CN113814397B - Porous Ag@Cu 2 O nano cell material and preparation method and application thereof - Google Patents
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Abstract
The invention relates to porous Ag@Cu 2 O nano cell material, and a preparation method and application thereof. The method synthesizes silver nanocubes first, and disperses the silver nanocubes in a mixed aqueous solution of copper nitrate and ammonium sulfate. The subsequent addition of the precipitant sodium hydroxide, due to the presence of ammonium sulphate, makes self-nucleating growth of the copper hydroxide in solution difficult, since ammonium ions can reversibly re-transform the copper hydroxide into copper ions. Silver has a lower work function than copper and can act as nucleation sites for copper hydroxide, so that copper hydroxide crystallites selectively grow on the surface of the silver nanocubes. And then adding ascorbic acid to reduce the microcrystals growing on the surface of the silver nanocubes into cuprous oxide microcrystals and an amorphous phase, and properly curing to obtain a target product. The preparation method is environment-friendly, simple in preparation procedure and easy to operate, and is convenient for industrial production; the obtained product can effectively improve the selectivity and the current density of methane in the electrocatalytic process, and has wide application prospect in the electrocatalytic field.
Description
Technical Field
The invention belongs to the technical fields of material science and electrochemistry, and particularly relates to a porous Ag@Cu 2 O nano cell material, and a preparation method and application thereof.
Background
Renewable energy driven oxidationCarbon electroreduction (CO) 2 RR) is to CO 2 A promising strategy for conversion to carbon neutral fuels and commodity chemicals. According to the current literature report, CO 2 There are a variety of products from C1 to C3 in RR. However, CO 2 RR technology economic analysis showed commercial CO 2 RR systems require operating current densities well above 100mA cm -2 Is economically feasible, however, at greater than 100mA cm -2 Only carbon monoxide (CO) with a comparatively considerable selectivity is requiredFormic acid (FE)>80%) and ethylene (70% fe).
Methane is CO 2 The simplest hydrocarbon product in RR is also a widely used fuel and chemical feedstock. However, methane has also proven to be a powerful greenhouse gas and studies have shown that the global carbon footprint due to leakage during methane use or production has severely threatened the global climate. Thus under normal pressure and temperature conditions, CO is catalyzed by electricity 2 RR converted methane can achieve the goals of the global carbon reduction program. To enhance electrocatalytic CO 2 RR selectivity to methane, previous reports have focused mainly on adjusting the morphology, particle size and material composition structure of Cu-based catalysts. To date, at a temperature of greater than 100mA cm -2 At the total current density of the system, methane selectivity exceeding 50% is rarely reported.
Disclosure of Invention
Aiming at the defects of the existing catalytic selectivity and efficiency, the invention provides a porous Ag@Cu 2 O nano cell material, and a preparation method and application thereof. The porous Ag@Cu 2 The O nano cell material can be used as a catalyst for high-efficiency electrocatalytic carbon dioxide to methane.
The aim of the invention can be achieved by the following technical scheme:
the invention firstly provides a porous Ag@Cu 2 O nano cell material, which is based on Ag and Cu 2 O is the nano cell structure of the shell, and the nano cell is a cavity structure with a porous surface. Abbreviated as Ag@Cu 2 ONCs。
In one embodiment of the invention, the porous Ag@Cu 2 The O nanocell material has an average size of between 120nm and 400nm, preferably between 180-200nm, further preferably an average size of 190nm.
The invention also provides the porous Ag@Cu 2 The preparation method of the O nano cell material comprises the following steps:
(1) Synthesizing silver nanocubes;
(2) Preparing a growth solution: dispersing the silver nanocubes prepared in the step (1) in polyvinylpyrrolidone aqueous solution, stirring at a high speed, uniformly mixing, adding copper nitrate trihydrate and ammonium sulfate, and stirring to balance;
(3) Porous Ag@Cu 2 Formation of O nanocell: dropwise adding a sodium hydroxide aqueous solution into the growth solution prepared in the step (2), continuously stirring after the dropwise adding, dropwise adding ascorbic acid into the solution, rapidly stirring for a certain time, and stopping to obtain the porous Ag@Cu 2 O nano cell material.
In one embodiment of the invention, the silver nanocubes in step (1) have a particle size of 60 to 80 nm, preferably 68 to 72 nm, more preferably about 70 nm.
