CN115109587A - Aluminum nanocluster with ultraviolet to near-ultraviolet fluorescence wavelength and preparation method and application thereof - Google Patents
Aluminum nanocluster with ultraviolet to near-ultraviolet fluorescence wavelength and preparation method and application thereof Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 71
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 aluminum halide Chemical class 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000006862 quantum yield reaction Methods 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 238000005580 one pot reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 22
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000008096 xylene Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
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- 238000005406 washing Methods 0.000 claims description 9
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012454 non-polar solvent Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- MQKXWEJVDDRQKK-UHFFFAOYSA-N bis(6-methylheptyl) butanedioate Chemical compound CC(C)CCCCCOC(=O)CCC(=O)OCCCCCC(C)C MQKXWEJVDDRQKK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- HWQXBVHZYDELQG-UHFFFAOYSA-L disodium 2,2-bis(6-methylheptyl)-3-sulfobutanedioate Chemical compound C(CCCCC(C)C)C(C(C(=O)[O-])S(=O)(=O)O)(C(=O)[O-])CCCCCC(C)C.[Na+].[Na+] HWQXBVHZYDELQG-UHFFFAOYSA-L 0.000 claims 1
- 238000003384 imaging method Methods 0.000 claims 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims 1
- PLXBWHJQWKZRKG-UHFFFAOYSA-N Resazurin Chemical compound C1=CC(=O)C=C2OC3=CC(O)=CC=C3[N+]([O-])=C21 PLXBWHJQWKZRKG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
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- 239000002824 redox indicator Substances 0.000 abstract description 2
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- 150000001875 compounds Chemical class 0.000 abstract 2
- 238000001514 detection method Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000005424 photoluminescence Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 4
- 230000004075 alteration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- HSSLDCABUXLXKM-UHFFFAOYSA-N resorufin Chemical compound C1=CC(=O)C=C2OC3=CC(O)=CC=C3N=C21 HSSLDCABUXLXKM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
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- 230000005540 biological transmission Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- YZYASTRURKBPPS-UHFFFAOYSA-N C(CCC(=O)OCCCCCC(C)C)(=O)OCCCCCC(C)C.[Na] Chemical compound C(CCC(=O)OCCCCCC(C)C)(=O)OCCCCCC(C)C.[Na] YZYASTRURKBPPS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 108020004414 DNA Proteins 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention discloses an aluminum nano-cluster with ultraviolet to near-ultraviolet fluorescence wavelength, a preparation method and application thereof, belonging to the field of synthesis and application of novel nano-cluster materials. According to the invention, aluminum halide is used as a reactant precursor, anion or cation surfactant is used for carrying out ion pairing on the synthesized aluminum nanocluster modified by the surface ligand, and a strong reducing agent one-pot method is utilized to prepare the ultra-small aluminum nanocluster which is uniformly dispersed, uniform in particle size, high in fluorescence quantum yield and adjustable and controllable from ultraviolet to near ultraviolet fluorescence wavelength. Meanwhile, the application prospect of the compound in the field of photocatalysis is shown through the reduction of the compound on the redox indicator resazurin. The invention realizes the fluorescent regulation of the central wavelength of the ultra-small aluminum nanocluster in the range from ultraviolet to near ultraviolet, and the enhanced fluorescent emission is hopeful to realize the application of the ultra-small aluminum nanocluster in the fields of illumination, sensing and photoelectric detection; meanwhile, the invention reports that the prepared ultra-small aluminum nano cluster has high-efficiency and stable photocatalytic performance, and is expected to realize large-scale practical application.
Description
Technical Field
The invention belongs to the field of synthesis and application of novel nano-cluster materials, and particularly relates to an ultra-small aluminum nano-cluster with ultraviolet to near-ultraviolet fluorescence wavelength regulated by different surfactants, and preparation and application thereof.
