CN112170859A - Preparation method of gold nanocluster - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides a preparation method of a gold nanocluster. The preparation method of the gold nanocluster comprises the following steps: preparing a mixed solution containing a reducing agent, a stabilizing agent and trivalent gold ions; adjusting the pH value of the mixed solution to be alkaline to obtain an alkaline mixed solution; and carrying out microwave treatment on the alkaline mixed solution to generate the gold nanoclusters. The preparation method of the gold nanocluster provided by the invention is used for carrying out microwave treatment on the alkaline mixed solution, so that the reduction efficiency and the synthesis efficiency of the alkaline mixed solution can be effectively improved, and the time of reduction reaction is remarkably shortened. And the microwave treatment can also play a synergistic role with a stabilizer, so that the consistency of the generated gold nanocluster product can be favorably controlled, and the gold nanoclusters are effectively prevented from being agglomerated. In addition, the microwave treatment can uniformly heat the alkaline mixed solution, and is suitable for the synthesis of the gold nanocluster with large sample size.
Description
Technical Field
The invention relates to a preparation method of a gold nanocluster.
Background
Gold nanoclusters (AuNCs) are interposed between Au atoms and Au nanoparticles, and generally consist of several to several tens of atoms, have a particle size generally smaller than 2nm, and are interposed between conventional organometallic compounds and crystalline metal nanoparticles, thus having a series of unique physical properties such as photoluminescence, quantum size effects, and the like. AuNCs have a size close to the wavelength range of the Fermi level of electrons, and exhibit strong luminescence properties.
Compared with the traditional organic fluorescent dye, rare earth fluorescent material and semiconductor fluorescent quantum dot, AuNCs has unique fluorescence adjustable property, higher Quantum Yield (QYs), simpler and milder preparation, is a novel ideal fluorescent material, and has wide application prospect in fluorescence sensing, biological labeling and cell imaging, biological identification, health diagnosis, environmental monitoring and homogeneous/heterogeneous catalysis. The fluorescence property of the gold nanoclusters is influenced by factors such as size, composition, ligand, metal valence, cluster charge, aggregation state and the like.
At present, the preparation of the gold nanocluster mainly adopts a traditional heating method, metal ions are reduced under a proper reducing agent, and the defects of long time consumption (usually 5-72 hours), low synthesis efficiency, high energy consumption, large particle size of prepared products, difficulty in realizing scale application and the like exist. AuNCs synthesized in the preparation process are easy to interact and irreversibly agglomerate, and the AuNCs are easily interfered by external factors, so that the change of fluorescence intensity is caused, and therefore, how to improve the stability and the synthesis efficiency of products is a key scientific problem to be solved by AuNCs.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a gold nanocluster to solve the technical problems of low synthesis and reaction efficiency, easy agglomeration and poor stability of the conventional preparation method of the gold nanocluster.
In order to achieve the purpose of the invention, the invention provides a preparation method of gold nanoclusters. The preparation method of the gold nanocluster comprises the following steps:
preparing a mixed solution containing a reducing agent, a stabilizing agent and trivalent gold ions;
adjusting the pH value of the mixed solution to be alkaline to obtain an alkaline mixed solution;
and carrying out microwave treatment on the alkaline mixed solution to generate the gold nanoclusters.
Compared with the prior art, the preparation method of the gold nanocluster provided by the invention has the advantages that the alkaline mixed solution is subjected to microwave treatment, the reduction efficiency and the synthesis efficiency of the alkaline mixed solution can be effectively improved, and the time of reduction reaction is remarkably shortened. Meanwhile, the microwave treatment can also play a synergistic role with a stabilizer, so that the consistency of the generated gold nanocluster product can be favorably controlled, the gold nanoclusters are effectively prevented from being agglomerated, in addition, the alkaline mixed solution can be uniformly heated through the microwave treatment, and the method is suitable for the synthesis of the gold nanoclusters in large sample quantity.
