CN114558569A - Gold and silver bimetal nanocluster and preparation method and application thereof - Google Patents
Gold and silver bimetal nanocluster and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a gold and silver bimetal nanocluster and a preparation method and application thereofMetal nanoclusters. The method avoids the addition of sodium hydroxide and common reducing agents such as sodium borohydride, hydrazine hydrate and the like in the synthesis process, and has the advantages of simple synthesis method, mild synthesis conditions and environmental friendliness. The prepared gold and silver bimetallic nanocluster is good in water solubility and stability, and has excellent catalytic performance and luminescence performance. The red fluorescent gold-silver bimetallic nanocluster prepared by the invention can be used for constructing vitamin B6The detection method of (2) can also be applied to a catalyst for reducing nitrophenol isomers.
Description
Technical Field
The invention relates to preparation of metal nanoclusters, in particular to gold and silver bimetallic nanoclusters and a preparation method and application thereof.
Background
When the size of the metal nanoparticles is reduced to the level of the electronic fermi wavelength, the plasma absorption disappears completely and molecular-like properties of discrete electronic states are generated, these ultra-small metal nanoparticles are called metal nanoclusters. Metal nanoclusters have unique advantages as catalysts due to their high specific surface area, enhanced charge carrier mobility, and unique surface electron structure. The properties of noble metal nanoclusters can be changed by changing the properties and size of the capping ligand, and more attention is paid to the fact that the metal nanoclusters are doped with one metal atom, and the electronic structure and the photophysical properties of the metal nanoclusters can be controlled or improved.
The gold-silver bimetallic nanocluster integrates the chemical and physical properties of gold and silver into one nanocluster through a synergistic effect, so that more excellent optical, electronic and catalytic properties are shown. The gold and silver bimetallic nanocluster as a novel fluorescence sensing and catalysis nanomaterial is widely concerned in the fields of analysis and detection, biosensing, catalysis and the like, and has a wide application prospect.
To date, a series of synthetic strategies for gold-silver bimetallic nanoclusters have been reported. For example, Yu et al first synthesizes silver nanocluster protected by Bovine Serum Albumin (BSA) through sodium borohydride reduction as a precursor, then mixes the precursor with chloroauric acid solution to carry out 3 hours of current displacement reaction, and centrifuges the mixture for 30 minutes to obtain the gold and silver bimetallic nanocluster (Materials Science & Engineering C, 2020, 109: 110525). Dai et al added a NaOH solution to Bovine Serum Albumin (BSA) as a protective agent and reacted at 37 ℃ for 12 hours to successfully prepare the gold-silver bimetallic nanoclusters. (Microchemical Journal, 2018, 139: 1-8). And (3) adding chloroauric acid and a silver source into methanol for uniform dispersion, adding triphenylphosphine and sodium borohydride, changing the solution into reddish brown after 12 hours, and purifying and separating to obtain the gold-silver bimetallic nanocluster (CN 112354567A). Liu et al prepared bimetallic nanoclusters protected by small molecules by a hydrothermal synthesis method, and reacted in an autoclave for 30 minutes by taking Adenosine Monophosphate (AMP) as a protective agent to prepare the gold and silver bimetallic nanoclusters. (Journal of Materials Chemistry C, 2017, 5: 9979-9985).
However, the currently reported synthesis method is complex in operation and high in equipment requirement, or reducing agents such as sodium hydroxide, hydrazine hydrate and sodium borohydride need to be added, so that negative effects on the environment are generated. Therefore, the green simple synthetic method has become the direction of the researchers in this field.
Vitamin B6As an important biological coenzyme, more than 100 metabolic reactions related to amino acids, fats and glucose are involved. It is also involved in the formation of erythrocytes, supporting the immune and nervous systems. Notably, vitamin B is present in the body6May be harmful to human health. Vitamin B6Deficiencies can lead to dermatitis, anemia, and neurological disorders, including confusion, weakness, and depression. Therefore, development and detection of vitamin B6The analysis method of (2) is of great significance.
