CN110028052B - Method for preparing hollow structure material based on carbon quantum dot template method - Google Patents
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Abstract
The invention discloses a method for preparing a hollow structure material based on a carbon quantum dot template method, which comprises the steps of utilizing carbon quantum dots to form micelles in an organic-water mixed solution in a self-assembly manner, adding a raw material for synthesizing the hollow structure material, loading the raw material on the surfaces of the carbon quantum dot micelles to form a core-shell structure precursor, and removing the carbon quantum dot template through washing or calcining to obtain the hollow structure material, wherein the carbon quantum dots are used as templates, have the characteristic similar to surface active substances, can form the micelles in a self-assembly manner and are used as hollow material synthesis templates without adding a surfactant; and the method for removing the carbon quantum dot template is simple, convenient and quick, the template is removed without dangerous methods such as etching and the like, the operation is safe and friendly, and the defects of single template, poor compatibility and difficult removal in the prior art are overcome.
Description
Technical Field
The invention relates to a hollow structure material, in particular to a method for preparing a hollow structure material by using carbon quantum dots as a template agent, and belongs to the field of material preparation.
Background
The intrinsic properties of the material are closely related to the composition, crystal structure, particle size, micro-morphology and the like of the material. The hollow structure material has wide application prospect in the fields of drug delivery, selective adsorption, catalysis, electrochemical energy storage and the like because of the characteristics of special morphology structure, low density, large porosity and the like. Among the numerous synthetic methods, the template method is considered to be the most direct and effective method.
The template method may be classified into a hard-film method and a soft-template method according to the template. The hard template has high stability and good narrow confinement effect, and the size and the appearance of the material can be strictly controlled. But the materials produced generally have less topography variation due to the uniqueness of the hard template structure. Meanwhile, the removal of the hard template usually requires the use of reagents such as HF, concentrated NaOH solution and the like, and has certain danger. The soft template mainly comprises various ordered polymers formed by amphiphilic molecules, such as vesicles, liquid crystals, micelles, microemulsions and the like. Compared with a hard template, the soft template has more various forms and is convenient to construct. The general steps of the template method include: (1) and (4) dispersing the template. The template was uniformly dispersed in the reaction solution. The process usually requires the addition of a suitable surfactant due to the incompatibility of the template with the target product, solvent, etc.; (2) generating a target product on the surface of the template; (3) and removing the template by methods such as etching and the like to obtain a hollow structure product. The analysis of the reaction mechanism can know that the searching of the template which has good compatibility and is easy to remove can simplify the reaction steps and improve the reaction efficiency.
Disclosure of Invention
Aiming at the defects of few template types, poor template compatibility, difficult template removal and the like in the preparation process of the conventional hollow material, the invention aims to provide the method for synthesizing the hollow structure material by using the carbon quantum dots as the template, and the method is simple and convenient to operate, good in template compatibility, easy to remove, safe and free of danger.
The invention provides a method for preparing a hollow structure material based on a carbon quantum dot template method, which comprises the following steps:
1) dispersing carbon quantum dots into an organic-water mixed solution, and forming carbon quantum dot micelles through self-assembly to obtain a mixed solution containing the carbon quantum dot micelles;
2) adding a raw material for synthesizing a hollow structure material into the mixed solution of the carbon-containing quantum dot micelle, and loading the raw material on the surface of the carbon quantum dot micelle through physical adsorption and/or chemical reaction to form a precursor with a core-shell structure;
3) and washing or calcining the precursor with the core-shell structure to remove the carbon quantum dot template, thus obtaining the carbon quantum dot template.
