CN113816417A - Black gallium oxide nano-particles and preparation method thereof - Google Patents
Black gallium oxide nano-particles and preparation method thereof Download PDFInfo
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 106
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000000137 annealing Methods 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 230000031700 light absorption Effects 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The invention discloses black gallium oxide nano particles and a preparation method thereof, white Ga is mixed2O3Mixing and grinding the nano particles and magnesium powder, and carrying out heat preservation reaction at 500-600 ℃ under a vacuum condition to obtain a third precursor; immersing the third precursor into water for ultrasonic dispersion, adding excessive dilute hydrochloric acid, stirring for 5-6h, washing the precipitate, and drying to obtain black gallium oxide nanoparticles; the invention is prepared by mixing white Ga2O3The nano particles and magnesium powder are subjected to vacuum annealing, oxygen vacancies are formed in white gallium oxide, so that the electronic property in a gallium oxide conduction band is changed, the gallium oxide material can absorb light in visible and near infrared regions, and further presents black, black gallium oxide nano particles which absorb visible light and near infrared light and have strong redox capability are obtained, the problem of narrow light absorption range of gallium oxide is solved, and effective support is provided for expanding the application of gallium oxide in photocatalysis and photoelectric devices.
Description
Technical Field
The invention belongs to the technical field of semiconductor preparation, and particularly belongs to black gallium oxide nanoparticles with high optical absorption, high carrier separation and strong redox and a preparation method thereof.
Background
Gallium oxide (Ga)2O3) As a third generation ultra-wide band gap semiconductor with the band gap of about 4.4eV-4.9eV, the third generation ultra-wide band gap semiconductor has been widely researched as a photoelectric device, a photocatalyst and a display in recent years due to the advantages of large band gap, high breakdown field strength, radiation damage resistance, low growth cost and the like. Compared with semiconductors such as SiC and GaN, the gallium oxide has better performance: higher withstand voltage, larger current and lower power consumption. The characteristics of gallium oxide make it have wide application prospect in many fields.
Gallium oxide has five isomers, and the most stable crystalline phase is monoclinic beta-phase gallium oxide. The wide band gap of gallium oxide gives it extremely high redox ability, however, gallium oxide works only in the deep ultraviolet region. It is well known that ultraviolet light accounts for only about 5% of the total solar energy, and gallium oxide has a limited ability to capture light, which is disadvantageous for photocatalytic reactions to utilize solar energy. Meanwhile, like most semiconductors, the photogenerated electrons and holes in gallium oxide can be rapidly recombined, which is not favorable for the photocatalytic reaction. In order to solve the two problems related to gallium oxide, the related scholars improve the photoresponse ability of gallium oxide and reduce the recombination efficiency of carriers by constructing a semiconductor heterojunction structure, which is a feasible method, but reduces the redox ability of gallium oxide while improving the light absorption ability and reducing the recombination of carriers. Therefore, it is an urgent challenge to find a new preparation method while maintaining the excellent redox ability of gallium oxide, improving the light absorption ability of gallium oxide and accelerating the carrier separation.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a black gallium oxide nanoparticle with high optical absorption, high carrier separation and strong oxidation reduction and a preparation method thereof, so as to solve the problems of narrow light absorption range, low carrier separation efficiency and the like of a gallium oxide material at present.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of black gallium oxide nano-particles comprises the following specific steps:
s1 extracting white Ga2O3Mixing and grinding the nano particles and magnesium powder, and carrying out heat preservation reaction at 500-600 ℃ under a vacuum condition to obtain a third precursor;
s2, immersing the third precursor into water for ultrasonic dispersion, adding excessive dilute hydrochloric acid, stirring for 5-6h, washing the precipitate, and drying to obtain black gallium oxide nanoparticles.
Further, in step S1, the magnesium powder is mixed with white Ga2O3The mole ratio of the nano-particles is 1.3-1.7.
Further, in step S1, the white Ga is mixed by grinding2O3The nano particles and the magnesium powder are put into a quartz tube, and the quartz tube is sealed in vacuum through oxyhydrogen flame.
