CN113073345B - Copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide and preparation method and application thereof - Google Patents
Copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide and a preparation method and application thereof. The catalyst is a supported bimetallic copper-based catalyst; the carrier is a carbon material or a metal material, and the active substance is a gold-copper heterojunction; the preparation method comprises the steps of preparing a binary metal copper-based catalyst by using a carbon material or a metal material as a carrier and sodium citrate and PDDA as stabilizers through an electrostatic self-assembly method, wherein the obtained catalyst has a gold-copper binary heterojunction. The invention can prepare the binary catalyst with different contact structures by regulating and controlling the surface coating of the metal particles by only regulating and controlling the type and the dosage of the stabilizer, and the catalyst has high selectivity for preparing ethanol by electrocatalytic reduction of carbon dioxide.
Description
Technical Field
The invention relates to a preparation method of a high-performance copper-based catalyst for electrocatalytic reduction of carbon dioxide, and a method for preparing ethanol by electrocatalytic reduction of carbon dioxide by adopting the catalyst.
Background
In recent years, the problems of energy crisis, global warming and the like are more and more prominent, and the search for sustainable development technology with economic benefits is urgent. The technology of electrocatalytic reduction of carbon dioxide is favored as a method for preparing various fuels and chemicals by using renewable energy sources to drive the reduction of greenhouse gas carbon dioxide. In various products of electrocatalytic reduction of carbon dioxide, compare to C 1 Products (such as CO and formate, etc.), ethylene, ethanol, etc. C 2+ The products are of great interest because of their higher energy efficiency and greater global market value. Due to C 1 Products (such as CO and formate, etc.) can be produced by 2 e-reduction over a variety of catalysts, so higher faradaic efficiencies and current densities are generally reported. However, C 2+ Products such as ethylene and ethanol have a similar reaction pathway, which makes it difficult to increase the selectivity and current density of a single product.
At present, copper is the only known electrocatalytic reduction process for carbon dioxide that can produce C 2+ The material of the product. However, since ethylene and ethanol generally have similar reaction pathways and correlationsBond intermediates, which often compete for production on copper-based catalysts. Recent studies have reported the use of copper-based catalysts in flow electrolysis cells by using gas diffusion electrodes to improve the selectivity of electrocatalytic reduction of carbon dioxide to ethylene. Although ethanol has the advantages of high energy density (26.8MJ/kg) and easiness in storage and transportation, the high selectivity and high current density of carbon dioxide to ethanol through electrocatalytic reduction still have great challenges, and the high ethanol selectivity and high current density are not researched and reported at present.
Therefore, the method for preparing the ethanol by electrocatalysis of the carbon dioxide by using the copper-based catalyst is very important, the intermetallic structure is reasonably designed, the way of generating ethylene is inhibited, the generation of an intermediate for generating the ethanol is promoted, and the selectivity of the ethanol on the copper-based catalyst is further improved. And by optimizing the structure on the copper-based catalyst gas diffusion electrode, high current density is obtained in the flow electrolytic cell, so that the industrial production of ethanol by electrocatalysis carbon dioxide reduction is possible.
Disclosure of Invention
The invention aims to provide a copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide and a preparation method and application thereof, aiming at the defects in the prior art. According to the method, a carbon material or a metal material is used as a carrier, sodium citrate and PDDA are used as stabilizers, a binary metal copper-based catalyst is prepared by an electrostatic self-assembly method, and the obtained catalyst has a gold-copper binary heterojunction. The invention can prepare the binary catalyst with different contact structures by regulating and controlling the surface coating of the metal particles by only regulating and controlling the type and the dosage of the stabilizer, and the catalyst has high selectivity for preparing ethanol by electrocatalytic reduction of carbon dioxide.
In order to solve the technical problems, the invention adopts the technical scheme that:
a copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide is a supported bimetallic copper-based catalyst; the carrier of the catalyst is a carbon material or a metal material, and the active substance is a gold-copper heterojunction; the load capacity is 20-60%; the molar ratio of gold to copper is 1-10: 1-10;
the carbon material is carbon black, graphene oxide, reduced graphene oxide, acetylene black or carbon nano tubes; the metal material is a foam nickel sheet, a foam copper sheet or a porous titanium sheet;
the gold-copper binary heterojunction is in one or more of a dumbbell shape, a candied gourd shape and a flower shape, and is formed by connecting gold nanoparticles and copper nanoparticles in series, namely, the atomic arrangement at a gold-copper interface is the cross arrangement between gold atoms and copper atoms.