In a preferred embodiment, the carbon quantum dots are obtained by reacting at least one of alcohol compounds, aldehyde compounds and ketone compounds in an alkaline solution. The carbon quantum dots finally obtained by a series of reactions such as aldol condensation and the like mainly carried out in alkaline solution through alcohol, aldehyde, ketone and the like also contain more oxygen-containing groups on the surface, so that the carbon quantum dots have certain characteristics, such as dispersibility in some polar organic solvents and poor dispersibility in water. Therefore, in a mixed solution of an organic solvent and water with a proper proportion, the carbon quantum dots have the property similar to a surfactant, can be self-assembled to form micelles, and simultaneously have the property of aggregating small molecules or particles due to the polar groups carried by the carbon quantum dots, so that the carbon quantum dots can be used as templates for synthesizing hollow materials.
In a more preferred embodiment, the alcohol compound includes at least one of ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, triacontanol, ethylene glycol, glycerol, allyl alcohol, benzyl alcohol, and phenethyl alcohol.
In a more preferred embodiment, the aldehyde compound includes at least one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, caprylic aldehyde, succinaldehyde, glutaraldehyde, hexanedial, nonanal, and decanal. Acetaldehyde is more preferred.
In a more preferred embodiment, the ketone compound includes at least one of acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, cyclohexanone, 2-heptanone, cycloheptanone, 2-octanone, cyclooctanone, 2-nonanone, decanone, undecanone, decadione, tridecanone, tetradecanone, pentadecanone, acetophenone, and methylacetophenone.
In a more preferred embodiment, the alkaline solution comprises at least one alkaline compound selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium acetate, and potassium acetate.
In a more preferred embodiment, the organic-aqueous mixed solution includes a mixed solution of water and at least one organic solvent selected from ethanol, acetone, benzyl alcohol, tetrahydrofuran, N-dimethylformamide, 1-methyl-2-pyrrolidone, and dimethylsulfoxide.
In a preferable scheme, the volume ratio of the organic solvent to the water in the organic-water mixed solution is 1: 1-3. The formation of carbon quantum dot micelles can be controlled by adjusting the proportion of the organic solvent and the water in the organic-water mixed solution, if the proportion of the organic solvent is too high, the carbon quantum dots are difficult to aggregate into micelles, and if the proportion of the water is too high, the carbon quantum dots cannot be dispersed and aggregated into particles, so that the carbon quantum dot micelles are not suitable for being used as hollow material templates. The size of the formed micelle particles can be regulated and controlled by the mixing ratio of the organic solvent and the water in a preferred range, so that the regulation of the size of the cavity of the hollow structure material is realized.
Preferably, the hollow structure material includes an organic polymer, a carbon material (such as nitrogen-doped carbon), a metal simple substance, an alloy, a metal oxide, a metal sulfide, a metal phosphide, and the like. The polymer such as polypyrrole and polyaniline is loaded on the surface of the carbon quantum dot micelle by polymerization reaction of pyrrole or aniline raw materials, and can be further calcined at high temperature to obtain the hollow nitrogen-doped carbon material. Simple metal substances, alloys and the like can be generated by the reduction reaction of metal ions on the surfaces of carbon quantum dots. The metal oxide can be adsorbed on the surface of the carbon quantum dot micelle as metal hydroxide, and the metal oxide, such as iron oxide, manganese oxide and the like, can be generated through subsequent high-temperature calcination. The metal sulfide can be generated by the in-situ reaction of a metal source and a sulfur source, and the metal sulfide is deposited on the surface of the carbon quantum dot micelle, for example, bismuth nitrate, sodium sulfide and the like are used for generating bismuth sulfide. The metal phosphide can be obtained by a method of forming a hollow structure precursor by using a carbon quantum dot as a template and then performing phosphorization, such as CoCl2·2H2And O and urea are used as raw materials to obtain a precursor product, and the precursor product is subjected to a phosphorization reaction in a tubular furnace by using sodium hypophosphite as a phosphorus source to obtain the hollow structure CoP.
In a preferable scheme, at least one of ethanol, acetone, benzyl alcohol, tetrahydrofuran, N-dimethylformamide, 1-methyl-2-pyrrolidone and dimethyl sulfoxide is adopted as a washing agent in the washing process.
