CN114433868A - Branched CuAu alloy nanocrystal and preparation method thereof - Google Patents
Branched CuAu alloy nanocrystal and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a branched CuAu alloy nanocrystal, which mainly comprises the following steps: mixing a copper chloride solution and a chloroauric acid solution according to a certain proportion, and stirring at 80-95 ℃ to obtain a mixed solution 1; adding a hydrochloric acid solution to obtain a mixed solution 2; adding ascorbic acid solution into the mixed solution 2 according to the proportion, and reacting for 5-6 hours at 90-100 ℃. The key point of the preparation technology is that the reaction rate of liquid phase reduction is controlled by reducing the pH value of the reaction liquid, so that the precursor is fully reduced into alloy instead of a composite material consisting of two metal simple substances. Correspondingly, the invention also discloses a branched CuAu alloy nanocrystal obtained by the preparation method disclosed above. The branched morphology has an obvious size effect, and the obtained product is expected to be applied to the high-efficiency electro-catalysis field.
Description
Technical Field
The invention relates to the technical field of metal nano material preparation, in particular to a preparation method of a branched CuAu alloy nano crystal.
Background
In recent years, CO has been accompanied2The emission amount increases year by year, and the sustainable development of the human society is seriously affected. Using electrochemical reduction means to convert CO2The conversion into value-added products is an important way for promoting carbon neutralization and relieving the problems of greenhouse effect and the like. However, the actual electro-reduction of CO2The problems of high overpotential, poor selectivity of products and the like exist in the process. To solve the above problems, the main effective means at present is to optimize the electrochemical conversion process from the catalyst point of view. Among many catalysts, Cu metal is the only one that can convert CO2A metal catalyst for efficient reduction to a multi-carbon product. However, in practical application, the conversion efficiency of metal Cu catalysis is too low, which seriously hinders the wide application of the metal Cu catalysis. To overcome these drawbacks, a new model for developing Cu-based nanoalloys has been proposed. The Cu-based nano alloy not only can effectively reduce the cost of the catalyst, but also can play a synergistic effect of bimetal and show a gained catalytic effect.
Many researches show that the CuAu alloy can achieve the effect of enhancing the stability and selectivity of the catalyst by changing the center of a d band and reducing the free energy of intermediate reaction. At present, the main methods for preparing CuAu alloy nanocrystals can be summarized as follows: a molten alloy method, a surface erosion method, a liquid phase method, and the like. Among the many methods, the preparation of CuAu alloy nanocrystals using a liquid phase reduction method is the most efficient and feasible method. The method has the characteristics of low requirement on equipment, simplicity in operation and the like.
However, the prior art also has the following problems:
1. the preparation temperature is too high and needs to be carried out under the protection of gas
In the process of preparing the CuAu alloy nanocrystalline by using a liquid phase reduction method, in order to ensure that a precursor is fully reacted, the traditional liquid phase preparation is always carried out at a higher temperature. In addition, in order to avoid an oxide layer on the surface of the nanocrystal at high temperature, the preparation process needs to be carried out under the protection atmosphere of inert gas or nitrogen and other gases.
For example: north China physical engineering patent right and the like successfully prepare CuAu alloy nanocrystalline particles (Ultrathin pore g-C) by taking copper acetate and gold nanoparticles as precursors and nitrogen as protective gas in an environment of 300 DEG C3N4nanosheets modified with AuCu alloy nanoparticles and CC coupling photothermal catalytic reduction of CO2Applied Catalysis B: Environmental,2020,266: 118618). However, the higher temperature and the addition of the gas shield not only increase the preparation cost of the nanocrystal, but also put higher demands on the production safety.