Nitrophenol is one of the most common nitroaromatic compounds due to the introduction of a strong electron-withdrawing group (-NO) on the benzene ring2) Making it toxic. Because of the solubility and stability of nitrophenols in water, if discharged into the environment without proper disposal, there is a negative impact on biological growth. If the water is introduced into domestic water through underground water, the water is in human bodyThe accumulation of the gene can cause cell canceration and gene mutation. Nitrophenol is classified as a "priority pollutant" by the United states national environmental protection agency (USEPA), and the concentration requirement of nitrophenol in drinking water is <0.06 mg/L. A new water treatment catalyst is actively explored to be an effective way for solving the problem of nitrophenol pollution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a gold and silver bimetallic nanocluster as well as a preparation method and application thereof.
In order to solve the technical problems, according to one aspect of the invention, the preparation method of the gold and silver bimetallic nanocluster is provided, wherein N-acetyl-L-cysteine is used as a protective agent and a reducing agent, a silver nitrate solution and a chloroauric acid solution are used as raw materials, the N-acetyl-L-cysteine solution, the silver nitrate solution and the chloroauric acid solution are mixed, and the gold and silver bimetallic nanocluster is obtained after heating and refluxing.
Further, in the preparation method, 3 parts by volume of N-acetyl-L-cysteine solution with the concentration of 10-35 mmol/L, 2 parts by volume of chloroauric acid solution with the concentration of 10 mmol/L and 2.5 parts by volume of silver nitrate solution with the concentration of 1.6-16 mmol/L are mixed, the heating temperature is controlled to be 60-90 ℃, reflux is carried out for 2-12 h, and the mixture is cooled to room temperature and then taken out to obtain the gold and silver bimetallic nanocluster aqueous solution. And then freeze-drying to remove the solvent water, thus obtaining the gold-silver bimetallic nanocluster.
Further, the concentration of the N-acetyl-L-cysteine solution is 20 mmol/L, and the concentration of the silver nitrate solution is 4 mmol/L.
Further, the N-acetyl-L-cysteine solution is mixed with chloroauric acid solution and silver nitrate solution and then refluxed for 12 hours at the temperature of 80 ℃.
Further, the molar ratio of the silver nitrate to the chloroauric acid is 1: 2.
According to the above method, N-acetyl-L-cysteine is a compound with a sulfhydryl group, and the sulfhydryl group has a certain reducibility and has a strong acting force with noble metals. The gold and silver bimetallic nanoclusters are synthesized in one step by adopting a reflux method, the addition of sodium hydroxide, reducing agents such as sodium borohydride, ascorbic acid and hydrazine hydrate is avoided in the synthesis process, and the method has the advantages of simplicity and convenience in synthesis method, mild synthesis conditions, high efficiency, environmental friendliness and the like.
According to another aspect of the present invention, there are provided gold-silver bimetallic nanoclusters prepared by the above-described method and applications thereof.
The gold and silver bimetallic nanoclusters prepared by the method are good in water solubility, good in stability, small in size, excellent in catalytic performance and light-emitting performance, the fluorescence emission of the gold and silver bimetallic nanoclusters is in a near infrared region, the maximum emission wavelength of the gold and silver bimetallic nanoclusters is 700 nm, and strong red fluorescence is presented when the gold and silver bimetallic nanoclusters are observed on a black background under ultraviolet light.
Therefore, according to another aspect of the present invention, the gold and silver bimetallic nanoclusters are claimed to be used for constructing vitamin B6The application of the fluorescence detection method of (4), wherein the detection limit is 1.46. mu. mol/L.
According to another aspect of the invention, the use of the gold and silver bimetallic nanoclusters as catalysts for the reduction of nitrophenol isomers is claimed.
Based on the application of the silver bimetallic nanocluster as a catalyst for reducing nitrophenol isomers, the invention also provides a method for reducing nitrophenol isomers, and the gold and silver bimetallic nanoclusters are added into a reaction system of nitrophenol isomer solution and sodium borohydride solution as the catalyst.
The nitrophenol isomers described above include o-nitrophenol, m-nitrophenol and p-nitrophenol.