In the preferable scheme, the calcining temperature is 400-800 ℃, and the time is 2-10 h. The preferable calcination time is 2-5 h. The temperature rise rate in the calcination process is 1-25 ℃/min, and more preferably 2-10 ℃/min.
In the scheme of the invention, the solid-liquid separation process adopted after the organic solvent is adopted for washing is vacuum filtration.
According to the scheme, the target product is obtained after the carbon quantum dot template is removed by washing with the organic solvent, and is dried in vacuum at the temperature of 50-100 ℃ for 4-10 hours.
Preferably, the size of the cavity of the hollow structure material is 10 nm-1 μm.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the method adopts the carbon quantum dots as the synthetic template of the hollow structure material for the first time, not only has the characteristic similar to surface active substances, but also can form the hollow template through self-assembly, can successfully obtain the hollow material, does not need to add a surfactant additionally, has simple, convenient and quick removal method of the carbon quantum dot template, does not need to use dangerous methods such as etching and the like to remove the template, is safe and friendly to operate, and overcomes the defects of single template, poor compatibility and difficult removal in the prior art.
According to the invention, the carbon quantum dots are used as the synthetic template of the hollow structure material, and the size of the cavity of the hollow structure material can be arbitrarily regulated and controlled in a larger range.
Drawings
FIG. 1 is a TEM image of the product of example 1;
FIG. 2 is a TEM image of the product of comparative example 1;
FIG. 3 is a TEM image of the product of comparative example 2;
FIG. 4 is a TEM image of the product of example 2;
FIG. 5 is a TEM image of a precursor in example 3;
FIG. 6 is a TEM image of the product of example 3.
Detailed Description
The following examples are intended to better illustrate the present invention and should not be construed as in any way limiting the scope of the invention as claimed.
Example 1
8g NaOH was mixed with 40mL of acetaldehyde (40% aqueous solution), and the mixture was stirred for 1 hour and allowed to stand for 72 hours. Neutralizing the reaction product to be neutral by using concentrated hydrochloric acid, centrifugally separating the product at the rotating speed of 8000r/min, and washing 3-5 times by using deionized water. Vacuum drying at 80 ℃ for 5h to obtain the orange yellow product carbon quantum dots. 0.2g of carbon quantum dots were dissolved in 40mL of ethanol under stirring, and then mixed with 60mL of 1M HCl uniformly to form micelles. Followed by the addition of 0.82g (NH) under ice-bath conditions (0-5 ℃)4)2S2O8As an oxidizing agent for initiating the polymerization reaction. And after ice bath is continued for 30min, 480 mu L of pyrrole monomer is added by a liquid transfer gun, after polymerization reaction is carried out for 8h under the ice bath condition, the product is separated by a vacuum filtration method, and is repeatedly washed by ethanol for several times, the internal template is removed, and then the product is washed by deionized water for 3-5 times. Drying in a vacuum drying oven at 80 deg.C for 5 hr to obtain black hollow polypyrrole with cavity size of about 100 nm. FIG. 1 is a transmission electron micrograph of hollow polypyrrole.
Comparative example 1
0.2g of the pre-synthesized carbon quantum dots were ultrasonically dispersed in 40mL of deionized water, and then mixed well with 60mL of 1M HCl. Followed by the addition of 0.82g (NH) under ice-bath conditions (0-5 ℃)4)2S2O8As an oxidizing agent for initiating the polymerization reaction. And (3) continuing ice-bath for 30min, adding 480 mu L of pyrrole monomer by using a liquid transfer gun, carrying out polymerization reaction for 8h under the ice-bath condition, separating a product by using a vacuum filtration method, and washing for 3-5 times by using ethanol and deionized water. Drying the mixture in a vacuum drying oven at 80 ℃ for 5 hours to obtain a black product. The product has no hollow structure. FIG. 2 is a transmission electron micrograph of the product.