Drawings
FIG. 1 is a schematic process flow diagram of a method for preparing gold nanoclusters according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, the term "and/or" describing an association relationship of associated objects means that there may be three relationships, for example, a and/or B, may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the description of the present invention, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as including the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides a preparation method of a gold nanocluster. The preparation method of the gold nanocluster has the process flow shown in figure 1, and comprises the following steps:
s01: preparing a mixed solution containing a reducing agent, a stabilizing agent and trivalent gold ions;
s02: adjusting the pH of the mixed solution prepared in the step S01 to be alkaline to obtain an alkaline mixed solution;
s02: the alkaline mixed solution prepared in step S02 is subjected to microwave treatment to generate gold nanoclusters.
Wherein, the reducing agent, the stabilizing agent and the trivalent gold ions in the step S01 form a reaction system for generating the gold nanoclusters.
In the mixed solution, trivalent gold ions are used as a gold element source for generating gold nanoclusters, and in one embodiment, the trivalent gold ions are preferably provided by one or more compounds selected from chloroauric acid, sodium chloroaurate and potassium chloroaurate. The compounds have good solubility, such as water solubility, and can be uniformly dispersed in the mixed solution, so that the consistency of the particle size, morphology and the like of the gold nanoclusters generated by the reduction reaction in the subsequent step S03 is improved. In another embodiment, the concentration of the gold source compound providing the trivalent gold ions in the mixed solution is 0.001% -2% by mass of the mixed solution. By adjusting and optimizing the concentration of the trivalent gold ions, the environment of the reduction reaction in the step S03 is optimized, so that the efficiency of generating the gold nanoclusters is improved, and the consistency of the gold nanoclusters is improved.
In one embodiment, the reducing agent preferably comprises one or more of egg albumin (CEW), Bovine Serum Albumin (BSA) sodium borohydride, and sodium citrate. In another embodiment, the concentration of the reducing agent is 0.001-10% by mass of the mixed solution. The preferable reducing agent has excellent reducibility, and can perform oxidation-reduction reaction with trivalent gold ions during the microwave treatment of step S03 to generate a gold simple substance and form gold nanoclusters in the reaction system. Egg white protein (CEW) and Bovine Serum Albumin (BSA) have three-dimensional structures and are excellent in biocompatibility, trivalent gold ions in a solution can be adsorbed and captured firstly, cysteine and tyrosine residues in the protein structures can reduce the trivalent gold ions into gold atoms or monovalent gold ions, and a protein framework provides a stable scaffold structure for forming nano-clusters. Therefore, egg white protein (CEW) and Bovine Serum Albumin (BSA) can be used as a stabilizer and a reducing agent. When the reducing agent is used, the reaction conditions are mild, but the reaction time is relatively long. The obtained gold nanocluster has excellent water solubility, stability and high fluorescence.
In one embodiment, the stabilizer preferably comprises one or more of egg white protein (CEW), Bovine Serum Albumin (BSA), 4-aminomauric acid (PAH), Glutathione (GSH), 11-mercaptoundecanoic acid, 1-amino 2-naphthol 4-sulfonic Acid (ANS), Dithiothreitol (DTT), cetyltrimethylammonium bromide (CTAB), 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA). In another embodiment, the concentration of the stabilizer is 0.001-10% by mass of the mixed solution. The preferred stabilizers are egg white protein (CEW), 4-aminomauric acid (PAH), 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA), and mixtures thereof. Compared with Bovine Serum Albumin (BSA), egg albumin (CEW) is rich in source, low in price and a green stabilizer. The structure of the 4-amino hippuric acid (PAH) and the 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA) simultaneously contains amino and carboxyl, the amino can generate complexation with gold atoms, and the carboxyl has negative charge and steric hindrance, so that the agglomeration of gold nanoclusters can be effectively prevented, and the carboxyl functional group can generate complexation with various substances such as heavy metals and the like, and the synthesis and functional modification can be completed in one step.
In addition, the solvent of the mixed solution in step S01 is preferably water, such as deionized water. The water is preferably used as a solvent, so that the dissolubility of a reducing agent, a stabilizing agent and a compound for providing trivalent gold ions can be effectively improved, the dispersion system of the mixed solution can be stable, the generation of the final product gold nanocluster is facilitated, and the uniformity of the gold nanocluster is good. Moreover, water is used as a solvent, so that the method is green, harmless, environment-friendly and low in cost.
