CN108866562B - Preparation method of self-supporting electrode material, self-supporting electrode material and electrolytic device - Google Patents

Preparation method of self-supporting electrode material, self-supporting electrode material and electrolytic device Download PDF

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CN108866562B
CN108866562B CN201810697549.9A CN201810697549A CN108866562B CN 108866562 B CN108866562 B CN 108866562B CN 201810697549 A CN201810697549 A CN 201810697549A CN 108866562 B CN108866562 B CN 108866562B
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CN108866562A (en
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王培侨
杨林月
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ENN Science and Technology Development Co Ltd
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    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide

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Abstract

The invention provides a preparation method of a self-supporting electrode material, which comprises the following steps: SnCl prepared by adding foamy copper at a first preset concentration4·5H2Soaking in O solution; SnCl with a second preset concentration4·5H2Mixing the O solution with a strong alkaline solution with a preset concentration, and adding a surfactant with a preset mass to obtain a mixed solution; placing the soaked foamy copper into the mixed solution, and carrying out hydrothermal reaction to obtain a composite material; SnCl with preset concentration2·2H2Adding an ethanol solution into the composite material for soaking; and at a preset temperature, putting the soaked composite material into a precious metal salt solution with a preset concentration, and reacting to obtain the electrode material. The catalyst for electrocatalytic reduction of carbon dioxide is improved in structure and appearance, the foamy copper is selected as a self-supporting framework, the tin oxide and the gold are loaded, the foamy copper is directly used for an electrode material, the manufacturing process is simple and short in flow path, the active sites of the carbon dioxide are increased, the conversion efficiency of the carbon dioxide is improved, and the hydrogen evolution potential is reduced.

Description

Preparation method of self-supporting electrode material, self-supporting electrode material and electrolytic device
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method of a self-supporting electrode material, the self-supporting electrode material and an electrolysis device.
Background
The main advantages of the electrocatalytic reduction technology are: no need of consuming chemical reagents, versatility, high energy efficiency, environmental compatibility, easy control, etc. The key component in electrochemical catalysis, which determines the high or low electrocatalytic activity, is the working electrode, which is a very important part of the electrochemical catalytic system. The common electrode causes pollution and passivation of the electrode surface due to the adsorption of electrocatalytic reaction products on the electrode surface, or greatly reduces the catalytic activity, catalytic reproducibility and stability due to the physical and chemical changes of the electrode surface after long-term use.
Such as in CO2In the electrocatalytic reduction of (2), the electrode material pair increases CO2Catalytic conversion efficiency is of critical importance. The existing catalyst for electrocatalytic reduction of carbon dioxide has the problems of low activity, low conversion rate and poor product selectivity, so that the preparation of the high-performance catalyst has important significance for effective utilization of carbon dioxide. Furthermore, it is possible to provide a liquid crystal display device,the catalyst prepared at the present stage is mostly required to be prepared into an electrode by adding a binder and activated carbon for coating, the preparation method has a complex process, the obtained electrode material has high contact resistance and reduces the contact area between the active material and an electrolyte, and the uneven coating of the obtained catalyst can also affect the conversion rate and the selectivity of a product.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a self-supporting electrode material, aiming at accelerating the electron collection and transfer rate in the electrochemical catalysis process, and simultaneously increasing the contact area of the electrode material and the electrolyte, wherein the CO is2The electrocatalytic process of (2) provides more active sites, thereby increasing the electrode reaction rate.
In one aspect, the present invention provides a method for preparing a self-supporting electrode material, comprising:
the method comprises the following steps: SnCl prepared by adding foamy copper at a first preset concentration4·5H2Soaking in O solution;
step two: SnCl with a second preset concentration4·5H2Mixing the O solution with a strong alkaline solution with a preset concentration, and adding a surfactant with a preset mass to obtain a mixed solution;
step three: putting the soaked foamy copper into the mixed solution, and carrying out hydrothermal reaction to obtain a composite material;
step four: SnCl with preset concentration2·2H2Adding an ethanol solution into the composite material for soaking;
step five: and at a preset temperature, putting the soaked composite material into a precious metal salt solution with a preset concentration, and reacting to obtain the electrode material.