The preparation method of the copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide comprises the following steps:
step 1: obtaining a precursor solution A according to the proportion that every 20-80 mg of soluble copper salt is dissolved in 25-80 mL of water; dissolving every 20-80 mg of chloroauric acid in 25-80 mL of water to obtain a precursor solution B; the soluble copper salt is copper chloride or copper nitrate;
step 2: under the stirring state, 50-300 mu L of PDDA is dripped into every 25-80 mL of precursor solution A to obtain solution C;
under the stirring state, 50-800 mu L of 0.05-0.5M sodium citrate solution is dripped into every 25-80 mL of precursor solution B to form solution D;
adding 5-100 mg of sodium borohydride into every 5-20 mL of ice water to form a solution E;
adding 5-50 mg of sodium borohydride into every 5-20 mL of ice water to form a solution F;
and step 3: dropwise adding every 5-20 mL of solution E into 25-80 mL of solution C under the condition of Ar atmosphere and ice-bath stirring, and stirring for 1-5 h to form solution G;
dripping every 5-20 mL of the solution F into every 25-80 mL of the solution D, and stirring for 1-5 hours to form a solution H;
and 4, step 4: dropwise adding the solution G in the step 3 into the solution H in the step 3, and stirring for 1-5 hours to obtain a solution I; volume ratio of solution G: and (3) solution H is 30-100: 30-100 parts;
and 5: the method comprises one of the following two modes:
when the carrier is a carbon material, weighing the carrier, and ultrasonically dispersing the carrier in an isometric mixed solution of isopropanol and deionized water to form a solution J; adding 1-6 mg of carrier into every 1-4 mL of mixed solution;
or, when the carrier is a metal material, immersing the carrier in a mixed solution of isopropanol and deionized water with equal volume to form a solution J;
step 6: dropwise adding the solution J in the step 5 into the solution I in the step 4 under a stirring state to form a solution K; volume ratio of solution J: solution I is 20-80: 30-200 parts of;
and 7: filtering and washing the solution K by using deionized water, and then placing the solution K in a vacuum drying oven for drying overnight at the temperature of 60-100 ℃ to obtain a catalyst loaded with a gold-copper binary heterojunction, namely a copper-based catalyst;
the application of the copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide, which is prepared by the method, is used for producing ethanol by electrocatalytic reduction of carbon dioxide, and comprises the following steps:
in a flowing electrolytic cell which is divided into a cathode tank and an anode tank by an anion exchange membrane, carrying out a constant potential electrocatalytic reduction reaction on carbon dioxide in a three-electrode system which takes a mercury/mercury oxide electrode as a reference electrode, foam nickel as a counter electrode and the material M as a working electrode;
wherein the constant potential is in the range of-0.40V to-1.2V vs RHE; the material M is a copper-based catalyst with a carrier made of a metal material, or carbon paper coated with the copper-based catalyst with the carrier made of a carbon material;
the electrolyte is KOH or KHCO 3 、NaHCO 3 Or NaOH solution with the concentration of 0.1-5M; the flow rate of the carbon dioxide gas is 15-30 sccm/50 mL;
the preparation method of the copper-based catalyst coated carbon paper comprises the following steps:
adding a Nafion solution into a dispersion liquid with the copper-based catalyst concentration of 1-10 mg/mL, then spraying the catalyst dispersion liquid on carbon paper, and drying at room temperature to obtain a working electrode;
wherein, per cm 2 Spraying 50-200 mu L of catalyst dispersion liquid on the carbon paper; the solvent of the dispersion is isopropanol; the volume ratio of the Nafion solution to the dispersion liquid is1: 10 to 100 parts; the concentration of the Nafion solution is 1 wt% -10 wt%.
