CN113463131B - Copper monatomic catalyst and preparation method and application thereof - Google Patents
Copper monatomic catalyst and preparation method and application thereof Download PDFInfo
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- CN113463131B CN113463131B CN202110850912.8A CN202110850912A CN113463131B CN 113463131 B CN113463131 B CN 113463131B CN 202110850912 A CN202110850912 A CN 202110850912A CN 113463131 B CN113463131 B CN 113463131B
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- 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
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
The invention relates to the technical field of electrocatalysis, in particular to a copper monatomic catalyst and a preparation method and application thereof. The invention discloses a preparation method of a copper monatomic catalyst, which is simple to operate, has good expansibility and is beneficial to cost control and efficiency guarantee in large-scale production. And the copper atom catalyst prepared by the preparation method has higher selectivity and current density for reducing methane by carbon dioxide.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a copper monatomic catalyst and a preparation method and application thereof.
Background
The rapid consumption of fossil fuels leads to environmental burdens and energy crisis. Excessive anthropogenic carbon dioxide emissions are a significant problem because it accelerates climate change, ocean acidification, crop reduction, extinction of animal species, and damage to human health. The removal of excess carbon dioxide from the atmosphere, particularly the conversion of carbon dioxide to fuel using renewable energy sources, is currently a global research effort. For this reason, controlling and minimizing the emission of carbon dioxide by various methods such as electrochemical, biochemical, photochemical, thermochemical and hydrothermal reduction of carbon dioxide for conversion into various valuable compounds while generating energy is one of the key tasks to solve this challenge. The carbon dioxide is converted into the chemical industrial product with high added value by using the renewable energy through an electrochemical method, so that the carbon dioxide can be recycled, the carbon cycle is realized, and the low-efficiency renewable energy can be effectively utilized. Over the past three decades, researchers have identified several materials capable of electrochemically reducing carbon dioxide in aqueous solutions, but none have been efficient and stable enough to be practical. Polycrystalline copper is currently the only metal capable of reducing carbon dioxide to a variety of valuable hydrocarbons and has been the focus of carbon dioxide reduction research. However, the product types of the polycrystalline copper catalytic carbon dioxide reduction are more than ten, so the selectivity of each product is very low, which obviously cannot reach the level of the industrial catalyst. Therefore, many researchers have performed many works around polycrystalline copper, including morphology control, particle size, multi-metal alloys, molecular modification, etc., and thus it is expected that the selectivity and current density of the carbon dioxide reduction product can be improved.
Disclosure of Invention
In view of this, the invention provides a copper monatomic catalyst, a preparation method and an application thereof, the preparation method of the copper monatomic catalyst is simple, and the prepared copper monatomic catalyst has higher selectivity and current density for reducing methane by carbon dioxide.
The specific technical scheme is as follows:
the invention provides a preparation method of a copper monatomic catalyst, which comprises the following steps:
step 1: mixing a copper source, a reducing agent and water to enable the solution to be light blue transparent solution;
step 2: adding a capping agent into the light blue transparent solution for mixing, adding carbon powder for mixing, then heating and carrying out acid washing to obtain the copper monatomic catalyst.
In step 1 of the present invention, the copper source is selected from CuCl 2 •2H 2 O, anhydrous CuCl 2 And CuSO 4 One or more than two of (a);
the reducing agent is glucose and/or 1, 2-hexadecanediol, preferably glucose, because glucose is low in cost and is non-toxic; the reducing agent is used for reducing copper ions into metal copper and has an induction effect on the appearance;
the molar ratio of the copper source to the reducing agent is 1 to 10 to 1;
the concentration of the copper source in the light blue transparent solution is 10mM to 30mM, and the concentration of the reducing agent is 10 to 50mM.
In step 2 of the invention, the capping agent is hexadecylamine and/or oleylamine, preferably hexadecylamine, wherein the hexadecylamine has lower cost, lower dosage in the same case and low toxicity; the capping agent is used for controlling the size of the copper nanocrystalline grown subsequently, so that the copper nanocrystalline can grow on the carbon powder in a smaller size;
the molar ratio of the capping agent to the copper source is 4 to 1;
the mass ratio of copper in the copper source to carbon powder is 1;
the heating temperature is 110 to 130 ℃, and the time is 2 to 3h;
the acid washing reagent is acetic acid;
the mass concentration of the acid washing reagent is 10-100%.
