CN113308707A - Gas diffusion electrode for electrochemical reduction of carbon dioxide - Google Patents
Gas diffusion electrode for electrochemical reduction of carbon dioxide Download PDFInfo
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- C25B3/26—Reduction of carbon dioxide
Abstract
The invention discloses a gas diffusion electrode for preparing hydrocarbon fuel by electrochemically reducing carbon dioxide. The process of obtaining the gas diffusion electrode is to select substrate materials with different hydrophobic properties as a first waterproof breathable layer substrate; carrying out high-temperature sintering or magnetron sputtering on the waterproof breathable substrate to complete further hydrophobic treatment of the gas diffusion electrode; finally, the conductivity and the electrocatalytic performance of the waterproof breathable electrode are improved by a spray gun spraying method. The influence of the key factors on the performance of electrochemical reduction of carbon dioxide is researched by changing conditions, so that an optimized gas diffusion electrode is obtained; the layered structure is arranged to prevent the electrolyte from overflowing and allow carbon dioxide gas to permeate in the alkaline flow electrolytic cell, so that an ideal gas-liquid-solid carbon dioxide-electrolyte-copper-based catalyst three-phase interface is formed for electrochemical carbon dioxide reduction reaction.
Description
Technical Field
The invention relates to a gas diffusion electrode for preparing hydrocarbon (oxygen) fuel by electrochemically reducing carbon dioxide, belonging to the field of carbon dioxide reduction.
Background
With the increase of the use of fossil fuels in modern society, the carbon cycle balance of the earth is seriously damaged, so that the content of carbon dioxide in the atmosphere is increased dramatically, and a series of problems such as global temperature rise (greenhouse effect) and sea level rise are caused. To solve the above problems, efficient capture of excess carbon dioxide and conversion of carbon dioxide to produce value-added useful chemicals have become a research focus of urgent attention of scientists. Abundant clean energy sources such as solar energy and wind energy can be converted into renewable electric energy, and the generation of value-added high-efficiency hydrocarbon (oxygen) fuel by electrochemical reduction of carbon dioxide is gradually becoming an effective and promising carbon dioxide recycling method. However, current carbon dioxide reduction reactions present some challenges in alkaline flow electrolyzers: the gas diffusion electrode is easy to overflow so as to influence the progress of the reduction reaction of carbon dioxide, and the side reaction of the gas diffusion electrode is caused to be electrolyzed, watered and separated out hydrogen so as to severely compete for consuming the reduction current. Therefore, there is a need to develop a new gas diffusion electrode with high efficiency, high selectivity, stability and low cost as a cathode electrode of an electrolytic cell to advance the large-scale application of electrochemical reduction of carbon dioxide technology.
In recent years, the main challenge of electrocatalytic reduction of carbon dioxide has been how to take advantage of low costThe carbon dioxide is reduced with high efficiency at the lowest energy consumption, however, the process usually obtains a plurality of reduction products comprising carbon monoxide (CO), formic acid (HCOOH) and methane (CH)4) Ethylene (C)2H4) And ethanol (C)2H5OH), etc., which increases the cost of product separation in the later period. Therefore, the invention mainly uses a catalyst with high activity and high selectivity on a high-energy-density product (multi-carbon fuel) (the current report reaches the consensus that a copper-based material has no substitutable superiority on the multi-carbon product), and when the catalyst is applied to a flow electrolytic cell system with lower internal resistance, the reduction current density can be greatly improved, and meanwhile, the current cell design can solve the problems of mass transfer limitation and slow reaction kinetics, so that the energy conversion efficiency is improved.
In the system for reducing carbon dioxide by an alkaline flow electrolytic cell, a gas diffusion electrode is used as a cathode electrode, one side of the gas diffusion electrode is communicated with liquid electrolyte, and the other side of the gas diffusion electrode is communicated with carbon dioxide, so that on one hand, the gas diffusion electrode is required to prevent the electrolyte from overflowing to a solid electrode and even permeating to the gas side, and serious water permeation and overflow are caused, so that the side reaction of water decomposition and hydrogen production is severe, and the reduction performance of the carbon dioxide is reduced; on the other hand, the capability of capturing carbon dioxide gas is regulated and controlled by certain waterproof and air-permeable performance, so that carbon dioxide can enter one side of the catalyst and contact with the electrolyte to form an ideal gas-liquid-solid (carbon dioxide-electrolyte-copper-based catalyst) three-phase interface to realize high-efficiency electrocatalytic carbon dioxide reduction performance.
Disclosure of Invention
The invention aims to provide a gas diffusion electrode which is applied to electrochemical reduction of carbon dioxide.
The technical solution for realizing the purpose of the invention is as follows:
a gas diffusion electrode for electrochemical reduction of carbon dioxide as a cathodic reduction electrode in an electrolytic cell, consisting essentially of rational design and research preparation capable of preventing electrolyte flooding and allowing gas permeation, wherein the electrode is prepared by the following method:
1) selecting a carrier as a base layer of a waterproof breathable layer in the gas diffusion electrode according to the hydrophobic treatment effect;
2) the gas diffusion electrode substrate layer is subjected to further hydrophobic treatment of the gas diffusion electrode through high-temperature sintering or magnetron sputtering;
3) the conductivity of the waterproof breathable electrode is enhanced through spray coating by a spray gun.
Preferably, the volume of the self-made liquid flow electrolytic cell reaction container is 1-20 mL, the pH range of the electrolyte is 7-14, an anion exchange membrane FAA-3-50 or FAB-PK-130 is used as the ion exchange membrane, and the flow rate of the electrolyte is 1-10 mL min-1The flow rate of the carbon dioxide gas is 20-100 mL min-1The whole reaction temperature range of the reactor is 20-30 ℃.