Background
The metal nanoclusters are a new nano material with great application potential due to the quantum confinement effect and the discrete electronic energy level state of the metal nanoclusters. Photoluminescence is one of the most attractive properties, and there are a number of applications based on photoluminescence, including chemical sensing, biological imaging, cell labeling, photodynamic therapy, drug delivery, and the like. The fluorescent metal nanoclusters exhibit excellent photostability and biocompatibility compared to conventional photoluminescent materials. However, the photoluminescence effect of most of the metal nanoclusters is still unsatisfactory at present, and the photoluminescence quantum yield is low (generally lower than 5%), and the fluorescence emission wavelength is mainly in the visible light and near infrared bands. Meanwhile, compared with the traditional noble metal nanocluster (gold or silver), the aluminum nanocluster has more and more researches on the aluminum nanocluster due to the characteristic of good metal resonance response of the aluminum nanocluster extending to an ultraviolet band.
At present, the research on the fluorescence characteristics of the metal nanoclusters mainly comprises the regulation and control of photoluminescence emission intensity and emission wavelength. Generally, the following methods are mainly used: (1) modifying the surface ligands; (2) doping metal; (3) aggregation-induced emission; (4) external environmental conditioning, etc.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the aluminum nano-cluster with the fluorescence wavelength from ultraviolet to near ultraviolet, and the preparation method and the application thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of ultra-small aluminum nanoclusters with ultraviolet to near-ultraviolet fluorescence wavelengths is characterized in that aluminum halide is used as a reactant precursor, anion or cation surfactants carry out ion pairing on the synthesized aluminum nanoclusters modified by surface ligands, and the ultra-small aluminum nanoclusters which are uniformly dispersed, uniform in particle size, high in fluorescence quantum yield and adjustable and controllable in ultraviolet to near-ultraviolet fluorescence wavelengths are prepared by a strong reducing agent one-pot method.
The anionic or cationic surfactant comprises tetraoctyl ammonium bromide (TOAB), Dodecyl Dimethyl Benzyl Ammonium Chloride (DDBAC), Dodecyl Dimethyl Amine Oxide (DDAO), or diisooctyl succinate sodium sulfonate (AOT).
The molar ratio of the surfactant to the reactant precursor aluminum halide is 1:1 to 1: 3.
The aluminum halide comprises aluminum chloride 、 And (3) aluminum bromide.
The strong reducing agent comprises: sodium borohydride (NaBH) 4 ) Or lithium aluminum hydride (LiAlH) 4 ) In general, the molar ratio of the strong reducing agent to the aluminum halide is ensured to be between 1:1 and 1: 2.
The surface ligand includes an oleophilic ligand or a hydrophilic ligand.
The preparation method comprises the following steps:
1) weighing 3mmol tetraoctylammonium bromide in a dry container, adding 100ml of anhydrous xylene, and performing ultrasonic dispersion until a clear and transparent solution is obtained;
2) adding 1mmol of anhydrous aluminum chloride serving as a reactant precursor into the solution obtained in the step 1) for ultrasonic dispersion until the solution is gradually changed from light yellow to a colorless, clear and transparent solution;
3) removing the internal air of the solution obtained in the step 2) by a double-calandria operation technology (schlenk line), and introducing argon to ensure that the reaction is carried out in an anhydrous and oxygen-free environment;
4) magnetically stirring the solution obtained in the step 3) for 30min, and slowly adding 1ml of 2.4mol/L lithium aluminum hydride (LiAlH) 4 ) The tetrahydrofuran solution and the reaction system are continuously magnetically stirred for 1 hour under the protection of inert gas atmosphere;
5) after the reaction in the step 4) is finished, adding absolute methanol or absolute ethanol to quench excessive reducing agent;
6) adding tetradecylphosphonic acid serving as a ligand into the reaction system quenched in the step 5), simultaneously raising the reaction temperature to 130 ℃, preserving the temperature for 4 hours, and magnetically stirring under the protection of argon atmosphere;
7) removing anhydrous xylene as solvent by rotary evaporation with a rotary evaporator to obtain white powder, and dispersing the powder in polar solvent or nonpolar solvent again for purification and filtration to remove excessive surfactant;
8) and (5) repeatedly carrying out the washing operation in the step 7), and storing the clear solution obtained after washing to obtain the ultra-small aluminum nanocluster of ultraviolet fluorescence.