The invention can etch the bulk of the copper nanocrystalline by acid cleaning, thereby depositing the monoatomic copper on the carbon powder, namely anchoring the copper monoatomic group by the functional group on the carbon powder.
The invention also provides application of the copper monatomic catalyst in electrocatalytic reduction of carbon dioxide.
In the invention, the copper monatomic catalyst can be used for electrocatalysis of carbon dioxide to be selectively reduced into methane, and the methane can be used as a hydrogen storage material and applied to a fuel cell.
The invention also provides an electrocatalytic reduction carbon dioxide electrode, comprising: the electrode comprises an electrode body and the copper monatomic catalyst coated on the electrode body.
According to the technical scheme, the invention has the following advantages:
the preparation method of the copper monatomic catalyst provided by the invention is simple to operate, has good expansibility, and is beneficial to cost control and efficiency guarantee in large-scale production. And the copper atom catalyst prepared by the preparation method has higher selectivity and current density for reducing methane by carbon dioxide.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without inventive labor.
FIG. 1 is a Scanning Electron Microscope (SEM) image of Cu/C obtained in example 1 and Cu-SAs-100% obtained in example 4, wherein (a) and (b) are Cu/C and (C) and (d) are Cu-SAs-100%;
FIG. 2 is an X-ray diffraction (XRD) pattern of Cu/C prepared in example 1 of the present invention and a copper monatomic catalyst prepared in examples 2 to 4;
FIG. 3 is X-ray diffraction (XRD) patterns of Cu/C obtained in example 1 and X-ray photoelectron spectroscopy (XPS) patterns obtained in examples 2 to 4, wherein (a) is a pattern of Cu/C and Cu-SAs-10%, cu-SAs-50%, cu-SAs-100% binding energy at 930 to 960 eV, and (b) is a pattern of Cu/C and Cu-SAs-10%, cu-SAs-50%, cu-SAs-100% binding energy at 395 to 410 eV;
FIG. 4 is a Faraday efficiency graph of the copper monatomic catalyst prepared in example 1 of the present invention and the copper monatomic catalyst prepared in examples 2 to 4, wherein (a) is a Faraday efficiency graph of the copper monatomic catalyst prepared in example 1 of the present invention, the Cu/C, the carbon dioxide, the Faraday efficiency graph of the copper monatomic catalyst prepared in example 2 of the present invention, the Cu-SAs-10% electroreduction carbon dioxide, the Cu-SAs-50% electroreduction carbon dioxide, the C, the Cu-SAs-100% electroreduction carbon dioxide, the Faraday efficiency graph of the copper monatomic catalyst prepared in example 3 of the present invention, the C, the Cu-SAs-100% electroreduction carbon dioxide, the Faraday efficiency graph of the copper monatomic catalyst prepared in example 4 of the present invention;
FIG. 5 is a graph of the partial current densities of Cu/C obtained in example 1 of the present invention and carbon dioxide obtained by the electro-reduction of copper monatomic catalysts in examples 2 to 4, wherein (a) is a graph of the partial current density of carbon dioxide obtained in example 1 of the present invention and obtained in the electro-reduction of copper monatomic catalyst Cu/C, (b) is a graph of the partial current density of carbon dioxide obtained in example 2 of the present invention and obtained in the electro-reduction of copper monatomic catalyst Cu-SAs-10%, wherein (C) is a graph of the partial current density of carbon dioxide obtained in example 3 of the present invention and obtained in the electro-reduction of copper monatomic catalyst Cu-SAs-50%, and wherein (d) is a graph of the partial current density of carbon dioxide obtained in example 4 of the present invention and obtained in the electro-reduction of copper monatomic catalyst Cu-SAs-100%.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding CuCl 2 •2H 2 O (0.17 g) and glucose (2.44 g) were dissolved in 80 mL of water to obtain a mixed solution (CuCl in mixed solution) 2 •2H 2 Concentration of O and glucose were both 12.5 mM), XC-72 carbon powder (64 mg) was added at a copper to carbon weight ratio of 1. The resulting pale blue emulsion was poured into an autoclave and heated in an oil bath with stirring at 120 ℃ for 2 h. Cooling to room temperature, adding deionized water, ethanol, n-hexyl alcoholWashing the alkane for multiple times to finally obtain the copper nanocrystalline carbon material catalyst with N 2 Next, the symbol is Cu/C.
