CN111438373B - Preparation method of copper-silver core-shell structure bimetal spherical nanoparticles - Google Patents
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Abstract
The invention belongs to the technical field of preparation of copper-silver core-shell structure spherical nanoparticles, and provides a preparation method of copper-silver core-shell structure bimetallic spherical nanoparticles aiming at the problem that the existing non-noble metal catalyst is easy to oxidize and deactivate. Under the condition of oil bath, carbon monoxide gas is used as a reducing agent, a two-step method is adopted, a copper core is prepared by heating, then an oleylamine solution of a silver organic compound is injected, the reaction is continued, after the reaction is finished, a product is ultrasonically and centrifugally washed by n-hexane, and the product is dispersed in the n-hexane. The prepared Cu @ Ag core-shell spherical nano particles have good carbon dioxide electroreduction catalytic capability and higher product selectivity in CO 2 The transformation and utilization field has great application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of copper-silver core-shell structure spherical nanoparticles, and particularly relates to a preparation method of copper-silver core-shell structure bimetal spherical nanoparticles. The size of the nano particles is controllable.
Background
With carbon dioxide (CO) in the atmosphere 2 ) The concentration is continuously increased, and the global warming and climate change are harmfulAre gradually regarded as important by human beings. How to directly introduce CO 2 The conversion into valuable chemical products is to deal with the greenhouse gas CO 2 Optimal solution to emissions challenges. Electrochemical catalytic reduction method as efficient CO 2 Treatment technique, can be used to treat CO 2 Electrocatalytic reduction to carbon monoxide (CO), methane (CH) 4 ) Methanol (CH) 3 OH, formic acid (HCOOH) and ethanol (C) 2 H 5 OH) and the like, has been widely noticed by people due to the advantages of clean production process, simple and controllable device, higher conversion efficiency, large-scale production and the like, and restricts CO 2 The key to the development and application of electrochemical reduction technology is how to develop CO with low cost, high selectivity and high efficiency 2 Electrochemically reducing the catalyst.
Metallic copper (Cu) in CO 2 The Cu catalyst shows excellent characteristics in the electro-reduction catalytic reaction, and can be used for directly electro-reduction catalyzing CO 2 Generating HCOOH, CH 3 OH and C 2 H 5 OH and other products with higher utilization value, but the non-noble metal catalysts have the defects of easy oxidation, difficult control of surface structure and composition, unstable performance and the like. The proposal for solving the problems is to coat non-noble metal with high conductivity, high stability and CO tolerance 2 The bimetallic material with the core-shell structure is prepared from a metal material with better electro-reduction catalytic performance.
Disclosure of Invention
The invention provides a preparation method of bimetallic spherical nano particles with a copper-silver core-shell structure, aiming at the problem that the existing non-noble metal catalyst is easy to oxidize and deactivate, and the prepared copper-core silver shell and size are controllable.
The invention adopts the following technical scheme: a process for preparing bimetal spherical nanoparticles with Cu-Ag core-shell structure includes such steps as heating to prepare Cu core, injecting the solution of organic Ag compound in oleylamine, reaction, ultrasonic washing with n-hexane, and dispersing the product in n-hexane.
The method comprises the following specific steps:
(1) Preparing a copper core: mixing 26mg of copper organic compound, 0-180 mu L of diphenyl ether and 9mL of oleylamine in a three-necked flask, placing the mixture in a 100 ℃ oil bath, completely discharging oxygen in the system by using a vacuum exhaust system, introducing carbon monoxide gas at the flow rate of 90 mL/min, raising the reaction temperature to 220 ℃ at the temperature rise rate of 10 ℃/6min, keeping the temperature at 220 ℃ for 2 hours, and cooling to 30 ℃;
(2) Preparing the copper-core silver-shell bimetal spherical nano particles: injecting 5mL of silver organic compound oleylamine solution with the concentration of 1.1mg/mL into the copper core product system prepared in the step (1) at the speed of 0.5 mL/h by a peristaltic pump, continuously introducing carbon monoxide during the process, keeping the temperature of the reaction system at 30 ℃, continuing to react for 1 hour after the silver organic compound is added, cooling to room temperature after the reaction is finished, performing ultrasonic treatment and 10000 r/g centrifugal washing on the product by adopting n-hexane for three times, and dispersing the final product into the n-hexane for later use.
