CN116870936A - Quantum dot/bismuth oxyhalide composite material and preparation method and application thereof - Google Patents
Quantum dot/bismuth oxyhalide composite material and preparation method and application thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 106
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 86
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 22
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical class C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical class S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 28
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims description 25
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- -1 halogen salt Chemical class 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229940073609 bismuth oxychloride Drugs 0.000 claims description 5
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000969 carrier Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- 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
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- 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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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/674—Halogenides
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/681—Chalcogenides
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/72—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus also containing halogen, e.g. halophosphates
- C09K11/722—Chalcogenides
Abstract
The invention relates to a quantum dot/bismuth oxyhalide composite material, a preparation method and application thereof, wherein the composite powder comprises a flaky bismuth oxyhalide matrix and quantum dot particles deposited on the surface of the bismuth oxyhalide matrix, and more than two quantum dot particles are deposited on the surface of each bismuth oxyhalide; the quantum dots are one or more of molybdenum disulfide quantum dots, black phosphorus quantum dots and titanium carbide quantum dots; the bismuth oxyhalide catalytic powder is prepared by adopting an oil bath heating method, the prepared morphology is in a highly uniform nano sheet shape, and the low reaction temperature is beneficial to mass industrialized production; the invention constructs the photogenerated electron transfer path by adopting the quantum dot and bismuth oxyhalide composite method, can greatly improve the separation and migration time of photogenerated carriers and promote the improvement of the photocatalytic degradation efficiency.
Description
Technical Field
The invention belongs to the field of composite catalysts, and particularly relates to a quantum dot/bismuth oxyhalide composite material, and a preparation method and application thereof.
Background
Bismuth oxyhalide has great application potential in the field of piezoelectricity-photocatalysis, but the practical use value is seriously affected by the problems of limited visible light absorption capacity, small specific surface area and the like due to the fact that the photo-generated electron hole pair is fast in recombination rate. The quantum dot with high conductivity and small volume can well solve the limitation of a single bismuth-based semiconductor in theory.
However, the current report of the composite catalyst powder is focused on preparation by a hydrothermal or solvothermal method, and the defects of the composite catalyst powder are mainly that the reaction temperature is high, the shape controllability is poor, so that active sites are reduced, the photocatalytic performance is reduced, and meanwhile, the industrial production is difficult to realize.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a quantum dot/bismuth oxyhalide composite material, a preparation method and application thereof, and the technical problems of high preparation temperature and poor shape controllability of a quantum dot/bismuth oxyhalide composite catalyst in the prior art are solved.
In order to achieve the technical purpose, the technical scheme of the invention provides quantum dot/bismuth oxyhalide composite powder:
the preparation method comprises a flaky bismuth oxyhalide matrix and quantum dot particles deposited on the surface of the bismuth oxyhalide matrix, wherein more than two quantum dot particles are deposited on the surface of each bismuth oxyhalide; the quantum dots are one or more of molybdenum disulfide quantum dots, black phosphorus quantum dots and titanium carbide quantum dots.
Further, the length and width of bismuth oxyhalide are both 50-300 nanometers, and the size of the quantum dot particles is 2-50 nanometers.
Further, the bismuth oxyhalide is one or more of bismuth oxyiodide, bismuth oxybromide and bismuth oxychloride.
The preparation method of the quantum dot/bismuth oxyhalide composite powder comprises the following steps:
(1) Taking bismuth oxyiodide and halogen salt as main materials, adding a first solvent for mixing, preparing bismuth oxyhalide suspension by an oil bath method, and controlling the temperature of the oil bath to be 60-80 ℃; centrifuging, drying and grinding the bismuth oxyhalide suspension to obtain bismuth oxyhalide powder;
mixing a quantum dot raw material with a second solvent, and obtaining a quantum dot solution by a liquid phase stripping method under an ultrasonic condition;
(2) Mixing bismuth oxyhalide powder with the quantum dot solution, heating in water bath to compound the quantum dot and bismuth oxyhalide, and performing post-treatment to obtain the quantum dot/bismuth oxyhalide compound powder.
