CN111375760B - Au-Ag nano core-shell material using carrageenan as reducing agent and preparation method and application thereof - Google Patents
Au-Ag nano core-shell material using carrageenan as reducing agent and preparation method and application thereof Download PDFInfo
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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Abstract
The invention discloses an Au-Ag nano core-shell material prepared by using carrageenan as a reducing agent and a preparation method thereof, wherein a chloroauric acid solution and an alkaline solution are added into a carrageenan aqueous solution, the mixture is uniformly shaken and reacts at 40-80 ℃, the reaction is cooled to room temperature after the reaction is finished, an orange solution which is a gold sol is obtained, a certain amount of silver nitrate solution and alkaline solution are added into the gold sol, the mixture is uniformly shaken and reacts at 80 ℃, and the Au-Ag nano core-shell material is obtained and comprises a nano gold core body and a nano silver shell layer, wherein the average particle size of the nano gold core body is 10 +/-5 nm, and the average particle size of the Au-Ag nano core-shell material is 30 +/-5 nm. It can be used as catalase-like enzyme for detecting hydrogen peroxide, preventing food from being oxidized or removing hydrogen peroxide in food. The Au-Ag nano core-shell material can develop color, a display agent is not required to be added in the process of detecting the hydrogen peroxide, the detection condition is mild, and the detection method is simple.
Description
Technical Field
The invention relates to a preparation method of a metal nano material, in particular to a method for preparing an Au-Ag nano core-shell material by taking carrageenan as a reducing agent, belonging to the field of catalytic materials and similar bio-enzyme research.
Background
It is well known that biological enzymes are a high molecular substance with good selectivity and high biocatalytic activity. The enzymes existing in organisms mainly comprise proteins, so the activity of the enzymes can be denatured and inactivated by other molecules and the influence of the surrounding environment (such as pH value, temperature, electromagnetic wave and the like), and the enzymes are often limited in storage, transportation and the like in the actual catalytic process. These factors limit the range of application of biological enzymes. Therefore, efforts have been made to develop bio-enzymes having catalytic properties similar to those of bio-enzymes. The artificial synthesized biological enzyme has catalytic activity similar to that of biological enzyme, but has more stable composition and structure and certain anti-interference property.
The hydrogen peroxide is slowly decomposed at normal temperature and pressure, but the decomposition speed is very slow, so that a catalyst is required to accelerate the decomposition process. In the modern times, the catalyst can greatly reduce the production cost and improve the production efficiency. The noble metal nano material has outstanding optical property, electrical property and catalytic property, and is widely applied to the fields of catalytic materials, biomedicine and the like. The noble metal in the noble metal nano material refers to eight metals of gold, silver, palladium, platinum, ruthenium, rhodium, osmium and iridium. With the technical research of the scientific field of China aiming at nano-grade materials, the nano-grade material synthesized by only one noble metal cannot meet the requirements of people on multifunctional materials. Therefore, how to design and synthesize the bimetallic nanometer material with unique appearance, size and physical and chemical properties becomes a research hotspot in the field of nanometer materials. The bimetal nano material has unique structure, morphology, optical property, electrical property and catalytic property, and shows good application prospect. It is therefore a class of materials that have been found to possess peroxidase-like catalytic properties. For example, patent CN107648263A discloses a gold-platinum bimetallic nanoparticle with catalase-like activity, based on which nanoparticles can improve hypoxia of tumor cells Thereby reducing the inhibition of tumor hypoxia microenvironment on immune cells and improving the killing capability of the immune cells; patent CN105372211 discloses Ag/Au bimetal nano-particles, under the action of oxygen, the nano-particles catalyze glucose to be oxidized and generate hydrogen peroxide, H in situ2O2The Ag component in the Ag/Au bimetallic nanometer is dissolved to enable the surface of the Ag/Au hollow nanosphere shell to have nanopores, so that the LSPR absorption peak position of the nanometer particle generates obvious red shift, the detection of glucose is realized, and because the glucose absorption amount required by the growth of cancer cells is larger than that of normal cells, the nanometer particle probe can effectively distinguish the normal cells from the cancer cells based on the sensitive reaction of the nanometer particles to the glucose, and the early diagnosis of the cancer is realized.