2. The morphology of the obtained product is not easy to control
Spherical nanoparticles are easy to aggregate and do not have a significant size effect. However, in the reports on the preparation of the CuAu alloy nanocrystals, the morphology of the obtained product is mostly spherical nanoparticles. The method for successfully preparing the CuAu alloy nanocrystals with other shapes has few reports. This is mainly because the growth of Cu-based alloy nanocrystals is not easily controlled by thermodynamics. Therefore, in order to obtain CuAu alloy nanocrystals with a high specific surface area, the presence of a surfactant is often required in the preparation. Zhou Li et al, Wuhan university, successfully prepared nano star-shaped CuAu alloy (Glucose Detection Devices and Methods Based on Metal-Organic Frameworks and Related Materials, advanced Functional Materials 2021,31, 6022103.) by using cupric chloride and chloroauric acid as precursors, hexadecylamine as surfactant and Glucose as reducing agent. Although the method realizes the one-step method for obtaining the anisotropic CuAu alloy, the extraction and cleaning of the product are more complicated. The hexadecylamine molecules adsorbed on the surface are not easy to remove, and the application performance of the material is directly influenced by the hexadecylamine molecules which are not removed.
Therefore, it has been an urgent technical problem in the art to develop an effective method for preparing a branched CuAu alloy nanocrystal to solve the above problems.
Disclosure of Invention
The invention overcomes the technical problems in the background technology and provides a preparation method of a branched CuAu alloy nanocrystal. The CuAu alloy nanocrystalline with high specific surface area is obtained under the condition that no surfactant is added. The surface of the obtained CuAu alloy nanocrystalline is free of organic ligands and oxides, secondary purification is not needed, and the operation steps are simple and easy to implement.
The specific operation comprises the following steps:
1) preparing a copper chloride solution with a certain concentration by using copper chloride as a solute and deionized water as a solvent;
2) preparing chloroauric acid solution with a certain concentration by taking deionized water as a solvent;
3) mixing the prepared chloroauric acid solution and copper chloride solution according to the ratio of 8: 55-8: 60, placing the mixture in an environment of 80-95 ℃ and stirring the mixture uniformly to obtain a mixed solution 1;
4) adding a certain amount of hydrochloric acid solution into the mixed solution 1, reducing the pH value environment in the reaction solution, and continuously stirring at 80-95 ℃ to obtain a mixed solution 2 (wherein the concentration of hydrochloric acid contained in the mixed solution 2 is 9-10 mmol/L);
5) preparing 0.9-1.0 mol/L ascorbic acid solution, and stirring at constant temperature of 50-60 ℃;
6) the prepared ascorbic acid solution is proportionally injected into the mixed solution 2 (the molar ratio of the ascorbic acid to the chloroauric acid contained in the mixed solution 2 is 130: 1-150: 1) reacting for 5-6 hours under rapid stirring at 90-100 ℃;
7) separating the obtained product by a centrifugal machine, dispersing the product into deionized water, performing ultrasonic treatment, performing secondary centrifugation, dispersing the product into ethanol, performing ultrasonic treatment, and drying the powder after secondary centrifugation in a blast drying oven.
Correspondingly, the invention also discloses a branched CuAu alloy nanocrystalline obtained by the preparation method. The beneficial effects of the implementation of the invention are as follows:
1. the obtained product has high purity and no impurities
The invention controls the forming speed of the nanocrystalline by adjusting the pH value environment of the reaction liquid in the preparation environment, thereby achieving the purpose of improving the purity of the product. The obtained product is an alloy nanocrystalline which is proved to be a complex of two simple metal substances through testing and does not contain oxides. The whole preparation time does not exceed 6 hours, and the filling of protective gas is not needed. The preparation process is simple and easy to realize.
2. The obtained product has high specific surface area
Compared with spherical nanocrystals which are easy to gather, the CuAu alloy nanocrystals obtained by the method are in a branched structure, and the diameter size is about 150-200 nm. The higher specific surface area makes the size effect obvious, and is helpful to improve the application performance.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sample obtained in example 1.
FIG. 2 is a SEM image of a sample obtained in example 1.
FIG. 3 is a SEM image of the sample obtained in example 2.
FIG. 4 is an X-ray diffraction pattern of the sample obtained in comparative example 1.