Relatively specifically, for different nitrophenol isomers, 0.5 mmol/L of o-nitrophenol solution, 0.5 mmol/L of m-nitrophenol solution and 0.12 mmol/L of p-nitrophenol solution are respectively mixed with 0.5 mL of 2 mg/mL of sodium borohydride solution and then added into a quartz cuvette, and the solution is still yellow and does not change. After 5 mg/mL of gold and silver bimetallic nanocluster aqueous solution of 25 muL is added into the mixed solution, the yellow color of the solution is continuously faded, and corresponding aminophenol is obtained through reaction under the catalytic action of the gold and silver bimetallic nanoclusters.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a transmission electron microscope image of the gold-silver bimetallic nanoclusters of example 5;
FIG. 2 is Zeta potential diagram of the gold and silver bimetallic nanoclusters of example 5;
FIG. 3 is the ultraviolet absorption spectrum and fluorescence excitation and emission spectrum of the luminescent gold-silver bimetallic nanoclusters of example 5;
FIG. 4 is an infrared spectrum of the gold and silver bimetallic nanoclusters and N-acetyl-L-cysteine of example 5; line a: N-acetyl-L-cysteine, line b: gold and silver bimetallic nanoclusters;
FIG. 5 is a diagram of the UV-VIS absorption spectrum of the catalytic reduction of o-nitrophenol by the gold and silver bimetallic nanoclusters of example 5; the inset shows the change in color of the solution before (left) and after (right) the reaction;
FIG. 6 is a diagram of the UV-VIS absorption spectrum of the catalytic reduction of m-nitrophenol by the gold and silver bimetallic nanoclusters of example 5; the inset shows the change in color of the solution before (left) and after (right) the reaction;
FIG. 7 is a graph of the UV-VIS absorption spectrum of catalytic reduction of p-nitrophenol by the gold and silver bimetallic nanoclusters of example 5; the inset shows the change in color of the solution before (left) and after (right) the reaction;
FIG. 8 shows the gold and silver bimetallic nanoclusters of example 5 vs. vitamin B6A responsive operating curve;
FIG. 9 shows the logarithmic change of fluorescence intensity of the red fluorescent gold-silver bimetallic nanoclusters and vitamin B in example 56Linear relationship between concentrations.
Detailed Description
Examples 1 to 7 are preparation methods of red fluorescent gold-silver bimetallic nanoclusters, examples 8 to 10 are application examples of the red fluorescent gold-silver bimetallic nanoclusters as catalysts for reducing nitrophenol isomers, and example 11 is red fluorescent gold-silver bimetallic nanoclustersClusters for the construction of vitamin B6Application example of the fluorescence detection method of (1).
Example 1
And mixing 3 mL of 20 mmol/L N-acetyl-L-cysteine solution, 2 mL of 10 mmol/L chloroauric acid solution and 2.5 mL of 2 mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 8 hours, and taking out after cooling to obtain the gold-silver bimetallic nanocluster aqueous solution. The fluorescence emission peak of the luminescent gold-silver bimetallic nanocluster is about 700 nm, and when the luminescent gold-silver bimetallic nanocluster is observed with a black background under ultraviolet light, relatively strong red fluorescence is presented, and the quantum yield is 0.17.
Example 2
Mixing 3 mL of 20 mmol/L N-acetyl-L-cysteine solution, 2 mL of 10 mmol/L chloroauric acid solution and 2.5 mL of 4 mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃, refluxing for 6 hours, and taking out after cooling to obtain the gold and silver bimetallic nanocluster aqueous solution. The fluorescence emission peak of the luminescent gold-silver bimetallic nanocluster is about 700 nm, and when the luminescent gold-silver bimetallic nanocluster is observed with a black background under ultraviolet light, relatively strong red fluorescence is presented, and the quantum yield is 0.21.
Example 3
Mixing 3 mL of 10 mmol/L N-acetyl-L-cysteine solution, 2 mL of 10 mmol/L chloroauric acid solution and 2.5 mL of 4 mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 12 hours, and taking out after cooling to obtain the gold-silver bimetallic nanocluster aqueous solution. The fluorescence emission peak of the luminescent gold-silver bimetallic nanocluster is about 700 nm, and when the luminescent gold-silver bimetallic nanocluster is observed on a black background under ultraviolet light, relatively strong red fluorescence is presented, and the quantum yield is 0.19.