Further, in the step (1), the halogen salt is one or more of bismuth oxyiodide, bismuth oxybromide and bismuth oxychloride; the molar ratio of bismuth oxyiodide to halogen salt is 1:1;
the first solvent adopts a mixed solution of glycol and deionized water; the molar volume ratio of the host material to the first solvent was 4mmol: (30-50 ml);
the heating time of the oil bath is 2-3 h.
Further, in the step (1), the second solvent is N-methyl pyrrolidone, ethanol solution or ammonia water solution; the quantum dot raw material is mixed with a second solvent after being ground, and the mass ratio of the quantum dot raw material to the second solvent is (0.01-0.2): 10.
further, in the step (1), the power of the ultrasonic condition is 120-150W, and the liquid phase stripping method is to carry out ultrasonic stripping for 60-300 minutes under an ice bath.
Further, in the step (2), the quantum dots account for 0.02-2% of the total weight of the bismuth oxyhalide powder.
Further, in the step (2), the water bath heating is carried out for 2-4 hours at the temperature of 40-80 ℃.
The quantum dot/bismuth oxyhalide composite powder is applied to the piezoelectric-photocatalyst.
Compared with the prior art, the invention has the beneficial effects that:
1. the bismuth oxyhalide catalytic powder is prepared by adopting the oil bath heating method, the prepared morphology is in the shape of highly uniform nano-sheets, and the low reaction temperature is favorable for mass industrialized production.
2. The invention constructs the photogenerated electron transfer path by adopting the quantum dot and bismuth oxyhalide composite method, can greatly improve the separation and migration time of photogenerated carriers and promote the improvement of the photocatalytic degradation efficiency.
3. The invention introduces mechanical energy through ultrasound, realizes the organic unification of optical energy and mechanical energy, and can further promote the efficient performance of catalytic reaction by taking the mechanical energy as an important driving force.
4. The invention widens the application range of the photocatalyst, can finish partial catalytic degradation under dark conditions, and has strong practical value.
5. The invention enhances the internal built-in electric field by using external driving force (mechanical energy) so as to improve the separation efficiency of the photo-generated carriers and the holes, namely enhances the photocatalysis performance by using the piezoelectric effect, and greatly improves the performance compared with single photocatalysis.
Drawings
Fig. 1 is an HRTEM image of the titanium carbide quantum dot/bismuth oxybromide composite powder prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern before and after use of the titanium carbide quantum dot/bismuth oxybromide composite powder prepared in example 1 of the present invention.
Fig. 3 is an EDX spectrum of the titanium carbide quantum dot/bismuth oxybromide composite powder prepared in example 1 of the present invention.
FIG. 4 is a fluorescence spectrum of the titanium carbide quantum dot/bismuth oxybromide composite powder prepared in example 1, example 10 and example 11.
FIG. 5 is a chart of BiOBr morphology at different temperatures, wherein (a) low temperature; (b) high temperature.
FIG. 6 is a graph of degradation (MV, 20mg/L,50 ml) under different conditions (a visible, b ultrasonic vibration, c visible and ultrasonic vibration).
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a preparation method of a quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
s1, taking bismuth oxyiodide and halogen salt as main materials, adding a first solvent for mixing, heating for 2-3 hours at 60-80 ℃ through an oil bath to obtain bismuth oxyhalide suspension, centrifuging, drying and grinding to obtain bismuth oxyhalide powder; wherein, the inorganic phase material adopted by the bismuth oxyhalide is one or more of bismuth oxyiodide, bismuth oxybromide and bismuth oxychloride;
s2, extracting a quantum dot solution from the block body by a liquid phase stripping method, wherein the extracted quantum dot solution is one or more of molybdenum disulfide quantum dots, black phosphorus quantum dots and titanium carbide quantum dots respectively;
s3, mixing the bismuth oxyhalide powder with a quantum dot solution, wherein after the combination, the quantum dot accounts for 0.02-2% of the total weight of the bismuth oxyhalide powder;
and S4, drying and grinding the modified piezoelectric-photocatalytic composite powder to obtain the quantum dot/bismuth oxyhalide piezoelectric-photocatalytic composite powder.