The other preparation method comprises the following steps:
1) weighing 0.01mol of diisooctyl succinate sodium sulfonate (AOT) in a dry container, adding 100ml of anhydrous xylene, and performing ultrasonic dispersion until a clear and transparent solution is obtained;
2）1.207g AlCl 3 ·6H 2 dissolving O in 5mL of Formamide (FA) to form a 1M precursor solution, adding to the solution obtained in step 1) above, and allowing [ FA to dissolve]/[AOT]In a molar ratio of (A), (B) to (C)W s ) Kept at 4;
3) removing the internal air of the solution obtained in the step 2) by a double-calandria operation technology (schlenk line), and introducing argon to ensure that the reaction is carried out in an anhydrous and oxygen-free environment;
4) magnetically stirring the solution obtained in the step 3) for 30min, and slowly adding 1ml of 2.4mol/L lithium aluminum hydride (LiA)lH 4 ) The tetrahydrofuran solution and the reaction system are continuously magnetically stirred for 1 hour under the protection of inert gas atmosphere;
5) after the reaction in the step 4) is finished, adding absolute methanol or absolute ethanol to quench excessive reducing agent;
6) adding tetradecylphosphonic acid serving as a ligand into the reaction system quenched in the step 5), simultaneously raising the reaction temperature to 130 ℃, preserving the temperature for 4 hours, and magnetically stirring under the protection of argon atmosphere;
7) removing anhydrous xylene as solvent by rotary evaporation with a rotary evaporator to obtain white powder, and dispersing the powder in polar solvent or nonpolar solvent again for purification and filtration to remove excessive surfactant;
8) and (5) repeatedly carrying out the washing operation in the step 7), and storing the clear solution obtained after washing to obtain the near-ultraviolet fluorescent ultra-small aluminum nano-cluster.
The ultra-small aluminum nano-cluster obtained by the preparation method is uniformly dispersed, has uniform particle size, has the fluorescence quantum yield higher than 20 percent and is the ultra-small aluminum nano-cluster with the ultraviolet or near-ultraviolet fluorescence wavelength of 2-4 nm.
The ultra-small aluminum nanocluster is used in the fields of photocatalysis, blue light LEDs, ultraviolet sensors or ultraviolet photoelectric detectors.
The invention has the beneficial effects that:
1) the ultra-small aluminum nano-cluster for regulating and controlling the wavelength of ultraviolet to near-ultraviolet fluorescence prepared by the invention has good dispersibility, high fluorescence quantum yield and adjustable and controllable fluorescence wavelength. The precise structure of the interior can be known, and further knowledge of the microstructure can be realized.
2) The ultra-small aluminum nanocluster prepared by the invention and used for regulating and controlling the wavelength of ultraviolet to near-ultraviolet fluorescence can be used in the fields of photocatalysis, blue-light LEDs, ultraviolet sensing, ultraviolet photoelectric detectors, biological imaging, chemical sensing and the like.
3) The ultra-small aluminum nanocluster regulated and controlled by the ultraviolet to near-ultraviolet fluorescence wavelength prepared by the invention has obvious advantages in the field of photocatalysis.
4) The synthetic route has the advantages of easily obtained raw materials, easily-implemented reaction conditions, easily-controlled operation and high product quality, and is an ultra-small aluminum nano cluster for regulating and controlling the wavelength from ultraviolet to near-ultraviolet fluorescence by using a solution method for the first time.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) and a spherical aberration correction transmission electron microscope (AC-TEM) of the small-sized uv to near-uv fluorescence wavelength-modulated ultra-small aluminum nanoclusters prepared in example 1, example 2, example 3, and example 4.
