CN115057473B - Preparation method of oxygen vacancy type ultrathin bismuth oxide nanosheets and method for generating thermal effect by utilizing low-frequency ultrasonic induction of oxygen vacancy type ultrathin bismuth oxide nanosheets - Google Patents
Preparation method of oxygen vacancy type ultrathin bismuth oxide nanosheets and method for generating thermal effect by utilizing low-frequency ultrasonic induction of oxygen vacancy type ultrathin bismuth oxide nanosheets Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 99
- 239000001301 oxygen Substances 0.000 title claims abstract description 99
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 91
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000002135 nanosheet Substances 0.000 title claims abstract description 89
- 230000000694 effects Effects 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000006698 induction Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 239000000523 sample Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 13
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 13
- 230000008859 change Effects 0.000 description 12
- 230000005855 radiation Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000002064 nanoplatelet Substances 0.000 description 8
- 230000009471 action Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- -1 superoxide anions Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/33—
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A preparation method of oxygen vacancy type ultrathin bismuth oxide nano-sheets and a method for generating a heat effect by utilizing low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheets belong to the technical field of sound and heat research. The invention aims to solve the problems that the existing bismuth oxide nano material is difficult to realize the nano width in diameter, the preparation method is poor in stability, and the acoustic and thermal effects need high strength and long-time focusing. The preparation method comprises the following steps: 1. preparing oxygen vacancy type bismuth oxide flower-like structure powder; 2. the disruption was performed using a cell disrupter. The method for generating the thermal effect by utilizing the low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet comprises the following steps: adding the oxygen vacancy type ultrathin bismuth oxide nano-sheet powder into water, and carrying out ultrasonic treatment on the oxygen vacancy type ultrathin bismuth oxide nano-sheet dispersion liquid by using an ultrasonic probe. The invention is used for preparing the oxygen vacancy type ultrathin bismuth oxide nano-sheet and generating a thermal effect by utilizing low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet.
Description
Technical Field
The invention belongs to the technical field of sound and heat research.
Background
The heavy metal bismuth (Bi, atomic number 83) element attracts research interests of scientific researchers due to the advantages of innocuity, low in-vivo reactivity, low price and the like, and comprises a material preparation methodPerformance research, application exploration, etc. Various bismuth-based materials, e.g. Bi metal, bi 2 S 3 、Bi 2 Se 3 、BiFeO 3 、AgBiS 2 、Bi 2 MoO 6 And the like are widely researched, and the catalytic performance, the photo-thermal performance, the piezoelectric performance, the thermoelectric performance and the like of the material are widely used in the fields of photocatalysis, treatment, diagnosis and the like.
Recently, the bismuth-based defect-rich nano material has the advantages of reducing the energy band width, promoting the separation of electrons and holes and the like due to the existence of a large number of defects, and improving the relevant properties of the material such as photocatalysis and the like. The oxygen vacancy type bismuth oxide nano material has good light absorption capacity in the ultraviolet-visible-near infrared light range, good photocatalysis performance is achieved, but photocatalysis and other performance application scenes are limited by the penetration depth of a light source. The ultrasonic has the advantages of high safety, no wound, good biological tolerance, controllable space and time, deep tissue penetration depth and the like, and is one of the excitation sources with the most extensive application prospect, especially in the biomedical field.
The preparation method of the oxygen vacancy type bismuth oxide nano material mainly comprises a hydrothermal method and a solid phase method, the diameter size of the material prepared by the hydrothermal method is mostly in micrometer width, the nanometer width in the aspect of diameter is difficult to realize, and the preparation method is poor in stability. And the acoustic-thermal effect of the existing oxygen vacancy type bismuth oxide nanosheets requires high-intensity and long-time focusing ultrasonic radiation.
Disclosure of Invention
The invention aims to solve the problems that the existing bismuth oxide nano material is difficult to realize the nano width in diameter, the stability of the preparation method is poor, and the acoustic-thermal effect needs high strength and long-time focusing, and further provides a preparation method of an oxygen vacancy type ultrathin bismuth oxide nano sheet and a method for generating the thermal effect by utilizing low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano sheet.