Preferably, in the step S1, the host material is a mixed solution of bismuth oxyiodide (2 mmol) and potassium iodide, potassium bromide or potassium chloride powder (2 mmol) (molar ratio 1:1), and the first solvent is ethylene glycol (20 ml) and deionized water (ultrapure water) (20 ml) (volume ratio 1:1). The nano flower structure is controllably prepared and regulated by using potassium iodide, so that the surface area and the reactive sites of the photocatalytic piezoelectric-photocatalytic powder are greatly improved.
Preferably, the preparation process of the quantum dot solution in the step S2 is as follows: taking an original block with a certain mass (accounting for 0.02-2% of the total mass of the prepared bismuth oxyhalide powder), uniformly grinding for 5 minutes, dissolving in a second solvent, and stripping for 60-300 minutes under ice bath ultrasonic (120-150 w). Wherein the second solvent is N-methyl pyrrolidone, ethanol solution (concentration 75%) or ammonia water solution (concentration 25%), and the mass ratio of the original block to the second solvent is (0.01-0.2): 10.
further preferably, the diameter of the quantum dots in the quantum dot solution in the step S2 is between 2 and 50 nanometers (observed in a high-resolution electron microscope).
Preferably, in the step S3, the bismuth oxyhalide and quantum dot solution compounding process: heating in water bath at 40-80 deg.c for 2-4 hr to obtain dark brown or grey mixed solution.
The composite powder of the quantum dot/bismuth oxyhalide consists of a bismuth oxyhalide matrix and quantum dot particles deposited on the surface, wherein two or more quantum dot particles are inlaid on the surface of each bismuth oxyhalide.
Preferably, the bismuth oxyhalide powder prepared by the invention is of a nano sheet structure, the diameter is 50-300 nanometers, the size of quantum dot particles is less than 50 nanometers, and the particles are concentrated at 2-8 nanometers.
The preparation method of the quantum dot/bismuth oxyhalide composite powder is applied to the field of piezoelectricity-photocatalysis, in particular to the preparation of the piezoelectricity-photocatalysis composite powder.
The piezoelectric-photocatalytic system comprises the quantum dot/bismuth oxyhalide composite powder, wherein an internal electric field is formed by driving the inside of the composite powder by external mechanical energy, and a photo-generated carrier comprises electrons and holes, and the photo-generated carrier respectively carries positive and negative charges, so that the photo-generated carrier respectively moves in opposite directions under the action of the internal electric field, thereby being beneficial to further improving the separation efficiency of the photo-generated carrier and the holes, and the photo-generated carrier, namely the separation of electrons and holes in space, can only have photocatalytic performance, namely degrading organic matters and the like, and further improving the photocatalysis efficiency by utilizing the piezoelectric effect.
According to the invention, the surface of the bismuth oxyhalide nanosheet is modified by quantum dots to form a compact heterostructure, a photo-generated carrier rapid transfer passage is constructed, and the high-efficiency piezoelectric-photocatalytic composite powder can be prepared by coupling mechanical energy generated by ultrasound.
The quantum dot/bismuth oxyhalide composite material has excellent visible light absorption capacity, stable piezoelectricity and larger specific surface area, and can be mainly used in the fields of energy conversion, nano-generators, piezoelectric-photocatalysis and the like. The quantum dot/bismuth oxyhalide composite catalyst powder can organically combine the photocatalysis heterojunction theory and the piezoelectric catalysis system, exert a synergistic effect, further promote the separation and migration of photogenerated carriers, overcome the defect of a single material and expand the application range of photocatalysis.
The invention is further illustrated by the following specific examples.