Example 2
Adding CuCl 2 •2H 2 O (0.17 g) and glucose (2.44 g) were dissolved in 80 mL of water to obtain a mixed solution (CuCl in the mixed solution) 2 •2H 2 Concentration of O and glucose were both 12.5 mM), XC-72 carbon powder (64 mg) was added at a copper to carbon weight ratio of 1. The light blue emulsion was formed and poured into an autoclave and heated in an oil bath with stirring at 120 ℃ for 2 h. After cooling to room temperature, repeatedly washing with deionized water, ethanol and normal hexane for many times, and heating and stirring the obtained precipitate in 10wt% acetic acid at 60 ℃ for 4 hours to carry out acid-washing etching operation; finally, the acetic acid is washed off to obtain the copper monatomic catalyst which is preserved in N 2 Next, the symbol is Cu-SAs-10%.
Example 3
Adding CuCl 2 •2H 2 O (0.17 g) and glucose (2.44 g) were dissolved in 80 mL of water to obtain a mixed solution (CuCl in mixed solution) 2 •2H 2 Concentration of O and glucose were both 12.5 mM), XC-72 carbon powder (64 mg) was added at a copper to carbon weight ratio of 1. The resulting pale blue emulsion was poured into an autoclave and heated in an oil bath with stirring at 120 ℃ for 2 h. After cooling to room temperature, repeatedly washing with deionized water, ethanol and normal hexane for many times, and heating and stirring the obtained precipitate in 50wt% acetic acid at 60 ℃ for 4 hours to carry out acid-washing etching operation; finally, the copper monatomic catalyst obtained after washing off the acetic acid is preserved in N 2 Next, the symbol is Cu-SAs-50%.
Example 4
Adding CuCl 2 •2H 2 O (0.17 g) and glucose (2.44 g) were dissolved in 80 mL of water to obtain a mixed solution (CuCl in the mixed solution) 2 •2H 2 Both O and glucose concentrations were 12.5 mM), XC-72 carbon powder (64 mg) was added in a ratio of copper to carbon 1, vigorously stirred for 5 h, and slowly added during this timeHexadecylamine (1.44 g). The light blue emulsion was formed and poured into an autoclave and heated in an oil bath with stirring at 120 ℃ for 2 h. After cooling to room temperature, repeatedly washing with deionized water, ethanol and normal hexane for many times, heating and stirring the obtained precipitate in 100wt% acetic acid at 60 ℃ for 4 hours to carry out acid-washing etching operation; finally, the acetic acid is washed off to obtain the copper monatomic catalyst which is preserved in N 2 Next, the symbol is Cu-SAs-100%.
FIG. 1 is a Scanning Electron Microscope (SEM) image of Cu/C and Cu-SAs-100%, and it can be seen that Cu/C before acid cleaning exists in a nano cube structure, and the square particle diameter is about 150 nm, while Cu-SAs-100% after acid cleaning does not exist in a nano cube, and spherical particles seen in the image are XC-72 carbon powder, which proves that acid cleaning can successfully etch away bulk copper.
FIG. 2 is an X-ray diffraction (XRD) diagram of Cu/C and Cu-SAs-10%, cu-SAs-50%, cu-SAs-100%, and it can be seen that Cu/C before pickling shows obvious polycrystalline copper structure, and obvious peaks of Cu (111), cu (200), and Cu (220) can be seen, while the original crystalline phase copper peak of the monoatomic copper catalyst after pickling has completely disappeared, and the remaining amorphous peak is XC-72 carbon powder peak, further confirming that the pickling etching can wash off the polycrystalline copper and form the copper monoatomic catalyst.
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) plot of Cu/C and Cu-SAs-10%, cu-SAs-50%, cu-SAs-100%, showing that Cu 2p before pickling shows a distinct copper peak, while the copper peak after pickling is significantly weaker, indicating that the copper content in carbon is significantly reduced. On the other hand, it can be found from N1s that the N peak in the copper monatomic catalyst after acid washing shifts toward the high binding energy direction, which indicates that N in the hexadecylamine remaining after acid washing is coordinated so that N in the hexadecylamine contributes to electrons. This also indicates the formation of a monatomic copper catalyst.
