanium oxide, and the conductivity of the black titanium oxide can be further enhanced due to the similar impurity levels.
The embodiments are described in a progressive manner with reference to the same and similar parts among the embodiments, and each embodiment is described with emphasis on differences from the other embodiments. In particular, for the system embodiment, since it is substantially similar to the method embodiment, the description is simple, and for the relevant points, reference may be made to the partial description of the method embodiment.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.
Claims (8)
1. A method for preparing black titanium oxide nanosheets by using a simple ball milling technology is characterized by comprising the following steps:
preparing a fluorine-containing titanium oxide precursor solution;
respectively measuring 20-30 parts of analytically pure butyl titanate and 5-10 parts of hydrofluoric acid solution with the concentration of 40% according to the volume parts, mixing, and placing in an ultrasonic cleaner for ultrasonic dispersion to obtain a fluorine-containing titanium oxide precursor solution;
step two, preparing the flaky titanium oxide nano powder by a hydrothermal method:
transferring the fluorine-containing titanium oxide precursor solution obtained in the first step into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oven, reacting for 20-30 hours, taking out, and naturally cooling;
after the reaction kettle is completely cooled, opening the reaction kettle, removing supernatant liquor, and performing centrifugal separation on the lower layer sol by using absolute ethyl alcohol and deionized water respectively;
washing with sodium hydroxide solution of 0.1mol/L concentration to eliminate fluoric ion on the surface of the powder while washing with distilled water to obtain neutral centrifugally deposited matter;
finally, placing the centrifuged precipitate in an oven for drying to prepare flaky titanium oxide nano powder;
step three, obtaining black titanium oxide nano sheets by using a ball milling technology:
and (3) placing the flaky titanium oxide nano powder obtained in the step two into a ball milling tank, and carrying out ball milling for 2-12 hours under the condition of high-energy ball milling to obtain black titanium oxide nano sheets.
2. The method for preparing black titanium oxide nanosheets by simple ball milling as claimed in claim 1, wherein during the ball milling process, the equation of the reaction is:
wherein □ is oxygen ion vacancy, x is defect ratio, (g) represents oxygen, and σ represents oxygen ion vacancy amount, and formula expression is TiO2-σ；
The equilibrium of the defects of the above reaction is:
in the formula
Represents an oxygen atom at an oxygen position in the crystal lattice; voRepresents an oxygen ion vacancy; denotes a charge with two positive charges; e' represents an electron, O2(g) Representing oxygen molecules.
3. The method for preparing black titanium oxide nanosheets by simple ball milling technology as claimed in claim 2, wherein 25 parts of butyl titanate and 6 parts of hydrofluoric acid solution are subjected to hydrothermal reaction for 24 hours, and the high-energy ball milling time is 12 hours.
4. The method for preparing black titanium oxide nanosheets by simple ball milling technique according to claim 3, wherein the black titanium oxide nanosheets, Ti, obtained by ball milling3+And Ti4+The content ratio is 0.45, and the forbidden band width is 2.25 eV.
5. The method for preparing black titanium oxide nanosheets by using the simple ball milling technique as recited in claim 1, wherein in the second step, the fluorine-containing titanium oxide precursor solution is transferred to a hydrothermal reaction kettle, and the hydrothermal reaction kettle is placed in an oven at 190 ℃ for hydrothermal reaction.
6. The method for preparing black titanium oxide nanosheets by simple ball milling technology as recited in claim 1, wherein in step two, the number of times of centrifugal separation using absolute ethanol and deionized water is three.
7. The method for preparing black titanium oxide nanosheets by using the simple ball milling technique according to claim 1, wherein in the second step, the centrifuged precipitate is placed in an oven at 60 ℃ for drying, and thus the flaky titanium oxide nanopowder is prepared.
8. The method for preparing black titanium oxide nano-sheets by using the simple ball milling technology as claimed in claim 1, wherein in the third step, the titanium oxide nano-powder is put into a ball milling tank for high energy ball milling, the ball-to-material ratio is 32:3, and the rotation speed is 1080 r/min.
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| CN112007627A (en) * | 2020-08-19 | 2020-12-01 | 西安近代化学研究所 | TiO 22Nanosheet, preparation method and application thereof |
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| CN102306550A (en) * | 2011-06-03 | 2012-01-04 | 厦门大学 | Method for preparing nano-branched titanium dioxide photoanode of dye sensitized solar cell |
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| CN116386928A (en) * | 2023-06-02 | 2023-07-04 | 山东科技大学 | Sodium alginate/titanium dioxide composite porous electrode material and preparation method thereof |
| CN116386928B (en) * | 2023-06-02 | 2023-08-04 | 山东科技大学 | Sodium alginate/titanium dioxide composite porous electrode material and preparation method thereof |
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