CN115608382A - Semiconductor nanocrystalline aggregate and preparation method and application thereof - Google Patents
Semiconductor nanocrystalline aggregate and preparation method and application thereof Download PDFInfo
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- CN115608382A CN115608382A CN202211299796.6A CN202211299796A CN115608382A CN 115608382 A CN115608382 A CN 115608382A CN 202211299796 A CN202211299796 A CN 202211299796A CN 115608382 A CN115608382 A CN 115608382A
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/23—
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- B01J35/39—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention belongs to the technical field of nano photocatalysis, and particularly relates to a semiconductor nanocrystalline aggregate, a preparation method thereof and application thereof in photocatalytic organic synthesis. The invention provides a preparation method of a semiconductor nanocrystal aggregate, which comprises the following steps: providing a monodisperse core-shell nanocrystal solution; purifying, namely performing surface treatment on the monodisperse core-shell nanocrystal solution to reduce the number of ligands on the surface of the nanocrystal to obtain the nanocrystal with insufficient ligand amount; dispersing the surface-treated nanocrystalline solution into an organic solvent to enable the nanocrystals to aggregate, thereby obtaining the nanocrystalline aggregate. The invention provides a preparation method of a semiconductor nanocrystal aggregate, which is simple and easy to control and is suitable for various types of nanocrystals. Compared with monodisperse spherical shell CdSe/CdS core-shell nanocrystals, the nanocrystal aggregate has higher photocatalytic efficiency.
Description
Technical Field
The invention belongs to the technical field of nano photocatalysis, and particularly relates to a semiconductor nanocrystal aggregate, a preparation method thereof and application thereof in photocatalytic organic synthesis.
Background
The semiconductor photocatalysis technology is an environment-friendly green chemical technology which is driven by taking solar energy as an energy source and taking a semiconductor material as a catalyst. The solar energy can be converted into chemical energy, heat energy and the like to be effectively utilized, and the characteristics of mild reaction conditions, simple operation, low cost, capability of catalyzing reactions which are difficult to carry out by the traditional method and the like are widely researched by scientific researchers in various countries. Among them, the semiconductor material of nanometer level is an emerging photocatalyst, which has received great attention due to its unique optical and optoelectronic properties.
Semiconductor nanocrystals include materials such as quantum dots, nanorods, and nanodiscs, and are generally composed of an internal inorganic crystal and a surface-coated organic ligand. Compared with the traditional photocatalyst of organic dye and bulk semiconductor material, the nanocrystal has the advantages of long service life of an excited state, adjustable oxidation-reduction potential, large extinction coefficient, wide spectrum absorption range, easy regulation and control of current carriers, large specific surface area and the like, and is widely used in the fields of photolysis of water to produce hydrogen, reduction of carbon dioxide, treatment of organic dye in sewage, photocatalytic organic conversion and the like.
Although semiconductor nanocrystals are widely used, the catalytic efficiency of using semiconductor nanocrystals as photocatalysts is generally low according to current reports. Research shows that a large number of organic ligands coated on the surface of the nanocrystalline can block transmission of photo-generated electrons and holes to acceptor molecules, so that the photocatalytic efficiency is reduced to a certain extent. There is literature showing that catalytic efficiency can be improved by removing or changing the surface ligands of the nanocrystals, as Erwin Reisner et al report in 2016 that the hydrogen production rate of ligand-free "bare" CdS quantum dots is 175 times higher than that of mercaptopropionic acid capped quantum dots. Emily a. Weiss et al, 2017 reported in the literature that C-C coupling rates of 1-phenylpyrrolidine and trans-phenylcinnamon sulfone could be increased by changing the ligand composition on the surface of CdS quantum dots. Besides, in addition to optimizing the surface of the quantum dot, self-assembly of the quantum dot is also a way to improve the photocatalytic efficiency, and wu li bead et al mentioned in 2019 that the quantum dot and the cocatalyst are encapsulated in a limited medium, such as micelle, because the movement of the quantum dot and the cocatalyst is greatly limited, the interaction between the quantum dot and the cocatalyst is changed from dynamic state to quasi-static state, thereby increasing the probability of interface electron transfer.