Preferably, the support species of the substrate material is selected from the group consisting of HESEN HCP120, HESEN HCP030N, YLS-30T and Polytetrafluoroethylene (PTFE).
Further, the carrier of the substrate material needs to be further subjected to high-temperature sintering treatment and hydrophobic modification treatment, wherein the temperature range is 200-400 ℃, and the reaction time range is 30-300 minutes. Or selecting a carrier of a substrate material to carry out magnetron sputtering and carrying out hydrophobic modification treatment, wherein the range of the material is copper target (99.99 percent), and the sputtering rate is
Preferably, copper powder or conductive carbon material is sprayed on the surface of the waterproof breathable electrode by a spray gun to improve the conductivity and electrocatalytic performance of the waterproof breathable electrode. Furthermore, the loading range of the copper powder is 0.1-5 mg cm-2Or the mass range of the conductive carbon powder is 0.1-3 mg cm-1The mass range of the crystalline flake graphite is 0.1-3 mg cm-1。
Furthermore, the mass concentration of the binders Nafion and PTFE is controlled within the range of 0.1-5 mg mL in the spraying process-1。
The electrochemical reaction is a carbon dioxide reduction reaction in a liquid flow electrolytic cell.
Compared with the prior art, the invention has the advantages that: (1) the method is suitable for different liquid flow electrolytic reaction tank devices, and is a universal reasonable design method of the gas diffusion electrode; (2) the screening of the first waterproof and breathable substrate layer overcomes the problem of serious liquid overflow in the traditional electrode, and simultaneously efficiently captures carbon dioxide to enable the carbon dioxide to penetrate through the electrode so as to form an ideal gas-liquid-solid (carbon dioxide-electrolyte-copper-based catalyst) three-phase interface for electrocatalysis carbon dioxide reduction reaction; (3) the reasonable design of the PTFE hydrophobic modification layer on the second layer is to reasonably improve the hydrophobic property of the PTFE hydrophobic modification layer through high-temperature sintering or magnetron sputtering, so that a gas diffusion electrode layer with excellent and efficient carbon dioxide reduction performance is realized; (4) the third layer of spraying layer is prepared by optimally regulating and controlling the use amounts of copper powder or conductive carbon powder, crystalline flake graphite and a binder Nafion or PTFE, so that the hydrophilic and hydrophobic characteristics are further constructed on the surface while the high-efficiency current collecting and conducting effect is realized.
Drawings
FIG. 1 is a schematic (left) and physical (right) representation of the carbon dioxide reduction reaction carried out in a flow cell according to the present invention.
FIG. 2 is a scanning electron field emission microscope (right) and a cell phone image (left) of the invention as applied to various substrate layer carriers and corresponding sprayed copper powder catalysts. Where a corresponds to HESEN HCP120, b corresponds to HESEN HCP030N, c corresponds to YLS-30T, d corresponds to PTFE-YLS-30T, and e corresponds to Polytetrafluoroethylene (PTFE).
FIG. 3 is a contact angle test of the hydrophilicity and hydrophobicity of various gas diffusion electrodes of the present invention. Wherein ABCDE is listed as corresponding to ESEN HCP120, HESEN HCP030N, YLS-30T, PTFE-YLS-30T and Polytetrafluoroethylene (PTFE) in that order. In addition, row a corresponds to the front contact angle before reaction, row b corresponds to the back contact angle before reaction, row c corresponds to the front contact angle after reaction, and row d corresponds to the back contact angle after reaction.
FIG. 4 is a field emission scanning electron micrograph of a copper-based catalyst of the present invention: spray coating method (upper) and magnetron sputtering method (lower).
FIG. 5 shows the reaction effect of example 1 of the present invention using HESEN HCP120 as a gas diffusion electrode substrate layer support in combination with sprayed copper catalyst for a flow cell.
FIG. 6 is a graph showing the distribution of products of electrochemical reduction of carbon dioxide using HESEN HCP030N as a gas diffusion electrode substrate layer carrier in combination with sprayed copper catalyst in example 2 of the present invention.
FIG. 7 is a graph of the product distribution from the first cycle (left) and the reactor effect after one day of use (right) for a flow cell using YLS-30T as a gas diffusion electrode substrate layer support in combination with sprayed copper catalyst for example 3 of the present invention.
FIG. 8 is a product distribution plot for a flow cell of example 4 of the present invention using hydrophobically treated YLS-30T as the gas diffusion electrode substrate layer in combination with sprayed copper catalyst using anion exchange membrane FAB-PK-130.
FIG. 9 is a product distribution plot for a flow cell of example 4 of the present invention using hydrophobically treated YLS-30T as the gas diffusion electrode substrate layer in combination with sprayed copper catalyst using anion exchange membrane FAA-3-50: first cycle (left) and one day after reaction (right).
FIG. 10 is a product distribution plot for a flow cell using PTFE as the gas diffusion electrode substrate layer in combination with a magnetron sputtering 300nm thick copper catalyst, example 5 of the present invention: first cycle (left) and one day after reaction (right). .
FIG. 11 is a product distribution plot for a flow cell using PTFE as the gas diffusion electrode substrate layer in combination with magnetron sputtering of a 100nm thick copper catalyst, example 6 of the present invention: first cycle (left) and one day after reaction (right). FIG. 12 is a product distribution plot for a flow cell using PTFE as the gas diffusion electrode substrate layer in combination with magnetron sputtering of a 600nm thick copper catalyst, example 7 of the present invention: first cycle (left) and one day after reaction (right).
FIG. 13 is a product distribution plot for a flow cell using PTFE as the gas diffusion electrode substrate layer in combination with magnetron sputtering of a 450nm thick copper catalyst, example 8 of the present invention: first cycle (left) and one day after reaction (right).