Example 1
The preparation method of the quantum dot/bismuth oxyhalide composite powder comprises the following steps:
s1, adding bismuth oxyiodide (2 mmol) and potassium bromide (2 mmol) into a mixed solution of ethylene glycol (20 ml) and deionized water (20 ml) (volume ratio 1:1) according to a molar ratio 1:1, putting into an oil bath, heating at 80 ℃ for two hours, cooling the reaction system to room temperature, centrifuging, drying and grinding to obtain bismuth oxybromide powder.
S2, taking an original titanium carbide block with a certain mass, uniformly grinding for 5 minutes, dissolving in 20 milliliters of ammonia water solution, carrying out ultrasonic stripping for 300 minutes (power 120-150 w) in an ice bath, centrifuging for 10 minutes at 11000 rotating speed by using a centrifuge, and filtering and precipitating to finally obtain the titanium carbide quantum dot solution.
S3, mixing the bismuth oxybromide powder with the titanium carbide quantum dot solution, and heating the mixture for 3 hours through a water bath at 70-80 ℃; the quantum dots account for 0.15 percent (calculated by the proportion of the raw materials) of the total weight of the bismuth oxybromide powder.
And S4, centrifuging, drying and grinding the modified titanium carbide quantum dot/bismuth oxybromide composite powder to obtain the titanium carbide quantum dot/bismuth oxybromide piezoelectric-photocatalytic composite powder.
Fig. 1 shows an HRTEM image of the titanium carbide quantum dot prepared in this example, which is uniformly spherical in size and smaller than 50nm, and has a diameter substantially distributed between 2 and 8 nm.
Fig. 2 shows XRD patterns before and after use of the titanium carbide quantum dot/bismuth oxybromide composite powder of the present embodiment, and the crystal structure is unchanged before and after use.
Fig. 3 is an EDX spectrum of the titanium carbide quantum dot/bismuth oxybromide composite powder, and it can be seen that the prepared powder substantially conforms to the design components.
Example 2
The preparation method of the quantum dot/bismuth oxyhalide composite powder comprises the following steps:
s1, adding bismuth oxyiodide (2 mmol) and potassium iodide into a mixed solution of ethylene glycol (20 ml) and deionized water (volume ratio 1:1) according to a molar ratio of 1:1, putting into an oil bath kettle, heating at 80 ℃ for two hours, cooling a reaction system to room temperature, centrifuging, drying and grinding to obtain bismuth oxyiodide powder.
S2, taking an original black phosphorus block with a certain mass, uniformly grinding for 5 minutes, dissolving in 20ml of N-methyl pyrrolidone solution, carrying out ultrasonic stripping for 60 minutes in an ice bath, centrifuging for 10 minutes at 11000 rotating speed by using a centrifuge, and filtering and precipitating to finally obtain the black phosphorus quantum dot solution.
S3, mixing the bismuth oxyiodide powder with a black phosphorus quantum dot solution, wherein after the bismuth oxyiodide powder is compounded, the quantum dots account for 0.05 percent of the total weight of the bismuth oxyiodide powder.
And S4, centrifuging, drying and grinding the modified black phosphorus quantum dot/bismuth oxyiodide composite powder to obtain the black phosphorus quantum dot/bismuth oxyiodide piezoelectric-photocatalytic composite powder.
Example 3
The preparation method of the quantum dot/bismuth oxyhalide composite powder comprises the following steps:
s1, adding bismuth oxyiodide (2 mmol) and potassium bromide into a mixed solution of ethylene glycol (20 ml) and deionized water (volume ratio 1:1) according to a molar ratio of 1:1, putting into an oil bath kettle, heating at 80 ℃ for two hours, cooling a reaction system to room temperature, centrifuging, drying and grinding to obtain bismuth oxybromide powder.
S2, taking an original black phosphorus block with a certain mass, uniformly grinding for 5 minutes, dissolving in 20ml of N-methyl pyrrolidone solution, carrying out ultrasonic stripping for 60 minutes in an ice bath, centrifuging for 10 minutes at 11000 rotating speed by using a centrifuge, and filtering and precipitating to finally obtain the black phosphorus quantum dot solution.