Further, the first preset concentration of SnCl in the first step4·5H2The concentration of O is 0-0.1 mol/L.
Further, in the second step, the strong alkaline solution is a sodium hydroxide or potassium hydroxide solution, and the second predetermined concentration of SnCl is4·5H2The concentration of O is 0.02g/ml-0.4g/ml, and the concentration of the sodium hydroxide or potassium hydroxide solution is 0.02g/ml-0.3 g/ml.
Further, the surfactant comprises any one of CTAB, PVP, SDS and SBS, and the content of the surfactant is 12.5mg/ml-25 mg/ml.
Further, the temperature of the hydrothermal reaction in the third step is 150-200 ℃.
Further, SnCl in the fourth step2·2H2The concentration of O is 0.2mg/ml-0.6 mg/ml.
Further, in the fifth step, the noble metal salt solution is a chloroauric acid, gold chloride or aurous chloride solution, the concentration of the chloroauric acid, gold chloride or aurous chloride solution is 1mmol/L-25mmol/L, and the reaction temperature is 40 ℃ to 80 ℃.
In another aspect, the present invention further provides a self-supporting electrode material, including: foam copper; the electrode material further includes: a tin oxide compound nanowire layer formed on the surface of the copper foam; and the noble metal simple substance is formed on the surface of the tin oxide compound nanowire layer.
Further, the noble metal simple substance is gold.
In another aspect, the invention further provides an electrolytic device comprising the self-supporting electrode material.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the structure and the appearance of the catalyst for electrocatalytic reduction of carbon dioxide are improved, and as the improved catalyst selects the foamy copper as a self-supporting framework and loads the tin oxide and the gold, the foamy copper is directly used for an electrode material, the manufacturing process is simple, the flow is short, the active sites of the carbon dioxide can be increased, the conversion efficiency of the carbon dioxide is improved, the hydrogen evolution potential is reduced, and the catalyst is suitable for industrial large-scale production.
Furthermore, by synthesizing the electrode material with the metal and oxide interface structure, the electron collection and transfer rate in the electrochemical catalysis process can be accelerated, the contact area of the electrode material and the electrolyte can be increased, more active sites are provided for the electrocatalysis process of carbon dioxide, and the electrode reaction rate is increased.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a flow chart of a method for preparing a self-supporting electrode material according to an embodiment of the present invention;
FIG. 2 is a Cu-SnO foam prepared in example 2 of the present invention2Scanning electron micrographs of the material;
FIG. 3 is a Cu-SnO foam prepared in example 2 of the present invention2An X-ray diffraction pattern of the material;
FIG. 4 is a graph comparing the electrocatalytic properties of the composite material of example 2 of the present invention and the copper foam material at the same time;
FIG. 5 is a graph of the electrocatalytic properties of the self-supporting electrode material prepared in example 2 of the present invention at various time points.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a self-supporting electrode material, including:
step one, S101: SnCl prepared by adding foamy copper at a first preset concentration4·5H2Soaking in O solution;
step two S102: SnCl with a second preset concentration4·5H2Mixing the O solution with a strong alkaline solution with a preset concentration, and adding a surfactant with a preset mass to obtain a mixed solution;
step three, S103: putting the soaked foamy copper into the mixed solution, and carrying out hydrothermal reaction to obtain a composite material;
step four S104: SnCl with preset concentration2·2H2Adding an ethanol solution into the composite material for soaking;
step five S105: and at a preset temperature, putting the soaked composite material into a precious metal salt solution with a preset concentration, and reacting to obtain the electrode material.
Specifically, before the first step S101, the copper foam is first cleaned. When the foam copper is cleaned, firstly, the foam copper is cleaned in acetone by ultrasonic for 10min to 20min, then the foam copper is put into dilute hydrochloric acid or dilute sulfuric acid with the mass fraction of 1 percent to 5 percent for ultrasonic cleaning for 5min to 15min, and finally the foam copper is dried for 1h to 6h in a vacuum environment at the temperature of 60 ℃ to 80 ℃. Before the second step S102, the copper foam is washed for 3 times by using deionized water and absolute ethyl alcohol respectively, and then dried for 0-2h in a vacuum environment at the temperature of 60-80 ℃.