The invention has the substantive characteristics that:
the method provides an idea for breaking through the bottleneck of the field of preparing ethanol by electrocatalysis of carbon dioxide, and the catalyst creatively utilizes carbon black as a carrier and combines an electrostatic self-assembly method and a colloid method to prepare the copper-based catalyst with different intermetallic structures. The catalyst related by the invention innovatively utilizes carbon black with a large specific surface area as a carrier, so that metal is uniformly distributed. The gold-copper binary heterojunction catalyst is prepared by introducing metal-gold and applying a colloid method with simple operation and mild conditions to combine with an electrostatic self-assembly method. The method brings the idea that the adsorption effect of intermetallic interaction on the intermediate in the reaction process is different, so that the product selectivity is different into the design of the catalyst, overcomes the defect of low selectivity of the traditional single-metal copper catalyst on ethanol (ethylene and ethanol are generated on the surface of the copper catalyst in a competitive way), prepares the gold-copper binary metal catalyst which can fully exert the intermetallic interaction to influence the adsorption advantage of the intermediate, and promotes the generation of the key intermediate in the ethanol generation process. The invention combines the static self-assembly method and the colloid method to prepare the copper-based catalyst with different intermetallic structures. And the current density in the reaction process can reach 500mA cm by further optimizing the structure of the gold-copper binary metal catalyst gas diffusion electrode -2 Solves the problems that the traditional single metal copper catalyst has poor selectivity to ethanol and can not reach the current density (more than 200mA cm) required by industrialization -2 ) And the like.
The invention has the beneficial effects that:
(1) the preparation method of the copper-based catalyst provided by the invention is novel, simple and easy, has mild and controllable conditions, and can accurately regulate and control the size and the dispersion degree of the metal particle size and the intermetallic interaction structure;
(2) and the influence of the intermetallic interaction on the generation of the intermediate in the reaction process is considered in the design of the catalyst, the generation mechanism of the ethanol and the intermetallic interaction are associated, the generation path of an ethylene competitive product is effectively inhibited, and the ethanol is selectively obtainedTo a great improvement. And the current density of ethanol prepared by electro-catalytic carbon dioxide reduction at-1V vs RHE can reach 500mA cm by adjusting and optimizing the catalyst in the flow electrolytic cell -2 . The reported selectivity of ethanol preparation by electrocatalytic reduction of carbon dioxide is 91%, but the current density in the reaction process is only 1.23mA cm -2 And the method is far from meeting the industrial requirement.
(3) The ethanol prepared by electrocatalytic reduction of carbon dioxide by the copper-based catalyst provided by the invention has high energy density, is easy to store and transport, and can provide a strategy for solving the problem of the current energy crisis.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a 20 wt% carbon black-supported gold-copper binary heterojunction catalyst prepared in example 1.
FIG. 2 is a Transmission Electron Microscope (TEM) image of a 40 wt% carbon black-supported gold-copper binary heterojunction catalyst prepared in example 1.
FIG. 3 is a Transmission Electron Microscope (TEM) image of a 60 wt% carbon black-supported gold-copper binary heterojunction catalyst prepared in example 2.
FIG. 4 is an XRD diffractogram of the catalysts of examples 1-3.
FIG. 5 is a bar graph of Faraday efficiencies of samples of examples 1-3 for preparing ethanol by electrocatalytic reduction of carbon dioxide.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to these examples. The experimental methods not specified in the examples are generally commercially available according to the conventional conditions and the conditions described in the manual, or according to the general-purpose equipment, materials, reagents and the like used under the conditions recommended by the manufacturer, unless otherwise specified.
The copper-based catalyst, the preparation method and the application provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Step 1: accurately weighing 23.8mg of copper chloride dihydrate, and dissolving in 50mL of water to form a precursor solution A; 21.5mg of chloroauric acid was weighed out and dissolved in 50mL of water to form a precursor solution B.
Step 2: dripping 200 mu L of PDDA into the precursor solution A in the step 1 under the stirring state to form a solution C; dripping 750 mu L of 0.1M sodium citrate solution into the precursor solution B in the step 1 under the stirring state to form a solution D; 47mg of sodium borohydride was dissolved in 15mL of ice water to form solution E, and 4.6mg of sodium borohydride was dissolved in 15mL of ice water to form solution F.