S3, mixing the bismuth oxybromide powder with a black phosphorus quantum dot solution, wherein after the bismuth oxybromide powder is compounded, the quantum dot accounts for 0.1 percent of the total weight of the bismuth oxybromide powder.
And S4, centrifuging, drying and grinding the modified black phosphorus quantum dot/bismuth oxybromide composite powder to obtain the black phosphorus quantum dot/bismuth oxybromide piezoelectric-photocatalytic composite powder.
Specific preparation examples and comparative examples of a preparation method of quantum dot/bismuth oxyhalide provided by the invention are listed in table 1. Table 1 examines the selection of bismuth oxyhalide materials (labeled A) in step S1. And S2, selecting quantum dot materials (marked as B). In the step S3, the quantum dots account for the total weight percentage of the bismuth oxyhalide powder (marked as C).
Table 1 selection of materials and weight percentages in various embodiments of the invention
FIG. 4 is a fluorescence spectrum of the titanium carbide quantum dot/bismuth oxybromide composite powder prepared in example 1, example 10 and example 11 of the present invention, with similar characteristic peaks.
Comparative example 1
The only difference from example 1 is that: the oil bath temperature in step S1 was adjusted to 120 ℃, and the other steps and conditions were the same as in example 1.
As shown in fig. 5, (a) is the morphology of the bismuth oxybromide powder prepared at a low temperature (80 ℃) in example 1, and (b) is the morphology of the bismuth oxybromide powder prepared at a high temperature (120 ℃) in comparative example 1, which are different, wherein the nano-platelet structure can be prepared at a low temperature.
Application example 1
Application test was performed on the photocatalytic powder prepared in example 2.
The prepared powder is subjected to piezoelectricity catalysis, photocatalysis and piezoelectricity photocatalysis respectively, a 400w halogen lamp and a 150w ultrasonic cleaner are adopted in the tests, the dosage of a powder sample is 0.1-1g/L, methyl violet (MV 20mg/L,50 ml) is adopted as a test solution, the test time is 1h, 3ml of solution is taken every 15min, supernatant is centrifugally taken, and the solution concentration is analyzed by a Uv-vis test. The test was cycled 10 times/application.
FIG. 6 is a graph of degradation (MV, 20mg/L,50 ml) under different conditions (a visible, b ultrasonic vibration, c visible and ultrasonic vibration). As can be seen from fig. 6, the photocatalytic condition is formed only under the action of visible light in (a) and the piezoelectric catalytic condition is formed only under the action of ultrasonic vibration in (b), the degradation effect is not as good as that of the visible light and ultrasonic vibration in (c) in 15min, the degradation rate is about 55% in 15min (the single action is only between 30 and 35%), the degradation balance is basically reached after 45min treatment, and the degradation rate is above 85%; the degradation rate of single visible light or ultrasonic treatment after 60min treatment is only about 55%, so that the quantum dot/bismuth oxyhalide composite catalyst powder can organically combine a photocatalysis heterojunction theory and a piezoelectric catalytic system and exert a synergistic effect.
Compared with the prior art, the invention provides quantum dot/bismuth oxyhalide composite piezoelectric-photocatalytic powder and a preparation method thereof, and the preparation method comprises the following steps: preparing bismuth oxyhalide by an oil bath heating method, drying and grinding to obtain bismuth oxyhalide powder; stripping the quantum dots from the bulk raw materials by a liquid phase stripping method; carrying out surface quantum dot deposition on bismuth oxyhalide powder by taking ethanol as a solvent to obtain quantum dot/bismuth oxyhalide composite powder; the mass of the compounded quantum dot accounts for 0.02-2% of the total weight of the bismuth oxyhalide; and drying and grinding the compounded powder to obtain the quantum dot/bismuth oxyhalide composite piezoelectric-photocatalytic powder. According to the invention, the oil bath heating method is adopted to carry out quantum dot modification on the surface of the bismuth oxyhalide powder, so that the interface combination property of the quantum dots and the bismuth oxyhalide powder is improved, the specific surface area of the composite catalyst is increased, the separation and migration of photo-generated carriers at a heterojunction interface are enhanced, the synergistic effect of mechanical energy and light energy is fully exerted, and the more efficient composite catalyst powder is constructed.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. A quantum dot/bismuth oxyhalide composite powder is characterized in that: the preparation method comprises a flaky bismuth oxyhalide matrix and quantum dot particles deposited on the surface of the bismuth oxyhalide matrix, wherein more than two quantum dot particles are deposited on the surface of each bismuth oxyhalide; the quantum dots are one or more of molybdenum disulfide quantum dots, black phosphorus quantum dots and titanium carbide quantum dots.