FIG. 14 is a product distribution diagram for a flow cell of example 9 of the present invention using PTFE as the gas diffusion electrode substrate layer in combination with magnetron sputtering of a 300nm thick copper catalyst using a PTFE emulsion as the binder instead of Nafion in the current collector layer: first cycle (left) and one day after reaction (right).
FIG. 15 is a product distribution diagram for a flow cell in example 10 of the present invention, which uses PTFE as a gas diffusion electrode substrate layer, and combines magnetron sputtering of a 300nm thick copper catalyst to reduce 1/4 the amount of carbon powder in the current collector layer.
FIG. 16 is a product distribution diagram for a flow electrolytic cell in example 11 of the present invention, which uses PTFE as a gas diffusion electrode substrate layer, and combines magnetron sputtering of a 300nm thick copper catalyst to increase the amount of carbon powder in a current collector layer by 4 times.
FIG. 17 is a graph showing the distribution of reduction products of example 5 of the present invention using PTFE as a gas diffusion electrode substrate layer in combination with magnetron sputtering of a 300nm thick copper catalyst in combination with gas phase and liquid phase product analysis.
Fig. 18 is an electrochemical impedance spectrum of a gas diffusion electrode constructed in accordance with the present invention for use in an alkaline flow cell.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Referring to fig. 1, the present invention prepares a gas diffusion electrode for use in electrochemical reduction of carbon dioxide according to the following steps:
the method comprises the following steps: as the gas diffusion electrode base layer, a base material having suitable waterproof gas permeability is selected and adjusted according to evaluation criteria for preventing overflow of the electrolyte and allowing gas permeability, and may be selected in the range of HESEN HCP120, HESEN HCP030N, YLS-30T and Polytetrafluoroethylene (PTFE);
step two: as the gas diffusion electrode, the hydrophobic treatment of the gas diffusion electrode is completed by high-temperature sintering or magnetron sputtering on the substrate layer. The high-temperature sintering temperature ranges from 200 ℃ to 400 ℃, and the reaction time ranges from 30 minutes to 300 minutes. Or selecting a carrier of a substrate material for magnetron sputtering, wherein the material range is copper target (99.99 percent), and the sputtering rate is
Step three: spraying copper powder or conductive carbon material on the surface of the waterproof breathable electrode by using a spray gun to improve the conductivity of the waterproof breathable electrodeSexual and electrocatalytic properties. Furthermore, the loading range of the copper powder is 0.1-5 mg cm-2Or the mass range of the conductive carbon powder is 0.1-3 mg cm-1The mass range of the crystalline flake graphite is 0.1-3 mg cm-1. Furthermore, the surface hydrophilicity and hydrophobicity is modified by regulating and controlling the binders Nafion and PTFE in the spray gun spraying process, and the mass concentration range is 0.1-5 mg mL-1。；
Step four: the prepared gas diffusion electrode is applied to the electrocatalytic carbon dioxide reduction reaction of the basic liquid flow electrolytic cell, the volume of a reaction container of the self-made liquid flow electrolytic cell is 1-20 mL, the pH range of the electrolyte is 7-14, an ion exchange membrane uses FAA-3-50 and FAB-PK-130, and the flow rate range of the electrolyte is 1-10 mL min-1The flow rate of the carbon dioxide gas is 20-100 mL min-1The whole reaction temperature range of the reactor is 20-30 ℃.
The present invention will be described in further detail with reference to specific embodiments.
Example 1
The method comprises the following steps: HESEN HCP120 is used as a carrier of a gas diffusion electrode basal layer;
step two: high-temperature sintering or magnetron sputtering hydrophobic treatment is not carried out;
step three: 10mg of copper powder catalyst and 40. mu.l of 5% Nafion were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water, and sonicated for 2 hours. Spraying copper catalyst dispersion liquid onto HESEN HCP120 substrate layer with spray gun, adjusting spray gun spraying knob to minimum in the process, selecting heating table to heat to rapidly volatilize solvent according to small amount of multiple spraying principle, and finally obtaining load of 1mg cm-2The catalyst of (1);
step four: assembling a gas diffusion electrode into a three-chamber liquid flow electrolytic cell, wherein a waterproof substrate layer faces to one side of a cathode electrolyte (1M KOH) cavity, a catalyst layer faces to one side of carbon dioxide, a saturated Ag/AgCl reference electrode is inserted into one side of the cathode electrolyte cavity, foam Ni is selected for an anode, 1M KOH is also selected for the electrolyte of the anode cavity, an anion exchange membrane FAB-PK-130 is selected for an ion exchange membrane between a cathode and an anode, and the volume of a self-made liquid flow electrolytic cell reaction container is 1mL20mL, the pH range of the electrolyte is 7-14, and the flow rate range of the electrolyte is 1-10 mL min-1The flow rate of the carbon dioxide gas is 20-100 mLmin-1The whole reaction temperature range of the reactor is 20-30 ℃.