Vitamin E is also called tocopherol, is an antioxidant and a nutrient with excellent performance, and is widely applied to the fields of medicines, foods, feeds, cosmetics and the like. The 2,3, 5-Trimethylhydroquinone (TMHQ) can be condensed with the side chain of isophytol to obtain the vitamin E, and is an important intermediate for synthesizing the vitamin E industrially. In recent years, the market demand for synthesizing the vitamin E from the TMHQ is large, but only a few companies produce the TMHQ in China at present and the demand of the vitamin E cannot be met. Due to insufficient domestic supply, china needs to import a large amount of TMHQ, so that the synthesized TMHQ has good application value and higher economic benefit. 2,3, 5-trimethylbenzoquinone is a good electron acceptor for semiconductor nanocrystals, is also a precursor for preparing TMHQ, and provides a possible way for synthesizing TMHQ by photocatalytic reduction of 2,3, 5-trimethylbenzoquinone by using nanocrystals.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a semiconductor nanocrystal aggregate, a preparation method thereof and application thereof in photocatalytic organic synthesis.
In order to solve the problems, the invention adopts the technical scheme that:
in a first aspect, the present invention provides a method for preparing a semiconductor nanocrystal aggregate, comprising the steps of:
providing a monodisperse core-shell nanocrystal solution;
purifying, namely performing surface treatment on the monodisperse core-shell nanocrystal solution to reduce the number of ligands on the surface of the nanocrystal to obtain the nanocrystal with insufficient ligand amount;
dispersing the surface-treated nanocrystalline solution into an organic solvent to enable the nanocrystals to aggregate, thereby obtaining the nanocrystalline aggregate.
Preferably, the thin shell layer of the core-shell nanocrystal is spherical or irregular hexahedron.
Preferably, the shell layer of the spherical core-shell nanocrystal is a thin layer with one atomic layer to four atomic layers, and the shell layer of the irregular hexahedron-shaped core-shell nanocrystal is a medium-thick layer with four atomic layers to ten atomic layers.
Preferably, the core layer and shell layer materials of the monodisperse core-shell nanocrystal are respectively and independently selected from at least one of oxides, sulfides, selenides and antimonides of transition metals.
Preferably, the core layer and shell layer materials of the monodisperse core-shell nanocrystal are each independently selected from at least one of CdS, cdSe, cdTe, znS, znSe, cuS, and MnS.
Preferably, the core layer of the monodisperse core-shell nanocrystal is CdSe, and the shell layer is CdS.
Preferably, the ligand in the monodisperse core-shell nanocrystal is at least one selected from carboxylate ligand, thiolate ligand, amine ligand, sulfur ligand and phosphine ligand, and is preferably oleylamine ligand with relatively weak coordination ability.
Preferably, the purification step comprises: adding a poor solvent of the nanocrystals into the monodisperse core-shell nanocrystal solution, centrifugally precipitating at a certain temperature, dispersing the nanocrystals into the good solvent, and repeating for multiple times; preferably, the poor solvent is selected from at least one of short-chain alcohol, acetone, acetonitrile and ethyl acetate, the short-chain alcohol is more preferably methanol, and the good solvent is selected from at least one of hexane, octane, toluene and chloroform, and is more preferably hexane.
Preferably, after purification, the number of surface ligands of the core-shell nanocrystal is reduced by more than 90%.
In a second aspect, the present invention also provides a semiconductor nanocrystal aggregate prepared by the preparation method described above.
In a third aspect, the invention also provides the application of the semiconductor nanocrystal aggregate in photocatalytic synthesis of 2,3, 5-trimethylhydroquinone.
Preferably, the method comprises the following steps:
preparing a semiconductor nanocrystal aggregate solution according to the preparation method as described above;
adding 2,3, 5-trimethylbenzoquinone, benzyl alcohol and a reaction solvent into the semiconductor nanocrystal aggregate solution;
the mixed solution was irradiated with 520nm green light, and the concentration of the product 2,3, 5-trimethylhydroquinone was monitored by sampling in the middle of the reaction using a sampling needle, and characterized and quantified by GC-FID.
Preferably, the reaction solvent is toluene or n-hexane.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of a semiconductor nanocrystal aggregate, which is simple and easy to control and is suitable for various types of nanocrystals. Compared with monodisperse spherical shell CdSe/CdS core-shell nanocrystals, the nanocrystal aggregate has higher photocatalytic efficiency. The invention also provides a photocatalysis system for synthesizing hydroquinone substances, compared with the traditional dispersed nanocrystalline, the nanocrystalline aggregate is used as the photocatalyst, the generation rate of hydroquinone can be obviously accelerated, and the reaction is a complete reaction without additionally adding an electron or hole sacrificial agent.
Drawings
FIG. 1 is a transmission electron microscope image of (a) dispersed nanocrystals, (b) surface-treated nanocrystal aggregates, and (c) particle size distribution of spherical shell CdSe/CdS core-shell nanocrystals synthesized in example 1 of the present invention.