Fig. 2 is a particle size distribution diagram of the ultra-small aluminum nanoclusters prepared in example 1, example 2, example 3 and example 4 and controlled by small-size ultraviolet to near-ultraviolet fluorescence wavelength.
Fig. 3 shows the absorption spectrum and photoluminescence spectrum (UV-Vis & PL) of the small-sized ultra-small aluminum nanoclusters with ultraviolet to near-ultraviolet fluorescence wavelength modulation prepared in example 1, example 2, example 3 and example 4.
Fig. 4 is a uv-vis absorption spectrum and a photocatalytic power fit plot of photocatalytic resazurin reduction under uv irradiation for the ultra-small aluminum nanoclusters prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1: preparation of ultra-small aluminum nanoclusters for ultraviolet fluorescence
A preparation method of a simple and efficient ultra-small aluminum nano cluster for controlling small-size 3.35 +/-0.65 nm ultraviolet fluorescence comprises the following steps:
1) and in the experiment preparation stage, the glass containers such as the three-neck flask and the like are placed in an oven to be baked for 8 hours at 140 degrees, and the used glass containers are ensured to be sufficiently dried. 100ml of anhydrous xylene was poured into the flask and sealed with a rubber stopper. Then 3mmol of tetra-n-octyl ammonium bromide (TOAB) is weighed and put into xylene for ultrasonic dispersion until clear and transparent colorless solution is obtained; then 1mmol of anhydrous aluminum chloride (AlCl) is weighed 3 ) Adding the prepared reverse micelle solution into the solution to be subjected to ultrasonic treatment until AlCl is obtained 3 Are equally dividedDispersed in the solution. The reaction system was connected under a double row pipe system, the internal air was removed, and the system was purged with an inert gas, argon, for 20min at a flow rate of 1L/min.
2) 1ml of lithium aluminum hydride (LiAlH) was added to the solution 4 ) Wherein the concentration of lithium aluminum hydride is 2.4mol/L and the solvent is Tetrahydrofuran (THF), and magnetically stirring at room temperature for one hour.
3) Adding absolute ethyl alcohol to the solution in the step 2) after the reaction is finished to quench incompletely reacted lithium aluminum hydride (LiAlH) 4 )；
4) Adding tetradecylphosphonic acid serving as a ligand into the solution reacted in the step 3), raising the reaction temperature to 130 ℃, and preserving the temperature for 4 hours; the whole experiment was carried out under argon atmosphere and assisted by magnetic stirring.
5) And (5) carrying out rotary evaporation on the solution obtained in the step 4) to remove the solvent anhydrous xylene to obtain white powder. The white powder was then redispersed with ethanol and the supernatant was filtered. And repeating the washing for three times, and taking and storing the final supernatant to obtain the ultra-small aluminum nanocluster with ultraviolet fluorescence.
By observing the microstructure and surface morphology of the synthesized ultra-small aluminum nanoclusters for ultraviolet fluorescence emission by HRTEM and ACTEM, FIG. 1 (a) shows that the prepared ultra-small aluminum nanoclusters for ultraviolet fluorescence emission are generally spherical and uniformly dispersed. The spherical aberration electron microscope image of fig. 1 (e part) shows the surface morphology of the synthesized ultra-small aluminum nanocluster emitted by ultraviolet fluorescence, which shows good crystallinity.
Except for AlCl 3 For those skilled in the art, aluminum bromide and the like can also be used.
Example 2: preparation of near ultraviolet emitting ultra-small aluminum nanoclusters
We prepared ultra-small aluminum nanoclusters for near-ultraviolet fluorescence emission by different molar ratios of polar solvent to surfactant. Wherein the surfactant is selected from anionic surfactant sodium diisooctyl succinate (AOT) and polar solvent is selected from Formamide (FA).