Further, in step S1, the heat preservation time is 10h-11h, and the temperature rise rate is 1 ℃/min.
Further, in step S2, the third precursor is immersed in deionized water for ultrasonic dispersion for 30 ± 5 min.
Further, in step S2, the concentration of the dilute hydrochloric acid solution is 1mol L-1。
Further, in step S2, the stirring speed is 700r/min-900 r/min.
Further, in step S2, deionized water is used for the washing, and the washing is performed until the supernatant is neutral.
Further, in step S2, the drying is performed at 60 + -5 deg.C for 12 + -1 h.
The invention also provides black gallium oxide nanoparticles prepared by the preparation method.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides black gallium oxide nanoparticles and a preparation method thereof, white gallium oxide is annealed in a vacuum reduction environment in which magnesium exists, oxygen ions of gallium oxide crystal lattices are separated, so that oxygen vacancies are formed, the periodicity of the crystal lattices is changed by the existence of the oxygen vacancies, and the electronic properties in a gallium oxide conduction band are changed, including band gap narrowing and band tail state forming, so that a gallium oxide material can absorb light in visible and near infrared regions, and further presents black, the black gallium oxide nanoparticles which can absorb visible light and near infrared light and have strong redox capability are obtained, the problem of narrow light absorption range of gallium oxide is solved, and effective support is provided for expanding the application of gallium oxide in photocatalysis and photoelectric devices.
The invention solves the problem of low carrier separation efficiency of the traditional semiconductor material, obtains the black gallium oxide material with high carrier separation, and provides a new thought and method for the follow-up research of the semiconductor material.
Drawings
FIG. 1: scanning Electron Microscope (SEM) images of high optical absorption, high carrier separation, strong redox black gallium oxide nanoparticles (fig. 1b) and white gallium oxide (fig. 1a) prepared by the present invention.
FIG. 2: the X-ray diffraction (XRD) spectrums of the black gallium oxide and the white gallium oxide which are high in optical absorption, high in carrier separation and strong in oxidation reduction capability are prepared.
FIG. 3: the ultraviolet-visible diffuse reflection spectrum (UV-vis DRS) images of the black gallium oxide and the white gallium oxide with high optical absorption, high carrier separation and strong redox capability prepared by the invention are shown, wherein the insets are real contrast images of the black gallium oxide and the white gallium oxide.
FIG. 4: the fluorescence spectrum (PL) diagram of the black gallium oxide and the white gallium oxide with high optical absorption, high carrier separation and strong oxidation reduction capability prepared by the invention has the excitation wavelength of 265 nm.
FIG. 5: the Electron Paramagnetic Resonance (EPR) diagram of the black gallium oxide and the white gallium oxide with high optical absorption, high carrier separation and strong redox capability prepared by the invention.
FIG. 6: the degradation curve graph of the black gallium oxide and white gallium oxide photocatalytic degradation rhodamine b with high optical absorption, high carrier separation and strong redox ability is prepared by the invention.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
The invention relates to a preparation method of black gallium oxide nano-particles with high optical absorption, high carrier separation and strong oxidation reduction, which comprises the following steps:
A. preparation of white gallium oxide: 0.526. + -. 0.0005g of gallium nitrate hydrate (Ga (NO)3)3·xH2O) is dissolved in 30 plus or minus 0.5ml of deionized water, and the mixture is placed on a magnetic stirrer to be stirred uniformly, and the stirring speed is controlled at 850 r/min. Several drops of ethylenediamine (NH) were added2CH2CH2NH2) Until the pH value of the solution is about 8. Transferring the mixed solution into a high-pressure kettle with polytetrafluoroethylene as a lining, placing the high-pressure kettle in an oven at the temperature of 120 +/-1 ℃ for 12 +/-0.1 h to complete a hydrothermal reaction, pouring out supernatant after the reaction is completed and the reaction kettle is naturally cooled, repeatedly washing the precipitate with deionized water and ethanol until the pH value of the supernatant is neutral, placing the precipitate in the oven and drying the precipitate at the temperature of 60 +/-5 ℃ for 12 +/-1 h to obtain a first precursor. Grinding the first precursor by using an agate mortar until particles with uniform granularity can be seen by naked eyes, putting the first precursor into an annealing furnace for heat treatment, annealing at 700 ℃ for 2h at the heating rate of 2 ℃/min to obtain white beta-phase Ga2O3And (3) nanoparticles.
