CN114622234B - Flexible gas diffusion electrode structure and application thereof in electrochemical reduction of carbon dioxide - Google Patents
Flexible gas diffusion electrode structure and application thereof in electrochemical reduction of carbon dioxide Download PDFInfo
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Abstract
The invention provides a flexible gas diffusion electrode, which comprises a basal layer, a catalytic layer, a polymer layer and an interface layer which are sequentially combined, wherein the basal layer is mainly composed of a porous high polymer film. The flexible gas diffusion electrode is bendable and squeezable, can bear the pressure difference formed by rapid gas generation in the flowing electrolytic cell, ensures the integrity and gas permeability of the gas diffusion electrode, and overcomes the defect that the graphite-based gas diffusion electrode is easy to crack under a certain pressure difference; SO 3-group grafted polymer layer introduced at one side of flexible gas diffusion electrode close to electrolyte, CO 2 The in-plane diffusion coefficient (D) of the layer is greater than the diffusion coefficient (D0) in the catholyte, thereby allowing CO to pass 2 The gas flows in the layer until CO 2 Reduction takes place at the catalytically active site, the CO being dissolved in the catholyte 2 The amount is reduced to lead most of CO 2 The reaction occurs at the three-phase interface of the surface of the catalyst and is not affected by CO 2 The limitation of solubility in aqueous solutions, thereby increasing the rate of ERC reaction.
Description
Technical Field
The invention belongs to the technical field of electrochemical reduction of carbon dioxide, and particularly relates to a flexible gas diffusion electrode structure, and a preparation technology and application thereof.
Background
Electrochemical reduction of CO 2 The (ERC) technique is to use electrical energy to convert CO 2 Reducing to target product to realize CO 2 A technique for transformation and efficient use. With other CO 2 Compared with the transformation technology, the ERC technology has outstanding advantagesThe method has the advantages that the operation is simple, the cost is low, water can be used as a hydrogen source for protonation, and CO can be realized at normal temperature and normal pressure 2 The high-efficiency conversion of the catalyst is realized, so that the energy consumption caused by hydrogen production, heating and pressurizing required by a chemical conversion technology is not required, and the equipment investment is low.
During the ongoing development of ERC technology, researchers have found that by using Gas Diffusion Electrodes (GDEs) with flowing catholyte, the electrocatalytic performance of these catalysts can be evaluated without regard to mass transfer limitations and local pH effects. I.e. to construct a so-called flow cell instead of a static H-cell in the traditional sense. In a flow cell, CO 2 Enters the cathode of the cell from the back of the gas diffusion layer, reacts with H+ from the electrolyte in the cathode catalytic layer to reduce, and the reduced product exits the cell through the gas diffusion layer. The flow battery not only can lighten CO 2 Mass transfer polarization due to low solubility in water, and suppression of hydrogen evolution side reaction and reduction of CO due to use of mobile electrolyte 2 Activation energy barrier and enhanced CC coupling between CO, thereby increasing C 2 Selectivity of the product.
However, in the prior structure exploration process of Gas Diffusion Electrode (GDE) for a flow cell, we found that GDE constructed by using porous graphite-based material as a gas diffusion substrate has the problems of low pressure resistance, easiness in flooding microporous channels with electrolyte under the action of capillary force, serious mass transfer polarization, low catalytic stability of the electrode, particularly the most prominent problems are crease and/or fracture of GDE along the section direction under the condition of pressurizing operation, GDE failure and CO 2 It is necessary to first dissolve in the catholyte before the reduction reaction can take place, thereby converting the flow cell into a conventional H-cell.
Disclosure of Invention
In order to solve the above problems of the GDE constructed by using a porous graphite-based material as a gas diffusion substrate, the present invention proposes to construct a Flexible Gas Diffusion Electrode (FGDE) using a porous polymer film as a substrate.
The invention provides a gas diffusion electrode, which comprises a basal layer, a catalytic layer, a polymer layer and an interface layer which are sequentially arranged, wherein the basal layer comprises a porous high polymer film; the thickness of the porous high molecular polymer film is any value between 5 μm and 100 μm. The porous high molecular polymer is not limited to a hydrophobic structure or a hydrophilic structure, and can be used for supporting an electrode, and a person skilled in the art can select a specific type according to actual situations.
Preferably, the pore size of the porous high molecular polymer film is any value between 0.1 μm and 5 μm; the porosity is any value between 60% and 90%.
Preferably, the skeleton material of the porous high polymer film is one of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE) and polypropylene (PP);
the polymerization degree of the porous high molecular polymer in the porous high molecular polymer film is more than or equal to 10 3 。
The preparation method of the conductive microporous layer, the catalyst layer and the polymer interface layer is one of knife coating and spraying.
As a preferable technical scheme, the thickness of the catalyst layer is 5-500 nm, the thickness of the polymer layer is 2-50 nm, and the thickness of the interface layer is 5-200 nm;
preferably the catalyst layer comprises a nanomaterial and a binder that are electrocatalytically active for ERC reactions;
preferably, the nano catalyst in the catalyst layer is one of nano metal particles, supported nano metal particles, carbon materials doped with strong electronegative elements or monoatomic metal catalysts;
preferably, the binder is one of polyvinylidene fluoride (PVDF) and perfluorosulfonic acid resin;
preferably, the mass ratio of the catalyst to the binder is 8:1-2:1;
preferably, the polymer layer comprises a porous high molecular polymer resin I.