Comparative example 2
0.2g of the carbon quantum dots synthesized beforehand was dispersed with stirring in 100mL of ethanol, and then mixed uniformly with 60mL of 1M HCl. Followed by the addition of 0.82g (NH) under ice-bath conditions (0-5 ℃)4)2S2O8After ice-bath for 30min, 480 mu L of pyrrole monomer is added, polymerization is carried out for 8h under the ice-bath condition, the product is separated by a vacuum filtration method, and the product is washed for 3-5 times by ethanol and deionized water. Drying the mixture in a vacuum drying oven at 80 ℃ for 5 hours to obtain a black product. The product has no hollow structure. FIG. 3 is a transmission electron micrograph of the product.
Example 2
And (2) placing 0.5g of the hollow polypyrrole product obtained in the example 1 into a tube furnace, introducing Ar protective gas, heating at the rate of 5 ℃/min, and calcining at 650 ℃ for 5 hours to obtain the black hollow nitrogen-doped carbon material with the cavity size of about 100 nm. FIG. 4 is a transmission electron microscope image of a hollow N-doped carbon material.
Example 3
0.2g of carbon quantum dots pre-synthesized by aldol condensation of acetaldehyde with sodium hydroxide was dissolved in 40mL of ethanol with stirring, and then mixed uniformly with 60mL of 1M HCl to form micelles. Followed by the addition of 0.82g (NH) under ice-bath conditions (0-5 ℃)4)2S2O8As an oxidizing agent for initiating the polymerization reaction. And (3) continuing ice-bath for 30min, adding 480 mu L of pyrrole monomer by using a liquid transfer gun, carrying out polymerization reaction for 8h under the ice-bath condition, separating a product by using a vacuum filtration method, and washing 3-5 times by using deionized water. Drying the mixture in a vacuum drying oven at 80 ℃ for 5h to obtain a black precursor. And (3) placing 0.5g of the precursor in a tube furnace, introducing Ar protective gas, heating at the rate of 5 ℃/min, and calcining at 650 ℃ for 5h to obtain a black hollow structure product with the cavity size of about 100 nm. The transmission electron microscope image of the precursor of the product is shown in FIG. 5, and the transmission electron microscope image of the product is shown in FIG. 6.
Example 4
0.2g of carbon quantum dots previously synthesized by aldol condensation of acetaldehyde under sodium hydroxide was dissolved in 40mL of ethanol under stirring, and then mixed uniformly with 80mL of 1M HCl to form micelles. After stirring for 0.5h in an ice bath (0-5 ℃), 70. mu.L of aniline was added, and ice bath was continued for 0.5h, followed by 35mg of K2CrO7And (3) as an oxidant, after ice-bath reaction for 8 hours, performing suction filtration to separate a black product, washing with ethanol for 3-5 times to completely remove the internal template, and washing with deionized water for several times. Vacuum drying at 80 deg.C for 5 hr to obtain hollow knotPolyaniline is formed, and the size of a cavity is about 300 nm.
Example 5
16g NaOH was mixed with 80mL acetone, stirred for 1h, and allowed to stand for 120 h. And neutralizing the reaction product to be neutral by using 1M diluted HCl, centrifugally separating the product at the rotating speed of 8000r/min, and washing for 3-5 times by using deionized water. Vacuum drying at 100 deg.c for 12 hr to obtain orange yellow carbon quantum dot product. 0.2g of carbon quantum dots are dissolved in 40mL of ethanol under the stirring condition, then mixed with 100mL of dilute NaOH solution, and the solution is adjusted to be about pH 8.5. 60mg of dopamine was added with stirring and stirred at 400r/min for 24 h. And separating the product by adopting a hollow suction filtration method, washing the product 3-5 times by using deionized water and ethanol, and completely removing the internal carbon quantum dot template. Drying in a vacuum drying oven at 80 deg.C for 5h to obtain hollow polydopamine with cavity size of about 500 nm.