In one embodiment of the present invention, the method for synthesizing silver nanocubes described in step (1) is as follows:
heating glycol, adding glycol solution of hydrochloric acid, stirring, and collecting AgNO 3 Adding ethylene glycol solution of polyvinylpyrrolidone into the reaction system, stirring, injecting the ethylene glycol solution of polyvinylpyrrolidone, exposing the reaction system in air for 6 hours, sealing, heating, mechanically stirring in the whole process to realize effective gas exchange, quenching the reaction in an ice bath immediately after the reaction is finished, and washing and collecting the product by acetone, ethanol and distilled water in sequence to obtain the silver nanocubes.
In one embodiment of the present invention, the method for synthesizing silver nanocubes described in step (1) provides a specific method of operation as follows:
5ml of Ethylene Glycol (EG) was previously added to a 25ml reaction flask,and heated at 105℃for 10 minutes, then 250. Mu.l of 60mM hydrochloric acid in EG were added. After stirring for 5 minutes, 5ml of 200mM AgNO was added in 10 seconds 3 To which EG solution was added. After stirring for an additional 5 minutes, 5ml of 120 mM polyvinylpyrrolidone (PVP) in EG was injected over 10 seconds. After exposing the reaction to air for 6 hours, the vials were capped, sealed, and heated to 140 ℃ for an additional 10 minutes. The mechanical stirring is always kept at 1000rpm throughout the process to achieve efficient gas exchange. After the reaction was completed, the reaction was immediately quenched in an ice bath for 20 minutes, and the collected product was washed with acetone, ethanol and distilled water in sequence, thus obtaining silver nanocubes.
In one embodiment of the invention, in the step (2), the addition amount of the copper nitrate trihydrate is 26-30 parts by weight, the addition amount of the ammonium sulfate is 55-60 parts by weight, and the addition amount of the silver nanocubes is 0.1-0.9 part by weight; preferably, the copper nitrate trihydrate is added in an amount of 28 to 29 parts by weight; the addition amount of the ammonium sulfate is 57-58 parts by weight; the addition amount of the silver nanocubes is 0.4-0.6 weight part; further preferably, the copper nitrate trihydrate is added in an amount of 28.6 parts by weight; the addition amount of the ammonium sulfate is 57.8 parts by weight; the addition amount of the silver nanocubes is 0.5 weight part.
In one embodiment of the present invention, in the step (3), the concentration of the aqueous sodium hydroxide solution is between 0.1 and 1M, preferably 0.2M; the concentration of the ascorbic acid is between 0.1 and 1M, preferably 0.1M.
In one embodiment of the present invention, in the step (3), the time of stirring after dropping the ascorbic acid is 5 to 20 minutes.
In one embodiment of the present invention, a specific implementation method of step (2) is provided, as follows:
dispersing the prepared Ag nanocubes between 0.1 and 0.9 weight parts in PVP water solution, stirring at high speed for 10 min, mixing well, and adding Cu (NO) 28.6 weight parts into the solution 3 ) 2 ·3H 2 O and 57.8 parts by weight of (NH 4 ) 2 SO 4 Stirred for 5 minutes for use as a growth solution.
In one embodiment of the present invention, a specific implementation method of step (3) is provided, as follows:
with a microinjection pump, 1.2ml min -1 2ml of a 0.2M aqueous NaOH solution was added dropwise to the above growth solution. After the completion of the dropwise addition, stirring was continued for 2 minutes, followed by 0.4ml min -1 3.5ml of a 0.1M aqueous solution of ascorbic acid was added to the above solution. After the dripping is finished, stirring is continued for 13 minutes, and stopping to obtain the porous Ag@Cu 2 O NCs。
The invention also provides the porous Ag@Cu 2 The application of the O nano cell material as a catalyst for high-efficiency electrocatalytic carbon dioxide to methane.
The method synthesizes silver nanocubes first, and disperses the silver nanocubes in a mixed aqueous solution of copper nitrate and ammonium sulfate. The subsequent addition of the precipitant sodium hydroxide, due to the presence of ammonium sulphate, makes self-nucleating growth of the copper hydroxide in solution difficult, since ammonium ions can reversibly re-transform the copper hydroxide into copper ions. Silver has a lower work function than copper and can act as nucleation sites for copper hydroxide, so that copper hydroxide crystallites selectively grow on the surface of the silver nanocubes. And then adding ascorbic acid to reduce the microcrystals growing on the surface of the silver nanocubes into cuprous oxide microcrystals and an amorphous phase, and properly curing to obtain a target product. The preparation method is environment-friendly, simple in preparation procedure and easy to operate, and is convenient for industrial production; the obtained product can effectively improve the selectivity and the current density of methane in the electrocatalytic process, and has wide application prospect in the electrocatalytic field.