And step 3: dropwise adding the solution E in the step 2 into the solution C in the step 2 under the condition of stirring in an Ar atmosphere and ice bath, stirring for 2 hours to form a solution G, dropwise adding the solution F in the step 2 into the solution D, and stirring for 2 hours to form a solution H.
And 4, step 4: after stirring, the solution G in the step 3 is dropwise added into the solution H in the step 3, and stirring is carried out for 2 hours to obtain a solution I.
And 5: an accurate weight of 80mg of carbon black was ultrasonically dispersed in an equal volume of a mixed solution of 10mL of isopropanol and 10mL of deionized water to form solution J.
Step 6: dropwise adding the solution J in the step 5 into the solution I in the step 4 under a stirring state to form a solution K;
and 7: and (3) carrying out suction filtration and washing on the solution K obtained in the step (6) by using 2L of deionized water, and then placing the solution K in a vacuum drying oven for drying overnight at 90 ℃ to obtain the gold-copper binary heterojunction catalyst loaded with 20 wt% of carbon black.
FIG. 1 is a transmission electron microscope photograph of a 20 wt% carbon black-supported gold-copper binary heterojunction catalyst prepared in example 1, from which it can be seen that the prepared gold-copper binary heterojunction nanoparticles are dispersed more uniformly on carbon black. Wherein the darker particles are gold nanoparticles and the lighter particles are copper nanoparticles. From the figure, the gold-copper binary heterojunction particles are in a dumbbell shape or a sugarcoated haws shape, and a plurality of gold-copper interfaces are formed, namely, the atoms at the interfaces are arranged in a cross arrangement between gold atoms and copper atoms, but the gold nanoparticles and the copper nanoparticles are not simply in physical contact. And this boundaryThe surface is the key for enhancing the adsorption of an important intermediate OCCO in the ethanol generation process, so that the OCCO is easier to be asymmetrically hydrogenated at a gold-copper interface to form an OCCOH intermediate, and finally points to main C 2 The product, namely ethanol is generated, so that a gold-copper interface exists, thereby being beneficial to preparing ethanol by electrocatalytic reduction of carbon dioxide.
Example 2
Step 1: accurately weighing 47.6mg of copper chloride dihydrate, and dissolving in 50mL of water to form a precursor solution A; 43.3mg of chloroauric acid was weighed out and dissolved in 50mL of water to form a precursor solution B.
And 2, step: dripping 200 mu L of PDDA solution into the precursor solution A in the step 1 under the stirring state to form a solution C; dripping 750 mu L of 0.1M sodium citrate solution into the precursor solution B in the step 1 under the stirring state to form a solution D; 94mg of sodium borohydride was weighed out and dissolved in 15mL of ice water to form solution E, and 9.2mg was weighed out and dissolved in 15mL of ice water to form solution F.
And step 3: dropwise adding the solution E in the step 2 into the solution C in the step 2 under the condition of stirring in an Ar atmosphere and ice bath, stirring for 2 hours to form a solution G, dropwise adding the solution F in the step 2 into the solution D1, and stirring for 2 hours to form a solution H.
And 4, step 4: after stirring, dropwise adding the solution G in the step 3 into the solution H in the step 3, and stirring for 2 hours to obtain a solution I.
And 5: accurately weighed 60mg of carbon black was ultrasonically dispersed in an equal volume of a mixed solution of 10mL of isopropanol and 10mL of deionized water to form solution J.
Step 6: dropwise adding the solution J in the step 5 into the solution I in the step 4 under stirring to form a solution K.
And 7: and (3) carrying out suction filtration and washing on the solution K obtained in the step (6) by using 2L of deionized water, and then placing the solution K in a vacuum drying oven for drying overnight at 90 ℃ to obtain the gold-copper binary heterojunction catalyst loaded with 40 wt% of carbon black.
Fig. 2 is a transmission electron microscope image of a 40 wt% carbon black loaded gold copper binary heterojunction catalyst prepared in example 2, from which it can be seen that the distribution of gold copper binary heterojunction nanoparticles on carbon black becomes increasingly tight as the gold copper loading increases. .
Example 3
Step 1: accurately weighing 71.5mg of copper chloride dihydrate, and dissolving the copper chloride dihydrate in 50mL of water to form a precursor solution A; precursor solution B was prepared by weighing 64.9mg of chloroauric acid in 50mL of water.