Disclosure of Invention
The invention aims to provide a preparation method of a catalase-like Au-Ag nano core-shell material, which is prepared by taking carrageenan as a reducing agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
the Au-Ag nano core-shell material prepared by using carrageenan as a reducing agent comprises a nano gold core body and a nano silver shell layer, wherein the average particle size of the nano gold core body is 10 +/-5 nm, and the average particle size of the Au-Ag nano core-shell material is 30 +/-5 nm.
A method for preparing Au-Ag nanometer core-shell material with carrageenan as reducing agent comprises adding chloroauric acid solution (HAuCl) into carrageenan water solution4) Mixing with alkaline solution, shaking, reacting at 40-80 deg.C, cooling to room temperature after reaction to obtain orange solution (gold sol), and adding silver nitrate solution (AgNO)3) And adding the alkali solution into the gold sol, shaking up, and reacting at 80 ℃ to obtain the Au-Ag nano core-shell material.
Preferably, in the preparation method, HAuCl4And AgNO3The molar mass ratio of (a) to (b) is 1:1 to 1:10, preferably 1: 8.
To enable HAuCl to react4And AgNO3Reducing, wherein the content of carragheenan in the preparation method is excessive.
Preferably, the alkaline solution is one of sodium hydroxide and potassium hydroxide solution.
Preferably, the reaction temperature of the chloroauric acid solution and the sodium hydroxide solution is 60 ℃.
The Au-Ag nano core-shell material prepared by the method is used as catalase-like enzyme. In particular, the method can be used for detecting hydrogen peroxide, such as detecting the content of the hydrogen peroxide in organisms, and can also be applied to the field of food, such as preventing food from being oxidized, removing the hydrogen peroxide in the food, and the like.
The specific method for determining the hydrogen peroxide content by taking the Au-Ag nano core-shell material as catalase-like enzyme comprises the steps of adding the Au-Ag nano core-shell material into a solution to be determined, catalyzing hydrogen peroxide in the solution to react, determining absorbance based on the change of the solution color, and further determining the hydrogen peroxide content. In the process, the color of the Au-Ag sol is changed from light pink to orange along with the reduction of the concentration of the hydrogen peroxide, and the material can be used as a color developing agent. In addition, when the Au-Ag nano core-shell material is used for hydrogen peroxide catalysis, the pH value of a reaction system is in a neutral range, and a good detection effect can be achieved at normal temperature.
The invention has the remarkable characteristics that:
(1) the Au-Ag nano core-shell material utilizes the metal silver as a shell layer to wrap the nano gold, so that the catalytic performance of the Au-Ag nano core-shell material is greatly improved, and the Au-Ag nano core-shell material has a good catalytic effect in the determination of hydrogen peroxide.
(2) The synthesis method of the Au-Ag nano core-shell material is simple, the synthesis process is green and pollution-free, the carrageenan can be used as a food additive, and the toxic and side effects are small.
(3) The Au-Ag nano core-shell material has smaller size, is distributed in carrageenan, and has better stability in a reaction system, thereby having lower requirements on reaction conditions.
(4) The Au-Ag nano core-shell material can develop color, a display agent is not required to be added in the process of detecting the hydrogen peroxide, the detection condition is mild, and the detection method is simple.