In a specific example, when water is used as the solvent, the mixed solution in step S01 is prepared as follows:
s011: respectively dissolving a reducing agent, a stabilizing agent and a gold source for providing trivalent gold ions, and respectively preparing an aqueous solution of the reducing agent, an aqueous solution of the stabilizing agent and an aqueous solution containing the trivalent gold ions;
s012: and mixing the aqueous solution of the reducing agent, the aqueous solution of the stabilizing agent and the aqueous solution containing the trivalent gold ions to prepare the mixed solution.
By controlling and optimizing the mixing ratio of each solution in step S012, the reducing agent, the stabilizer and the trivalent gold ion are preferably controlled as follows:
the concentration of the reducing agent in the mixed solution is 0.001% -10%, the concentration of the stabilizing agent in the mixed solution is 0.001% -10%, and the concentration of the trivalent gold ions in the mixed solution is 0.001% -2%.
By optimizing the preparation method of the mixed solution, the solution of each component can form a stable reaction system, so that the efficiency and the uniformity of the final product, namely the gold nanocluster are improved.
The adjustment of the pH of the mixed solution in step S02 may be carried out by using a conventional alkali solution, preferably by adjusting so that the pH of the mixed solution is 9 to 13, that is, the pH of the alkaline mixed solution in step S02 is 9 to 13. So as to fully play the roles of a reducing agent and a stabilizing agent, improve the efficiency of reduction reaction and ensure that the generated gold nanoclusters have good uniformity. In particular embodiments, the pH of the mixed solution may be adjusted to, but is not limited to, a sodium hydroxide solution.
The microwave treatment in the step S02 can effectively heat the alkaline mixed solution, and the reactants vibrate under the action of microwaves, so that the efficiency of the reduction reaction is improved, the generation efficiency of the final product gold nanocluster is improved, the particle size of the gold nanocluster is effectively reduced, and the uniformity of the gold nanocluster is ensured. In one embodiment, the power of the microwave treatment is 100-. Further, under the preferred microwave power, the time of the microwave treatment is 5-60 min. By optimizing the power of microwave treatment or further optimizing the time, the efficiency of reduction reaction is improved, the generation efficiency of the final product gold nanocluster is improved, the particle size of the gold nanocluster is reduced, and the uniformity of the gold nanocluster is improved.
In a further embodiment, the microwave treatment in step S03 is accompanied by a step of stirring the alkaline mixed solution. Thus, the stirring treatment assists the microwave treatment, further improves the dispersion uniformity of each component in the mixed solution, further improves the efficiency of the reduction reaction and the generation efficiency of the final product gold nanocluster, reduces the particle size of the gold nanocluster, and improves the uniformity of the gold nanocluster.
In addition, in order to obtain pure final product gold nanoclusters, in a further embodiment, after the microwave treatment, i.e. the reduction reaction, in step S03 is completed, a separation and purification treatment step of the final product gold nanoclusters is further included to remove unreacted reducing agents, stabilizing agents and other ions. In a specific embodiment, the separation process may be, but is not limited to, a coprecipitation process or a high-speed centrifugation process. The purification treatment may be, but not exclusively, washing the precipitate with deionized water.
Therefore, the preparation method of the gold nanocluster in the embodiment of the invention performs microwave treatment on the alkaline mixed solution, can effectively improve the reduction efficiency of the alkaline mixed solution, and can significantly shorten the time of the reduction reaction, for example, the microwave treatment for preparing the gold nanocluster according to the preparation method of the gold nanocluster in the embodiment of the invention shortens the time of the reduction reaction to only within 1 hour, and the reaction time is generally significantly reduced within 4 to 72 hours compared with the reaction time of the traditional hydrothermal synthesis method.
And the microwave treatment can also play a synergistic role with a stabilizer, so that the consistency of the generated gold nanocluster product can be favorably controlled, and the gold nanoclusters are effectively prevented from being agglomerated, and if the gold nanoclusters prepared by the embodiment of the invention are detected, the particle size of the gold nanoclusters is 1-5 nm.
In addition, the microwave treatment or the further auxiliary stirring treatment can uniformly heat the alkaline mixed solution, and the method is suitable for the synthesis of large sample amount of the gold nanocluster, for example, the one-time synthesis amount can reach 5L. And the traditional hydrothermal synthesis method usually has the synthesis amount of less than 50ml and is only suitable for small-amount experiments or production.