2. The quantum dot/bismuth oxyhalide composite powder according to claim 1, wherein: the length and width of bismuth oxyhalide are 50-300 nanometers, and the size of the quantum dot particles is 2-50 nanometers.
3. The quantum dot/bismuth oxyhalide composite powder according to claim 1, wherein: the bismuth oxyhalide is one or more of bismuth oxyiodide, bismuth oxybromide and bismuth oxychloride.
4. A method for preparing the quantum dot/bismuth oxyhalide composite powder according to any one of claims 1 to 3, which is characterized in that: the method comprises the following steps:
(1) Taking bismuth oxyiodide and halogen salt as main materials, adding a first solvent for mixing, preparing bismuth oxyhalide suspension by an oil bath method, and controlling the temperature of the oil bath to be 60-80 ℃; centrifuging, drying and grinding the bismuth oxyhalide suspension to obtain bismuth oxyhalide powder;
mixing a quantum dot raw material with a second solvent, and obtaining a quantum dot solution by a liquid phase stripping method under an ultrasonic condition;
(2) Mixing bismuth oxyhalide powder with the quantum dot solution, heating in water bath to compound the quantum dot and bismuth oxyhalide, and performing post-treatment to obtain the quantum dot/bismuth oxyhalide compound powder.
5. The method for preparing the quantum dot/bismuth oxyhalide composite powder according to claim 4, which is characterized in that: in the step (1), the halogen salt is one or more of bismuth oxyiodide, bismuth oxybromide and bismuth oxychloride; the molar ratio of bismuth oxyiodide to halogen salt is 1:1;
the first solvent adopts a mixed solution of glycol and deionized water; the molar volume ratio of the host material to the first solvent was 4mmol: (30-50 ml);
the heating time of the oil bath is 2-3 h.
6. The method for preparing the quantum dot/bismuth oxyhalide composite powder according to claim 4, which is characterized in that: in the step (1), the second solvent is N-methyl pyrrolidone, ethanol solution or ammonia water solution; the quantum dot raw material is mixed with a second solvent after being ground, and the mass ratio of the quantum dot raw material to the second solvent is (0.01-0.2): 10.
7. the method for preparing the quantum dot/bismuth oxyhalide composite powder according to claim 4, which is characterized in that: in the step (1), the power of the ultrasonic condition is 120-150W, and the liquid phase stripping method is to carry out ultrasonic stripping for 60-300 minutes in an ice bath.
8. The method for preparing the quantum dot/bismuth oxyhalide composite powder according to claim 4, which is characterized in that: in the step (2), the quantum dots account for 0.02-2% of the total weight of the bismuth oxyhalide powder.
9. The method for preparing the quantum dot/bismuth oxyhalide composite powder according to claim 4, which is characterized in that: in the step (2), the water bath heating is carried out for 2-4 hours at the temperature of 40-80 ℃.
10. Use of the quantum dot/bismuth oxyhalide composite powder according to any one of claims 1 to 3 as a piezo-photocatalyst.
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| CN117463396B (en) * | 2023-12-28 | 2024-02-27 | 山东赫达集团股份有限公司 | Quantum dot/HPMC/bismuth oxyhalide composite material and preparation method and application thereof |
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