Specifically, in the step S101, SnCl with the first preset concentration4·5H2The concentration of O is 0-0.1mol/L, and the soaking time is 1-5 h.
Specifically, in step S102, the strongly alkaline solution may be a sodium hydroxide solution or a potassium hydroxide solution, and SnCl with a second predetermined concentration4·5H2The concentration of O is 0.02g/ml-0.4g/ml, and the concentration of the sodium hydroxide or potassium hydroxide solution is 0.02g/ml-0.3 g/ml.
Specifically, the surfactant comprises any one of CTAB, PVP, SDS and SBS, and the content of the surfactant is 12.5mg/ml-25 mg/ml.
Specifically, in the third step S103, the soaked copper foam may be placed in the mixed solution, and the two may be placed in a 100ml hydrothermal reaction kettle for hydrothermal reaction at a temperature of 150 ℃ to 200 ℃ for 10h to 20 h. .
Specifically, SnCl in step four S1042·2H2The concentration of O is 0.2mg/ml-0.6mg/ml, and the soaking time is 2h-10 h. .
Specifically, in step S105, the noble metal salt solution can be a chloroauric acid, gold chloride or aurous chloride solution, the concentration of the chloroauric acid, gold chloride or aurous chloride solution is 1mmol/L-25mmol/L, the reaction temperature is 40 ℃ to 80 ℃, and the reaction time is 1min to 10 min.
It can be understood that, through the improvement of the structure and the shape of the catalyst for electrocatalytic reduction of carbon dioxide, the improved catalyst selects the foamy copper as the self-supporting framework and loads the tin oxide and the gold, and the foamy copper is directly used for the electrode material, so that the preparation process is simple, the flow is short, the active sites of the carbon dioxide can be increased, the conversion efficiency of the carbon dioxide is improved, the hydrogen evolution potential is reduced, and the catalyst is suitable for industrial large-scale production.
Furthermore, by synthesizing the electrode material with the metal and oxide interface structure, the electron collection and transfer rate in the electrochemical catalysis process can be accelerated, the contact area of the electrode material and the electrolyte can be increased, more active sites are provided for the electrocatalysis process of carbon dioxide, and the electrode reaction rate is increased.
Specifically, the preparation of the self-supporting electrode material can be carried out as follows:
step 1: SnCl with foamed copper in 0-0.1mol/L4·5H2Soaking in O solution for 1-5 h.
Step 2: respectively preparing 0.02g/ml-0.4g/ml SnCl4·5H2O solution A and 0.02g/ml-0.3g/ml sodium hydroxide or potassium hydroxide solution B, slowly adding solution A into solution B, continuously stirring for a certain time, adding 12.5mg/ml-25mg/ml surfactant, and continuously stirring for a certain time to synthesize solution C.
And step 3: and (3) placing the foamy copper into the solution C prepared in the step (2), and carrying out hydrothermal reaction at the temperature of 150-200 ℃ for 10-20 h to finally obtain the composite material.
And 4, step 4: preparing 0.2mg/ml-0.6mg/ml SnCl2·2H2Adding the composite material prepared in the step 3 into SnCl by using an O ethanol solution2·2H2Soaking in ethanol solution for 2-10 hr.
And 5: and (3) reacting the composite material treated in the step (4) with a chloroauric acid solution of 1mmol/L-25mmol/L for 1min-10min at the temperature of 40-80 ℃, and finally preparing the electrode material.
Specifically, the foamy copper is immersed in SnCl with the concentration of 0-0.1mol/L4·5H2Soaking in O solution for 1-5 hr due to Sn4+So that a layer of SnO is loaded on the surface of the copper foam in advance2Seed crystals beneficial to subsequent SnO2And (3) forming nano clusters in a guiding manner, wherein the step can be preceded by cleaning the foam copper, mainly for removing oil stains and oxides on the surface of the foam copper. Firstly, ultrasonic cleaning is carried out in acetone for 10-20min, and then ultrasonic cleaning is carried out in 1-5% diluted hydrochloric acid or diluted sulfuric acid for 5-15 min. Finally vacuum drying for 1-6h at 60-80 ℃.