Example 4
Mixing 3 mL of 20 mmol/L N-acetyl-L-cysteine solution, 2 mL of 10 mmol/L chloroauric acid solution and 2.5 mL of 4 mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 60 ℃, refluxing for 12 hours, and taking out after cooling to obtain the gold and silver bimetallic nanocluster aqueous solution. The fluorescence emission peak of the luminescent gold-silver bimetallic nanocluster is about 700 nm, and when the luminescent gold-silver bimetallic nanocluster is observed with a black background under ultraviolet light, relatively strong red fluorescence is presented, and the quantum yield is 0.15.
Example 5
Mixing 3 mL of 20 mmol/L N-acetyl-L-cysteine solution, 2 mL of 10 mmol/L chloroauric acid solution and 2.5 mL of 4 mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃, refluxing for 12 hours, and taking out after cooling to obtain the gold and silver bimetallic nanocluster aqueous solution. The fluorescence emission peak of the luminescent gold-silver bimetallic nanocluster is about 700 nm, and the luminescent gold-silver bimetallic nanocluster presents strong red fluorescence when observed with a black background under ultraviolet light, and the quantum yield is 0.25. The good luminous performance can be still maintained after continuous ultraviolet irradiation for 50 min, the fluorescence intensity is basically kept unchanged, and the photobleaching resistance is good.
And analyzing the distribution form and the size of the prepared gold and silver bimetallic nanoclusters through a transmission electron microscope. As shown in figure 1, the synthesized gold and silver bimetallic nanoclusters are in spherical distribution and have good monodispersity, and the average particle size of the gold and silver bimetallic nanoclusters is 1.23 nm.
Adding 1 mL of acetic acid buffer solution (HAc-NaAc buffer solution, pH =7, 50 mmol/L) and 100 mu L of gold and silver bimetal nanocluster solution into a reagent bottle, and detecting the Zeta potential after carrying out ultrasonic treatment for 20 min. As shown in FIG. 2, the Zeta potential value of the gold and silver bimetallic nanocluster is-44.9 mV, which indicates that the prepared nanocluster is negatively charged and has good stability.
Adding 1 mL of acetic acid buffer solution (HAc-NaAc buffer solution, pH =7, 50 mmol/L) and 100 μ L of gold and silver bimetal nanocluster solution into a fluorescence cuvette, and measuring an ultraviolet absorption spectrum and a fluorescence excitation and emission spectrum of the gold and silver bimetal nanocluster, wherein as shown in figure 3, the fluorescence emission peak of the luminescent gold and silver bimetal nanocluster is located in a near infrared region, and the maximum emission wavelength is 700 nm.
The changes of the vibration energy level and the rotation energy level of molecules in the prepared gold-silver bimetallic nanocluster solution are researched. Weighing a small amount of the gold and silver bimetallic nanocluster solid powder and the N-acetyl-L-cysteine powder prepared in the example 5, respectively mixing and grinding the solid powder and the N-acetyl-L-cysteine powder with a certain amount of potassium bromide powder, Tabletting, placing in an infrared spectrometer for 400 cm of 4000 plus materials-1The absorption spectrum in the wavenumber range is scanned. As shown in FIG. 4, comparing FTIR spectra of the two, S-H stretched band (2547 cm) of N-acetyl-L-cysteine was clearly observed-1) The loss of the gold-silver bimetallic nanocluster in the infrared spectrum shows that the N-acetyl-L-cysteine molecule protects the gold-silver bimetallic nanocluster in the form of thiolate. To 3394 cm-1The absorption peak at (b) is assigned to upsilonOHAnd upsilon, a secondary amineNHCu-Ag bimetallic nanocluster and N-acetyl-L-cysteineC=ORespectively appear at 1702 cm-1And 1717 cm-1Delta of a secondary amineNHRespectively appearing at 1532 cm-1And 1533 cm-1Here, the slight shift of the absorption peak may be related to the interaction between the gold and silver bimetallic nanoclusters and N-acetyl-L-cysteine. The above results indicate that N-acetyl-L-cysteine is attached to the gold and silver bimetallic nanoclusters in the form of thiolate.