B. Preparing black gallium oxide: in a glove box, magnesium powder with the molar ratio of 1.3-1.7 and the white beta-phase Ga prepared in the step A are mixed2O3Grinding and uniformly mixing the nano particles in an agate mortar to obtain a second precursor; the second precursor was charged into a quartz tube, and vacuum-sealed by means of an oxyhydrogen flame. And placing the sealed quartz tube in an annealing furnace, carrying out heat preservation reaction at 500-600 ℃ for 10-11h at the heating rate of 1 ℃/min to obtain a third precursor. After natural cooling, the third precursor is immersed into deionized water for ultrasonic separationDispersing for 30 + -5 min, and adding 1mol L of the mixture-1Dilute hydrochloric acid solution and stir for 5-6h, and the stirring speed is controlled at 700-900 r/min. Washing with deionized water for several times, and drying in a 60 + -5 deg.C oven for 12 + -1 h to obtain black gallium oxide;
white gallium oxide is annealed in a reducing environment in the presence of magnesium, resulting in the dissociation of oxygen ions from the gallium oxide lattice, thereby forming oxygen vacancies. The periodicity of the crystal lattice is changed by the existence of the oxygen vacancy, so that the electronic properties in the conduction band of the gallium oxide are changed, including band gap narrowing and band tail state forming, and the gallium oxide material can absorb light in visible and near infrared regions to further show black.
In the step B:
(1) for safety reasons, the milling and mixing of magnesium powder and gallium oxide must be carried out in a glove box filled with argon and milled uniformly to ensure sufficient contact between the magnesium powder and the gallium oxide.
(2) Magnesium powder was chosen because of its metal reactivity which meets the requirements of the experiment and its relative safety.
(3) In order to completely reduce white gallium oxide to black gallium oxide, an excess of magnesium powder is required.
(4) The oxyhydrogen flame is selected for vacuum sealing in order to ensure that the reaction environment is nearly free of oxygen.
(5) The annealing treatment in the annealing furnace is a necessary condition for generating oxygen vacancies.
(6) The product was ultrasonically dispersed in deionized water to remove salts that may be present while precipitating unreacted magnesium powder.
(7) The excessive dilute hydrochloric acid can not only remove magnesium powder and magnesium oxide, but also can not react with black gallium oxide.
Example 1:
A. preparation of white gallium oxide: 0.526g of gallium nitrate hydrate (Ga (NO)3)3·xH2O) is dissolved in 30ml of deionized water and is placed on a magnetic stirrer to be stirred uniformly, and the stirring speed is controlled at 850 r/min. Several drops of ethylenediamine (NH) were added2CH2CH2NH2) Until the pH of the solution is about 8. Transferring the mixed solution into polytetrafluoroethyleneThe hydrothermal reaction was completed in a lined autoclave and placed in an oven at 120 ℃ for 12 hours. And after the reaction is finished and the reaction kettle is naturally cooled, pouring out supernatant liquid, repeatedly washing the precipitate with deionized water and ethanol, and drying the precipitate in an oven at 60 ℃ for 12 hours to obtain a first precursor. Grinding the first precursor by using an agate mortar until particles with uniform granularity can be seen by naked eyes, putting the first precursor into an annealing furnace for heat treatment, annealing at 700 ℃ for 2h at the heating rate of 2 ℃/min to obtain white beta-phase Ga2O3And (3) nanoparticles. Hydrothermal method and white Ga obtained by post-annealing2O3An irregular nanoparticle structure with pores is shown (as shown in FIG. 1a), and the diameter of the nanoparticle is about 550-620 nm.