FIG. 5 is a field emission scanning electron micrograph of the sample obtained in comparative example 1.
FIG. 6 is an X-ray diffraction pattern of the sample obtained in comparative example 2.
Detailed Description
The method takes deionized water as a solvent, copper chloride and chloroauric acid as precursors, hydrochloric acid solution as a pH regulator, ascorbic acid as a reducing agent and a structure directing agent. The whole reaction temperature does not exceed 100 ℃. In the preparation process, the purity of the CuAu alloy nanocrystal is improved by regulating and controlling the reaction rate.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples and accompanying drawings, wherein all reagents are commercially available without further purification unless otherwise specified.
Example 1: preparation of branched CuAu alloy nanocrystals 1
The specific operation steps are as follows:
1) preparing 19 ml of copper chloride solution with the concentration of 15 mmol/l by using copper chloride as a solute and deionized water as a solvent;
2) preparing 4 ml of chloroauric acid with the concentration of 10 mmol/L;
3) mixing the chloroauric acid and copper chloride, uniformly stirring by using a magnetic stirrer, and then placing at 90 ℃ to obtain a mixed solution 1;
4) adding 2.5 ml of hydrochloric acid solution with the concentration of 0.1 mol/L into the mixed solution 1, and continuously stirring for 5 minutes at 90 ℃ to obtain mixed solution 2;
5) preparing 1.0 mol/L ascorbic acid, and stirring at a constant temperature of 60 ℃ for 3 minutes;
6) adding 6 ml of the ascorbic acid solution into the mixed solution 2, and stirring for 5 hours at 90 ℃;
7) and separating the obtained product by using a centrifugal machine, dispersing the product into deionized water, performing ultrasonic treatment, performing secondary centrifugation, dispersing the product into ethanol, performing ultrasonic treatment, and drying the powder subjected to secondary centrifugation in a blast drying oven at 60 ℃ for 10 hours.
In order to determine the components of the obtained sample, the obtained sample is subjected to an X-ray diffraction test, and the result is shown in FIG. 1, and the X-ray diffraction pattern diffraction peak of the obtained sample is located between standard diffraction JCPDS cards (3-1005) of elemental Cu and standard diffraction JCPDS cards (4-748) of elemental Au. In addition, the oxide does not contain characteristic peaks of other oxides. Thus, the obtained product is proved to be high-purity CuAu alloy nanocrystalline.
It can be seen from the sem picture of fig. 2 in the description of the drawings that: the CuAu alloy nanocrystals obtained in example 1 were branched. The diameter of the nanocrystal of each branch structure is about 150-200 nanometers. Compared with the traditional preparation method, the preparation method provided by the invention does not assist the growth of the nanocrystalline by virtue of a surfactant. The formation of the branched structure may mainly result from the addition of excess ascorbic acid (the stoichiometric ratio far exceeds the number of moles of the precursor) in step 5-6, and the ascorbic acid solution acts as a morphology directing agent to induce the initial alloy nanocrystals to form branched morphologies by curing.
Example 2: preparation of branched CuAu alloy nanocrystals
The specific operation steps are as follows:
1) preparing 40 ml of copper chloride solution with the concentration of 15 mmol/l by using copper chloride as a solute and deionized water as a solvent;
2) preparing 8 milliliters of chloroauric acid with the concentration of 10 millimole/liter;
3) mixing the chloroauric acid and copper chloride, uniformly stirring by using a magnetic stirrer, and then placing at 90 ℃ to obtain a mixed solution 1;
4) adding 5 ml of hydrochloric acid solution with the concentration of 0.1 mol/L into the mixed solution 1 to obtain a mixed solution 2, and continuously stirring for 5 minutes at 90 ℃ to obtain a mixed solution 2;
5) preparing ascorbic acid with the concentration of 0.9 mol/L, and stirring for 5 minutes at the constant temperature of 60 ℃;
6) adding 12 ml of the ascorbic acid solution into the mixed solution 2, and stirring for 5 hours at 90 ℃;
7) and separating the obtained product by using a centrifugal machine, dispersing the product into deionized water, performing ultrasonic treatment, performing secondary centrifugation, dispersing the product into ethanol, performing ultrasonic treatment, and drying the powder subjected to secondary centrifugation in a blast drying oven at 60 ℃ for 12 hours.