FIG. 2 is a transmission electron microscope image of (a) dispersed nanocrystals, (b) surface-treated nanocrystal aggregates, (c) a distribution of triangular nanocrystals (height corresponding to side length) and (d) a distribution of tetragonal nanocrystals (side length) of CdSe/CdS core/shell nanocrystals having medium-thickness shells, which were synthesized in example 2 and simultaneously containing triangles and cubes, according to the present invention.
FIG. 3 is the chemical reaction formula of the constructed photocatalytic system for synthesizing 2,3, 5-trimethylhydroquinone.
FIG. 4 is a graph showing the change of the concentration of 2,3, 5-trimethylhydroquinone photocatalytically formed in example 3 and comparative example 1 according to the present invention with respect to the time of light irradiation.
FIG. 5 is a graph showing the change of the concentration of 2,3, 5-trimethylhydroquinone photocatalytically formed in example 4 and comparative example 2 according to the present invention with respect to the time of light irradiation.
FIG. 6 (a) is a transmission electron micrograph (b) of the dispersed spherical CdSe nanocrystals used in comparative example 3, which is a graph showing the concentration of 2,3, 5-trimethylhydroquinone photocatalytically formed in example 5 and comparative example 3 according to the present invention as a function of the time of illumination.
FIG. 7 (a) is a transmission electron micrograph (b) of dispersed CdSe/CdS point-and-rod structured nanocrystals used in comparative example 4, which is a graph showing the change of the concentration of 2,3, 5-trimethylhydroquinone photocatalytically formed in example 6 and comparative example 4 according to the present invention with respect to the time of light irradiation.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
In the embodiment of the invention, several different types of semiconductor nanocrystal aggregates are prepared and are respectively used for photocatalytic organic synthesis of hydroquinone substances.
In a first aspect, embodiments of the present invention provide a method for preparing a semiconductor nanocrystal aggregate, in which an organic solvent is added to a semiconductor nanocrystal solution with a small amount of surface ligand, and the semiconductor nanocrystal solution is aggregated to directly prepare the semiconductor nanocrystal aggregate. The method comprises the following steps:
step one, synthesizing a monodisperse semiconductor nanocrystal of a target type;
step two, purification is carried out, the number of ligands on the surface of the nanocrystalline is reduced, and nanocrystalline with insufficient ligand amount is obtained;
and step three, dispersing the surface-treated nanocrystals into a certain amount of organic solvent to enable the nanocrystals to aggregate, thereby obtaining nanocrystal aggregates.
In the invention, the purification operation in the first step is as follows: poor solvents for quantum dots (methanol, acetone, acetonitrile, chloroform, ethyl acetate, etc.) are added to the quantum dot solution to reduce the number of nanocrystal ligands by more than 95%, with methanol being preferred.
In the invention, the organic solvent in the second step is specifically one of toluene, n-hexane or cyclohexane.
In a second aspect, embodiments of the present invention provide a semiconductor nanocrystal aggregate obtained by the above preparation method.
The semiconductor nanocrystal aggregate comprises II B-VI A group, IV A-VI B group and perovskite quantum dots) and core-shell structure nanocrystals which are formed by combining the II B-VI A group, the IV A-VI B group and the perovskite quantum dots and have different shell thicknesses and different shell appearances, and CdSe, cdSe/CdS core-shell structures, cdSe/CdS dot-rod structures and CdSe/ZnSe core-shell structure nanocrystals with different sizes are preferably selected.
The semiconductor nanocrystal aggregate can be characterized by an ultraviolet-visible absorption spectrum, a steady-state fluorescence spectrum, a transient fluorescence spectrum, a transmission electron microscope, an X-ray diffraction pattern, an X-ray photoelectron spectrum, a dynamic light scattering particle size analyzer and the like.
Compared with dispersed nanocrystals, the semiconductor nanocrystal aggregate obtained by the invention has higher photocatalytic efficiency.
In a third aspect, embodiments of the present invention provide an application of the semiconductor nanocrystal aggregate in the construction of a photocatalytic system.
In the present invention, the photocatalytic system comprises: the semiconductor nanocrystal aggregate prepared as described above, an electron acceptor, a hole acceptor, a reaction solvent, and visible light.
In the invention, the electron acceptor is selected from quinone substances, and the hole acceptor is selected from alcohol substances.
In the invention, the reaction solvent is one of toluene, n-hexane, cyclohexane, and two-phase solution of toluene, n-hexane and cyclohexane and acetonitrile.
In the invention, the visible light is more than 500nm, and the common green light of 520nm can be provided by an LED lamp, a laser and the like.