B. Preparing black gallium oxide: in a glove box, 0.0385g of magnesium powder and 0.2g of white beta-phase Ga obtained in step A were mixed2O3Grinding and uniformly mixing the nano particles in an agate mortar to obtain a second precursor; the second precursor was charged into a quartz tube and vacuum-sealed by means of an oxyhydrogen flame. And (3) placing the sealed quartz tube in an annealing furnace, and carrying out heat preservation reaction for 10h at 500 ℃ at the heating rate of 1 ℃/min to obtain a third precursor. After natural cooling, the third precursor is immersed into deionized water for ultrasonic dispersion for 30min, and then 4ml of 1mol L of the third precursor is added-1Dilute hydrochloric acid solution and stir for at least 5h, and the stirring speed is controlled at 700 r/min. And washing with deionized water for several times, and drying in an oven at 60 ℃ for 12h to obtain black gallium oxide. Black Ga2O3The irregular nanoparticle structure (as shown in fig. 1b) is still present, and the main morphological features of the surface are changed, and more pores are present.
In order to characterize the crystal quality of gallium oxide nanoparticles, XRD spectroscopy was performed on black gallium oxide samples using a DX-2700 type X-ray diffractometer, and the results are shown in fig. 2. In FIG. 2, significant β -Ga is found2O3The diffraction peak intensity of black gallium oxide is close to that of white gallium oxide, which indicates that the obtained black gallium oxide has high crystal quality.
Using an ultraviolet-visible spectrophotometer model F-7000,characterization of Black Ga2O3The optical absorption properties of the particles, the results are shown in FIG. 3. It is obvious from the figure that white gallium oxide has strong absorption in the far ultraviolet band (200-; however, the prepared black gallium oxide has absorption in the ultraviolet band, and the absorption range of the black gallium oxide extends to the visible light band. The optical band gap of the black gallium oxide is calculated through a corresponding Tauc formula, and compared with the optical band gap of the white gallium oxide of 4.54eV, the optical band gap of the black gallium oxide prepared by the metal reduction method is reduced to 3.81 eV.
A Hitach F-7000 type fluorescence spectrometer is used for researching the migration and recombination processes of photo-generated electron-hole pairs in the semiconductor, and a PL spectrogram of black and white gallium oxide under the excitation of 265nm light is shown in figure 4. It is evident from the figure that the spectral intensity of black gallium oxide is greatly reduced compared to white gallium oxide, which indicates that the separation efficiency of the photo-generated electron-hole pairs of black gallium oxide is very high.
A BRUKER E500-9.5/12 spectrometer was used to characterize the presence of oxygen vacancies in black gallium oxide, and figure 5 is an EPR plot of black, white gallium oxide at room temperature. As is evident from the figure, black gallium oxide has a strong signal peak at g ═ 1.99, while white gallium oxide has no distinct resonance peak, indicating the presence of oxygen vacancies in black gallium oxide.
The photocatalytic redox ability of gallium oxide was tested using a xenon lamp model S350500 and a uv-vis spectrophotometer model TU-1901. FIG. 6 is a graph showing the degradation curves of 50mg black gallium oxide and 50mg white gallium oxide respectively in 50mL of 10mg/L rhodamine b solution through photocatalytic degradation, and it can be seen from the graph that the photocatalytic degradation time of black gallium oxide is shortened from 120min to less than 50min compared with white gallium oxide, and the photodegradation efficiency is greatly improved.
The prepared black gallium oxide is still black after being placed at room temperature for half a year, and the color does not turn white or deteriorate along with time, which shows that the black gallium oxide prepared by the invention has good stability at room temperature;
example 2
Step a is the same as example 1;
and B:
preparing black gallium oxide: in a glove box, 0.0334g of magnesium powder and 0.2g of white beta-phase Ga obtained in step A were mixed2O3Grinding and uniformly mixing the nano particles in an agate mortar to obtain a second precursor; the second precursor was charged into a quartz tube and vacuum-sealed by means of an oxyhydrogen flame. And (3) placing the sealed quartz tube in an annealing furnace, and carrying out heat preservation reaction at 550 ℃ for 11h at the heating rate of 1 ℃/min to obtain a third precursor. After natural cooling, the third precursor is immersed into deionized water for ultrasonic dispersion for 35min, and then 4ml of 1mol L of the third precursor is added-1Dilute hydrochloric acid solution and stir for 5h, and the stirring speed is controlled at 700-900 r/min. Washing with deionized water for several times, and drying in an oven at 55 ℃ for 13h to obtain black gallium oxide.