HESEN HCP120 as the gas diffusion electrode substrate layer, as shown in the right figure of FIG. 2a, the field emission scanning electron microscope shows that the material is formed into a carbon paper substrate by the staggered arrangement of a plurality of irregular large and small holes. The hydrophilic and hydrophobic performances of the sample are evaluated through a contact angle experiment, 5 mul of ultrapure water solution is taken by a liquid transfer gun in the experimental process and is dripped on a test platform, and the contact angle of water is measured. As shown in fig. 3a (a), the HESEN HCP120 has a positive contact angle of approximately 114 °, fig. 3a (b) shows a negative contact angle of approximately 113 °, and both contact angles are greater than 90 ° demonstrating that the material exhibits hydrophobic properties. The morphology of the copper powder catalyst sprayed on the substrate layer by the spray gun is shown in the left picture of fig. 2a, the copper powder catalyst is dispersed in the center of the substrate, a circle of copper conductive adhesive tape leading-out electrode is pasted around the copper powder catalyst, and a layer of non-conductive Kapton adhesive tape is pasted on the outermost layer. The prepared electrodes were tested in a three-chamber flow cell. The EIS curve of the electrochemical impedance spectrum is shown in FIG. 14, and the internal resistance of the liquid flow electrolytic reaction cell is about 2.5 omega. As shown in fig. 5, at a given reduction potential, the electrolyte quickly permeates from the cathode liquid chamber into the carbon dioxide gas chamber, rendering the reaction inoperable, since the waterproof permeable layer material is not sufficient to prevent flooding. The substrate layer HESEN HCP120 after the reaction had a front contact angle of approximately 50 ° (3a (c)) and a back contact angle of approximately 44 ° (fig. 3a (d)), demonstrating that the material has exhibited hydrophilic properties.
Example 2
The method comprises the following steps: HESEN HCP030N as a support for a gas diffusion electrode substrate layer;
step two: high-temperature sintering or magnetron sputtering hydrophobic treatment is not carried out;
step three: 10mg of copper powder catalyst and 40. mu.l of 5% Nafion were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water, and sonicated for 2 hours. Spraying the copper catalyst dispersion to HESEN HCP030N substrate layer with spray gun, wherein spray gun spraying knob is adjusted to minimum in the process, and spraying principle is based on small amount of multiple timesSimultaneously, a heating table is selected for heating to quickly volatilize the solvent, and finally the load capacity is 1mg cm-2The catalyst of (1);
step four: assembling a gas diffusion electrode into a three-chamber liquid flow electrolytic cell, enabling a waterproof substrate layer to face one side of a cathode electrolyte (1M KOH) cavity, enabling a catalyst layer to face one side of carbon dioxide, inserting a saturated Ag/AgCl reference electrode into one side of the cathode electrolyte cavity, selecting foamed Ni as an anode, selecting 1MKOH for electrolyte of an anode cavity, selecting an anion exchange membrane FAB-PK-130 for an ion exchange membrane between a cathode and an anode, enabling the volume of a reaction container of the self-made liquid flow electrolytic cell to be 1 mL-20 mL, enabling the pH range of the electrolyte to be 7-14, and enabling the flow rate range of the electrolyte to be 1-10 mL min-1The flow rate of the carbon dioxide gas is 20-100 mL min-1The whole reaction temperature range of the reactor is 20-30 ℃.
The HESEN HCP030N was used as the gas diffusion electrode base layer, and as shown in the right panel of fig. 2b, the carbon paper was shown to be denser by field emission scanning electron microscopy than the HESEN HCP 120. The hydrophilic and hydrophobic performances of the sample are evaluated through a contact angle experiment, 5 mu l of ultrapure water solution is taken by a liquid transfer gun in the experimental process and is dripped on a test platform, and the contact angle is measured. As shown in fig. 3b (a), HESEN HCP030N had a front contact angle of approximately 150 °, and fig. 3b (b) showed a back contact angle of approximately 126 °, indicating that the material is hydrophobic and the front side has superhydrophobic properties. Spraying copper powder catalyst on the surface by using a spray gun, wherein the sprayed material is as shown in the left picture of figure 2b, the copper-based catalyst is only sprayed in the center of the substrate, a circle of copper conductive adhesive tape leading-out electrode is pasted around the copper-based catalyst, and a layer of Kapton non-conductive adhesive tape is pasted on the outermost layer. When the gas diffusion electrode is applied to a three-chamber liquid flow electrolytic reaction cell, the electrochemical impedance spectrum EIS curve is shown in FIG. 14, the internal resistance of the liquid flow electrolytic cell is about 2.0 omega, and the conductivity of the liquid flow electrolytic cell is proved to be improved to a certain extent compared with HESEN HCP 120. As shown in fig. 6, the reduction reaction is mainly carbon dioxide reduction within 30 minutes before the low potential when the certain reduction voltage is-0.50V (vs. Reversible Hydrogen Electrode (RHE), in which the potential is calibrated by RHE) to-3.00V, but the electrolyte quickly overflows to the catalyst side from-1.25V of 40min, so that the competitive reaction produces hydrogen violently, and the faradaic efficiency of hydrogen production is greatly increased to over 90%. After about 40min, the electrolyte quickly seeps from the cathode liquid cavity into the carbon dioxide gas cavity, so that the carbon dioxide reduction reaction cannot be carried out. After testing the reaction, the contact angle was found to be approximately 90 ° for HESEN HCP030N front face, as shown in fig. 3b (c), and 120 ° for back face, as shown in fig. 3b (d), indicating that the front face is turned from hydrophobic to hydrophilic, resulting in flooding.
Example 3
The method comprises the following steps: YLS-30T is used as a carrier of a gas diffusion electrode basal layer;
step two: high-temperature sintering or magnetron sputtering hydrophobic treatment is not carried out;
step three: 10mg of copper powder catalyst and 40. mu.l of 5% Nafion were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water, and sonicated for 2 hours. Spraying the copper catalyst dispersion liquid on a YLS-30T substrate layer by using a spray gun, wherein the spray gun spraying knob is adjusted to be minimum in the process, and according to the principle of small amount of multiple spraying, a heating table is simultaneously selected for heating to quickly volatilize the solvent, so that the finally obtained load is 1mg cm-2The catalyst of (1);
step four: assembling the prepared electrode into a three-chamber liquid flow electrolytic cell, wherein a waterproof substrate layer of a gas diffusion electrode faces one side of a cathode electrolyte (1M KOH) cavity, a catalyst layer of the gas diffusion electrode faces one side of carbon dioxide, an Ag/AgCl reference electrode is selected to be involved in one side of the cathode electrolyte cavity, meanwhile, foam Ni is selected as an anode, the electrolyte of the anode cavity also selects 1M KOH electrolyte, an ion exchange membrane between a cathode and an anode selects an anion exchange membrane FAB-PK-130, the volume of a self-made liquid flow electrolytic cell reaction container is 1-20 mL, the pH range of the electrolyte is 7-14, and the flow rate range of the electrolyte is 1-10 mL min-1The flow rate of the carbon dioxide gas is 20-100 mL min-1The whole reaction temperature range of the reactor is 20-30 ℃.