In the invention, a material with Ag as the center and Cu is synthesized 2 Ag@Cu with O as shell 2 O nano cell structure (Ag@Cu) 2 O NCs), by using silver nanocubes as CO generator, the generated CO overflows to Cu 2 The cascade reaction further occurs on the O-shell. In addition, cu 2 The O shell has enrichment function on CO, so that the local CO solubility is greatly improved, and the CH can be effectively improved finally 4 Is selected from the group consisting of selectivity and partial current density. Which in a flowing electrolytic cell shows a concentration of approximately 200mA cm -2 Current density and methane faraday efficiency of 80%.
Compared with the prior art, the invention has the beneficial effects that:
by integrating the tandem effect and the spatial threshold effect, the CO coverage and H adsorption are effectively regulated, thereby changing the electrocatalytic CO 2 The reaction path of RR and moderate CO coverage can greatly promote CH 4 Inhibit hydrogen evolution reaction and C 2+ And (3) generating a product. For high selectivity, CH is produced with high efficiency 4 A viable strategy is provided.
Drawings
FIG. 1 is a diagram showing Ag@Cu prepared in embodiment 1 of the present invention 2 TEM image of O nanoparticles;
FIG. 2 is a graph showing Ag@Cu prepared in example 1 of the present invention 2 SEM image of O nanoparticles;
FIG. 3 is a graph showing Ag@Cu prepared in example 1 of the present invention 2 Counting the particle size distribution of the O nano particles;
FIG. 4 is a graph showing Ag@Cu prepared in example 1 of the present invention 2 Electrocatalytic CO of O nanoparticles 2 Product distribution;
FIG. 5 is a graph showing Ag@Cu prepared in example 1 of the present invention 2 Electrocatalytic CO of O nanoparticles 2 Current density;
FIG. 6 is a graph of Ag@Cu prepared in example 2 of the present invention 2 SEM and TEM images of O nanoparticles;
FIG. 7 is a graph showing Ag@Cu prepared in example 3 of the present invention 2 SEM and TEM images of O nanoparticles.
Detailed Description
The invention firstly provides a porous Ag@Cu 2 O nano cell material, which is based on Ag and Cu 2 O is the nano cell structure of the shell, and the nano cell is a cavity structure with a porous surface. Abbreviated as Ag@Cu 2 O NCs。
In one embodiment of the invention, the porous Ag@Cu 2 The O nanocell material has an average size of between 120nm and 400nm, preferably between 180-200nm, further preferably an average size of 190nm.
The invention also provides the porous Ag@Cu 2 O nano cell materialThe preparation method of (2) comprises the following steps:
(1) Synthesizing silver nanocubes;
(2) Preparing a growth solution: dispersing the silver nanocubes prepared in the step (1) in polyvinylpyrrolidone aqueous solution, stirring at a high speed, uniformly mixing, adding copper nitrate trihydrate and ammonium sulfate, and stirring to balance;
(3) Porous Ag@Cu 2 Formation of O nanocell: dropwise adding a sodium hydroxide aqueous solution into the growth solution prepared in the step (2), continuously stirring after the dropwise adding, dropwise adding ascorbic acid into the solution, rapidly stirring for a certain time, and stopping to obtain the porous Ag@Cu 2 O nano cell material.
In one embodiment of the invention, the silver nanocubes in step (1) have a particle size of 60 to 80 nm, preferably 68 to 72 nm, more preferably about 70 nm.
In one embodiment of the present invention, the method for synthesizing silver nanocubes described in step (1) is as follows:
heating glycol, adding glycol solution of hydrochloric acid, stirring, and collecting AgNO 3 Adding ethylene glycol solution of polyvinylpyrrolidone into the reaction system, stirring, injecting the ethylene glycol solution of polyvinylpyrrolidone, exposing the reaction system in air for 6 hours, sealing, heating, mechanically stirring in the whole process to realize effective gas exchange, quenching the reaction in an ice bath immediately after the reaction is finished, and washing and collecting the product by acetone, ethanol and distilled water in sequence to obtain the silver nanocubes.