Secondly, the reactants after the microwave treatment are separated and purified, and unreacted reactants or impurity ions can be effectively removed, so that the purity of the gold nanoclusters is improved, the adverse influence of the impurities on the performance of the purity of the gold nanoclusters, such as fluorescence performance, is avoided, and the stability of the performance of the gold nanoclusters is improved.
The preparation method of gold nanoclusters according to the embodiment of the present invention is illustrated by a plurality of specific examples.
Because the preparation method of the embodiment has the advantages and the prepared gold nanoclusters are small in particle size, the applicability of the gold nanoclusters is effectively improved, for example, the applicability of the gold nanoclusters in the fields of fluorescent materials, fluorescence sensing, biomarkers and cell imaging, biological identification, health diagnosis, environment monitoring, homogeneous/heterogeneous catalysis and the like is improved, and the application effect can be improved.
Example one
This example provides a method for preparing gold nanoclusters. The preparation method of the gold nanocluster comprises the following steps:
s1: respectively dissolving sodium borohydride, 4-amino hippuric acid and chloroauric acid in water to respectively prepare an aqueous solution of sodium borohydride, an aqueous solution of 4-amino hippuric acid and an aqueous solution of chloroauric acid;
mixing an aqueous solution of sodium borohydride, an aqueous solution of 4-aminohippuric acid and an aqueous solution of chloroauric acid to prepare a mixed aqueous solution containing trivalent gold ions; wherein the mass percent concentration of the sodium borohydride is 0.001 percent, the mass percent concentration of the 4-amino hippuric acid is 0.001 percent, and the mass percent concentration of the trivalent gold ion is 0.001 percent; the total mass of the final mixed solution was 100 g;
s2: dropwise adding a sodium hydroxide solution into the mixed aqueous solution obtained in the step S1, and adjusting the pH value of the mixed aqueous solution to 9 to obtain an alkaline mixed solution;
s3: and (4) placing the alkaline mixed solution obtained in the step S2 into a microwave reactor for microwave treatment, and carrying out oxidation-reduction reaction for 30min under the conditions of microwave power of 100W and magnetic stirring.
Example two
This example provides a method for preparing gold nanoclusters. The preparation method of the gold nanocluster comprises the following steps:
s1: respectively dissolving egg white protein (CEW), 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA) and chloroauric acid in water to respectively prepare an aqueous solution of the egg white protein (CEW), an aqueous solution of the 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA) and an aqueous solution of the chloroauric acid;
mixing an aqueous solution of egg white protein (CEW), an aqueous solution of 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA) and an aqueous solution of chloroauric acid to prepare a mixed aqueous solution containing trivalent gold ions; wherein, the mass percentage concentration of egg white protein (CEW) is 10%, the mass percentage concentration of 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA) is 10%, and the mass percentage concentration of trivalent gold ions is 2%; the total mass of the final mixed solution was 5000 g;
s2: dropwise adding a sodium hydroxide solution into the mixed aqueous solution obtained in the step S1, and adjusting the pH value of the mixed aqueous solution to 13 to obtain an alkaline mixed solution;
s3: and (4) placing the alkaline mixed solution obtained in the step S2 into a microwave reactor for microwave treatment, and carrying out oxidation-reduction reaction for 60min under the condition of mechanical stirring at the microwave power of 1000W.
EXAMPLE III
This example provides a method for preparing gold nanoclusters. The preparation method of the gold nanocluster comprises the following steps:
s1: respectively dissolving sodium citrate, 4-amino hippuric acid, 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA) and chloroauric acid in water to respectively prepare an aqueous solution of sodium citrate, an aqueous solution of 4-amino hippuric acid, an aqueous solution of 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA) and an aqueous solution of chloroauric acid;
mixing an aqueous solution of sodium citrate, an aqueous solution of 4-aminohippuric acid, an aqueous solution of 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA) and an aqueous solution of chloroauric acid to prepare a mixed aqueous solution containing trivalent gold ions; wherein, the mass percent concentration of the sodium citrate is 3.8 percent, the mass percent concentration of the 4-amino hippuric acid is 2 percent, the mass percent concentration of the 1,2, 3-triazole-4, 5-dicarboxylic acid (TADA) is 2 percent, and the mass percent concentration of the trivalent gold ions is 1 percent; the total mass of the final mixed solution was 500 g;
s2: dropwise adding a potassium hydroxide solution into the mixed aqueous solution obtained in the step S1, and adjusting the pH value of the mixed aqueous solution to 12 to obtain an alkaline mixed solution;
s3: and (4) placing the alkaline mixed solution obtained in the step S2 into a microwave reactor for microwave treatment, and carrying out oxidation-reduction reaction for 5min under the condition of magnetic stirring at the microwave power of 500W.