YLS-30T is used as a gas diffusion electrode substrate layer, as shown in the right diagram of figure 2c, a field emission scanning electron microscope shows that the carbon paper substrate has a relatively compact structure, the hydrophilic and hydrophobic performance of the carbon paper substrate is evaluated through a contact angle experiment, 5 mu l of ultrapure water solution is taken by a liquid transfer gun in the experiment process, and is dripped onto a test platform, and the contact angle of water is measured. As shown in fig. 3c (a), the YLS-30T front contact angle is approximately 154 °, and fig. 3c (b) shows the back contact angle is approximately 142 °, indicating that the front side has superhydrophobic properties. Spraying copper powder catalyst on the substrate by a spray gun, wherein the sprayed material is as shown in the left picture of figure 2c, the copper-based catalyst is only sprayed at the center of the substrate, a circle of copper conductive adhesive tape leading-out electrode is pasted around the copper-based catalyst, and a layer of Kapton non-conductive adhesive tape is pasted on the outermost layer. The prepared electrode is assembled in a three-chamber liquid flow electrolytic cell, the EIS curve of the electrochemical impedance spectrum is shown in FIG. 14, and the internal resistance of the liquid flow electrolytic cell is about 2.0 omega. As shown in fig. 7, at a reduction potential (-0.5V to-3.0V), in the first reaction cycle, the reduction reaction is mainly carbon dioxide reduction, the low potential is mainly to generate CO, and as the voltage increases, the reduction product begins to change to the generation of carbon dioxide mainly ethylene, and the faradaic efficiency of ethylene can be up to about 35%, and the faradaic efficiency of the hydrogen-generating side reaction is controlled at 20%. One day after the first cycle, it was found that the electrolyte overflowed into the carbon dioxide gas chamber, so that the hydrogen production side reaction was severe, and the faraday efficiency was greatly increased, thereby making it impossible to perform the process. The contact angle after the reaction is tested, as shown in fig. 3c (c), the front contact angle of YLS-30T is about 145 degrees, and fig. 3c (d) shows that the back contact angle is about 136 degrees, which indicates that the front is converted from a super-hydrophobic structure to a hydrophobic structure, and the long-time reaction can also cause the occurrence of electrolyte overflow.
Example 4
The method comprises the following steps: YLS-30T is used as a gas diffusion electrode base layer;
step two: brushing a layer of PTFE emulsion on YLS-30T, pasting a PTFE membrane with the aperture of 0.22 mu m and the thickness of 5 mu m, and calcining for 2h at 360 ℃ in a muffle furnace;
step three: 10mg of copper powder catalyst and 40. mu.l of 5% Nafion were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water, and sonicated for 2 hours. Spraying the copper catalyst dispersion liquid onto a PTFE-YLS-30T substrate layer by using a spray gun, wherein a spray knob of the spray gun is adjusted to be minimum in the process, and according to a small quantity of multi-time spraying principle, a heating table is simultaneously selected for heating to quickly volatilize the solvent, and finally the load capacity is obtained1mg cm-2The catalyst of (1);
step four: assembling the prepared electrode into a three-chamber liquid flow electrolytic cell, wherein a waterproof substrate layer faces one side of a cathode electrolyte (1M KOH) cavity, a catalyst layer faces one side of carbon dioxide gas, a saturated Ag/AgCl reference electrode is inserted into one side of the cathode electrolyte cavity, foam Ni is selected as an anode, the electrolyte of the anode cavity also selects 1MKOH, an ion exchange membrane selects anion exchange membranes FAB-PK-130 and FAA-3-50, the volume of a self-made liquid flow electrolytic cell reaction container is 1-20 mL, the pH range of the electrolyte is 7-14, and the flow rate range of the electrolyte is 1-10 mL min-1The flow rate of the carbon dioxide gas is 20-100 mLmin-1The whole reaction temperature range of the reactor is 20-30 ℃.
PTFE-YLS-30T is used as a gas diffusion electrode substrate layer, and as shown in the right diagram of FIG. 2d, a field emission scanning electron microscope shows that the material is a relatively dense carbon paper substrate formed by staggered arrangement of large and small apertures. The hydrophilic and hydrophobic performances of the sample are evaluated through a contact angle experiment, 5 mul of ultrapure water solution is taken by a liquid transfer gun in the experimental process and is dripped on a test platform, and the contact angle of water is measured. As shown in fig. 3d (a), the PTFE-YLS-30T front contact angle is approximately 154 °, fig. 3d (b) shows the back contact angle is approximately 155 °, and both the back and front contact angles are greater than 150 ° indicating its superhydrophobic behavior. Spraying copper powder catalyst on the surface by using a spray gun, wherein the sprayed material is as shown in the left picture of figure 2d, the copper-based catalyst is only sprayed in the center of the substrate, a circle of copper conductive adhesive tape leading-out electrode is pasted around the copper-based catalyst, and a layer of Kapton non-conductive adhesive tape is pasted on the outermost layer. The prepared electrode is applied to a three-chamber liquid flow electrolytic cell, the electrochemical impedance spectrum EIS curve of the electrode is shown in figure 14, and the internal resistance of the liquid flow electrolytic cell is about 2.5 omega. At a given reduction voltage (-0.50V to-3.00V), as shown in FIG. 8(FAB-PK-130) and FIG. 9(FAA-3-50), in a cycle reaction time (about 2h), the reduction reaction is mainly carbon dioxide reduction, the low potential is mainly CO generation, the reduction product begins to be shifted to the generation of carbon dioxide and mainly ethylene along with the increase of the voltage, the maximum Faraday efficiency of about 35% can be obtained by the ethylene, and the Faraday efficiency of the hydrogen-generating side reaction is controlled to be 20%. After one day of the first circulation, the electrolyte is found not to overflow to the carbon dioxide gas chamber, which shows that the scheme can effectively inhibit the hydrogen production side reaction, and the Faraday efficiency is kept at about 20 percent. The contact angle after the reaction is tested, as shown in fig. 3d (c), the front contact angle of the PTFE-YLS-30T is approximately 156 °, and fig. 3d (d) shows that the back contact angle is approximately 150 °, which indicates that the front and back surfaces still maintain the super-hydrophobic property, and the long-time reaction does not cause the overflow of the electrolyte.