The preparation method of the oxygen vacancy type ultrathin bismuth oxide nano-sheet comprises the following steps:
1. dissolving sodium bismuthate and sodium hydroxide into water, stirring at room temperature to obtain a mixed solution, placing the mixed solution into a hydrothermal reaction kettle, reacting for 2-20 hours at 150-210 ℃, centrifuging at a differential speed to collect a solid product, and drying to obtain oxygen vacancy type bismuth oxide flower-like structure powder;
the mass ratio of the sodium bismuthate to the sodium hydroxide is 1 (0.5-3);
2. adding oxygen vacancy type bismuth oxide flower-like structure powder into a mixed solution of water and ethanol, performing ultrasonic dispersion, crushing for 10-20 hours by using a cell crusher under the conditions that the power of the crusher is 500-800W and the temperature is 0-45 ℃ after ultrasonic treatment, standing at room temperature after crushing, taking upper suspension after standing, performing centrifugal separation, and finally drying under the condition that the temperature is 50-60 ℃ to obtain the oxygen vacancy type ultrathin bismuth oxide nano-sheet powder.
The method for generating the heat effect by utilizing the low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet comprises the following steps of: adding the oxygen vacancy type ultrathin bismuth oxide nano-sheet powder into water to obtain an oxygen vacancy type ultrathin bismuth oxide nano-sheet dispersion liquid with the concentration of 20-300 mug/mL, and carrying out ultrasonic power of 0.5W/cm 2 ～1.2W/cm 2 Under the condition of (1) using an ultrasonic probe to ultrasonically treat the oxygen vacancy type ultrathin bismuth oxide nano-sheet dispersion liquid with the concentration of 20-300 mug/mL for 10-100 s.
The beneficial effects of the invention are as follows:
the invention adopts the low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet to generate the thermal effect, and has the advantages of mature method, simple process and high acoustic-thermal conversion efficiency. The preparation method of the oxygen vacancy type ultrathin bismuth oxide nano-sheet has good stability, and the nano-sheet material with stable crystal phase structure and good sheet shape can be obtained by repeated experiments for 8 times. Because of the existence of the surface activity, the nano-sheets can not be agglomerated, and the dispersed sheet morphology can be still maintained after the nano-sheets are stood for 7 days.
The principle of producing good acoustic-thermal effect is that the nano-sheet structure has excellent piezoelectric performance, can generate spontaneous electric polarization phenomenon under the tiny pressure generated by ultrasonic radiation, induces an internal electric field, and causes separation and rapid movement of electrons and holes. While the fast movement of electrons will produce a good resultGood thermal effect of 1.2W/cm 2 Under power, the temperature of the ultrasonic wave is raised by 40 ℃ for 100 seconds, and excellent sound and heat performance is shown. Whereas the only literature reported for the acoustic and thermal materials such as metal-red phosphorus composite nanoplatelets (adv. Mater.2021,33,2006047) is only 1.0W/cm 2 Under the power, the temperature can be raised by 20 ℃ only after continuous ultrasonic treatment for 25 min.
In addition, the oxygen vacancy type ultrathin bismuth oxide nano-sheet has good piezoelectric catalysis performance, can generate a large amount of active oxygen species under the action of low-power ultrasound, and has wide application prospects in the fields of renewable energy sources (such as water decomposition and carbon dioxide emission reduction), environmental remediation (such as organic pollutant degradation), cell stimulation, catalytic treatment and the like.