Example 6
Mixing 3 mL of 20 mmol/L N-acetyl-L-cysteine solution, 2 mL of 10 mmol/L chloroauric acid solution and 2.5 mL of 1.6 mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 90 ℃ and refluxing for 2 h, and taking out after cooling to obtain the gold and silver bimetallic nanocluster aqueous solution. The fluorescence emission peak of the luminescent gold-silver bimetallic nanocluster is about 700 nm, and when the luminescent gold-silver bimetallic nanocluster is observed with a black background under ultraviolet light, relatively strong red fluorescence is presented, and the quantum yield is 0.13.
Example 7
Mixing 3mL of 35mmol/L N-acetyl-L-cysteine solution, 2 mL of 10 mmol/L chloroauric acid solution and 2.5 mL of 16mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃, refluxing for 12 hours, and taking out after cooling to obtain the gold and silver bimetallic nanocluster aqueous solution. The fluorescence emission peak of the luminescent gold-silver bimetallic nanocluster is about 700 nm, and when the luminescent gold-silver bimetallic nanocluster is observed on a black background under ultraviolet light, relatively strong red fluorescence is presented, and the quantum yield is 0.18.
Comparative example 1
Mixing 3mL of 20 mmol/L N-acetyl-L-cysteine aqueous solution and 2.5 mL of 4 mmol/L silver nitrate aqueous solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃, refluxing for 12 h, cooling and taking out to obtain the silver nanocluster. The fluorescence emission peak of the silver nanocluster is 494 nm, and the fluorescence intensity is continuously reduced under continuous ultraviolet irradiation, which indicates that the light stability of the silver nanocluster is poor.
This comparative example, which is a comparative example to example 5, was used to further illustrate the advantages of the process of the present invention, and the luminescent silver nanoclusters were synthesized using N-acetyl-L-cysteine and silver nitrate aqueous solution as raw materials by a heating reflux method. Through comparison, the fluorescence emission of the gold and silver bimetallic nanocluster synthesized by the method obviously red-shifts to a near infrared region, the maximum emission peak is located at 700 nm, and the red fluorescence-emitting nanomaterial is more favorable for reducing interference. And has good light stability, and is beneficial to realizing the application in the actual life.
Comparative example 2
Adding N-acetyl-L-cysteine (3 mL, 20 mmol/L) and chloroauric acid aqueous solution (2 mL, 10 mmol/L) into a 50 mL round-bottom flask, stirring the mixed solution uniformly, refluxing at 80 ℃ for 12 h, and taking out after cooling to obtain the gold nanoclusters. The gold nanoclusters do not show fluorescence when observed with a black background under ultraviolet light.
This comparative example, which is a comparative example to example 5, was used to further illustrate the advantages of the process of the present invention, and gold nanoclusters were synthesized by a heating reflux method using N-acetyl-L-cysteine and an aqueous solution of chloroauric acid as raw materials. The gold nanoclusters prepared by the comparative example do not fluoresce as can be seen by comparison.
Example 8
Catalytic application of gold-silver bimetallic nanocluster in o-nitrophenol reduction reaction
The aqueous gold and silver bimetallic nanocluster solution prepared in example 5 was lyophilized and then prepared into an aqueous solution with a concentration of 5 mg/mL.
2.5 mL of 0.5 mmol/L o-nitrophenol solution and 0.5 mL of 2 mg/mL sodium borohydride solution are added into the sample cell, and the solution is still yellow and does not change. And (3) adding 25 mu L of the 5 mg/mL gold and silver bimetallic nanocluster aqueous solution, and measuring the change of the absorbance at 416 nm. As shown in FIG. 5, the absorbance at 416 nm decreased with time, the o-nitrophenol was all reduced to o-aminophenol after 12 min, and the yellow color of the solution faded.
Example 9
Catalysis application of gold-silver bimetallic nanocluster in m-nitrophenol reduction reaction
The gold and silver bimetallic nanocluster aqueous solution prepared in example 5 was freeze-dried and then prepared into an aqueous solution with a concentration of 5 mg/mL.