Step 2: dripping 200 mu L of PDDA solution into the precursor solution A in the step 1 under the stirring state to form a solution C; dripping 750 mu L of 0.1M sodium citrate solution into the precursor solution B in the step 1 under the stirring state to form a solution D; 141.8mg of sodium borohydride was weighed out and dissolved in 15mL of ice water to form solution E, and 46.1mg of sodium borohydride was weighed out and dissolved in 15mL of ice water to form solution F.
And step 3: dropwise adding the solution E in the step 2 into the solution C in the step 2 under the conditions of Ar atmosphere and ice-bath stirring, stirring for 2 hours to form a solution G, dropwise adding the solution F in the step 2 into the solution D, and stirring for 2 hours to form a solution H.
And 4, step 4: after stirring, dropwise adding the solution G in the step 3 into the solution H in the step 3, and stirring for 2 hours to obtain a solution I.
And 5: accurately weighed 40mg of carbon black was ultrasonically dispersed in an equal volume of a mixed solution of 10mL of isopropanol and 10mL of deionized water to form solution J.
Step 6: dropwise adding the solution J in the step 5 into the solution I in the step 4 under stirring to form a solution K.
And 7: and (3) carrying out suction filtration and washing on the solution K obtained in the step (6) by using 2L of deionized water, and then placing the solution K in a vacuum drying oven for drying overnight at 90 ℃ to obtain the gold-copper binary heterojunction catalyst loaded with 60 wt% of carbon black.
Fig. 3 is a transmission electron microscope image of the 60 wt% carbon black loaded gold copper binary heterojunction catalyst prepared in example 3, which shows that the gold copper binary heterojunction nanoparticles begin to agglomerate on the carbon black as the gold copper loading is increased to 60%. .
FIG. 4 is an XRD diffraction pattern of the binary heterojunction catalysts with different gold and copper loadings prepared in examples 1-3, and it can be seen from the pattern that the prepared catalysts have characteristic peaks of Au and CuO. And it can be observed that the peak strength of Au and CuO increases with the increase of the loading amount of Au and cu, indicating that the amount of metal on the surface of the catalyst increases. And the 60% loading catalyst prepared in example 3 exhibited the strongest spike, indicating that the catalyst surface metal particles began to agglomerate in large amounts to form large particles, resulting in the appearance of a spike.
Examples 4 to 6
The specific method for producing ethanol by electrocatalytic reduction of carbon dioxide by using a copper-based catalyst comprises the following steps:
in a flow electrolytic cell which is divided into a cathode tank and an anode tank by an anion exchange membrane, a mercury/mercury oxide electrode is taken as a reference electrode, foamed nickel is taken as a counter electrode, and 1cm multiplied by 1cm carbon paper coated with 2mg of copper-based catalyst is taken as a working electrode to carry out electrocatalytic reduction reaction on carbon dioxide. The preparation method of the working electrode comprises the following steps: 10mg of the catalyst prepared in examples 1 to 3 was dispersed in 5mL of isopropyl alcohol, 10. mu.L of Nafion solution was added, and then the catalyst dispersion was sprayed onto 1 cm. times.1 cm of carbon paper 5 times with an air spray gun, 200. mu.L each time, and dried at room temperature to obtain a working electrode. In the electroreduction test, 1M potassium hydroxide solution is used as electrolyte, and a constant potential reduction test is carried out under the condition of continuously introducing carbon dioxide, wherein the constant potential range is-0.40V-1.2V vs RHE.
Fig. 5 is a performance diagram of samples of examples 4 to 6 for preparing ethanol by electrocatalytic reduction of carbon dioxide, and it can be seen that the catalyst with the gold-copper binary heterojunction structure prepared by the electrostatic self-assembly method has good ethanol selectivity, which shows that the structure has a promoting effect on the formation of intermediates in the ethanol production pathway. And when the loading of gold and copper is 40%, the best selectivity (43%) is presented to ethanol, which indicates that the gold and copper heterojunction structure beneficial to ethanol generation exists at most under the loading, and when the loading is further increased to 60%, the ethanol selectivity is rather reduced, which indicates that the loading is too large, and particles are agglomerated, so that active sites are covered and the ethanol selectivity is reduced, which is also consistent with the phenomenon observed in a transmission electron microscope (fig. 3).