Drawings
FIG. 1 is a transmission electron microscope photograph, a is an oxygen vacancy type bismuth oxide flower-like structure prepared in the first step of the example, and b is an oxygen vacancy type ultrathin bismuth oxide nano-sheet prepared in the second step of the example;
FIG. 2 is an X-ray diffraction chart, 1 is oxygen vacancy type ultrathin bismuth oxide nano-sheet powder prepared in the first step of the embodiment, and 2 is a corresponding standard card;
FIG. 3 is an X-ray photoelectron spectrum of the ultrathin bismuth oxide nanosheet powder with oxygen vacancies prepared in the first step of the example, wherein 1 is lattice oxygen peak separation, 2 is surface adsorption oxygen peak separation, and 3 is oxygen vacancy peak separation;
FIG. 4 is an atomic force microscope photograph showing a concentration of 100. Mu.g/mL of an oxygen vacancy type ultrathin bismuth oxide nanosheet dispersion liquid after standing at room temperature for 7d and a measurement result of the size in example I, a is an atomic force microscope photograph, b is a measurement result of the size, 1 is a measurement result of the size of the nanosheet 1 in a drawing, and 2 is a measurement result of the size of the nanosheet 2 in a drawing;
FIG. 5 is a graph showing the temperature change of the ultra-thin bismuth oxide nanoplatelet dispersion of different concentrations of oxygen vacancies in example one, 1 water, 2 100 μg/mL,3 200 μg/mL, and 4 300 μg/mL, under irradiation of ultrasonic power of 1.2W/cm;
FIG. 6 is a graph showing the temperature change of an oxygen vacancy type ultrathin bismuth oxide nanosheet dispersion liquid having a concentration of 100. Mu.g/mL in example one, 1 being 0.72W/cm, under different ultrasonic power radiations 2 2 is 0.96W/cm 2 3 is 1.2W/cm 2 ；
FIG. 7 is a graph showing the temperature rise and fall curves of an oxygen vacancy type ultrathin bismuth oxide nanosheet dispersion liquid having a concentration of 300. Mu.g/mL in example one by ultrasonic irradiation for 3 cycles, 1 is the temperature rise and fall curve at an ultrasonic power of 1.2W/cm 2 2 is a temperature change curve of a natural cooling process;
FIG. 8 is a graph showing that the oxygen vacancy type ultrathin bismuth oxide nanosheet dispersion liquid having a concentration of 500. Mu.g/mL was dispersed at 1.2W/cm in example one 2 An electron spin resonance spectrogram under the action of ultrasound, wherein 1 is superoxide anion, 2 is singlet oxygen, and 3 is hydroxyl radical;
FIG. 9 is a graph showing that the dispersion of oxygen-vacancy-type ultrathin bismuth oxide nanoplatelets having a concentration of 500. Mu.g/mL was conducted at 1.2W/cm in example one 2 An ultraviolet-visible absorption spectrum chart of 3,3', 5' -tetramethyl benzidine color change reaction is catalyzed under the ultrasonic action, wherein 1 is 2min,2 is 4min,3 is 6min,4 is 8min, and 5 is 10min.
Detailed Description
The first embodiment is as follows: the preparation method of the oxygen vacancy type ultrathin bismuth oxide nano-sheet is carried out according to the following steps:
1. dissolving sodium bismuthate and sodium hydroxide into water, stirring at room temperature to obtain a mixed solution, placing the mixed solution into a hydrothermal reaction kettle, reacting for 2-20 hours at 150-210 ℃, centrifuging at a differential speed to collect a solid product, and drying to obtain oxygen vacancy type bismuth oxide flower-like structure powder;
the mass ratio of the sodium bismuthate to the sodium hydroxide is 1 (0.5-3);
2. adding oxygen vacancy type bismuth oxide flower-like structure powder into a mixed solution of water and ethanol, performing ultrasonic dispersion, crushing for 10-20 hours by using a cell crusher under the conditions that the power of the crusher is 500-800W and the temperature is 0-45 ℃ after ultrasonic treatment, standing at room temperature after crushing, taking upper suspension after standing, performing centrifugal separation, and finally drying under the condition that the temperature is 50-60 ℃ to obtain the oxygen vacancy type ultrathin bismuth oxide nano-sheet powder.
In the embodiment, aqueous solution of sodium hydroxide and sodium bismuthate is used as reactants, a low-temperature hydrothermal reaction is adopted to obtain a three-dimensional flower-like structure of micron-sized oxygen vacancy type bismuth oxide, and then stripping and crushing effects of a cell crusher are combined to prepare the oxygen vacancy type ultrathin bismuth oxide nano-sheet.
In this embodiment, the dispersion was subjected to flower-like structure disruption and lamellar structure exfoliation by a commercial cell disruption instrument.
The beneficial effects of this embodiment are:
the embodiment adopts the low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet to generate a thermal effect, and has the advantages of mature method, simple process and high acoustic-thermal conversion efficiency. The preparation method of the oxygen vacancy type ultrathin bismuth oxide nano-sheet has good stability, and the nano-sheet material with stable crystal phase structure and good sheet shape can be obtained by repeated experiments for 8 times. Because of the existence of the surface activity, the nano-sheets can not be agglomerated, and the dispersed sheet morphology can be still maintained after the nano-sheets are stood for 7 days.