In one embodiment of the present invention, the method for synthesizing silver nanocubes described in step (1) provides a specific method of operation as follows:
5ml of Ethylene Glycol (EG) was previously added to a 25ml reaction flask and heated at 105℃for 10 minutes, followed by 250. Mu.l of 60mM hydrochloric acid in EG. After stirring for 5 minutes, 5ml of 200mM AgNO was added in 10 seconds 3 To which EG solution was added. After stirring for an additional 5 minutes, 5ml of 120 mM polyvinylpyrrolidone (PVP) in EG was injected over 10 seconds. After exposing the reaction to air for 6 hours, the vials were capped and sealedThe temperature was raised to 140℃and heated for another 10 minutes. The mechanical stirring is always kept at 1000rpm throughout the process to achieve efficient gas exchange. After the reaction was completed, the reaction was immediately quenched in an ice bath for 20 minutes, and the collected product was washed with acetone, ethanol and distilled water in sequence, thus obtaining silver nanocubes.
In one embodiment of the invention, in the step (2), the addition amount of the copper nitrate trihydrate is 26-30 parts by weight, the addition amount of the ammonium sulfate is 55-60 parts by weight, and the addition amount of the silver nanocubes is 0.1-0.9 part by weight; preferably, the copper nitrate trihydrate is added in an amount of 28 to 29 parts by weight; the addition amount of the ammonium sulfate is 57-58 parts by weight; the addition amount of the silver nanocubes is 0.4-0.6 weight part; further preferably, the copper nitrate trihydrate is added in an amount of 28.6 parts by weight; the addition amount of the ammonium sulfate is 57.8 parts by weight; the addition amount of the silver nanocubes is 0.5 weight part.
In one embodiment of the present invention, in the step (3), the concentration of the aqueous sodium hydroxide solution is between 0.1 and 1M, preferably 0.2M; the concentration of the ascorbic acid is between 0.1 and 1M, preferably 0.1M.
In one embodiment of the present invention, in the step (3), the time of stirring after dropping the ascorbic acid is 5 to 20 minutes.
In one embodiment of the present invention, a specific implementation method of step (2) is provided, as follows:
dispersing the prepared Ag nanocubes between 0.1 and 0.9 weight parts in PVP water solution, stirring at high speed for 10 min, mixing well, and adding Cu (NO) 28.6 weight parts into the solution 3 ) 2 ·3H 2 O and 57.8 parts by weight of (NH 4 ) 2 SO 4 Stirred for 5 minutes for use as a growth solution.
In one embodiment of the present invention, a specific implementation method of step (3) is provided, as follows:
with a microinjection pump, 1.2ml min -1 2ml of a 0.2M aqueous NaOH solution was added dropwise to the above growth solution. After the completion of the dropwise addition, stirring was continued for 2 minutes, followed by 0.4ml min -1 Will be 3.5ml of 0.1MAn aqueous solution of ascorbic acid was added to the above solution. After the dripping is finished, stirring is continued for 13 minutes, and stopping to obtain the porous Ag@Cu 2 O NCs。
The invention also provides the porous Ag@Cu 2 The application of the O nano cell material as a catalyst for high-efficiency electrocatalytic carbon dioxide to methane.