We also enhance the hydrophobicity of the gas diffusion electrode by hot pressing a PTFE membrane on the hydrophobic carbon paper macroporous layerThe occurrence of flooding under high current density is prevented, and the stability of the electrode under high current density is improved. By optimizing the method, the gas diffusion electrode loaded with the gold-copper binary heterojunction catalyst can be enabled to have the current density of 500mA cm -2 The time is stable for more than 1 hour.
Example 7
The other steps are the same as example 4 except that the electrolyte is a sodium hydroxide solution of the same concentration.
Example 8
Step 1: accurately weighing 23.8mg of copper chloride dihydrate, and dissolving in 50mL of water to form a precursor solution A; 21.5mg of chloroauric acid was weighed out and dissolved in 50mL of water to form a precursor solution B.
Step 2: dripping 200 mu L of PDDA into the precursor solution A in the step 1 under the stirring state to form a solution C; dripping 750 mu L of 0.1M sodium citrate solution into the precursor solution B in the step 1 under the stirring state to form a solution D; 47mg of sodium borohydride was dissolved in 15mL of ice water to form solution E, and 4.6mg of sodium borohydride was dissolved in 15mL of ice water to form solution F.
And step 3: dropwise adding the solution E in the step 2 into the solution C in the step 2 under the condition of stirring in an Ar atmosphere and ice bath, stirring for 2 hours to form a solution G, dropwise adding the solution F in the step 2 into the solution D, and stirring for 2 hours to form a solution H.
And 4, step 4: after stirring, dropwise adding the solution G in the step 3 into the solution H in the step 3, and stirring for 2 hours to obtain a solution I.
And 5: a1.5 cm by 2.4cm format foamed nickel support was cut out with a mass of 80 mg.
Step 6: the carrier in step 5 is placed in the solution I in step 4 under stirring.
And 7: and (3) performing suction filtration and washing on the mixture obtained in the step (6) by using 2L of deionized water (eluting a stabilizer on the surface of metal particles on the foamed nickel so that the prepared gold-copper nano particles loaded on the foamed nickel can be directly used as a gas diffusion electrode), and placing the obtained mixture in a vacuum drying oven for drying overnight at 90 ℃ to obtain the gold-copper binary heterojunction catalyst loaded with 20 wt% of foamed nickel.
The embodiment can show that the invention can use the stabilizing agents with different charges on the surface to prepare the catalyst with the gold-copper binary heterojunction structure by the electrostatic self-assembly method, and the quantity and the dispersion degree of the gold-copper serial interfaces on the catalyst can be adjusted by adjusting the feeding ratio of the gold-copper and the carriers; the particle size can be controlled by regulating the stirring speed and the addition amount of the stabilizer, and the bimetal nanoparticles with different contact structures can be prepared by regulating the difference of charges carried by the stabilizer; the dispersion degree of the metal nano particles on the carrier can be changed by adjusting the addition amount of the stabilizer, so that the size and the dispersion degree of the metal particle size and the intermetallic interaction structure can be accurately regulated and controlled; the finally optimized carbon black loaded gold-copper binary heterojunction catalyst with the loading of 40 wt% has the best activity of preparing ethanol by electrocatalytic reduction of carbon dioxide, and is due to the gold-copper interface active sites with the most exposed surfaces and the better dispersibility.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
The invention is not the best known technology.