In a fourth aspect, embodiments of the present invention provide the use of the above-described photocatalytic system for the synthesis of 2,3, 5-trimethylhydroquinone. The method comprises the following steps:
step one, preparing a semiconductor nanocrystalline aggregate solution;
step two, adding 2,3, 5-trimethylbenzoquinone, benzyl alcohol and a reaction solvent into the semiconductor nanocrystal aggregate solution;
and step three, placing the mixed solution under 520nm green light for irradiation to generate the 2,3, 5-trimethylhydroquinone.
In the invention, the reaction for synthesizing the 2,3, 5-trimethylhydroquinone can be carried out at room temperature without heating.
In the invention, the reaction solvent is one of toluene, normal hexane, cyclohexane, and two-phase solution of the toluene, the normal hexane, the cyclohexane and acetonitrile.
The present invention will now be described in further detail with reference to specific embodiments and with reference to the accompanying drawings. The following examples are some, but not all, examples of the present invention.
Example 1
A method for preparing a spherical thin shell CdSe/CdS core-shell nanocrystal aggregate comprises the following steps:
(1) Preparing CdSe core nano-crystal: 0.2mmol of cadmium oxide, 0.8mmol of stearic acid and 3mL of octadecene are added into a 50mL three-necked flask, nitrogen is blown at room temperature for slow stirring for 10min, and the temperature is raised to 260 ℃ to dissolve the cadmium oxide. And dispersing 1mmol of selenium powder into 10mL of ODE, and performing ultrasonic treatment for 15min to obtain 0.1mol/L selenium suspension. And (3) quickly injecting 1mL of selenium suspension into a rapidly-stirred three-neck flask, keeping stirring and heating for 7min to obtain the CdSe nano-crystalline solution with the diameter of about 2.8 nm. Stopping reaction, taking out the nanocrystal solution, putting the nanocrystal solution into a glass bottle filled with acetone and methanol mixed solution precipitator for precipitation, centrifuging, dissolving the precipitate in toluene, adding methanol again for precipitation, centrifuging, and dissolving the precipitate in n-hexane for later use.
(2) Growing the CdS shell: 0.0175mmol of cadmium chloride, 0.4mmol of cadmium acetate dihydrate, 1.2mmol of oleic acid, 0.4mmol of decacid and 8mL of octadecene are added into a 50mL three-neck flask, nitrogen is blown at the temperature of 150 ℃ for slow stirring for 30min, and all purified CdSe nanocrystal solution is injected. And dispersing 1mmol of sulfur powder into 10mL of ODE, and performing ultrasonic treatment until the sulfur powder is completely dissolved to obtain 0.1mol/L sulfur octadecene (S-ODE) solution. And then heating to 260 ℃, dripping an S-ODE solution into the flask by using an automatic sample injector when the temperature reaches 230 ℃, keeping stirring and heating for 20min to obtain a spherical shell CdSe/CdS core-shell nanocrystal solution with the diameter of about 4.7 nm. Stopping the reaction, taking out the nanocrystal solution, putting the nanocrystal solution into a glass bottle filled with acetone and methanol mixed solution precipitator for precipitation, centrifuging, and dissolving the precipitate in toluene; methanol was added for precipitation, centrifuged, the precipitate was dissolved in toluene and the procedure was repeated 3 times.
(3) 100nmol of spherical shell CdSe/CdS core-shell quantum dots, 2mL of oleylamine, 1mL of 0.1mol/L S-ODE and 1mL of ODE are added into a 50mL three-neck flask, nitrogen is blown at room temperature to stir for 10min at a slow speed, and the temperature is raised to 120 ℃ and kept for 20min. Methanol was added at room temperature for precipitation, centrifuged, the precipitate was dissolved in toluene, 0.1mL of Trioctylphosphine (TOP) was added and mixed well, and left overnight.
(4) And adding methanol to the spherical thin shell CdSe/CdS core-shell nanocrystal solution subjected to ligand exchange for precipitation and purification, so that the number of ligands on the surface of the nanocrystal is reduced, the nanocrystal with insufficient ligands is obtained, and the nanocrystal is generally purified by using methanol for 2 times. And (3) adding 1mL of n-hexane into a glove box to dissolve the nanocrystal precipitate, and then adding a certain amount of n-hexane to aggregate the nanocrystals to obtain the spherical thin shell CdSe/CdS core-shell nanocrystal aggregate.
Example 2
A method for preparing a CdSe/CdS core-shell nanocrystal aggregate with a medium-thickness shell containing triangles and cubes simultaneously comprises the following steps:
(1) The same procedure as in example 1 for synthesizing CdSe quantum dots.