Specifically, the product of the step 1 is immersed into the solution C to generate hydrothermal reaction, and SnO is controlled2And forming nano clusters on the surface of the foam copper. The temperature of the hydrothermal reaction is 150-200 ℃, and the hydrothermal time is 10-20 h. Wherein the solution C is SnCl with the concentration of 0.02g/ml to 0.4g/ml4·5H2The O solution is slowly added into sodium hydroxide or potassium hydroxide solution with the concentration of 0.02g/ml to 0.3g/ml, and Sn is accelerated under the alkaline condition4+Hydrolysis to Sn (OH)6 2-Precipitating to further form SnO under the condition of high-temperature hydrothermal2The nano-cluster is attached to the surface of the foam copper, so that the specific surface area of the foam copper is increased, the contact area of an electrode material and electrolyte is increased, and the electron collection and transfer rate in the electrochemical process is accelerated. Stirring for a period of time, adding a surfactant of 12.5mg/ml to 25mg/ml, wherein the surfactant can be CTAB or PVP or SDS or SBS. The surfactant plays a crucial role in the formation of tin dioxide, on one hand, the presence of the surfactant reduces the surface tension of the solution and reduces the required energy to form a new phase, and on the other hand, the surfactant reacts with Sn during the reaction2+Formation of ion pairs to promote SnO2Growth of the nanocrystal orientation. The growth of tin oxide nanophase can be controlled and guided by the use of surfactants.
Specifically, the product is immersed into SnCl with the concentration of 0.2mg/ml to 0.6mg/ml2·2H2Soaking in O solution for 2-8 h. In the process, a layer of Sn is loaded on the surface of the composite material prepared in the process2+Which is likely to react with the subsequently added chloroauric acid to form gold on the surface of the composite material.
Specifically, the product is immersed in chloroauric acid or AuCl with the concentration of 1-25mmol/L3In the solution, the reaction temperature is 40-80 ℃, and the reaction time is 1-10 min. After the reaction is finished, the final product Cu foam/SnO can be obtained2a/Au composite material. The loading of gold can further reduce the hydrogen evolution potential and provide more active sites for the electrocatalytic reduction of carbon dioxide.
As can be understood, the copper foam as a self-supporting material has a multi-stage pore structure, and after a layer of tin oxide nanoclusters are loaded on the copper foam, the higher specific surface area of the copper foam is further increased, the contact area of an electrode material and an electrolyte is increased, the electron collection and transfer rate in an electrochemical process is accelerated, and the copper foam/SnO is formed by Cu foam/SnO2After a layer of gold is further loaded on the surface of the catalyst, the hydrogen evolution potential can be reduced, and more active sites are provided for the electrocatalytic reduction of carbon dioxide.
In another possible embodiment based on the above embodiment, there is also provided a self-supporting electrode material, the self-supporting electrode material comprising copper foam; the electrode material further includes: a tin oxide compound nanowire layer formed on the surface of the copper foam; and forming a noble metal simple substance on the surface of the tin oxide compound nanowire layer. The simple substance of the noble metal is gold.
In another possible embodiment based on the above embodiment, there is also provided an electrolysis device comprising the above self-supporting electrode material.
The following description will discuss a method for producing a self-supporting electrode material according to the present invention with reference to representative examples.
Example 1
1. Cutting 2x3cm foam copper, and ultrasonically cleaning in 40ml acetone for 10min to remove oil stain on the surface; then placing the mixture into 30ml of diluted hydrochloric acid with the mass fraction of 1% for ultrasonic cleaning for 5min, removing oxides on the surface, then respectively cleaning the mixture for 3 times by using deionized water and absolute ethyl alcohol, and finally drying the mixture for 1h in a vacuum drying oven at the temperature of 60 ℃.
2. Soaking the foam copper treated in the step 1 in 0mol/L SnCl4·5H2O solution for 1 hour. Then washing with deionized water and absolute ethyl alcohol for 3 times respectively, and finally drying in a vacuum drying oven at 60 ℃ for 0 h.