2.5 mL of m-nitrophenol solution with the concentration of 0.5 mmol/L and 0.5 mL of sodium borohydride solution with the concentration of 2 mg/mL are added into the sample cell, and the solution is still yellow and does not change. And (3) adding 25 mu L of the 5 mg/mL gold and silver bimetallic nanocluster aqueous solution, and measuring the change of absorbance at 390 nm. As shown in FIG. 6, the absorbance at 390 nm decreased with time, and after 5 min, m-nitrophenol was completely reduced to m-aminophenol, and the yellow color of the solution faded.
Example 10
Catalysis application of gold-silver bimetallic nanocluster in p-nitrophenol reduction reaction
The aqueous gold and silver bimetallic nanocluster solution prepared in example 5 was lyophilized and then prepared into an aqueous solution with a concentration of 5 mg/mL.
2.5 mL of 0.12 mmol/L p-nitrophenol solution and 0.5 mL of 2 mg/mL sodium borohydride solution are added into the sample cell, and the solution is still yellow and does not change. And (3) adding 25 mu L of the 5 mg/mL gold and silver bimetallic nanocluster aqueous solution, and measuring the change of absorbance at 400 nm. As shown in FIG. 7, the absorbance at 400 nm decreased with time, a new absorption peak appeared at 300 nm, p-nitrophenol was completely reduced to p-aminophenol after 8 min, and the yellow color of the solution faded.
Example 11
Red fluorescent gold and silver bimetallic nanocluster in vitamin B6In the detection of
Taking the red fluorescent honeysuckle and honeysuckle prepared in the example 5Adding 100 μ L of metal nanocluster aqueous solution and 1 mL of acetic acid buffer (HAc-NaAc buffer, pH =7, 50 mmol/L) into a fluorescence cuvette, and adding vitamin B with different concentrations6The fluorescence spectrum of the solution was measured at an excitation wavelength of 320 nm. As shown in FIG. 8, with vitamin B6The concentration of the solution is increased, and the fluorescence of the red fluorescent gold-silver bimetallic nanocluster is gradually quenched; as shown in FIG. 9, the logarithmic change in fluorescence intensity and vitamin B6Is linear with the change in fluorescence intensity in log (F)0is/F) wherein F0And F each represents vitamin B6Fluorescence intensity of the gold-silver bimetallic nanoclusters in the absence and in the presence ranges from 17.8 μmol/L to 286 μmol/L in detection linearity.
The regression equation of the gold and silver bimetallic nanoclusters obtained through linear fitting is as follows: y =0.00250x +0.00251 with linear coefficient R2=0.997, detection limit 1.46 μmol/L. The red fluorescent gold-silver bimetallic nanocluster can be applied to vitamin B in biological samples6And (5) detecting the content.
The embodiments described herein are only examples of a part of this application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (10)
1. A preparation method of gold and silver bimetallic nanoclusters is characterized by comprising the following steps: taking N-acetyl-L-cysteine as a protective agent and a reducing agent, and taking a silver nitrate solution and a chloroauric acid solution as raw materials; and mixing the N-acetyl-L-cysteine solution, the silver nitrate solution and the chloroauric acid solution, and heating and refluxing to obtain the gold and silver bimetallic nanocluster.
2. The method of claim 1, wherein: mixing 3 parts by volume of N-acetyl-L-cysteine solution with the concentration of 10-35 mmol/L, 2 parts by volume of chloroauric acid solution with the concentration of 10 mmol/L and 2.5 parts by volume of silver nitrate solution with the concentration of 1.6-16 mmol/L, controlling the heating temperature to be 60-90 ℃ for refluxing for 2-12 h, cooling to room temperature, taking out to obtain the gold-silver bimetallic nanocluster aqueous solution, and then freeze-drying to remove solvent water to obtain the gold-silver bimetallic nanocluster.
3. The method of claim 1, wherein: the concentration of the N-acetyl-L-cysteine solution is 20 mmol/L, and the concentration of the silver nitrate solution is 4 mmol/L.
4. The method of claim 1, wherein: the N-acetyl-L-cysteine solution is mixed with chloroauric acid solution and silver nitrate solution and then refluxed for 12 hours at the temperature of 80 ℃.