Example 5
The method comprises the following steps: a PTFE film with the aperture of 0.45 mu m and the thickness of 0.2mm is used as a gas diffusion electrode substrate layer;
step two: copper target material with purity of 99.99 percent
The copper catalyst is formed on the PTFE substrate by magnetron sputtering at the speed of (1) to form the copper catalyst, and the thickness of the copper catalyst is 300 nm;
step three: 10mg of Lion carbon powder and 10mg of crystalline flake graphite were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water with 40. mu.l of 5% Nafion, and subjected to ultrasonic treatment for 2 hours. Spraying carbon powder and crystalline flake graphite dispersion liquid onto the same catalyst layer by using a spray gun, wherein the spray gun spraying knob is adjusted to be minimum in the process, and according to a small quantity of multiple spraying principles, a heating table is simultaneously selected for heating to quickly volatilize the solvent, and finally the loading capacity of 1mg cm is obtained-2And a carbon powder layer of 1mg cm-2The flake graphite layer of (a);
step four: assembling the prepared electrode into a three-chamber liquid flow electrolytic cell, enabling a waterproof substrate layer to face one side of a cathode electrolyte (1M KOH) cavity, enabling a catalyst layer to face one side of carbon dioxide gas, enabling a saturated Ag/AgCl reference electrode to participate in one side of the cathode electrolyte cavity, selecting foamed Ni as an anode, enabling the electrolyte of the anode cavity to also select 1MKOH, enabling an ion exchange membrane to select FAB-PK-130, enabling the volume of a self-made liquid flow electrolytic cell reaction container to be 1-20 mL, enabling the pH range of the electrolyte to be 7-14, and enabling the flow rate of the electrolyte to be 1-10 mL min-1The flow rate of the carbon dioxide gas is 20-100 mLmin-1The whole reaction temperature range of the reactor is 20-30 ℃.
PTFE is used as a gas diffusion electrode substrate layer, and as shown in the right diagram of FIG. 2e, a field emission scanning electron microscope shows that the material has a relatively dense structure. The hydrophilic and hydrophobic performances of the sample are evaluated through a contact angle experiment, 5 mul of ultrapure water solution is taken by a liquid transfer gun in the experimental process and is dripped on a test platform, and the contact angle of water is measured. As shown in fig. 3e (a), the contact angle of PTFE on the front side is approximately 150 °, and fig. 3e (b) shows that the contact angle of PTFE on the back side is approximately 120 °, indicating that the front side has superhydrophobic properties. As shown in the left picture of fig. 2e, the copper-based catalyst is obtained by magnetron sputtering on the front surface, conductive carbon powder and crystalline flake graphite are sprayed on the surface of the copper-based catalyst to form a current collector layer, a circle of copper conductive adhesive tape leading-out electrode is pasted around the current collector layer, and a layer of Kapton non-conductive adhesive tape is pasted on the outermost layer. The prepared electrode is used in a three-chamber liquid flow electrolytic cell, the EIS curve of the electrochemical impedance spectrum is shown in figure 14, and the internal resistance of the liquid flow electrolytic reaction cell is about 3.5 omega. As shown in FIG. 10, given a reduction voltage (-0.50V to-3.00V), in the first reaction cycle, the reduction reaction is mainly carbon dioxide reduction, the low potential is mainly CO generation, carbon dioxide is mainly ethylene generated with the increase of the voltage, the maximum Faraday efficiency of about 40% can be obtained for ethylene, and the Faraday efficiency of the hydrogen-production side reaction is controlled to be 10%. After one day of the first circulation, the electrolyte does not overflow to the carbon dioxide gas chamber, so that the competitive hydrogen production reaction can be effectively inhibited, and the hydrogen production Faraday efficiency is always below 20%. The contact angle after the reaction is tested, as shown in fig. 3e (c), the front contact angle of the PTFE is about 150 °, and fig. 3d (d) shows that the back contact angle is about 120 °, indicating that the hydrophilic and hydrophobic properties of the front and back sides are not changed, so that the electrolyte overflow is not caused after the reaction for a long time.