3. 0.8g of SnCl was taken out4·5H2Preparing solution A from O and 40ml of deionized water, preparing solution B from 0.8g of NaOH and 40ml of deionized water, slowly adding the solution A into the solution B under the condition of magnetic stirring, continuously stirring for 10min, then adding 1g of CTAB, and continuously stirring for 10min to obtain a mixed solution.
4. And adding the mixed solution and the treated foamy copper into a 100ml hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal temperature is 150 ℃ and the hydrothermal time is 10 hours. After the hydrothermal treatment, the mixture is repeatedly washed by deionized water and absolute ethyl alcohol and finally dried in a vacuum drying oven at 70 ℃.
5. Take 4mg SnCl2·2H2Dissolving O in 20ml ethanol solution, magnetically stirring for 10min, and adding the obtained Cu-SnO2The composite material is soaked for 2 hours at room temperature, repeatedly washed by deionized water and absolute ethyl alcohol, and finally dried in a vacuum drying oven at 70 ℃.
6. The sample obtained by the above reaction was put into a beaker containing 20ml of absolute ethanol, and then 20. mu.l of 1mmol/L HAuCl was added dropwise to the above solution4. And heating in a 40 deg.C water bath for 1 min.
In the self-supporting electrode material with high specific surface area and multi-layer structure prepared by the preparation method of the self-supporting electrode material of the embodiment, in an electrolytic cell with an H-shaped structure, a cation exchange membrane is adopted as a diaphragm in the middle, an electrolyte is 0.1M sodium bicarbonate aqueous solution at 10mA/cm2At current density of，CO2The faradaic efficiency of conversion to CO is as high as 20%. The preparation method of the self-supporting electrode material has the advantages of simple preparation process, short flow, low equipment dependence and suitability for industrial large-scale production.
Example 2
1. Cutting 2x3cm foam copper, and ultrasonically cleaning in 40ml acetone for 15min to remove oil stain on the surface; then placing the mixture into 30ml of dilute hydrochloric acid with the mass fraction of 2.5 percent for ultrasonic cleaning for 10min to remove oxides on the surface, then respectively cleaning the mixture for 3 times by using deionized water and absolute ethyl alcohol, and finally drying the mixture for 3h in a vacuum drying oven at 70 ℃.
2. Soaking the foam copper treated in the step 1 in 0.05mol/L SnCl4·5H2O solution for 2.5 hours. Then washing with deionized water and anhydrous ethanol for 3 times, and drying in a vacuum drying oven at 70 deg.C for 1 hr.
3. 12g of SnCl are respectively taken4·5H2Preparing solution A from O and 40ml of deionized water, preparing solution B from 4g of NaOH and 40ml of deionized water, slowly adding the solution A into the solution B under the condition of magnetic stirring, continuously stirring for 10min, then adding 1.48g of CTAB, and continuously stirring for 10min to obtain a mixed solution.
4. And adding the mixed solution and the treated foamy copper into a 100ml hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal temperature is 175 ℃, and the hydrothermal time is 15 hours. After the hydrothermal treatment, the mixture is repeatedly washed by deionized water and absolute ethyl alcohol and finally dried in a vacuum drying oven at 70 ℃.
5. Taking 10mg SnCl2·2H2Dissolving O in 20ml ethanol solution, magnetically stirring for 10min, and adding the obtained Cu-SnO2The composite material is soaked for 6 hours at room temperature, repeatedly washed by deionized water and absolute ethyl alcohol, and finally dried in a vacuum drying oven at 70 ℃.
6. The sample obtained by the above reaction was put into a beaker containing 20ml of absolute ethanol, and then 20. mu.l of 10mmol/L HAuCl was added dropwise to the above solution4. And heating in a water bath at 60 deg.C for 4.5 min.
Utilizing the self-supporting of the present embodimentPreparation method of support electrode material, Cu-SnO successfully synthesized2The material is shown in figures 2 and 3, and SnO with nano-cluster morphology is successfully prepared on the surface of the copper foam2And then after the negative gold reaction, the surface appearance changes little. The prepared self-supporting electrode material with high specific surface area and multi-layer structure is arranged in an H-shaped electrolytic cell, a cation exchange membrane is adopted as a diaphragm in the middle, and the electrolyte is 0.1M sodium bicarbonate water solution at the concentration of 10mA/cm2At current density of (3), CO2The faradaic efficiency of conversion to CO is as high as 72%. The preparation method of the self-supporting electrode material has the advantages of simple preparation process, short flow, low equipment dependence and suitability for industrial large-scale production.