Test examples
The electrochemical carbon dioxide reduction performance tests of examples 1 to 4 were carried out in a flow cell under conditions of normal temperature and normal pressure, in which both the cathode and anode electrolytes were 1M KOH.
Each of the monoatomic copper catalysts prepared in examples 1 to 4 was reacted with BPreparing 1mg/mL solution of alcohol-water solution (containing 1/100 nafion adhesive), and dropping 300uL solution in 0.5cm 2 The carbon paper of the gas diffusion layer is dried and then used as a working electrode for testing. A flow electrolytic cell is used as a reaction device, a gas diffusion electrode and a three-electrode system, and the performance of the monatomic copper catalyst on the electro-reduction of carbon dioxide is electrochemically tested by an electrochemical workstation (CHI 650C, china). The catalyst is loaded on carbon paper with a gas diffusion layer to be used as a working electrode, an Ag/AgCl electrode (saturated KCl solution) is used as a reference electrode, a Pt sheet is used as a counter electrode, and chambers of a cathode and an anode are separated by an anion exchange membrane (SELEMION). In the electrolysis process, a mass flow controller (Brooks GF 40) is arranged to ensure that the flow rate of carbon dioxide flowing into the cathode electrolytic cell is 5sccm, and the rotating speed of a peristaltic pump (Cole-Parmer) is set to be 65 rpm so as to control the flow rate of the electrolyte (1M KOH) with the anode and the cathode. All testing procedures were performed at room temperature. The test adopts constant voltage electrolysis, and the voltage is from-0.7V to-1.1V vs.
FIG. 4 is a Faraday diagram showing the faradaic efficiencies of the monatomic copper catalysts prepared in examples 1 to 4 for the electroreduction of carbon dioxide. It can be seen from figure 4 that the copper monatomic catalyst after complete pickling shows a good selectivity for methane, with faradaic efficiency on methane as high as 57.3% at-1.0V vs. rhe, the more negative the potential. While the selectivity of the incompletely acid-washed copper monatomic catalyst to methane is slightly reduced and there is a significant drop at high potential, which may be due to the reduction of active sites caused by the agglomeration of copper at high potential, eventually causing a reduction in the selectivity to methane.
FIG. 5 is a plot of the partial current densities for the electroreduction of carbon dioxide by the monatomic copper catalysts prepared in examples 1-4. From FIG. 5, it can be seen that the acid-washed copper monatomic catalysts all showed a relatively high methane partial current density, and particularly, the partial current density of Cu-SAs-100% to methane after complete acid-washing exceeded 200mA/cm 2 。
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. The preparation method of the copper monatomic catalyst is characterized by comprising the following steps:
step 1: mixing a copper source, a reducing agent and water to enable the solution to be light blue transparent solution;
step 2: adding a capping agent into the light blue transparent solution for mixing, adding carbon powder for mixing, then heating, and carrying out acid washing to obtain a copper monatomic catalyst;
the reducing agent is glucose and/or 1, 2-hexadecanediol; the capping agent is hexadecylamine and/or oleylamine.
2. The method of claim 1, wherein the copper source is selected from the group consisting of CuCl 2 ·2H 2 O, anhydrous CuCl 2 And CuSO 4 One or more than two of them.
3. The preparation method according to claim 1, wherein the molar ratio of the copper source to the reducing agent is 1;
the molar ratio of the capping agent to the copper source is (4);
the mass ratio of copper in the copper source to the carbon powder is 1.
4. The method according to claim 1, wherein the acid washing is carried out using acetic acid as a reagent.
5. The production method according to claim 4, wherein the mass concentration of the acetic acid is 10 to 100%.
6. The method according to claim 1, wherein the heating is carried out at a temperature of 110 to 130 ℃ for 2 to 3 hours.
7. A copper monatomic catalyst produced by the production method according to any one of claims 1 to 6.
8. Use of the copper monatomic catalyst of claim 7 in the electrocatalytic reduction of carbon dioxide.
9. An electrocatalytic reduction carbon dioxide electrode, comprising: an electrode body and a copper monatomic catalyst of claim 7 coated thereon.
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