Example 6
The method comprises the following steps: a PTFE film with the aperture of 0.45 mu m and the thickness of 0.2mm is used as a gas diffusion electrode substrate layer;
step two: copper target material with purity of 99.99 percent
The copper catalyst is formed on the PTFE substrate by magnetron sputtering at the speed of 100 nm;
step three: 10mg of Lion carbon powder and 10mg of crystalline flake graphite were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water with 40. mu.l of 5% Nafion, and subjected to ultrasonic treatment for 2 hours. Spraying carbon powder and crystalline flake graphite dispersion liquid onto the same catalyst layer by using a spray gun, wherein the spray gun spraying knob is adjusted to be minimum in the process, and according to a small quantity of multiple spraying principles, a heating table is simultaneously selected for heating to quickly volatilize the solvent, and finally the loading capacity of 1mg cm is obtained-2And a carbon powder layer of 1mg cm-2The flake graphite layer of (a);
step four: the prepared electrode is assembled into a three-chamber liquid flow electrolytic cell, a reduction voltage (-0.50V to-3.00V) is given, as shown in figure 11, in the first cycle reaction, the reduction reaction is mainly carbon dioxide reduction, CO is mainly generated at low potential and high potential, and the Faraday efficiency of the hydrogen generation side reaction is about 20%. After one day, the second round of circulating reaction shows that the hydrogen production is violent, and the Faraday efficiency is as high as 50%.
Example 7
The method comprises the following steps: a PTFE film with the aperture of 0.45 mu m and the thickness of 0.2mm is used as a gas diffusion electrode substrate layer;
step two: copper target material with purity of 99.99 percent
The Cu-PTFE catalyst is formed by magnetron sputtering on a PTFE substrate at the speed of (1) to form the Cu-PTFE catalyst, and the thickness of the Cu-PTFE catalyst is 600 nm;
step three: 10mg of Lion carbon powder and 10mg of crystalline flake graphite were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water with 40. mu.l of 5% Nafion, and subjected to ultrasonic treatment for 2 hours. Spraying carbon powder and crystalline flake graphite dispersion liquid onto the same catalyst layer by using a spray gun, wherein the spray gun spraying knob is adjusted to be minimum in the process, and according to a small quantity of multiple spraying principles, a heating table is simultaneously selected for heating to quickly volatilize the solvent, and finally the loading capacity of 1mg cm is obtained-2And a carbon powder layer of 1mg cm-2The flake graphite layer of (a);
step four: the prepared electrode is assembled into a three-chamber liquid flow electrolytic cell, a reduction voltage (-0.50V to-3.00V) is given, as shown in figure 12, in the first cycle reaction time, the reduction reaction is mainly carbon dioxide reduction, the low potential is mainly used for producing CO, the reduction product begins to turn to the generation of carbon dioxide which is mainly ethylene along with the increase of the voltage, the maximum faradaic efficiency of ethylene can be about 35%, and the faradaic efficiency of the side hydrogen production can be always inhibited by about 20%. After one day, through the second round of circulating reaction, the hydrogen production by competing side reaction is found to be violent, and the hydrogen Faraday efficiency is up to 40%.
Example 8
The method comprises the following steps: a PTFE film with the aperture of 0.45 mu m and the thickness of 0.2mm is used as a gas diffusion electrode substrate layer;
step two: copper target material with purity of 99.99 percent
The Cu-PTFE catalyst is formed by magnetron sputtering on a PTFE substrate at the speed of 450 nm;
step three: 10mg of Lion carbon powder and 10mg of crystalline flake graphite were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water with 40. mu.l of 5% Nafion, and subjected to ultrasonic treatment for 2 hours. Spraying carbon powder and crystalline flake graphite dispersion liquid onto the same catalyst layer by using a spray gun, wherein the spray gun spraying knob is adjusted to be minimum in the process, and according to a small quantity of multiple spraying principles, a heating table is simultaneously selected for heating to quickly volatilize the solvent, and finally the loading capacity of 1mg cm is obtained-2And a carbon powder layer of 1mg cm-2The flake graphite layer of (a);
step four: the prepared electrode is assembled into a three-chamber liquid flow electrolytic cell, a reduction voltage (-0.50V to-3.00V) is given, as shown in figure 13, in the first cycle reaction time, the reduction reaction is mainly carbon dioxide reduction, the low potential mainly generates CO, the reduction product begins to turn to carbon dioxide generation which is mainly ethylene generation along with the increase of the voltage, about 37 percent of faradaic efficiency can be obtained at the maximum, and the faradaic efficiency of hydrogen production side reaction is about 10 percent. The second circulation reaction after one day still has high-efficiency carbon dioxide reduction performance, the Faraday efficiency of ethylene is maintained, and the Faraday efficiency of hydrogen production side reaction is about 20%.
Example 9
The method comprises the following steps: a PTFE film with the aperture of 0.45 mu m and the thickness of 0.2mm is used as a gas diffusion electrode substrate layer;
step two: copper target material with purity of 99.99 percent
The copper catalyst is formed on the PTFE substrate by magnetron sputtering at the speed of (1) to form the copper catalyst, and the thickness of the copper catalyst is 300 nm;
step three: adding 10mg of Lion carbon powder and 10mg of crystalline flake graphite into 40 mul of 20% PTFE to 750 mul of mixed solution of ethylene glycol and 250 mul of ultrapure water, and carrying out ultrasonic treatment for 2 h; spraying carbon powder and crystalline flake graphite dispersion liquid onto the same catalyst layer by using a spray gun, wherein the spray gun spraying knob is adjusted to be minimum in the process, and according to a small quantity of multiple spraying principles, a heating table is simultaneously selected for heating to quickly volatilize the solvent, and finally the loading capacity of 1mg cm is obtained-2And a carbon powder layer of 1mg cm-2The flake graphite layer of (a);
step four: the prepared electrode is assembled into a three-chamber liquid flow electrolytic cell, the reduction voltage is given (-0.50V to-3.00V), as shown in figure 14, in the first cycle reaction time, the reduction reaction is mainly carbon dioxide reduction, the low potential is mainly CO generation, and the reduction product begins to turn to carbon dioxide generation which is mainly ethylene generation along with the increase of the voltage, about 35% of Faraday efficiency can be obtained at the highest, and the Faraday efficiency of hydrogen production side reaction is about 20%. The second circulation reaction after one day can not keep the reduction performance of the dioxitane, and the Faraday efficiency of the hydrogen production side reaction is higher.