As shown in FIG. 4, which is an electrocatalytic reduction of CO2The obtained I-t curve is tested, and the electrocatalytic reduction of CO can be seen from the graph2The resulting hydrocarbon products are mainly ethane and ethylene.
As shown in FIG. 5, which is an electrocatalytic reduction of CO obtained at different reaction times2The obtained image of the gas product composition analysis shows that CO can be converted by the electrocatalytic method2Is converted into CO.
Example 3
1. Cutting 2x3cm foam copper, and ultrasonically cleaning in 40ml acetone for 15min to remove oil stain on the surface; then placing the mixture into 30ml of dilute hydrochloric acid with the mass fraction of 2.5 percent for ultrasonic cleaning for 10min to remove oxides on the surface, then respectively cleaning the mixture for 3 times by using deionized water and absolute ethyl alcohol, and finally drying the mixture for 3h in a vacuum drying oven at 70 ℃.
2. Soaking the foam copper treated in the step 1 in 0.05mol/L SnCl4 & 5H2O solution for 2.5 hours. Then washing with deionized water and anhydrous ethanol for 3 times, and drying in a vacuum drying oven at 70 deg.C for 1 hr.
3. 7.6g of SnCl were taken out respectively4·5H2Preparing solution A from O and 40ml of deionized water, preparing solution B from 6.4g of NaOH and 40ml of deionized water, slowly adding solution A into solution B under the condition of magnetic stirring, continuously stirring for 10min, adding 1.5g of CTAB, and continuously stirring for 10min to obtain mixed solutionAnd (4) liquid.
4. And adding the mixed solution and the treated foamy copper into a 100ml hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal temperature is 175 ℃, and the hydrothermal time is 15 hours. After the hydrothermal treatment, the mixture is repeatedly washed by deionized water and absolute ethyl alcohol and finally dried in a vacuum drying oven at 70 ℃.
5. Take 8mg SnCl2·2H2Dissolving O in 20ml ethanol solution, magnetically stirring for 10min, and adding the obtained Cu-SnO2The composite material is soaked for 6 hours at room temperature, repeatedly washed by deionized water and absolute ethyl alcohol, and finally dried in a vacuum drying oven at 70 ℃.
6. The sample obtained by the above reaction was put into a beaker containing 20ml of absolute ethanol, and then 20. mu.l of 12.5mmol/L HAuCl was added dropwise to the above solution4. And heating in a water bath at 60 deg.C for 4.5 min.
The self-supporting electrode material with high specific surface area and multi-layer structure prepared by the preparation method of the self-supporting electrode material adopts a cation exchange membrane as a diaphragm in the middle of an electrolytic cell with an H-shaped structure, and the electrolyte is 0.1M sodium bicarbonate aqueous solution at 10mA/cm2At current density of (3), CO2The faradaic efficiency of conversion to CO is as high as 50%. The preparation method of the self-supporting electrode material has the advantages of simple preparation process, short flow and low equipment dependence, and is suitable for industrial large-scale production.
Example 4
1. Cutting 2x3cm foam copper, and ultrasonically cleaning in 40ml acetone for 20min to remove oil stain on the surface; then placing the mixture into 30ml of dilute hydrochloric acid with the mass fraction of 5% for ultrasonic cleaning for 15min to remove oxides on the surface, then respectively cleaning the mixture for 3 times by using deionized water and absolute ethyl alcohol, and finally drying the mixture for 6h in a vacuum drying oven at the temperature of 80 ℃.
2. Soaking the foam copper treated in the step 1 in 0.1mol/L SnCl4·5H2O solution for 5 hours. Then washing with deionized water and anhydrous ethanol for 3 times, and drying in a vacuum drying oven at 80 deg.C for 2 hr.
3. Respectively taking 16g of SnCl4·5H2Preparing solution A from O and 40ml of deionized water, preparing solution B from 12g of NaOH and 40ml of deionized water, slowly adding the solution A into the solution B under the condition of magnetic stirring, continuously stirring for 10min, then adding 2g of CTAB, and continuously stirring for 10min to obtain a mixed solution.