The principle of producing good acoustic-thermal effect is that the nano-sheet structure has excellent piezoelectric performance, can generate spontaneous electric polarization phenomenon under the tiny pressure generated by ultrasonic radiation, induces an internal electric field, and causes separation and rapid movement of electrons and holes. The fast movement of electrons will produce good thermal effect at 1.2W/cm 2 Under power, the temperature of the ultrasonic wave is raised by 40 ℃ for 100 seconds, and excellent sound and heat performance is shown. Whereas the only literature reported for the acoustic and thermal materials such as metal-red phosphorus composite nanoplatelets (adv. Mater.2021,33,2006047) is only 1.0W/cm 2 Under the power, the temperature can be raised by 20 ℃ only after continuous ultrasonic treatment for 25 min.
In addition, the oxygen vacancy type ultrathin bismuth oxide nano-sheet has good piezoelectric catalysis performance, can generate a large amount of active oxygen species under the action of low-power ultrasound, and has wide application prospects in the fields of renewable energy sources (such as water decomposition and carbon dioxide emission reduction), environmental remediation (such as organic pollutant degradation), cell stimulation, catalytic treatment and the like.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the volume ratio of the sodium bismuthate to the water in the first step is 1g (17-25 mL). The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the room temperature stirring in the first step is specifically stirring for 30 min-3 h under the conditions of room temperature and rotating speed of 500-2000 rpm. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the differential centrifugal collection in the first step is specifically to centrifuge for 3-8 min under the condition that the differential centrifugal rotating speed is 500-2000 rpm. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the volume ratio of the mass of the oxygen vacancy type bismuth oxide flower-like structure powder to the mixed solution of water and ethanol in the second step is 1g (20-100 mL); the volume ratio of water to ethanol in the mixed solution of water and ethanol in the second step is 1 (0.3-3). The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the ultrasonic dispersion in the second step is specifically carried out under the condition that the power is 200W-480W, and the ultrasonic dispersion is carried out for 30 min-2 h. The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the crushing in the second step is an intermittent crushing mode, wherein the crushing is carried out for 1s to 3s, and the crushing is stopped for 3s to 5s. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: step two, adding a surfactant in the crushing process; the addition amount of the surfactant is 0.5-3% of the mass percentage of the mixed solution of water and ethanol; the surfactant is polyvinylpyrrolidone, cetyl trimethyl ammonium bromide or Tween 20. The other is the same as in embodiments one to seven.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: and in the second step, standing for 5-10 h at room temperature. The others are the same as in embodiments one to eight.
Detailed description ten: the method for generating the heat effect by utilizing the low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet in the embodiment comprises the following steps of: adding the oxygen vacancy type ultrathin bismuth oxide nano-sheet powder into water to obtain an oxygen vacancy type ultrathin bismuth oxide nano-sheet dispersion liquid with the concentration of 20-300 mug/mL, and carrying out ultrasonic power of 0.5W/cm 2 ～1.2W/cm 2 Under the condition of (1) using an ultrasonic probe to ultrasonically treat the oxygen vacancy type ultrathin bismuth oxide nano-sheet dispersion liquid with the concentration of 20-300 mug/mL for 10-100 s.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the preparation method of the oxygen vacancy type ultrathin bismuth oxide nano-sheet comprises the following steps:
1. dissolving sodium bismuthate and sodium hydroxide into water, stirring for 1h at room temperature and a rotating speed of 800 rpm to obtain a mixed solution, placing the mixed solution into a hydrothermal reaction kettle, reacting for 17h at a temperature of 185 ℃, centrifuging at a differential speed to collect a solid product, and drying at a temperature of 60 ℃ to obtain oxygen vacancy type bismuth oxide flower-like structure powder;
the mass ratio of the sodium bismuthate to the sodium hydroxide is 1:0.81; the volume ratio of the sodium bismuthate to the water is 1 g/21 mL;
2. adding oxygen vacancy type bismuth oxide flower-like structure powder into a mixed solution of water and ethanol, performing ultrasonic dispersion for 2 hours under the condition of 400W of power, crushing for 12 hours by using a cell crusher under the condition of 600W of crusher power and 0-45 ℃ of temperature after ultrasonic treatment, standing for 5 hours at room temperature after crushing, taking upper suspension after standing, performing centrifugal separation, and finally drying under the condition of 60 ℃ of temperature to obtain oxygen vacancy type ultrathin bismuth oxide nano-sheet powder;
the volume ratio of the mass of the oxygen vacancy type bismuth oxide flower-like structure powder to the mixed solution of water and ethanol is 1g to 40mL; the volume ratio of the water to the ethanol in the mixed solution of the water and the ethanol is 1:1.2.