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
Preparation of porous Ag@Cu for electrocatalytic carbon dioxide reduction 2 O nano cell catalyst material:
(1) 5ml of Ethylene Glycol (EG) was previously added to a 25ml reaction flask and heated at 105℃for 10 minutes, followed by 250. Mu.l of 60mM hydrochloric acid in EG;
(2) After stirring the above solution for 5 minutes, 5ml of 200mM AgNO was added in 10 seconds 3 To which EG solution was added. After stirring for another 5 minutes, 5ml of 120 mM polyvinylpyrrolidone (PVP) in EG was injected over 10 seconds;
(3) After exposing the reaction to air for 6 hours, the vials were capped, sealed, and heated to 140 ℃ for an additional 10 minutes. The whole mechanical stirring is always kept at 1000rpm so as to realize effective gas exchange;
(4) Immediately after the reaction was completed, the reaction was quenched in an ice bath for 20 minutes, and the collected product was washed with acetone, ethanol and distilled water in sequence;
(5) Dispersing 0.5mg of the prepared Ag nanocubes in 50ml of 2mM PVP aqueous solution, stirring at a high speed for 10 minutes, and uniformly mixing;
(6) Subsequently 28.6mg of Cu (NO) was added to the above solution 3 ) 2 ·3H 2 O and 57.8mg (NH) 4 ) 2 SO 4 Stirring for 5 minutes to serve as a growth solution;
(7) With a microinjection pump, 1.2ml min -1 2ml of a 0.2M aqueous NaOH solution was added dropwise to the above growth solution. After the completion of the dropwise addition, stirring was continued for 2 minutes, followed by 0.4ml min -1 3.5ml of a 0.1M aqueous solution of ascorbic acid was added to the above solution;
(8) After the dripping is completed, stirring is continued for 13 minutes, and the porous Ag@Cu can be obtained 2 O NCs；
(9) The specific morphology of the nanocell was characterized by TEM and SEM, as shown in fig. 1 and 2. The synthesized highly uniform nano-cells have a surface porous cavity structure, ag is positioned in the middle of the cells, and the particle size statistics of FIG. 3 show that Ag@Cu is the same 2 The average size of the O NCs is 191.4+/-0.9 nm;
(10) 1mg of sample powder was mixed in 100ml of isopropanol solution, and then dispersed by ultrasound for 15 minutes. Next, 120. Mu.l of the prepared slurry was sprayed on 1X 1cm 2 Is provided. Then drying the working electrode at room temperature in isopropanol atmosphere to carry out subsequent test;
(11) Electrocatalytic CO 2 The anode of the RR test system adopts foam nickel, the reference electrode adopts an Ag/AgCl electrode, and the foam nickel is measured by a digital mass flow controller (Horiba) at a speed of 50cm 3 min -1 High purity CO at a constant flow rate 2 Is fed into the air chamber. The electrolyte was 1M KOH and was pumped through a two-channel peristaltic pump at 20ml min -1 Is circulated in both the yin and yang chambers. The cell resistance (R) measured by electrochemical impedance spectroscopy at 1M KOH at open circuit was 1.7 Ω, and an ohmic resistance correction of 85% was used in the measurement. Finally testing the sample to electrically catalyze CO 2 RR product distribution is shown in FIG. 4, at-1.2V RHE Exhibit the highest CH 4 Selectivity of FE CH4 =74±2%; the measured current densities are shown in fig. 5. Tested electrocatalytic CO 2 The stability test is shown in figure 6.
Example 2
Preparation of porous Ag@Cu for electrocatalytic carbon dioxide reduction 2 O nano cell catalyst material:
(1) 5ml of Ethylene Glycol (EG) was previously added to a 25ml reaction flask and heated at 105℃for 10 minutes, followed by 250. Mu.l of 60mM hydrochloric acid in EG;
(2) After stirring the above solution for 5 minutes, 5ml of 200mM AgNO was added in 10 seconds 3 To which EG solution was added. After stirring for another 5 minutes, the mixture was stirred for 10 seconds5ml of 120 mM polyvinylpyrrolidone (PVP) in EG solution was injected;
(3) After exposing the reaction to air for 6 hours, the vials were capped, sealed, and heated to 140 ℃ for an additional 10 minutes. The whole mechanical stirring is always kept at 1000rpm so as to realize effective gas exchange;
(4) Immediately after the reaction was completed, the reaction was quenched in an ice bath for 20 minutes, and the collected product was washed with acetone, ethanol and distilled water in sequence;
(5) Dispersing 0.3mg of the prepared Ag nanocubes in 50ml of 2mM PVP aqueous solution, stirring at a high speed for 10 minutes, and uniformly mixing;
(6) Subsequently 28.6mg of Cu (NO) was added to the above solution 3 ) 2 ·3H 2 O and 57.8mg (NH) 4 ) 2 SO 4 Stirring for 5 minutes to serve as a growth solution;
(7) With a microinjection pump, 1.2ml min -1 2ml of a 0.2M aqueous NaOH solution was added dropwise to the above growth solution. After the completion of the dropwise addition, stirring was continued for 2 minutes, followed by 0.4ml min -1 3.5ml of a 0.1M aqueous solution of ascorbic acid was added to the above solution;
(8) After the dripping is completed, stirring is continued for 13 minutes, and the porous Ag@Cu can be obtained 2 O NCs-2, as shown in FIG. 6.