(2) Growing the CdS shell: 0.0175mmol of cadmium chloride, 0.5mmol of cadmium acetate dihydrate, 1.55mmol of oleic acid, 0.52mmol of decacid and 5mL of octadecene are added into a 50mL three-neck flask, nitrogen is blown at the temperature of 150 ℃ for slow stirring for 30min, and all purified CdSe nanocrystal solution is injected. And dispersing 1mmol of sulfur powder into 10mL of ODE, and performing ultrasonic treatment until the sulfur powder is completely dissolved to obtain 0.1mol/L sulfur octadecene (S-ODE) solution. And then heating to 260 ℃, dripping an S-ODE solution into the flask by using an automatic sample injector when the temperature reaches 230 ℃, keeping stirring and heating for 40min to obtain the CdSe/CdS (cadmium selenide/cadmium sulfide) core-shell nanocrystal with a medium-thickness shell, wherein the medium-thickness shell simultaneously contains triangles (the side length is about 6.7 nm) and cubes (the side length is about 6.4 nm). Stopping the reaction, taking out the nanocrystalline solution, putting the nanocrystalline solution into a glass bottle filled with a precipitator of the mixed solution of acetone and methanol for precipitation, centrifuging, and dissolving the precipitate in toluene; methanol was added for precipitation, centrifuged, the precipitate was dissolved in toluene, and the operation was repeated 3 times.
(3) 100nmol of CdSe/CdS core-shell nano-crystal with triangular and cubic medium-thickness shells, 2mL of oleylamine, 1mL of 0.1mol/L of S-ODE and 1mL of ODE are added into a 50mL three-neck flask, nitrogen is blown at room temperature to slowly stir for 10min, the temperature is increased to 120 ℃, and the temperature is kept for 20min. Methanol is added at room temperature for precipitation, the mixture is centrifuged, the precipitate is dissolved in toluene, 0.1mL of Trioctylphosphine (TOP) is added and mixed evenly, and the mixture is placed overnight.
(4) And adding methanol into the CdSe/CdS core-shell nanocrystal solution with the medium-thickness shell layers of the triangle and the cube after ligand exchange for precipitation and purification, so as to reduce the number of the ligands on the surface of the nanocrystal and obtain the nanocrystal with insufficient ligand, wherein the nanocrystal is generally purified by using methanol for 2 times. And (3) adding 1mL of n-hexane into a glove box to dissolve the nanocrystal precipitate, and then adding a certain amount of n-hexane to aggregate the nanocrystals to obtain the spherical thin shell CdSe/CdS core-shell nanocrystal aggregate.
Example 3
An application of 2,3, 5-trimethylhydroquinone in photocatalytic synthesis based on a spherical thin shell CdSe/CdS core-shell nanocrystal aggregate. Comprises the following steps:
taking spherical thin-shell CdSe/CdS core-shell nanocrystal aggregates (the amount of the nanocrystal aggregates is determined by an absorption spectrum, ensuring that the absorbance of the ultraviolet-visible absorption spectrum of the nanocrystals in the reaction solution at 520nm is 0.1), 0.5mL of 0.1mol/L of 2,3, 5-trimethylbenzoquinone, 2mL of 0.4mol/L of benzyl alcohol and toluene (supplementing toluene until the total volume of the solution is 4 mL) into a 15mL glass bottle, and placing the mixed solution under a 6W 520nm LED lamp for irradiation. The concentration of the product 2,3, 5-trimethylbenzoquinone was monitored by sampling the reaction using a sampling needle, and characterized and quantified by GC-FID.
Comparative example 1
An application of 2,3, 5-trimethylhydroquinone prepared by photocatalysis based on dispersed spherical shell CdSe/CdS core-shell nano-crystals. Comprises the following steps:
taking dispersed spherical shell CdSe/CdS core-shell nanocrystals (the amount of the dispersed nanocrystals is determined by an absorption spectrum, ensuring that the absorbance of the ultraviolet-visible absorption spectrum of the nanocrystals in the reaction solution at 520nm is 0.1), 0.5mL of 0.1mol/L of 2,3, 5-trimethylbenzoquinone, 2mL of 0.4mol/L benzyl alcohol and toluene (supplementing toluene until the total volume of the solution is 4 mL) into a 15mL glass bottle, and placing the mixed solution under a 6W 520nm LED lamp for irradiation. The concentration of the product 2,3, 5-trimethylbenzoquinone was monitored by sampling the reaction using a sampling needle, and characterized and quantified by GC-FID.