To explore the morphology of the resulting product, we performed scanning electron microscopy tests on the samples. As can be seen from the picture of FIG. 3 in the description of the drawings, the CuAu alloy nanocrystals obtained in example 2 still have a branched shape.
Comparative example 1: effect of pH enhancement of reaction solution on product 1 (alkaline solution Environment)
The technical key point of the invention is that the pH value of the liquid phase reduction reaction liquid is reduced by adding the hydrochloric acid solution, so that the reaction rate is reduced, and the precursor is fully reduced to form the alloy instead of a compound consisting of two metal simple substances. To verify this, we performed the procedure of comparative example 1. The specific operation is as follows:
1) preparing 19 ml of copper chloride solution with the concentration of 15 mmol/l by using copper chloride as a solute and deionized water as a solvent;
2) preparing 4 ml of chloroauric acid with the concentration of 10 mmol/L;
3) mixing the chloroauric acid and copper chloride, uniformly stirring by using a magnetic stirrer, and then placing at 90 ℃ to obtain a mixed solution 1;
4) adding 150 mg of potassium chloride powder into the mixed solution 1, stirring uniformly, then continuously adding 300 mg of potassium bicarbonate powder, and continuously stirring at 90 ℃ to obtain a mixed solution 2;
5) preparing ascorbic acid with the concentration of 1.0 mol/L, and stirring at the constant temperature of 60 ℃ for 3 minutes;
6) adding 6 ml of the ascorbic acid solution into the mixed solution 2, and stirring for 5 hours at 90 ℃;
7) and separating the obtained product by using a centrifugal machine, dispersing the product into deionized water, performing ultrasonic treatment, performing secondary centrifugation, dispersing the product into ethanol, performing ultrasonic treatment, and drying the powder subjected to secondary centrifugation in a blast drying oven at 60 ℃ for 10 hours.
In comparison with example 1, comparative example 1 changed the "5 ml hydrochloric acid solution of 0.1 mol/l concentration" of step 4 to "150 mg of potassium chloride powder was added, and after stirring well, 300 mg of potassium bicarbonate powder was further added". Wherein, the potassium bicarbonate powder is added to increase the pH value of the reaction liquid and accelerate the reaction process. The addition of potassium chloride powder was to exclude the effect of chloride ions in the crude hydrochloric acid solution.
As shown in FIG. 4, the diffraction peaks of the product obtained in comparative example 1 correspond to JCPDS cards 3-1005, which are standard diffraction of Cu, and JCPDS 4-748, which are standard diffraction of elemental Au. The results demonstrate that the product obtained in comparative example 1 is a composite of elemental Cu and elemental Au metal.
This gives: when the reaction solution is in an alkaline environment, the obtained product cannot generate CuAu nano-crystals due to the too fast reduction of the precursor. In addition, the appearance of the obtained product is changed correspondingly under the change of preparation conditions and the reduction rate of the copper chloride. As shown in the scanning electron microscope picture of fig. 5, the obtained product is in the form of nanoparticles and cannot be in the form of branches.