Claims (5)
1. A copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide is characterized in that the catalyst is a supported bimetallic copper-based catalyst; the carrier of the catalyst is a carbon material or a metal material, and the active substance is a gold-copper heterojunction; the load capacity is 20-60%; the molar ratio of gold to copper is 1-10: 1-10;
the carbon material is carbon black, graphene oxide, reduced graphene oxide, acetylene black or carbon nano tubes; the metal material is a foam nickel sheet, a foam copper sheet or a porous titanium sheet;
the gold-copper binary heterojunction is in one or more of a dumbbell shape, a candied gourd shape and a flower shape, and is formed by connecting gold nanoparticles and copper nanoparticles in series, namely the atomic arrangement at a gold-copper interface is the cross arrangement between gold atoms and copper atoms;
the preparation method of the copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide comprises the following steps:
step 1: obtaining a precursor solution A according to the proportion that every 20-80 mg of soluble copper salt is dissolved in 25-80 mL of water; dissolving every 20-80 mg of chloroauric acid in 25-80 mL of water to obtain a precursor solution B; the soluble copper salt is copper chloride or copper nitrate;
and 2, step: under the stirring state, 50-300 mu L of PDDA is dripped into every 25-80 mL of precursor solution A to obtain solution C;
under the stirring state, 50-800 mu L of 0.05-0.5M sodium citrate solution is dripped into every 25-80 mL of precursor solution B to form solution D;
adding 5-100 mg of sodium borohydride into every 5-20 mL of ice water to form a solution E;
adding 5-50 mg of sodium borohydride into every 5-20 mL of ice water to form a solution F;
and step 3: dropwise adding every 5-20 mL of solution E into 25-80 mL of solution C under the condition of Ar atmosphere and ice-bath stirring, and stirring for 1-5 h to form solution G;
dripping every 5-20 mL of the solution F into every 25-80 mL of the solution D, and stirring for 1-5 hours to form a solution H;
and 4, step 4: dropwise adding the solution G in the step 3 into the solution H in the step 3, and stirring for 1-5 hours to obtain a solution I; volume ratio of solution G: and (3) solution H is 30-100: 30-100 parts;
and 5: the method comprises one of the following two modes:
when the carrier is a carbon material, weighing the carrier, and ultrasonically dispersing the carrier in an isometric mixed solution of isopropanol and deionized water to form a solution J; adding 1-6 mg of carrier into every 1-4 mL of mixed solution;
or, when the carrier is a metal material, immersing the carrier in a mixed solution of isopropanol and deionized water with equal volume to form a solution J;
step 6: dropwise adding the solution J in the step 5 into the solution I in the step 4 under a stirring state to form a solution K; volume ratio of solution J: solution I is 20-80: 30-200 parts of;
and 7: and (3) filtering and washing the solution K by using deionized water, and drying to obtain the catalyst loaded with the gold-copper binary heterojunction, namely the copper-based catalyst.
2. The copper-based catalyst for preparing ethanol by electrocatalytic reduction of carbon dioxide according to claim 1, wherein the drying in step 7 of the preparation method is drying overnight at 60-100 ℃ in a vacuum drying oven.
3. Use of a high performance copper-based catalyst prepared according to the process of claim 1 for the electrocatalytic reduction of carbon dioxide to ethanol.
4. Use of the copper-based catalyst for the electrocatalytic reduction of carbon dioxide to ethanol prepared according to the process of claim 3, characterized by comprising the steps of:
in a flowing electrolytic cell which is divided into a cathode tank and an anode tank by an anion exchange membrane, carrying out a constant potential electrocatalytic reduction reaction on carbon dioxide in a three-electrode system which takes a mercury/mercury oxide electrode as a reference electrode, foam nickel as a counter electrode and the material M as a working electrode;
wherein the constant potential is in the range of-0.40V to-1.2V vs RHE; the material M is a copper-based catalyst with a carrier made of a metal material, or carbon paper coated with the copper-based catalyst with the carrier made of a carbon material;
the electrolyte is KOH or KHCO 3 、NaHCO 3 Or NaOH solution with the concentration of 0.1-5M; the flow rate of the carbon dioxide gas is 15 to 30sccm/50 mL.
5. The use of the copper-based catalyst prepared by the method of claim 4 for preparing ethanol by electrocatalytic reduction of carbon dioxide, wherein the preparation method of the copper-based catalyst coated carbon paper comprises the following steps:
adding a Nafion solution into a dispersion liquid with the copper-based catalyst concentration of 1-10 mg/mL, then spraying the catalyst dispersion liquid on carbon paper, and drying at room temperature to obtain a working electrode;
wherein, per cm 2 Spraying 50-200 mu L of catalyst dispersion liquid on the carbon paper; the solvent of the dispersion is isopropanol; the volume ratio of the Nafion solution to the dispersion is 1: 10 to 100 parts; the concentration of the Nafion solution is 1 wt% -10 wt%.
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