Example 3
Step a is the same as example 1;
and B:
preparing black gallium oxide: in a glove box, 0.0436g of magnesium powder and 0.2g of white beta-phase Ga from step A were mixed2O3Grinding and uniformly mixing the nano particles in an agate mortar to obtain a second precursor; the second precursor was charged into a quartz tube and vacuum-sealed by means of an oxyhydrogen flame. And (3) placing the sealed quartz tube in an annealing furnace, and carrying out heat preservation reaction for 10h at the temperature of 600 ℃, wherein the heating rate is 1 ℃/min, so as to obtain a third precursor. After natural cooling, the third precursor is immersed into deionized water for ultrasonic dispersion for 25min, and then 4ml of 1mol L of the third precursor is added-1And (5) diluting the hydrochloric acid solution and stirring for 6 hours, wherein the stirring speed is controlled at 800 r/min. Washing with deionized water for several times, and drying in a 65 ℃ oven for 11h to obtain black gallium oxide.
The results prove that the black gallium oxide nanoparticles prepared by the method have the advantages of high optical absorption, high carrier separation, strong redox capability and the like, and provide effective support for expanding the application of gallium oxide in photocatalysis and photoelectric devices. In addition, the invention provides a new idea and method for the subsequent research of semiconductor materials.
Claims (10)
1. A preparation method of black gallium oxide nanoparticles is characterized by comprising the following specific steps:
s1 extracting white Ga2O3Mixing and grinding the nano particles and magnesium powder, and carrying out heat preservation reaction at 500-600 ℃ under a vacuum condition to obtain a third precursor;
s2, immersing the third precursor into water for ultrasonic dispersion, adding excessive dilute hydrochloric acid, stirring for 5-6h, washing the precipitate, and drying to obtain black gallium oxide nanoparticles.
2. The method as claimed in claim 1, wherein in step S1, the Mg powder is mixed with white Ga2O3The mole ratio of the nano-particles is 1.3-1.7.
3. The method as claimed in claim 1, wherein the step S1 comprises grinding the mixed white Ga2O3The nano particles and the magnesium powder are put into a quartz tube, and the quartz tube is sealed in vacuum through oxyhydrogen flame.
4. The method of claim 1, wherein in step S1, the temperature maintaining time is 10h to 11h, and the temperature increasing rate is 1 ℃/min.
5. The method of claim 1, wherein in step S2, the third precursor is immersed in deionized water and ultrasonically dispersed for 30 ± 5 min.
6. The method as claimed in claim 1, wherein the diluted hydrochloric acid solution has a concentration of 1mol L in step S2-1。
7. The method as claimed in claim 1, wherein in step S2, the stirring speed is 700r/min-900 r/min.
8. The method as claimed in claim 1, wherein in step S2, the washing is performed with deionized water, and the supernatant is neutral.
9. The method for preparing black gallium oxide nanoparticles according to claim 1, wherein in step S2, the drying is performed at 60 ± 5 ℃ for 12 ± 1 h.