4. And adding the mixed solution and the treated foamy copper into a 100ml hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal temperature is 200 ℃ and the hydrothermal time is 20 hours. After the hydrothermal treatment, the mixture is repeatedly washed by deionized water and absolute ethyl alcohol and finally dried in a vacuum drying oven at 70 ℃.
5. Taking 12mg SnCl2·2H2Dissolving O in 20ml ethanol solution, magnetically stirring for 10min, and adding the obtained Cu-SnO2The composite material is soaked for 10 hours at room temperature, repeatedly washed by deionized water and absolute ethyl alcohol, and finally dried in a vacuum drying oven at 70 ℃.
6. The sample obtained by the above reaction was put into a beaker containing 20ml of absolute ethanol, and then 20. mu.l of 25mmol/L HAuCl was added dropwise to the above solution4. And heating in a water bath at 80 deg.C for 10 min.
The self-supporting electrode material with high specific surface area and multi-layer structure prepared by the preparation method of the self-supporting electrode material adopts a cation exchange membrane as a diaphragm in the middle of an electrolytic cell with an H-shaped structure, and the electrolyte is 0.1M sodium bicarbonate aqueous solution at 10mA/cm2At current density of (3), CO2The faradaic efficiency of conversion to CO is as high as 62%. The preparation method of the self-supporting electrode material has the advantages of simple preparation process, short flow and low equipment dependence, and is suitable for industrial large-scale production.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (9)

1. A method for preparing a self-supporting electrode material, comprising:
the method comprises the following steps: SnCl prepared by adding foamy copper at a first preset concentration4•5H2Soaking in O solution;
step two: SnCl with a second preset concentration4•5H2Mixing the O solution with a strong alkaline solution with a preset concentration, and adding a surfactant with a preset mass to obtain a mixed solution;
step three: putting the soaked foamy copper into the mixed solution, and carrying out hydrothermal reaction to obtain a composite material;
step four: SnCl with preset concentration2•2H2Adding an ethanol solution into the composite material for soaking;
step five: at a preset temperature, putting the soaked composite material into a precious metal salt solution with a preset concentration, and reacting to obtain an electrode material; the noble metal salt solution is chloroauric acid, gold chloride or gold chloride solution; the obtained electrode material is of a structure of foam copper/SnO2The composite material of/Au.
2. The method for preparing a self-supporting electrode material of claim 1, wherein the first predetermined concentration of SnCl is determined in the first step4•5H2The concentration of O is 0-0.1 mol/L.
3. The method for preparing a self-supporting electrode material as claimed in claim 1, wherein in the second step, the strongly alkaline solution is sodium hydroxide or potassium hydroxide solution, and the second predetermined concentration of SnCl is4•5H2The concentration of O is 0.02g/ml-0.4g/ml, and the concentration of the sodium hydroxide or potassium hydroxide solution is 0.02g/ml-0.3 g/ml.
4. The method for preparing a self-supporting electrode material as claimed in claim 1, wherein the surfactant comprises any one of CTAB, PVP, SDS and SBS, and the content of the surfactant is 1g-2 g.
5. The method for preparing the self-supporting electrode material as claimed in claim 1, wherein the temperature of the hydrothermal reaction in the third step is 150-200 ℃.
6. The method for preparing a self-supporting electrode material according to claim 1, wherein SnCl is present in the fourth step2•2H2The concentration of O is 0.2mg/ml-0.6 mg/ml.
7. The method for preparing a self-supporting electrode material according to claim 1, wherein in the step five, the concentration of the chloroauric acid, gold chloride or gold chlorite solution is 1mmol/L-25mmol/L, and the reaction temperature is 40 ℃ to 80 ℃.
8. A self-supporting electrode material comprising: foam copper; characterized in that the electrode material further comprises: a tin oxide compound nanowire layer formed on the surface of the copper foam; and the noble metal simple substance gold is formed on the surface of the tin oxide compound nanowire layer.
9. An electrolysis device comprising the self-supporting electrode material of claim 8.
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