1) In the experiment preparation stage, a three-neck flask and other glass containers are placed in an oven for baking at 140 ℃ for 8 hours to ensure the used glassThe container is sufficiently dry. 100ml of anhydrous xylene was poured into the flask, respectively, and sealed with a rubber stopper. 0.01mol of AOT is weighed out and dissolved in anhydrous xylene to ensure that the concentration is 0.1M. 1.207g AlCl 3 ·6H 2 O was dissolved in 5mL formamide to form a 1M precursor solution. By adding a certain amount of AlCl 3 ·6H 2 Formamide solution of O, [ FA ]]/[AOT]In a molar ratio of (A), (B) to (C)W s ) Held at 4. The reaction system was connected to a double row tube system, the internal air was removed, and the system was purged with an inert gas, argon, for 20min at a flow rate of 1L/min.
2) 1ml of lithium aluminum hydride (LiAlH) was added to the solution 4 ) Wherein the concentration of lithium aluminum hydride is 2.4mol/L and the solvent is Tetrahydrofuran (THF), and magnetically stirring at room temperature for one hour.
3) Adding absolute ethyl alcohol to the solution in the step 2) after the reaction is finished to quench incompletely reacted lithium aluminum hydride (LiAlH) 4 )；
After four hours of reaction, ethanol was added to the solution to quench the reaction.
4) Adding tetradecylphosphonic acid into the solution reacted in the step 3) as a surface ligand, raising the reaction temperature to 130 ℃, and preserving the temperature for 4 hours; the whole experiment process is carried out in the argon atmosphere and is assisted by magnetic stirring;
5) and (3) performing rotary evaporation on the solution in the step 4) to remove the solvent anhydrous xylene to obtain white powder, and then re-dispersing the white powder in n-hexane. And extracting to obtain the surface-modified ultra-small aluminum nanoclusters by utilizing the difference of the solubility of AOT in Dimethylformamide (DMF) and cyclohexane.
By observing the microstructure and surface morphology of the synthesized near-ultraviolet fluorescence-emitting ultra-small aluminum nanoclusters HRTEM and ACTEM, FIG. 1 (section d) shows that the prepared ultraviolet fluorescence-emitting ultra-small aluminum nanoclusters are generally spherical and uniformly dispersed. The spherical aberration electron microscope image of fig. 1 (e part) shows the surface morphology of the synthesized ultra-small aluminum nanocluster emitted by ultraviolet fluorescence, which shows good crystallinity.
Example 3 and example 4
In specific examples 3 and 4, we achieved the fluorescence wavelength modulation shown in fig. 3 by changing the kind of cationic surfactant. Wherein the cationic surfactant Dodecyl Dimethyl Benzyl Ammonium Chloride (DDBAC) was used in example 3 and Dodecyl Dimethyl Amine Oxide (DDAO) was used in example 4. Specific embodiments reference is made to example 1.
For the above embodiment, it was observed that the fluorescence wavelength was red-shifted from 297nm to 415nm with a significant increase in quantum yield by changing the ultra-small aluminum nanocluster surface ion coordination (as shown in table 1 below).
TABLE 1
| Sample(s) | Absorption Peak (nm) | Fluorescence wavelength (nm) | Quantum yield (%) |
| TOAB-AlNCs | 273 | 293 | 21.6% |
| DDBAC-AlNCs | 266 | 300 | 15.4% |
| DDAO-AlNCs | 275 | 312 | 21.4% |
| AOT-AlNCs | 337 | 425 | 7.8% |
Example 5 photocatalytic application of ultra-small aluminum nanoclusters
The spectral response of the prepared ultra-small aluminum nanocluster is in an ultraviolet band, and the photon energy of the ultra-small aluminum nanocluster is higher than that of the nano structures corresponding to other wavelengths, so that the efficiency of the photocatalyst based on the ultra-small aluminum nanocluster is higher. The specific photocatalytic experiment steps are as follows:
1) different masses of the prepared ultra-small aluminum nanoclusters were added to a 1.5mg/L solution of resazurin (Rz) in a 3ml cuvette. And also in blank control experiments.