Drawings
FIG. 1 is a photograph of different AuNPs samples obtained in example 1, wherein a is 20. mu. L, b, 50. mu. L, c and 100. mu.L;
FIG. 2 is a photograph of different AuNPs samples obtained in example 2, wherein a is 40 ℃, b is 60 ℃ and c is 80 ℃;
FIG. 3 is a UV spectrum of the product obtained in example 3 with different raw material volume ratios;
FIG. 4 is TEM image and EDX image of AuNPs and Au-Ag nano-materials obtained in examples 1 and 3, wherein a is TEM image of AuNPs, b is TEM image of Au-Ag, c is TEM image of Au-Ag, and d is EXD image of Au-Ag;
FIG. 5 is a photograph of the AgNPs sol obtained in example 4;
FIG. 6 is a UV spectrum of hydrogen peroxide catalyzed by different catalysts in example 5, wherein AuNPs, AgNPs and Au-Ag are comparative samples without hydrogen peroxide;
FIG. 7 is a graph showing the UV spectrums and the reaction effects of Au-Ag, a product obtained in example 3.
Detailed Description
In order to more specifically illustrate the method of the present invention, examples of the present invention are given below, but the application of the present invention is not limited thereto.
Example 1
0.5g of carrageenan powder was dissolved in 100mL of secondary water, and the mixture was heated and stirred for 1 hour. 10mL of the above solution was added to 20. mu.L, 50. mu.L, 100. mu.L of 0.02M chloroauric acid solution and 50. mu.L of 0.01M sodium hydroxide solution, respectively, shaken well, and placed in an electric hot air drying oven to react at 60 ℃ for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the results are shown in FIG. 1.
FIG. 1 shows that the optimal addition of 50 μ L of chloroauric acid gives the gold sol with purple color, no precipitate and the best effect, and the gold sol prepared under the conditions is marked as AuNPs.
Example 2
0.5g of carrageenan powder was dissolved in 100mL of secondary water, and the mixture was heated and stirred for 1 hour. 10mL of the above solution was added to 50. mu.L of 0.02M chloroauric acid solution and 50. mu.L of 0.01M sodium hydroxide solution, shaken well, placed in an electric hot air drying oven, and reacted at 40 ℃, 60 ℃ and 80 ℃ for 12 hours, respectively. After the reaction was completed, the reaction mixture was cooled to room temperature, and the results are shown in FIG. 2.
FIG. 2 shows that the optimal reaction temperature is 60 ℃, and the obtained gold sol is purple, has no precipitate and has the best effect.
Example 3
0.5g of carrageenan powder was dissolved in 100mL of secondary water, heated and stirred for 1 hour. 10mL of the above solution was added with 50. mu.L of 0.02M chloroauric acid solution and 50. mu.L of 0.01M sodium hydroxide solution, shaken well, placed in an electric hot air drying oven, and reacted at 60 ℃ for 12 hours. After the reaction is finished, cooling to room temperature, preparing the prepared 1ml of gold sol, 0.02M of silver nitrate solution with different volumes, 200 mu L of 0.01M of sodium hydroxide solution and secondary water into solution with the volume of 2ml, shaking up, placing in an electric heating forced air drying oven, and reacting for 2h at 80 ℃ to obtain the orange Au-Ag nano core-shell material.
Raw material regulation and control (HAuCl) in Au-Ag synthesis process4:AgNO3) The volume ratio is (a)1:1(b)1:2(c)1:4(d)1:8(e)1:10, and different Au-Ag nano core-shell materials are obtained. 1mL of the Au-Ag nano core-shell material with different volume ratios of the raw materials is added into 1mL of secondary water, the mixture is fully shaken and shaken up, and the ultraviolet scanning result is shown in figure 3.
FIG. 3 shows the results in HAuCl4:AgNO3Is 1: when 8, the optical response of the catalyst is best. The sample prepared under this condition was labeled Au-Ag.
As shown in FIG. 4, compared with AuNPs, the Au-Ag particles are significantly larger in size, the average particle size is 30nm, and the fact that nanogold with the particle size of 10nm is used as the inner core and the carrageenan is used for reducing AgNO 3Synthesizing the Au-Ag core-shell material taking the nano-silver as the shell. EDS analysis chart is used for element determination, and the result proves that the alloy contains two elements of Au and Ag.