The differential centrifugal collection in the first step is specifically carried out under the condition that the differential centrifugal rotating speed is 2000 revolutions per minute for 3 minutes.
The crushing in the second step is an intermittent crushing mode, wherein the crushing is carried out for 3s and the crushing is stopped for 5s.
Step two, adding a surfactant in the crushing process; the addition amount of the surfactant is 1 percent of the mass percentage of the mixed solution of water and ethanol; the surfactant is Tween 20.
The preparation method of the first embodiment is used for carrying out repeated experiments for 8 times, so that the nano sheet material with stable crystal phase structure and good sheet morphology can be obtained.
FIG. 1 is a transmission electron microscope photograph, a is an oxygen vacancy type bismuth oxide flower-like structure prepared in the first step of the example, and b is an oxygen vacancy type ultrathin bismuth oxide nano-sheet prepared in the second step of the example; as can be seen from the figure, the flower-like structure is formed by overlapping thin sheets, and the size is more than 1 mu m; the length of the nano-sheet is about 500nm, overlapping connection does not exist between the sheets, and the dispersibility is good.
FIG. 2 is an X-ray diffraction chart, 1 is oxygen vacancy type ultrathin bismuth oxide nano-sheet powder prepared in the first step of the embodiment, and 2 is a corresponding standard card; the nano-sheet has a good crystal structure and is in good conformity with standard cards.
FIG. 3 is an X-ray photoelectron spectrum of the ultrathin bismuth oxide nanosheet powder with oxygen vacancies prepared in the first step of the example, wherein 1 is lattice oxygen peak separation, 2 is surface adsorption oxygen peak separation, and 3 is oxygen vacancy peak separation; from the figure, the prepared nanoplatelets have a large number of oxygen vacancies present.
The oxygen vacancy type ultrathin bismuth oxide nano-sheet prepared by the method is used for generating a thermal effect by low-frequency ultrasonic induction, and the method comprises the following steps of: adding the oxygen vacancy type ultrathin bismuth oxide nano-sheet powder into water to obtain an oxygen vacancy type ultrathin bismuth oxide nano-sheet dispersion liquid with the concentration of 100 mug/mL, 200 mug/mL, 300 mug/mL and 500 mug/mL, and the ultrasonic power is equal to that of the dispersion liquid0.72W/cm 2 、0.96W/cm 2 1.2W/cm 2 Under the condition of (1) using an ultrasonic probe to ultrasonically treat an oxygen vacancy type ultrathin bismuth oxide nano-sheet dispersion liquid with the concentration of 100 mug/mL, 200 mug/mL, 300 mug/mL and 500 mug/mL for 100s; the medical ultrasonic couplant is smeared on the outer side of the sample container and is used for effectively transmitting ultrasonic radiation, and a thermal imager is used for recording the change curve of the temperature of the solution along with ultrasonic time. After the ultrasonic process is finished, the dispersion liquid is naturally cooled, the temperature change condition of the cooling stage is recorded until the temperature is reduced to the room temperature, a first heating and cooling cycle is completed, the heating and cooling cycle process is repeated twice, the temperature change curves of the three circulating dispersion liquid along with time are recorded respectively, and the stability of the sound and heat properties of the oxygen vacancy type ultrathin bismuth oxide nano sheet is studied.