2) Before the light, these suspensions were stirred in the dark to ensure that an adsorption equilibrium was established on the surface of Rz.
3) The experimental and blank controls were then simultaneously irradiated with a 350mW uv lamp having a peak wavelength of 400 nm. The uv-vis absorption spectra were recorded every two minutes.
Since Rz is a redox indicator, it can be judged whether to reduce to Resorufin (RF) by changing its color from blue (Rz) to pink (RF), as shown in fig. 4 (part a). Without the addition of the ultra-small aluminum nanocluster sample, photocatalytic decolorization of Rz is not achieved under Ultraviolet (UV) illumination, as shown in fig. 4 (part b). It can also be seen that the photocatalytic activity and efficiency of ultra-small aluminum nanoclusters increases as the mass of the ultra-small aluminum nanoclusters increases. The effect of the initial concentration of the solution on the rate of photocatalytic degradation of most organic compounds is described by quasi-first order kinetics which are fitted according to the Langmuir-Hinshelwood model: in (a), (b)C/C 0 )=-kt whereinkIs the rate constant of the quasi-first order reaction. The first order rate constant obtained (k) 0.0662, 0.06046, 0.04845 and 0.03656 min respectively -1 (corresponding to ultra-small aluminum nanoclusters of different masses, respectively) shows good resultsThe photocatalytic activity of the nano-alumina photocatalyst shows wide application prospect in the field of photocatalysis based on ultra-small aluminum nano-clusters.
For those skilled in the art, the ultra-small aluminum nanoclusters prepared in the embodiments can also be used for manufacturing a GaN-based blue LED by using ultraviolet to near-ultraviolet fluorescence emission, and the ultraviolet plasmons thereof are used for improving the quantum yield of natural fluorescence of biomolecules (such as DNA, peptides and proteins) to realize ultraviolet biosensing and manufacturing solar blind detectors and the like by using the separated electron energy level and strong absorption of UVB band.
The embodiments in the above description can be further combined or replaced, and the embodiments are only described as preferred examples of the present invention, and do not limit the concept and scope of the present invention, and various changes and modifications made to the technical solution of the present invention by those skilled in the art without departing from the design concept of the present invention belong to the protection scope of the present invention. The scope of the invention is given by the appended claims and any equivalents thereof.
Claims (10)
1. A preparation method of ultra-small aluminum nanoclusters with ultraviolet to near-ultraviolet fluorescence wavelengths is characterized in that aluminum halide is used as a reactant precursor, anion or cation surfactants carry out ion pairing on the synthesized aluminum nanoclusters modified by surface ligands, and a strong reducing agent one-pot method is utilized to prepare the ultra-small aluminum nanoclusters which are uniformly dispersed, uniform in particle size, high in fluorescence quantum yield and adjustable and controllable in ultraviolet to near-ultraviolet fluorescence wavelengths.
2. The method of claim 1, wherein the anionic or cationic surfactant comprises tetraoctylammonium bromide (TOAB), dodecyldimethylbenzylammonium chloride (DDBAC), dodecyldimethylammonium oxide (DDAO), or sodium diisooctylsulfosuccinate (AOT).
3. The method of claim 1, wherein the molar ratio of the surfactant to the reactant precursor aluminum halide is from 1:1 to 1: 3.
4. The method of claim 1 wherein the aluminum halide comprises aluminum chloride 、 And (3) aluminum bromide.
5. The method of claim 1, wherein the strong reducing agent comprises: sodium borohydride (NaBH) 4 ) Or lithium aluminum hydride (LiAlH) 4 ) Generally, the molar ratio of the strong reducing agent to the aluminum halide is ensured to be between 1:1 and 1: 2.