Example 3
Preparation of porous Ag@Cu for electrocatalytic carbon dioxide reduction 2 O nano cell catalyst material:
(1) 5ml of Ethylene Glycol (EG) was previously added to a 25ml reaction flask and heated at 105℃for 10 minutes, followed by 250. Mu.l of 60mM hydrochloric acid in EG;
(2) After stirring the above solution for 5 minutes, 5ml of 200mM AgNO was added in 10 seconds 3 To which EG solution was added. After stirring for another 5 minutes, 5ml of 120 mM polyvinylpyrrolidone (PVP) in EG was injected over 10 seconds;
(3) After exposing the reaction to air for 6 hours, the vials were capped, sealed, and heated to 140 ℃ for an additional 10 minutes. The whole mechanical stirring is always kept at 1000rpm so as to realize effective gas exchange;
(4) Immediately after the reaction was completed, the reaction was quenched in an ice bath for 20 minutes, and the collected product was washed with acetone, ethanol and distilled water in sequence;
(5) Dispersing 0.9mg of the prepared Ag nanocubes in 50ml of 2mM PVP aqueous solution, stirring at a high speed for 10 minutes, and uniformly mixing;
(6) Subsequently 28.6mg of Cu (NO) was added to the above solution 3 ) 2 ·3H 2 O and 57.8mg (NH) 4 ) 2 SO 4 Stirring for 5 minutes to serve as a growth solution;
(7) With a microinjection pump, 1.2ml min -1 2ml of a 0.2M aqueous NaOH solution was added dropwise to the above growth solution. After the completion of the dropwise addition, stirring was continued for 2 minutes, followed by 0.4ml min -1 3.5ml of a 0.1M aqueous solution of ascorbic acid was added to the above solution;
(8) After the dripping is completed, stirring is continued for 13 minutes, and the porous Ag@Cu can be obtained 2 O NCs-3, FIG. 7.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (1)
1. Porous Ag@Cu 2 The preparation method of the O nano cell material is characterized in that the O nano cell material takes Ag as a center and Cu 2 O is a nano cell structure of the shell, the nano cell is a cavity structure with a porous surface, and the porous Ag@Cu is prepared by the method 2 The average size of the O nano cell material is 180-200 nm; by using silver nanocubes as CO generator, the generated CO overflows to Cu 2 The O shell is further subjected to series reaction, cu 2 The O shell has enrichment function on CO, improves the solubility of local CO,thereby finally effectively improving the CH 4 Is selected from the group consisting of selectivity and partial current density;
the preparation method comprises the following steps:
(1) Synthesizing silver nanocubes;
(2) Preparing a growth solution: dispersing the silver nanocubes prepared in the step (1) in polyvinylpyrrolidone aqueous solution, stirring and mixing uniformly, adding copper nitrate trihydrate and ammonium sulfate, and stirring to balance;
(3) Porous Ag@Cu 2 Formation of O nanocell: dropwise adding a sodium hydroxide aqueous solution into the growth solution prepared in the step (2), continuously stirring after the dropwise adding, dropwise adding ascorbic acid into the solution, and stirring to obtain the porous Ag@Cu 2 O nano cell material;
the silver nanocubes in the step (1) have the particle size of 68-72 nanometers, and the synthesis method of the silver nanocubes in the step (1) comprises the following steps:
heating glycol, adding glycol solution of hydrochloric acid, stirring, and collecting AgNO 3 Adding ethylene glycol solution of polyvinylpyrrolidone into the reaction system, stirring, injecting the ethylene glycol solution of polyvinylpyrrolidone, exposing the reaction system in air for 6 hours, sealing, heating, mechanically stirring in the whole process to realize effective gas exchange, quenching the reaction in an ice bath immediately after the reaction is finished, and washing and collecting products by acetone, ethanol and distilled water in sequence to obtain silver nanocubes;
in the step (2), the addition amount of the copper nitrate trihydrate is 28.6 parts by weight; the addition amount of the ammonium sulfate is 57.8 parts by weight; the addition amount of the silver nanocubes is 0.5 weight part;
the porous Ag@Cu 2 The application of the O nano cell material as a catalyst for high-efficiency electrocatalytic carbon dioxide to methane;
in the step (3), the concentration of the sodium hydroxide aqueous solution is 0.2M, the concentration of the ascorbic acid is 0.1M, and the stirring time is 5-20 minutes after the dropping of the ascorbic acid.
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