FIG. 4 is a graph showing the concentration of 2,3, 5-trimethylhydroquinone produced by photocatalysis in example 3 and comparative example 1 as a function of illumination time, from which we can see that the spherical shell CdSe/CdS core-shell nanocrystal aggregates have higher catalytic rates than the dispersed nanocrystals.
Example 4
An application of photo-catalytic synthesis of 2,3, 5-trimethylhydroquinone based on a medium-thickness shell CdSe/CdS core-shell nano-crystalline aggregate containing triangles and cubes simultaneously. Comprises the following steps:
taking a CdSe/CdS core-shell nanocrystal aggregate (the amount of the nanocrystal aggregate is determined by an absorption spectrum, and the absorbance of the ultraviolet-visible absorption spectrum of the nanocrystal in the reaction solution at 520nm is ensured to be 0.1), 0.5mL of 0.1mol/L2, 3, 5-trimethylbenzoquinone, 2mL of 0.4mol/L benzyl alcohol and toluene (toluene is supplemented until the total volume of the solution is 4 mL) into a 15mL glass bottle, and placing the mixed solution under a 520W LED lamp with the wavelength of 520nm for irradiation. The concentration of the product 2,3, 5-trimethylbenzoquinone was monitored by sampling the reaction using a sampling needle, and characterized and quantified by GC-FID.
Comparative example 2
An application of 2,3, 5-trimethylhydroquinone is prepared by photo-catalytic synthesis of dispersed CdSe/CdS core-shell nano-crystals with triangle and cube middle-thick shells. Comprises the following steps:
taking dispersed CdSe/CdS core-shell nanocrystals with medium-thickness shells containing triangles and cubes simultaneously (the amount of the dispersed nanocrystals is determined by an absorption spectrum, and ensuring that the absorbance of the ultraviolet-visible absorption spectrum of the nanocrystals in the reaction solution at 520nm is 0.1), 0.5mL of 0.1mol/L2, 3, 5-trimethylbenzoquinone, 2mL of 0.4mol/L benzyl alcohol and toluene (toluene is supplemented until the total volume of the solution is 4 mL) into a 15mL glass bottle, and placing the mixed solution under a 6W 520nm LED lamp for irradiation. The concentration of the product 2,3, 5-trimethylbenzoquinone was monitored by sampling the reaction using a sampling needle, and characterized and quantified by GC-FID.
FIG. 5 is a graph showing the change of concentration of 2,3, 5-trimethylhydroquinone produced by photocatalysis according to illumination time in example 4 and comparative example 2, from which we can see that the medium-thickness shell CdSe/CdS core-shell nanocrystal aggregates containing triangles and cubes have higher catalytic rate than the dispersed nanocrystals.
Example 5
An application of 2,3, 5-trimethylhydroquinone in photocatalytic synthesis based on spherical CdSe nanocrystalline aggregates. Comprises the following steps:
taking spherical CdSe nanocrystal aggregates (the amount of the nanocrystal aggregates is determined by an absorption spectrum, ensuring that the absorbance of the ultraviolet-visible absorption spectrum of the nanocrystals in the reaction solution at 520nm is 0.1), 0.5mL of 0.1mol/L of 2,3, 5-trimethylbenzoquinone, 2mL of 0.4mol/L of benzyl alcohol and toluene (supplementing toluene till the total volume of the solution is 4 mL) into a 15mL glass bottle, and placing the mixed solution under a 520-nm LED lamp of 6W for irradiation. The concentration of the product 2,3, 5-trimethylbenzoquinone was monitored by sampling the reaction using a sampling needle, and characterized and quantified by GC-FID.
Comparative example 3
An application of 2,3, 5-trimethylhydroquinone in photocatalytic synthesis based on dispersed spherical CdSe nanocrystals. Comprises the following steps:
and (3) taking the dispersed spherical CdSe nanocrystals (the amount of the dispersed nanocrystals is determined by an absorption spectrum, ensuring that the absorbance of the ultraviolet-visible absorption spectrum of the nanocrystals in the reaction solution at 520nm is 0.1), 0.5mL of 0.1mol/L2, 3, 5-trimethylbenzoquinone, 2mL of 0.4mol/L benzyl alcohol and toluene (supplementing toluene till the total volume of the solution is 4 mL) into a 15mL glass bottle, and placing the mixed solution under a 6W 520nm LED lamp for irradiation. The concentration of the product 2,3, 5-trimethylbenzoquinone was monitored by sampling the reaction using a sampling needle, and characterized and quantified by GC-FID.
FIG. 6 is a graph showing the concentration of 2,3, 5-trimethylhydroquinone produced by photocatalysis in example 5 and comparative example 3 as a function of illumination time, from which we can see that spherical CdSe nanocrystal aggregates have higher catalytic rates than dispersed nanocrystals.