Example 6
Mixing 12g NaOH with 40mL absolute ethyl alcohol, reacting for 1h under the condition of stirring, and continuing to stand and react for 360 h. And taking out the supernatant to obtain the dispersion liquid of the carbon quantum dots. And dialyzing the carbon quantum dot dispersion liquid for 60h by a dialysis bag with the molecular cut-off of 2000, and vacuum-drying for 24h at 80 ℃ to obtain a carbon quantum dot solid. 0.2g of carbon quantum dots are dissolved in 20mL of ethylene glycol and uniformly dispersed by ultrasonic. And 0.73g Bi (NO) was added3)3·5H2And O, ultrasonic dispersion. Mix with 40mL of deionized water and stir for 0.5 h. 0.86g of thiourea was added to the mixed solution, stirred for 5min, and the mixed solution was transferred to a 100mL reaction vessel and subjected to hydrothermal reaction at 120 ℃ for 8 h. And cooling to room temperature, carrying out suction filtration to separate a product, and washing with ethanol and deionized water for several times to obtain the hollow-structure bismuth sulfide with the cavity size of about 300 nm.
Claims (7)
1. A method for preparing a hollow structure material based on a carbon quantum dot template method is characterized by comprising the following steps: the method comprises the following steps:
1) dispersing carbon quantum dots into an organic-water mixed solution, and forming carbon quantum dot micelles through self-assembly to obtain a mixed solution containing the carbon quantum dot micelles;
2) adding a raw material for synthesizing a hollow structure material into the mixed solution of the carbon-containing quantum dot micelle, and loading the raw material on the surface of the carbon quantum dot micelle through physical adsorption and/or chemical reaction to form a precursor with a core-shell structure;
3) the core-shell structure precursor is obtained by washing or calcining to remove the carbon quantum dot template;
the carbon quantum dots are obtained by reacting at least one of alcohol compounds, aldehyde compounds and ketone compounds in an alkaline solution;
the organic-water mixed solution comprises a mixed solution formed by at least one organic solvent of ethanol, acetone, benzyl alcohol, tetrahydrofuran, N-dimethylformamide, 1-methyl-2-pyrrolidone and dimethyl sulfoxide and water;
the volume ratio of the organic solvent to the water in the organic-water mixed solution is 1: 1-3.
2. The method for preparing the hollow structure material based on the carbon quantum dot template method according to claim 1, characterized in that:
the alcohol compound comprises at least one of ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, triacontanol, ethylene glycol, glycerol, allyl alcohol, benzyl alcohol and phenethyl alcohol;
the aldehyde compound comprises at least one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, heptaldehyde, octanal, succinaldehyde, glutaraldehyde, hexanal, nonanal and decanal;
the ketone compound comprises at least one of acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, cyclohexanone, 2-heptanone, cycloheptanone, 2-octanone, cyclooctanone, 2-nonanone, decanone, undecanone, decadione, tridecanone, tetradecanone, pentadecanone, acetophenone and methyl acetophenone.
3. The method for preparing the hollow structure material based on the carbon quantum dot template method according to claim 1, characterized in that: the alkaline solution contains at least one alkaline compound of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium acetate and potassium acetate.
4. The method for preparing the hollow structure material based on the carbon quantum dot template method according to claim 1, characterized in that: the hollow structure material comprises an organic polymer, a metal simple substance, an alloy, a metal oxide, a metal sulfide or a metal phosphide.
5. The method for preparing the hollow structure material based on the carbon quantum dot template method according to claim 1, characterized in that: in the washing process, at least one of ethanol, acetone, benzyl alcohol, tetrahydrofuran, N-dimethylformamide, 1-methyl-2-pyrrolidone and dimethyl sulfoxide is used as a washing agent.
6. The method for preparing the hollow structure material based on the carbon quantum dot template method according to claim 1, characterized in that: the calcining temperature is 600-800 ℃, and the time is 2-10 h.
7. The method for preparing the hollow structure material based on the carbon quantum dot template method according to claim 1, characterized in that: the size of the cavity of the hollow structure material is 10 nm-1 mu m.
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