5. The method of claim 1, wherein: the molar ratio of the silver nitrate to the chloroauric acid is 1: 2.
6. The gold and silver bimetallic nanoclusters produced by the method of any one of claims 1 to 5.
7. The use of the gold and silver bimetallic nanoclusters of claim 6 for constructing vitamin B6The use of the fluorescence detection method of (1).
8. Use of the gold and silver bimetallic nanoclusters of claim 6 as a catalyst for reducing nitrophenol isomers.
9. A method of reducing nitrophenol isomers, characterized by: adding the gold and silver bimetallic nanoclusters as described in claims 1-5 as a catalyst into a reaction system of nitrophenol isomer solution and sodium borohydride solution.
10. The method of claim 9, wherein: the nitrophenol isomers include o-nitrophenol, m-nitrophenol and p-nitrophenol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116020453A (en) * | 2022-10-09 | 2023-04-28 | 西北工业大学 | Gold-silver nano alloy and ultra-clean preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160054328A1 (en) * | 2013-03-22 | 2016-02-25 | Council Of Scientific And Industrial Research | One pot process for the prepration of gold quantum clusters |
| CN105598465A (en) * | 2016-01-08 | 2016-05-25 | 山西大学 | Preparing method and application of fluorogold nanoparticles |
| CN109810694A (en) * | 2019-01-23 | 2019-05-28 | 山西大学 | A kind of water-soluble copper namo fluorescence probe and the preparation method and application thereof |
| CN110591702A (en) * | 2019-09-19 | 2019-12-20 | 山西大学 | Preparation method and application of aggregation-induced luminescent silver nanocluster |
| CN111624183A (en) * | 2020-06-05 | 2020-09-04 | 深圳职业技术学院 | Fluorescent array sensor based on gold clusters and gold nanoparticles and preparation method and application thereof |
| CN112122621A (en) * | 2020-09-23 | 2020-12-25 | 山东大学 | Preparation method of gold and silver bimetallic nanocluster capable of generating near-infrared electrochemiluminescence radiation |
| CN112354567A (en) * | 2020-11-10 | 2021-02-12 | 安徽大学 | Preparation method of gold and silver bimetallic nanocluster and application of gold and silver bimetallic nanocluster in sewage degradation |
-
2022
- 2022-01-27 CN CN202210098612.3A patent/CN114558569B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160054328A1 (en) * | 2013-03-22 | 2016-02-25 | Council Of Scientific And Industrial Research | One pot process for the prepration of gold quantum clusters |
| CN105598465A (en) * | 2016-01-08 | 2016-05-25 | 山西大学 | Preparing method and application of fluorogold nanoparticles |
| CN109810694A (en) * | 2019-01-23 | 2019-05-28 | 山西大学 | A kind of water-soluble copper namo fluorescence probe and the preparation method and application thereof |
| CN110591702A (en) * | 2019-09-19 | 2019-12-20 | 山西大学 | Preparation method and application of aggregation-induced luminescent silver nanocluster |
| CN111624183A (en) * | 2020-06-05 | 2020-09-04 | 深圳职业技术学院 | Fluorescent array sensor based on gold clusters and gold nanoparticles and preparation method and application thereof |
| CN112122621A (en) * | 2020-09-23 | 2020-12-25 | 山东大学 | Preparation method of gold and silver bimetallic nanocluster capable of generating near-infrared electrochemiluminescence radiation |
| CN112354567A (en) * | 2020-11-10 | 2021-02-12 | 安徽大学 | Preparation method of gold and silver bimetallic nanocluster and application of gold and silver bimetallic nanocluster in sewage degradation |
Non-Patent Citations (4)
| Title |
|---|
| 杨正丽: "金基双金属纳米团簇制备及其在分析检测中的应用" * |
| 杨正丽: "金基双金属纳米团簇制备及其在分析检测中的应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑(月刊)》 * |
| 马诚: "维生素B2、维生素B6检测中金/银纳米材料的制备与应用" * |
| 马诚: "维生素B2、维生素B6检测中金/银纳米材料的制备与应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑(月刊)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116020453A (en) * | 2022-10-09 | 2023-04-28 | 西北工业大学 | Gold-silver nano alloy and ultra-clean preparation method and application thereof |
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