Example 6
An application of 2,3, 5-trimethylhydroquinone synthesized by photocatalysis based on CdSe/CdS point-rod structure nanocrystalline aggregates. Comprises the following steps:
taking CdSe/CdS point-rod structure nanocrystal aggregates (the amount of the nanocrystal aggregates is determined by an absorption spectrum, ensuring that the absorbance of the ultraviolet-visible absorption spectrum of the nanocrystals in the reaction solution at 520nm is 0.1), 0.5mL of 0.1mol/L of 2,3, 5-trimethylbenzoquinone, 2mL of 0.4mol/L of benzyl alcohol and toluene (supplementing toluene till the total volume of the solution is 4 mL) into a 15mL glass bottle, and placing the mixed solution under a 6W 520nm LED lamp for irradiation. The concentration of the product 2,3, 5-trimethylbenzoquinone was monitored by sampling the reaction using a sampling needle, and characterized and quantified by GC-FID.
Comparative example 4
An application of 2,3, 5-trimethylhydroquinone in photocatalytic synthesis based on dispersed spherical CdSe nanocrystals. Comprises the following steps:
and (3) taking dispersed CdSe/CdS point-rod structure nanocrystals (the amount of the dispersed nanocrystals is determined by an absorption spectrum, and ensuring that the absorbance of the ultraviolet-visible absorption spectrum of the nanocrystals in the reaction solution at 520nm is 0.1), 0.5mL of 0.1mol/L2, 3, 5-trimethylbenzoquinone, 2mL of 0.4mol/L benzyl alcohol and toluene (supplementing toluene till the total volume of the solution is 4 mL) in a 15mL glass bottle, and placing the mixed solution under a 6W 520nm LED lamp for irradiation. The concentration of the product 2,3, 5-trimethylbenzoquinone was monitored by sampling the reaction using a sampling needle, and characterized and quantified by GC-FID.
FIG. 7 is a graph showing the concentration of 2,3, 5-trimethylhydroquinone produced by photocatalysis in example 6 and comparative example 4 as a function of illumination time, from which we can see that CdSe/CdS point-rod structure nanocrystal aggregates have a higher catalytic rate than dispersed nanocrystals.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (13)
1. A method for preparing a semiconductor nanocrystal aggregate is characterized by comprising the following steps:
providing a monodisperse core-shell nanocrystal solution;
purifying, namely performing surface treatment on the monodisperse core-shell nanocrystal solution to reduce the number of ligands on the surface of the nanocrystal to obtain the nanocrystal with insufficient ligand amount;
dispersing the surface-treated nanocrystal solution into an organic solvent to enable nanocrystals to aggregate, thereby obtaining a nanocrystal aggregate.
2. The method according to claim 1, wherein the thin shell layer of the core-shell nanocrystal is spherical or irregular hexahedral.
3. The preparation method according to claim 2, wherein the shell layer of the spherical core-shell nanocrystal is a thin layer of one atomic layer to four atomic layers, and the shell layer of the irregular hexahedral core-shell nanocrystal is a medium-thick layer of four atomic layers to ten atomic layers.
4. The preparation method according to claim 1, wherein the core layer and the shell layer of the monodisperse core-shell nanocrystal are each independently selected from at least one of an oxide, sulfide, selenide and antimonide of a transition metal.
5. The preparation method according to claim 4, wherein the core layer and shell layer materials of the monodisperse core-shell nanocrystal are each independently selected from at least one of CdS, cdSe, cdTe, znS, znSe, cuS and MnS.
6. The method according to claim 5, wherein the core layer of the monodisperse core-shell nanocrystal is CdSe and the shell layer is CdS.
7. The method according to claim 1, wherein the ligand in the monodisperse core-shell nanocrystal is at least one selected from a carboxylate ligand, a thiolate ligand, an amine ligand, a sulfur ligand, and a phosphine ligand, and is preferably an oleylamine ligand having a relatively weak coordination ability.
8. The method of claim 1, wherein the purifying step comprises: adding a poor solvent of the nanocrystals into the monodisperse core-shell nanocrystal solution, centrifugally precipitating at a certain temperature, dispersing the nanocrystals into the good solvent, and repeating for multiple times; preferably, the poor solvent is selected from at least one of short-chain alcohol, acetone, acetonitrile and ethyl acetate, the short-chain alcohol is more preferably methanol, and the good solvent is selected from at least one of hexane, octane, toluene and chloroform, and is more preferably hexane.