The organic compound of copper is copper acetylacetonate, i.e. Cu (acac) 2 (ii) a The organic compound of silver is silver trifluoroacetate, namely AgCF 3 COO。
The method adopts a two-step method, firstly prepares the copper core and then grows the silver shell, successfully prepares the adjustable copper-silver core-shell bimetal spherical nano particles with a plurality of sizes (10.0 +/-1.6, 8.4 +/-0.7 and 6.7 +/-0.6 nm), and the X-ray powder diffraction (XRD) test result shows that the product is the composition of Cu and Ag single metal, but the composition of CuAg alloy is not found; the ultraviolet visible spectrum test result shows that two surface plasma resonance peaks of the product respectively correspond to Cu (about 600 nm) and Ag (about 400 nm) single metal, and the resonance absorption peak of the CuAg alloy does not appear; indicating that the resulting product is a bimetal rather than a copper silver alloy.
The size control is mainly regulated and controlled by the amount of diphenyl ether in the reaction, and the sizes of 0, 90 and 180 mu L of diphenyl ether are respectively as follows: 10.0 plus or minus 1.6 nm,8.4 plus or minus 0.7 nm and 6.7 plus or minus 0.6nm.
Further subjecting the product to CO 2 An electroreduction catalysis test shows that the prepared Cu @ Ag core-shell spherical nano-particles have good carbon dioxide electroreduction catalysis capability and higher product selectivity, and CO is subjected to electroreduction catalysis 2 The transformation and utilization field has great application prospect.
Drawings
FIG. 1 is a TEM image of copper-silver core-shell bimetallic spherical nanoparticles prepared by a two-step method; in the figure: a is a transmission diagram of the product obtained in example 1; b is a transmission diagram of the product obtained in example 2; c is a transmission plot of the product obtained in example 3;
FIG. 2 is an XRD spectrogram of a copper-silver core-shell bimetallic spherical nanoparticle prepared by a two-step method;
FIG. 3 is a diagram of the UV-Vis spectra of the Cu-Ag core-shell bimetal spherical nanoparticles prepared by a two-step method;
FIG. 4 is a Faraday efficiency curve for carbon dioxide electrocatalytic reduction of Cu-Ag core-shell bimetallic spherical nanoparticles with size of 6.7 + -0.6 nm.
Detailed Description
Example 1: preparation of copper nuclei, 26mg of copper acetylacetonate, 0. Mu.L of diphenyl ether and 9mL of oleylamine were mixed in a three-necked flask and placed in an oil bath at 100 ℃. The oxygen in the system is completely discharged by utilizing a vacuum exhaust system, carbon monoxide gas is introduced at the flow rate of 90 mL/min, then the reaction temperature is increased to 220 ℃ at the heating rate of 10 ℃/6min, the reaction is kept at 220 ℃ for 2 hours, and the temperature is cooled to 30 ℃.
And (2) preparing a silver shell, namely injecting 5mL of 1.1mg/mL silver trifluoroacetate oleylamine solution into the prepared copper core product system at the speed of 0.5 mL/h by using a peristaltic pump, continuously introducing carbon monoxide during the process, keeping the temperature of the reaction system at 30 ℃, continuing to react for 1 hour after the silver precursor is added, cooling to room temperature after the reaction is finished, performing ultrasonic centrifugal washing on the product by using n-hexane, and dispersing the final product in the n-hexane for later use.
As shown in a diagram in fig. 1, the transmission diagram of the product shows that the product is spherical nanoparticles with the size distribution of 10.0 +/-1.6 nm; the obtained product is copper-silver bimetal rather than copper-silver alloy according to XRD and UV spectrums.
Example 2: preparation of copper nuclei, 26mg of copper acetylacetonate, 90. Mu.L of diphenyl ether and 9mL of oleylamine were mixed in a three-necked flask and placed in an oil bath at 100 ℃. The oxygen in the system is completely discharged by utilizing a vacuum exhaust system, carbon monoxide gas is introduced at the flow rate of 90 mL/min, then the reaction temperature is increased to 220 ℃ at the heating rate of 10 ℃/6min, the reaction is kept at 220 ℃ for 2 hours, and the temperature is cooled to 30 ℃.
And (2) preparing a silver shell, namely injecting 5mL of 1.1mg/mL silver trifluoroacetate oleylamine solution into the prepared copper core product system at the speed of 0.5 mL/h by using a peristaltic pump, continuously introducing carbon monoxide during the process, keeping the temperature of the reaction system at 30 ℃, continuing to react for 1 hour after the silver precursor is added, cooling to room temperature after the reaction is finished, performing ultrasonic centrifugal washing on the product by using n-hexane, and dispersing the final product in the n-hexane for later use.