Example 4
0.5g of carrageenan powder was dissolved in 100mL of secondary water, and the mixture was heated and stirred for 1 hour. 10mL of the above solution was added with 50. mu.L of 0.02M silver nitrate solution and 50. mu.L of 0.01M sodium hydroxide solution, shaken well, and placed in an electric hot air drying oven to react at 60 ℃ for 12 hours. After the reaction is finished, the reaction product is cooled to room temperature, and as shown in fig. 5, the obtained yellow solution is silver sol and is marked as AgNPs.
Example 5
Collecting 200 μ L of 1.0 × 10-3M hydrogen peroxide, and 1mL of secondary water and 1mL of AuNPs (a) prepared in examples 1, 3 and 4 were added,Au-Ag (c) and AgNPs (b), shaking up fully, reacting for 6min at normal temperature. The uv scan results are shown in figure 6.
FIG. 6 shows that AuNPs have no catalytic action on hydrogen peroxide, and Au-Ag nano core-shell materials have stronger catalytic action than AgNPs.
The Au-Ag prepared in example 3 was added to hydrogen peroxide solutions of different concentrations, 0. mu.M, 90. mu.M, 290. mu.M and 540. mu.M, respectively, and the total volume of the reaction system was 2mL, followed by sufficient shaking and reaction at room temperature for 6 min. The results of the uv scan are shown in figure 7.
Fig. 7 shows that under the same other conditions, in a certain range, the color of the Au-Ag sol changes from orange to light pink with the increase of the hydrogen peroxide concentration, and the catalytic effect is more remarkable.
Claims (7)
1. A process for preparing Au-Ag nano core-shell material with carrageenin as reducer includes such steps as adding the solution of chloroauric acid and alkaline solution to the aqueous solution of carrageenin, shaking up, and reaction at 40-80%oC, reacting, cooling to room temperature after the reaction is finished to obtain a purple solution, namely gold sol, adding a certain amount of silver nitrate solution and alkaline solution into the gold sol, shaking up, and stirring at 80 DEG CoReacting under C to obtain Au-Ag nano core-shell material;
the Au-Ag nano core-shell material comprises a nano gold core body and a nano silver shell layer, wherein the average particle size of the nano gold core body is 10 +/-5 nm, and the average particle size of the Au-Ag nano core-shell material is 30 +/-5 nm;
the Au-Ag nano core-shell material is applied as catalase-like.
2. The method for preparing Au-Ag nano core-shell material by using carrageenan as reducing agent according to claim 1, wherein HAuCl is added in the preparation method4And AgNO3The molar mass ratio of (a) to (b) is 1:1 to 1: 10.
3. The method for preparing Au-Ag nano core-shell material by using carrageenan as reducing agent according to claim 2, wherein HAuCl is added in the preparation method4And AgNO3The molar mass ratio of (a) to (b) is 1: 8.
4. The method for preparing the Au-Ag nano core-shell material by using the carrageenan as the reducing agent according to claim 3, wherein the alkaline solution is one of sodium hydroxide and potassium hydroxide solution.
5. The method for preparing the Au-Ag nano core-shell material by using the carrageenan as the reducing agent according to claim 4, wherein the reaction temperature of the chloroauric acid solution and the sodium hydroxide solution is 60 ℃.
6. The application of the Au-Ag nano core-shell material prepared by the preparation method of preparing the Au-Ag nano core-shell material by using carrageenan as a reducing agent according to claim 1 as catalase-like enzyme is characterized by being used for detecting hydrogen peroxide to prevent food from being oxidized or remove the hydrogen peroxide in the food.
7. The Au-Ag nano core-shell material prepared according to the claim 6 is applied as catalase-like enzyme, and the specific method for determining the hydrogen peroxide content by using the Au-Ag nano core-shell material as catalase-like enzyme is characterized in that the Au-Ag nano core-shell material is added into a solution to be measured to catalyze the hydrogen peroxide in the solution to react, and the absorbance is determined based on the change of the solution color, so that the hydrogen peroxide content is determined.
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