10. Black gallium oxide nanoparticles, characterized by being obtained by the production method according to any one of claims 1 to 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080038906A1 (en) * | 2004-10-01 | 2008-02-14 | Noboru Ichinose | Method for Producing P-Type Ga2o3 Film and Method for Producing Pn Junction-Type Ga2o3 Film |
| CN102671651A (en) * | 2012-06-07 | 2012-09-19 | 浙江大学 | Method for preparing mesoporous beta-Ga2O3 nanorod photocatalyst by using PEG (polyethylene glycol) as template |
| CN110304654A (en) * | 2019-07-30 | 2019-10-08 | 陕西科技大学 | A kind of amorphous photonic crystal schemochrome material compound based on black titanium dioxide and silica and preparation method thereof |
| CN110937636A (en) * | 2019-11-29 | 2020-03-31 | 中科芯(苏州)微电子科技有限公司 | Preparation method and application of black tungsten trioxide nanosheet |
| CN113066902A (en) * | 2021-03-25 | 2021-07-02 | 北京邮电大学 | Method for regulating and controlling photoelectric response performance of epsilon-phase gallium oxide through oxygen vacancy concentration |
| CN113461052A (en) * | 2021-07-08 | 2021-10-01 | 中国科学技术大学 | Black oxygen-enriched vacancy bismuth subcarbonate nanosheet and preparation method and application thereof |
-
2021
- 2021-10-20 CN CN202111223317.8A patent/CN113816417A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080038906A1 (en) * | 2004-10-01 | 2008-02-14 | Noboru Ichinose | Method for Producing P-Type Ga2o3 Film and Method for Producing Pn Junction-Type Ga2o3 Film |
| CN102671651A (en) * | 2012-06-07 | 2012-09-19 | 浙江大学 | Method for preparing mesoporous beta-Ga2O3 nanorod photocatalyst by using PEG (polyethylene glycol) as template |
| CN110304654A (en) * | 2019-07-30 | 2019-10-08 | 陕西科技大学 | A kind of amorphous photonic crystal schemochrome material compound based on black titanium dioxide and silica and preparation method thereof |
| CN110937636A (en) * | 2019-11-29 | 2020-03-31 | 中科芯(苏州)微电子科技有限公司 | Preparation method and application of black tungsten trioxide nanosheet |
| CN113066902A (en) * | 2021-03-25 | 2021-07-02 | 北京邮电大学 | Method for regulating and controlling photoelectric response performance of epsilon-phase gallium oxide through oxygen vacancy concentration |
| CN113461052A (en) * | 2021-07-08 | 2021-10-01 | 中国科学技术大学 | Black oxygen-enriched vacancy bismuth subcarbonate nanosheet and preparation method and application thereof |
Non-Patent Citations (11)
| Title |
|---|
| JAILL JEONG AND YOUNG HO HAN: "Electrical properties of MgO-doped BaTiO3", 《PHYS. CHEM. CHEM. PHYS.》 * |
| JONG-YEOL JUNG, ET AL.: "Morphological and crystal structural characterization of Ga2O3 particles synthesized by acontrolled precipitation and polymerized complex method", 《CERAMICS INTERNATIONAL》 * |
| SEON HO CHA AND YOUNG HO HAN: "Effects of Mn doping on dielectric properties of Mg-doped BaTiO3", 《JOURNAL OF APPLIED PHYSICS》 * |
| YU YANG AND PING ZHANG: "Dissociation of H2 molecule on the β-Ga2O3 (100)B surface: The critical role of oxygen vacancy", 《PHYSICS LETTERS A》 * |
| 刘丹丹 等: "纳米氧化物光催化剂的缺陷调控研究进展", 《稀有金属》 * |
| 吴功德: "《环境催化基础及应用》", 31 October 2019, 中国环境出版集团 * |
| 周卫 等: "《黑色二氧化钛可见光催化材料的制备与应用》", 31 July 2020, 黑龙江大学出版社 * |
| 周正华: "《纳米材料开发使用及质量检测技术标准应用手册》", 30 April 2005, 银声音像出版社 * |
| 郑永顺，路大勇: "Mg 掺杂 BaTiO3介电陶瓷中氧空位缺陷的EPＲ监控", 《吉林化工学院学报》 * |
| 高家诚 等: "真空热处理对纳米 TiO2-x可见光催化的影响", 《功能材料与器件学报》 * |
| 黄晓君 等: "氧化镓光催化剂的制备及其在水处理应用的研究进展", 《应用化工》 * |
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