FIG. 4 is an atomic force microscope photograph showing a concentration of 100. Mu.g/mL of an oxygen vacancy type ultrathin bismuth oxide nanosheet dispersion liquid after standing at room temperature for 7d and a measurement result of the size in example I, a is an atomic force microscope photograph, b is a measurement result of the size, 1 is a measurement result of the size of the nanosheet 1 in a drawing, and 2 is a measurement result of the size of the nanosheet 2 in a drawing; from the figure, the nano-sheet still has a sheet structure with the size of about 500nm after standing, the thickness is about 6nm, no agglomeration occurs, and the dispersibility is good.
FIG. 5 is a graph showing the temperature change of the ultra-thin bismuth oxide nanoplatelet dispersion of different concentrations of oxygen vacancies in example one, 1 water, 2 100 μg/mL,3 200 μg/mL, and 4 300 μg/mL, under irradiation of ultrasonic power of 1.2W/cm; according to the graph, under the condition of low power excitation, the dispersion liquid of the 100s nanosheet material can be subjected to 1.2W/cm ultrasonic radiation, so that the heating effect at about 40 ℃ can be realized, and the heating amplitude is sequentially improved along with the increase of the material concentration; under the same conditions, the heating effect of pure water is only about 10 ℃.
FIG. 6 is a graph showing the temperature change of an oxygen vacancy type ultrathin bismuth oxide nanosheet dispersion liquid having a concentration of 100. Mu.g/mL in example one, 1 being 0.72W/cm, under different ultrasonic power radiations 2 2 is 0.96W/cm 2 3 is 1.2W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the From the graph, the nano-sheet dispersion liquid is respectively heated to 29.0 ℃, 46.3 ℃ and 61.6 ℃ when the ultrasonic radiation is carried out for 100 seconds, and the heating effect is improved along with the increase of the powerThe effect is obvious.
FIG. 7 is a graph showing the temperature rise and fall curves of an oxygen vacancy type ultrathin bismuth oxide nanosheet dispersion liquid having a concentration of 300. Mu.g/mL in example one by ultrasonic irradiation for 3 cycles, 1 is the temperature rise and fall curve at an ultrasonic power of 1.2W/cm 2 And 2 is a temperature change curve of a natural cooling process. From the graph, the ultrasonic radiation of the dispersion liquid of the nano-sheets can be quickly heated to 70 ℃ for 100 seconds, the ultrasonic radiation can be quickly heated to 70 ℃ again for 100 seconds after natural cooling, the continuous three-time heating effect is unchanged, and the stability of the heating effect of the nano-sheets is verified.
FIG. 8 is a graph showing that the oxygen vacancy type ultrathin bismuth oxide nanosheet dispersion liquid having a concentration of 500. Mu.g/mL was dispersed at 1.2W/cm in example one 2 Electron spin resonance spectrum under the action of ultrasound, 1 is superoxide anion, 2 is singlet oxygen, and 3 is hydroxyl radical. From the graph, signal peaks derived from three active oxygen species, superoxide anions, hydroxyl radicals and singlet, demonstrate the ability of the nanoplatelet material to generate active oxygen species under low power ultrasonic radiation.
FIG. 9 is a graph showing that the dispersion of oxygen-vacancy-type ultrathin bismuth oxide nanoplatelets having a concentration of 500. Mu.g/mL was conducted at 1.2W/cm in example one 2 An ultraviolet-visible absorption spectrum chart of 3,3', 5' -tetramethyl benzidine color change reaction is catalyzed under the ultrasonic action, wherein 1 is 2min,2 is 4min,3 is 6min,4 is 8min, and 5 is 10min. From the figure, the active oxygen species generated by the nano-sheet dispersion liquid can catalyze 3,3', 5' -tetramethyl benzidine to realize the color change reaction, and the good catalytic effect of the system is proved.