As shown in the b diagram in fig. 1, the transmission diagram of the product shows that the product is spherical nanoparticles with the size distribution of 8.4 +/-0.7 nm; the obtained product is copper-silver bimetal rather than copper-silver alloy according to XRD and UV spectrums.
Example 3: preparation of copper nuclei, 26mg of copper acetylacetonate, 180. Mu.L of diphenyl ether and 9mL of oleylamine were mixed in a three-necked flask and placed in an oil bath at 100 ℃. The oxygen in the system is completely discharged by utilizing a vacuum exhaust system, carbon monoxide gas is introduced at the flow rate of 90 mL/min, then the reaction temperature is increased to 220 ℃ at the heating rate of 10 ℃/6min, the reaction is kept at 220 ℃ for 2 hours, and the temperature is cooled to 30 ℃.
And (2) preparing a silver shell, namely injecting 5mL of 1.1mg/mL silver trifluoroacetate oleylamine solution into the prepared copper core product system at the speed of 0.5 mL/h by using a peristaltic pump, continuously introducing carbon monoxide during the process, keeping the temperature of the reaction system at 30 ℃, continuing to react for 1 hour after the silver precursor is added, cooling to room temperature after the reaction is finished, performing ultrasonic centrifugal washing on the product by using n-hexane, and dispersing the final product in the n-hexane for later use.
As shown in the c diagram in fig. 1, the transmission diagram of the product shows that the product is spherical nanoparticles with a size distribution of 6.7 ± 0.6nm; the obtained product is copper-silver bimetal rather than copper-silver alloy according to XRD and UV spectrums.
Further subjecting the product to CO 2 The electroreduction catalytic test shows that the experimental data are shown in the table 1,6.7 +/-0.6 nm Cu @ Ag core-shell spherical nano-particlesThe faradaic efficiency curves for electrocatalytic reduction of carbon dioxide are shown in figure 4. The products were dominated by ethylene at voltages of-3.50V, -3.00V and-2.75V (vs. Ag/AgCl), by formic acid at cell voltages of-2.25V (vs. Ag/AgCl), and by carbon monoxide at lower cell voltages of-2.00V and-1.75V (vs. Ag/AgCl).
Table 1 shows the relationship between the carbon dioxide electrocatalytic reduction product and the potential of the copper-silver core-shell bimetallic spherical nanoparticles with the size of 6.7 +/-0.6 nm.
Claims (1)
1. For CO 2 The preparation method of the electroreduction-catalyzed copper-core silver-shell bimetal spherical nano particle is characterized by comprising the following steps of: under the condition of oil bath, carbon monoxide gas is used as a reducing agent, a two-step method is adopted, a copper core is prepared by heating, then an oleylamine solution of a silver organic compound is injected, the reaction is continued, after the reaction is finished, a product is ultrasonically and centrifugally washed by n-hexane, and the product is dispersed in the n-hexane;
the method comprises the following specific steps:
(1) Preparing a copper core: mixing 26mg of copper organic compound, 0-180 mu L of diphenyl ether and 9mL of oleylamine in a three-necked flask, placing the mixture in a 100 ℃ oil bath, completely discharging oxygen in the system by using a vacuum exhaust system, introducing carbon monoxide gas at the flow rate of 90 mL/min, raising the reaction temperature to 220 ℃ at the temperature rise rate of 10 ℃/6min, keeping the temperature at 220 ℃ for 2 hours, and cooling to 30 ℃;
(2) Preparing copper-core silver-shell bimetallic spherical nanoparticles: injecting 5mL of silver organic compound oleylamine solution with the concentration of 1.1mg/mL into the copper core product system prepared in the step (1) at the speed of 0.5 mL/h by a peristaltic pump, continuously introducing carbon monoxide during the injection, keeping the temperature of the reaction system at 30 ℃, continuing to react for 1 hour after the silver organic compound is added, cooling to room temperature after the reaction is finished, performing ultrasonic treatment and 10000 r/g centrifugal washing on the product by adopting n-hexane for three times, and dispersing the final product into the n-hexane for later use;
the organic compound of copper is copper acetylacetonate, i.e. Cu (acac) 2 (ii) a The organic compound of silver is silver trifluoroacetate, namely AgCF 3 COO。
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| CN114000177A (en) * | 2021-11-12 | 2022-02-01 | 江苏大学 | Ag @ Cu2O core-shell structure nanosphere catalyst and preparation method and application thereof |
| CN114700497B (en) * | 2022-03-18 | 2024-03-29 | 昆明理工大学 | Preparation method of Cu-Ag alloy with pomegranate-like structure |
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