6. The method of claim 1, wherein the surface ligand comprises an oleophilic ligand or a hydrophilic ligand.
7. The method of claim 1, comprising the steps of:
1) weighing 3mmol tetraoctylammonium bromide in a dry container, adding 100ml of anhydrous xylene, and performing ultrasonic dispersion until a clear and transparent solution is obtained;
2) adding 1mmol of anhydrous aluminum chloride serving as a reactant precursor into the solution obtained in the step 1) for ultrasonic dispersion until the solution is gradually changed from light yellow to a colorless, clear and transparent solution;
3) removing the internal air of the solution obtained in the step 2) by a double-calandria operation technology (schlenk line), and introducing argon to ensure that the reaction is carried out in an anhydrous and oxygen-free environment;
4) magnetically stirring the solution obtained in the step 3) for 30min, and slowly adding 1ml of 2.4mol/L lithium aluminum hydride (LiAlH) 4 ) The tetrahydrofuran solution and the reaction system are continuously magnetically stirred for 1 hour under the protection of inert gas atmosphere;
5) after the reaction in the step 4) is finished, adding absolute methanol or absolute ethanol to quench excessive reducing agent;
6) adding tetradecylphosphonic acid serving as a ligand into the reaction system quenched in the step 5), simultaneously raising the reaction temperature to 130 ℃, preserving the temperature for 4 hours, and magnetically stirring under the protection of argon atmosphere;
7) removing anhydrous xylene as solvent by rotary evaporation with a rotary evaporator to obtain white powder, and dispersing the powder in polar solvent or nonpolar solvent again for purification and filtration to remove excessive surfactant;
8) and (5) repeatedly carrying out the washing operation in the step 7), and storing the clear solution obtained after washing to obtain the ultra-small aluminum nanocluster of ultraviolet fluorescence.
8. The method of claim 1, comprising the steps of:
1) weighing 0.01mol of diisooctyl succinate sodium sulfonate (AOT) in a dry container, adding 100ml of anhydrous xylene, and performing ultrasonic dispersion until a clear and transparent solution is obtained;
2）1.207g AlCl 3 ·6H 2 dissolving O in 5mL of Formamide (FA) to form a 1M precursor solution, adding to the solution obtained in step 1) above, and allowing [ FA to dissolve]/[AOT]The molar ratio of (a) to (b) is maintained at 4;
3) removing the internal air of the solution obtained in the step 2) by a double-calandria operation technology (schlenk line), and introducing argon to ensure that the reaction is carried out in an anhydrous and oxygen-free environment;
4) magnetically stirring the solution obtained in the step 3) for 30min, and slowly adding 1ml of 2.4mol/L lithium aluminum hydride (LiAlH) 4 ) The tetrahydrofuran solution and the reaction system are continuously magnetically stirred for 1 hour under the protection of inert gas atmosphere;
5) after the reaction in the step 4) is finished, adding absolute methanol or absolute ethanol to quench excessive reducing agent;
6) adding tetradecylphosphonic acid serving as a ligand into the reaction system quenched in the step 5), simultaneously raising the reaction temperature to 130 ℃, preserving the temperature for 4 hours, and magnetically stirring under the protection of argon atmosphere;
7) removing anhydrous xylene as solvent by rotary evaporation with a rotary evaporator to obtain white powder, and dispersing the powder in polar solvent or nonpolar solvent again for purification and filtration to remove excessive surfactant;
8) and (5) repeatedly carrying out the washing operation in the step 7), and storing the clear solution obtained after washing to obtain the near-ultraviolet fluorescent ultra-small aluminum nano-cluster.
9. The ultra-small aluminum nanoclusters obtained by the preparation method according to any one of claims 1 to 8, wherein the ultra-small aluminum nanoclusters are ultra-small aluminum nanoclusters which are uniformly dispersed, have uniform particle size and fluorescence quantum yield higher than 20% and have a fluorescence wavelength of 2 to 4nm in ultraviolet or near ultraviolet.
10. The ultra-small aluminum nanocluster of claim 9, being used in the fields of photocatalysis, blue LED, uv sensing, uv detectors, bio-imaging, or chemical sensing.
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