Comparative example 2: effect of pH enhancement of reaction solution on product 2 (neutral solution Environment)
To further verify the effect of the pH of the reaction solution on the overall preparation, we also performed the procedure of comparative example 2. The specific operation is as follows:
1) preparing 19 ml of copper chloride solution with the concentration of 15 mmol/l by using copper chloride as a solute and deionized water as a solvent;
2) preparing 4 ml of chloroauric acid with the concentration of 10 mmol/L;
3) mixing the chloroauric acid and copper chloride, uniformly stirring by using a magnetic stirrer, and then placing at 90 ℃ to obtain a mixed solution 1;
4) preparing ascorbic acid with the concentration of 1.0 mol/L, and stirring at the constant temperature of 60 ℃ for 2 minutes;
5) adding 6 ml of the ascorbic acid solution into the mixed solution 1, and stirring for 5 hours at 90 ℃;
6) and separating the obtained product by using a centrifugal machine, dispersing the product into deionized water, performing ultrasonic treatment, performing secondary centrifugation, dispersing the product into ethanol, performing ultrasonic treatment, and drying the powder subjected to secondary centrifugation in a blast drying oven at 60 ℃ for 10 hours.
In comparison with example 1, comparative example 2 omits the procedure of "adding 2.5 ml of 0.1 mol/l hydrochloric acid solution to mixed solution 1 and continuing stirring at 90 ℃ for 5 minutes to obtain mixed solution 2" in the example operation. Since no hydrochloric acid solution was added, the whole liquid phase preparation was carried out in a neutral environment, and the X-ray diffraction results of the obtained product are shown in fig. 6. Compared with example 1, the product obtained in comparative example 2 contains a large amount of CuAu nanocrystals and a small amount of other diffraction peaks (corresponding to the elementary Cu and the Cu)2O). This phenomenon is due to: even in a neutral environment, the reduction of copper chloride is not inhibited at all, and the excessively fast reaction results in the formation of alloy nanocrystals, but also the reduction to elemental Cu and Cu oxides.
Thus, step 4 in example 1 of the present invention is a necessary prerequisite for obtaining CuAu alloy nanocrystals having a highly pure branched structure.
It should be noted that the above described is a preferred embodiment of the invention, and that it is obvious to a person skilled in the art that several modifications and adaptations can be made without departing from the principle of the invention, and these modifications and adaptations are also considered to be within the scope of the invention.
Claims (3)
1. A preparation method of a branched CuAu alloy nanocrystal is characterized by comprising the following specific operation steps:
1) copper chloride is used as solute, deionized water is used as solvent, copper chloride solution with certain concentration is prepared,
2) preparing chloroauric acid solution with a certain concentration by taking deionized water as a solvent;
3) mixing the prepared chloroauric acid solution and copper chloride solution according to a certain molar ratio, stirring uniformly, and placing in an environment of 80-95 ℃ to obtain a mixed solution 1;
4) adding a certain amount of hydrochloric acid solution into the mixed solution 1, and continuously stirring at 80-95 ℃ to obtain a mixed solution 2;
5) preparing an ascorbic acid solution with a certain concentration, and stirring at a constant temperature of 50-60 ℃;
6) proportionally injecting the prepared ascorbic acid solution into the mixed solution 2, and reacting for 5-6 hours under rapid stirring at 90-100 ℃;
7) separating the obtained product by a centrifugal machine, dispersing the product into deionized water, performing ultrasonic treatment, performing secondary centrifugation, dispersing the product into ethanol, performing ultrasonic treatment, and drying the powder after secondary centrifugation in a blast drying oven.
2. The method of claim 1, wherein the method comprises the steps of:
the molar ratio of the mixed chloroauric acid solution and copper chloride solution in the step 3) is 8: 55 to 8: 60 intervals;
after the hydrochloric acid solution is added, the concentration of the hydrochloric acid in the obtained mixed solution 2 is in a range of 9-10 millimoles/liter;
the concentration of the prepared ascorbic acid solution in the step 5) is in the range of 0.9-1.0 mol/L;
the molar ratio of the ascorbic acid solution added in the step 6) to the chloroauric acid contained in the mixed solution 2 is 130: 1 to 150: 1 interval;
the temperature in the air-blast drying oven in the step 7) is preferably in the range of 40 to 80 ℃.
3. A branched CuAu alloy nanocrystal obtained by the method for producing a branched CuAu alloy nanocrystal according to claims 1 to 2.
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