Example 10
The method comprises the following steps: a PTFE film with the aperture of 0.45 mu m and the thickness of 0.2mm is used as a gas diffusion electrode substrate layer;
step two: copper target material with purity of 99.99 percent
The copper catalyst is formed on the PTFE substrate by magnetron sputtering at the speed of (1) to form the copper catalyst, and the thickness of the copper catalyst is 300 nm;
step three: 10mg of Lion carbon powder and 10mg of crystalline flake graphite were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water, 40. mu.l of 5% Nafion was added,and (5) carrying out ultrasonic treatment for 2 h. Spraying carbon powder and crystalline flake graphite dispersion liquid onto the same catalyst layer by using a spray gun, wherein the spray gun spraying knob is adjusted to be minimum in the process, and according to a small quantity of multiple spraying principles, a heating table is simultaneously selected for heating to quickly volatilize the solvent, so that the finally obtained load is 0.25mg cm-2And 0.25mg cm of carbon powder-2The flake graphite layer of (a);
step four: the prepared electrode was assembled into a three-chamber flow cell. As shown in fig. 15, given a reduction voltage (-0.50V to-3.00V), in the first cycle reaction time, the reduction reaction is mainly carbon dioxide reduction, the low potential is mainly CO production, and as the voltage increases, the reduction product begins to turn to the generation of carbon dioxide mainly ethylene, about 40% of faradaic efficiency can be obtained at the maximum, and the faradaic efficiency of the hydrogen production side reaction is about 10%.
Example 11
The method comprises the following steps: a PTFE film with the aperture of 0.45 mu m and the thickness of 0.2mm is used as a gas diffusion electrode substrate layer;
step two: copper target material with purity of 99.99 percent
The copper catalyst is formed on the PTFE substrate by magnetron sputtering at the speed of (1) to form the copper catalyst, and the thickness of the copper catalyst is 300 nm;
step three: 10mg of Lion carbon powder and 10mg of crystalline flake graphite were added to a mixed solution of 750. mu.l of ethylene glycol and 250. mu.l of ultrapure water with 40. mu.l of 5% Nafion, and subjected to ultrasonic treatment for 2 hours. Spraying carbon powder and crystalline flake graphite dispersion liquid onto the same catalyst layer by using a spray gun, wherein the spray gun spraying knob is adjusted to be minimum in the process, and according to a small quantity of multiple spraying principles, a heating table is simultaneously selected for heating to quickly volatilize the solvent, and finally the load capacity of 4mg cm is obtained-2And 4mg cm of carbon powder-2The flake graphite layer of (a);
step four: the prepared electrode was assembled into a three-chamber flow cell. As shown in fig. 16, given a reduction voltage (-0.50V to-3.00V), in the first cycle reaction time, the reduction reaction is mainly carbon dioxide reduction, the low potential is mainly CO production, and as the voltage increases, the reduction product begins to turn to the generation of carbon dioxide mainly ethylene, about 25% of faradaic efficiency can be obtained at the maximum, and the faradaic efficiency of the hydrogen production side reaction is about 20%.
Claims (10)
1. A gas diffusion electrode for electrochemical reduction of carbon dioxide, characterized in that it is obtained by:
selecting a carrier as a base layer of a waterproof breathable layer in the gas diffusion electrode according to the hydrophobic treatment effect;
the gas diffusion electrode substrate layer is subjected to further hydrophobic treatment of the gas diffusion electrode through high-temperature sintering or magnetron sputtering;
the conductivity of the waterproof breathable electrode is enhanced through spraying.
2. The gas diffusion electrode of claim 1, wherein the support for the substrate material is HESEN HCP120, HESEN HCP030N, YLS-30T or polytetrafluoroethylene.
3. The gas diffusion electrode according to claim 1, wherein the carrier of the base material is subjected to hydrophobic modification treatment at a temperature ranging from 200 to 400 ℃ for a reaction time ranging from 30 to 300 minutes, while being sintered at a high temperature.
4. Gas diffusion electrode according to claim 3, characterized in that the hydrophobic modification treatment is carried out during magnetron sputtering of a carrier of the substrate material, the material range being 99.99% of the copper target, the sputtering rate being
5. The gas diffusion electrode of claim 4, wherein the magnetron sputtering has a thickness in the range of 100 to 600nm and a loading in the range of 0.1 to 5mg cm-2。
6. The gas diffusion electrode of claim 1 wherein copper powder, flake graphite or conductive carbon powder material is spray coated on the surface of the waterproof gas permeable electrode layer by a spray gun for enhancing the conductivity and electrocatalytic properties of the waterproof gas permeable electrode.
7. The gas diffusion electrode of claim 6 wherein the copper powder loading is in the range of 0.1 to 5mg cm-2Or the mass range of the conductive carbon powder is 0.1-3 mg cm-1The mass range of the crystalline flake graphite is 0.1-3 mg cm-1。
8. The gas diffusion electrode of claim 6 or 7, wherein during spraying, a control is added, and the binder is one or both of perfluorosulfonic acid Nafion and PTFE, and the mass concentration ranges from 0.1 to 5mg mL-1。
9. Use of a gas diffusion electrode for electrochemical reduction of carbon dioxide based on any of claims 1-8 as a cathode electrode in an alkaline flow cell.
10. The use of claim 9, wherein the volume of the alkaline flow cell is 1mL to 20mL, the pH of the electrolyte is 7 to 14, the anion exchange membrane is FAA-3-50 or FAB-PK-130, and the flow rate of the electrolyte is 1 to 10mL min-1The flow rate of the carbon dioxide gas is 20-100 mL min-1The whole reaction temperature range is 20-30 ℃.
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