Comparative example 1
The chinese invention patent 201610109113.4 provides a preparation method of gold nanoclusters: will contain Au3+Adding the compound into a BSA (bovine serum albumin) aqueous solution or a DNA (deoxyribonucleic acid) aqueous solution or a glutathione aqueous solution, and mixing the BSA, the DNA or the glutathione: au coating3+1-3: 2-9; adjusting pH to 9-13, stirring at 20-50 deg.C for 10-20h, and dialyzing for 36-48h to obtain gold nanoclusters.
Therefore, compared with the existing preparation method of the gold nanocluster, the preparation method of the gold nanocluster by the microwave method provided by the embodiment of the invention has the advantages that the synthesis time is reduced to within 1 hour, and the technical problem of low synthesis and reaction efficiency of the existing preparation method of the gold nanocluster is well solved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A preparation method of gold nanoclusters comprises the following steps:
preparing a mixed solution containing a reducing agent, a stabilizing agent and trivalent gold ions;
adjusting the pH value of the mixed solution to be alkaline to obtain an alkaline mixed solution;
and carrying out microwave treatment on the alkaline mixed solution to generate the gold nanoclusters.
2. The method of claim 1, wherein: the power of the microwave treatment is 100-1000W; and/or
The pH value of the alkaline mixed solution is 9-13.
3. The method of claim 1 or 2, wherein: the microwave treatment time is 5-60 min.
4. The method of claim 1, wherein: the reducing agent comprises one or more of egg white protein, bovine serum albumin, sodium borohydride and sodium citrate; and/or
The compound for providing the trivalent gold ions comprises one or more of chloroauric acid, sodium chloroaurate and potassium chloroaurate; and/or
The stabilizer comprises one or more of egg white protein, bovine serum albumin, 4-aminohippuric acid, glutathione, 11-mercaptoundecanoic acid, 1-amino-2-naphthol 4-sulfonic acid, dithiothreitol, hexadecyltrimethylammonium bromide and 1,2, 3-triazole-4, 5-dicarboxylic acid.
5. The production method according to any one of claims 1,2 and 4, wherein: the concentration of the trivalent gold ions is 0.001% -2%; and/or
The concentration of the reducing agent is 0.001% -10%; and/or
The concentration of the stabilizer is 0.001-10%.
6. The production method according to any one of claims 1,2 and 4, wherein: the solvent of the mixed solution is water.
7. The method of claim 6, wherein: the mixed solution is prepared according to the following method:
respectively dissolving a reducing agent, a stabilizing agent and a gold source for providing trivalent gold ions, and respectively preparing an aqueous solution of the reducing agent, an aqueous solution of the stabilizing agent and an aqueous solution containing the trivalent gold ions;
mixing the aqueous solution of the reducing agent, the aqueous solution of the stabilizing agent and the aqueous solution containing the trivalent gold ions to prepare a mixed solution; the concentration of the reducing agent in the mixed solution is 0.001% -10%, the concentration of the stabilizing agent in the mixed solution is 0.001% -10%, and the concentration of the trivalent gold ions in the mixed solution is 0.001% -2%.
8. The production method according to any one of claims 1,2, 4 and 7, wherein: the microwave treatment process is accompanied by a step of stirring the alkaline mixed solution.
9. The production method according to any one of claims 1,2, 4 and 7, wherein: after the step of microwave treatment, the method also comprises the steps of carrying out solid-liquid separation treatment and purification treatment on the reaction mixed liquid after the microwave treatment.
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