Claims (9)
1. The method for generating the heat effect by low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet is characterized by comprising the following steps of: adding the oxygen vacancy type ultrathin bismuth oxide nano-sheet powder into water to obtain an oxygen vacancy type ultrathin bismuth oxide nano-sheet dispersion liquid with the concentration of 20-300 mug/mL, and carrying out ultrasonic power of 0.5W/cm 2 ～1.2W/cm 2 Under the condition of (1), utilizing an ultrasonic probe to ultrasonically treat the oxygen vacancy type ultrathin bismuth oxide nano-sheet dispersion liquid with the concentration of 20-300 mug/mL for 10-100 s;
the oxygen vacancy type ultrathin bismuth oxide nano-sheet is prepared by the following steps:
1. dissolving sodium bismuthate and sodium hydroxide into water, stirring at room temperature to obtain a mixed solution, placing the mixed solution into a hydrothermal reaction kettle, reacting for 2-20 hours at 150-210 ℃, centrifuging at a differential speed to collect a solid product, and drying to obtain oxygen vacancy type bismuth oxide flower-like structure powder;
the mass ratio of the sodium bismuthate to the sodium hydroxide is 1 (0.5-3);
2. adding oxygen vacancy type bismuth oxide flower-like structure powder into a mixed solution of water and ethanol, performing ultrasonic dispersion, crushing for 10-20 hours by using a cell crusher under the conditions that the power of the crusher is 500-800W and the temperature is 0-45 ℃ after ultrasonic treatment, standing at room temperature after crushing, taking upper suspension after standing, performing centrifugal separation, and finally drying under the condition that the temperature is 50-60 ℃ to obtain the oxygen vacancy type ultrathin bismuth oxide nano-sheet powder.
2. The method for generating a thermal effect by low-frequency ultrasonic induction of oxygen vacancy type ultrathin bismuth oxide nano-sheets according to claim 1, wherein the mass-to-water volume ratio of sodium bismuthate in the step one is 1g (17-25) mL.
3. The method for generating a heat effect by low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet according to claim 1, wherein the stirring at room temperature in the first step is particularly carried out for 30-3 h under the conditions of room temperature and rotating speed of 500-2000 rpm.
4. The method for generating a thermal effect by low-frequency ultrasonic induction of oxygen vacancy type ultrathin bismuth oxide nano-sheets according to claim 1, wherein the differential centrifugal collection in the step one is specifically centrifugal for 3-8 min under the condition that the differential centrifugal rotation speed is 500-2000 rpm.
5. The method for generating a thermal effect by low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet according to claim 1, wherein the volume ratio of the mass of the oxygen vacancy type bismuth oxide flower-like structure powder to the mixed solution of water and ethanol in the second step is 1g (20-100 mL); the volume ratio of water to ethanol in the mixed solution of water and ethanol in the second step is 1 (0.3-3).
6. The method for generating a heat effect by low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet according to claim 1, wherein the ultrasonic dispersion in the second step is specifically carried out under the condition of 200-480W of power for 30 min-2 h.
7. The method for generating a heat effect by low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet according to claim 1, wherein the crushing in the second step is an intermittent crushing mode, wherein the crushing is carried out for 1s to 3s, and the stopping is carried out for 3s to 5s.
8. The method for generating a thermal effect by low-frequency ultrasonic induction of oxygen vacancy type ultrathin bismuth oxide nano-sheets according to claim 1, which is characterized in that a surfactant is added in the crushing process in the second step; the addition amount of the surfactant is 0.5-3% of the mass percentage of the mixed solution of water and ethanol; the surfactant is polyvinylpyrrolidone, cetyl trimethyl ammonium bromide or Tween 20.
9. The method for generating a thermal effect by low-frequency ultrasonic induction of the oxygen vacancy type ultrathin bismuth oxide nano-sheet according to claim 1, which is characterized in that the second step is carried out at room temperature for 5-10 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107522227A (en) * | 2017-08-22 | 2017-12-29 | 河南师范大学 | A kind of method that ultrasonic method prepares the bismoclite flat crystal with oxygen defect |
| CN111035761A (en) * | 2019-12-13 | 2020-04-21 | 国家纳米科学中心 | Sensitizer for radiotherapy and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH01246140A (en) * | 1988-03-25 | 1989-10-02 | Agency Of Ind Science & Technol | Production of bismuth (iii) oxide |
| CN107522227A (en) * | 2017-08-22 | 2017-12-29 | 河南师范大学 | A kind of method that ultrasonic method prepares the bismoclite flat crystal with oxygen defect |
| CN111035761A (en) * | 2019-12-13 | 2020-04-21 | 国家纳米科学中心 | Sensitizer for radiotherapy and preparation method and application thereof |
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| Title |
|---|
| 氯氧化铋(BiOCl)纳米片的制备及光催化性能研究;卫世乾;李建辉;李大鹏;;化工新型材料(第05期);全文 * |
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