9. The preparation method according to claim 1, wherein after purification, the number of surface ligands of the core-shell nanocrystal is reduced by more than 90%.
10. The semiconductor nanocrystal aggregate produced by the production method as set forth in any one of claims 1 to 9.
11. Use of the semiconductor nanocrystal aggregate of claim 10 for photocatalytic synthesis of 2,3, 5-trimethylhydroquinone.
12. Use according to claim 11, characterized in that it comprises the following steps:
preparing a semiconductor nanocrystal aggregate solution according to the preparation method described in any one of claims 1 to 9;
adding 2,3, 5-trimethylbenzoquinone, benzyl alcohol and a reaction solvent into the semiconductor nanocrystal aggregate solution;
the mixed solution was irradiated with 520nm green light, and the concentration of the product 2,3, 5-trimethylhydroquinone was monitored by sampling in the middle of the reaction using a sampling needle, and characterized and quantified by GC-FID.
13. Use according to claim 12, characterized in that the reaction solvent is toluene or n-hexane.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060172133A1 (en) * | 2004-08-17 | 2006-08-03 | Imad Naasani | Synthesis of highly luminescent colloidal particles |
| US20140017485A1 (en) * | 2012-07-13 | 2014-01-16 | Csem Centre Suisse D'electronique Et De Microtechnique Sa Recherche Et Developpement | Assembly comprising j-aggregates |
| CN104312580A (en) * | 2014-09-11 | 2015-01-28 | 东南大学 | Preparation method of large size doped core-shell structure semiconductor nanocrystal |
| CN109603855A (en) * | 2018-12-26 | 2019-04-12 | 吉林师范大学 | A kind of CdSe/CdS core-shell photocatalyst and its preparation method and application with surface ligand |
| CN110041911A (en) * | 2019-05-30 | 2019-07-23 | 深圳扑浪创新科技有限公司 | A kind of preparation method of CdSe/CdS quantum rod |
| CN111019637A (en) * | 2018-10-09 | 2020-04-17 | Tcl集团股份有限公司 | Preparation method of core-shell structure nanocrystal |
| CN112159652A (en) * | 2020-09-18 | 2021-01-01 | 大连民族大学 | Preparation method of CdSe/CdS core-shell structure quantum dot |
| CN113429973A (en) * | 2021-06-08 | 2021-09-24 | 南通大学 | Preparation method of inorganic ligand modified CdSe/CdS @ ZnO quantum dot |
| CN114789252A (en) * | 2022-04-11 | 2022-07-26 | 嘉兴学院 | Preparation method of nanocrystalline superlattice material |
-
2022
- 2022-10-24 CN CN202211299796.6A patent/CN115608382A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060172133A1 (en) * | 2004-08-17 | 2006-08-03 | Imad Naasani | Synthesis of highly luminescent colloidal particles |
| US20140017485A1 (en) * | 2012-07-13 | 2014-01-16 | Csem Centre Suisse D'electronique Et De Microtechnique Sa Recherche Et Developpement | Assembly comprising j-aggregates |
| CN104312580A (en) * | 2014-09-11 | 2015-01-28 | 东南大学 | Preparation method of large size doped core-shell structure semiconductor nanocrystal |
| CN111019637A (en) * | 2018-10-09 | 2020-04-17 | Tcl集团股份有限公司 | Preparation method of core-shell structure nanocrystal |
| CN109603855A (en) * | 2018-12-26 | 2019-04-12 | 吉林师范大学 | A kind of CdSe/CdS core-shell photocatalyst and its preparation method and application with surface ligand |
| CN110041911A (en) * | 2019-05-30 | 2019-07-23 | 深圳扑浪创新科技有限公司 | A kind of preparation method of CdSe/CdS quantum rod |
| CN112159652A (en) * | 2020-09-18 | 2021-01-01 | 大连民族大学 | Preparation method of CdSe/CdS core-shell structure quantum dot |
| CN113429973A (en) * | 2021-06-08 | 2021-09-24 | 南通大学 | Preparation method of inorganic ligand modified CdSe/CdS @ ZnO quantum dot |
| CN114789252A (en) * | 2022-04-11 | 2022-07-26 | 嘉兴学院 | Preparation method of nanocrystalline superlattice material |
Non-Patent Citations (2)
| Title |
|---|
| 廖晨: "金属表面、光学多层膜和谐振腔对量子点光学性质的调制特性研究", 《中国博士学位论文全文数据库》, no. 2017, pages 1 * |
| 廖晨: "金属表面、光学多层膜和谐振腔对量子点光学性质的调制特性研究", 中国博士学位论文全文数据库, no. 2017, pages 1 * |
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