As a preferable technical scheme, a microporous conductive layer is arranged between the basal layer and the catalytic layer, and the thickness of the microporous conductive layer is 10 nm-1000 nm;
preferably the conductive microporous layer comprises highly conductive carbon and a binder;
preferably, the high-conductivity carbon in the conductive microporous layer is one of graphite powder and active carbon, and the particle size is 0.5-2 mu m; the binder is one of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and perfluorinated sulfonic acid resin; the mass ratio of the high conductive carbon to the binder is 9:1-2:1.
As a preferable technical scheme, the main components of the interface layer are porous high polymer resin II and catalyst particles;
in the interface layer, the mass ratio of the polymer resin to the catalyst particles is 9:1-5:1.
The porous resins of the present invention are of the type commonly used in the art for polymer layers.
As a preferable technical scheme, the polymer resin I in the polymer layer is an organic high polymer resin containing hydrophilic groups; the hydrophilic group is preferably an acrylic group, a sulfonic group, an acryl sulfonic group or a quaternary amine group.
As a preferable embodiment, the catalyst particles in the interface layer are the same as the elements of the catalyst particles in the catalytic layer; the polymer resin II in the interface layer is the same as the polymer resin I in the polymer layer.
As a preferable technical scheme, CO 2 The gas has a gas diffusion coefficient within the interface layer that is greater than the diffusion coefficient in the catholyte. CO 2 The gas has a gas diffusion coefficient (D) in the interface layer that is greater than the diffusion coefficient in the catholyte, i.e. ensures a large part of the CO 2 The reduction reaction takes place within the gas diffusion electrode rather than into the catholyte.
The flexible gas diffusion electrode can be applied to CO2 electrochemical reduction, and is particularly suitable for the CO2 electrochemical reduction technology using a flowing electrolytic cell, wherein the pH value of electrolyte in the electrolytic cell is=6-14.
The invention also provides a carbon dioxide electrochemical reduction electrolytic cell which comprises any one of the gas diffusion electrodes and is used for electrolyzing the obtained C 2 The product accounts for 60 to 80 percent of the total reaction product volume ratio, and the C of the invention 2 The product comprises C 2 H 4 、C 2 H 5 OH。
Advantageous effects
Compared with the existing porous graphite-based gas diffusion electrode, the flexible gas diffusion electrode prepared by the method has the following characteristics:
(1) The flexible gas diffusion electrode is bendable and squeezable, can bear the pressure difference formed by rapid gas generation in the flowing electrolytic cell, ensures the integrity and gas permeability of the gas diffusion electrode, and overcomes the defect that the graphite-based gas diffusion electrode is easy to break under a certain pressure difference.
(2) Grafting SO introduced at one side of flexible gas diffusion electrode close to electrolyte 3 - Radical polymer layer, CO 2 The in-plane diffusion coefficient (D) in this layer is greater than the diffusion coefficient (D) in the catholyte 0 ) Thereby making CO 2 The gas flows in the layer until CO 2 Reduction occurs in the presence of catalyst reduction, and CO dissolved in the catholyte 2 The amount is reduced to lead most of CO 2 The reaction occurs at the three-phase interface of the surface of the catalyst and is not affected by CO 2 The limitation of solubility in aqueous solutions, thereby increasing the rate of ERC reaction.
(3) In the interfacial layer of the flexible gas diffusion electrode, the catalyst particles and the polymer are mixed to obtain a 3D morphology with catalyst and polymer permeation pathways. Such FGDE will maximize the three-phase reaction interface in an extended three-dimensional (3D) morphology, enabling ERC reactions to be performed at higher current conditions.
(4) The polymer layer can prolong the retention time of carbon dioxide on the surface of the catalytic layer and increase the conversion rate of carbon dioxide, but when the thickness is too high, the proton transfer speed can be reduced, the hydrogenation reduction speed of carbon dioxide is delayed, the reduction speed of carbon dioxide is reduced, and the generation speed and the selectivity of a product are affected.
Drawings
FIG. 1 is a schematic diagram of a flexible gas diffusion electrode structure according to the present invention, showing a FGDE structure based on a porous polymer film and its interfacial characteristics in ERC reactions.
1. A porous polymer film; 2. a conductive microporous layer; 3. a catalytic layer; 4. a polymer layer; 5. an interfacial layer.
Detailed Description
A Flexible Gas Diffusion Electrode (FGDE) is prepared from porous high-molecular polymer film as substrate, and sequentially constructing conductive microporous layer, catalyst layer, polymer layer and interface layer. The conductive microporous layer comprises high conductive carbon and a binder; the catalyst layer comprises a nanomaterial with electrocatalytic activity on ERC reaction and a binder. The polymer layer is a high molecular polymer resin layer, the skeleton of the polymer resin has the same chemical composition as the substrate material, contains hydrophobic groups, and has a side chain grafted with hydrophilic groups, so that the liquid-solid interface layer has both hydrophobic and hydrophilic functions; the interface layer is mainly made of porous high polymer resin and is added with a small amount of catalyst particles.
Comparative example 1
(1) Pretreatment of graphite-based porous carbon paper: with a porosity of 82%, a thickness of 190 μm and an area of 10cm 2 The carbon paper (TGP-H-030, manufactured by Toli Corp., japan) is used as a base material, which is soaked in acetone at room temperature for 10min to remove surface grease, and then dried by high-purity argon;
(2) Preparation of graphite-based Gas Diffusion Electrode (GDE): mixing Cu particles with the particle size of 20nm, a perfluorosulfonic acid resin (Nafion) solution and isopropanol, wherein the mass ratio of the Cu particles to the perfluorosulfonic acid resin is 7:3, the mass ratio of the isopropanol to the perfluorosulfonic acid resin solution is 8:1, performing ultrasonic dispersion on the mixture for 30min, spraying the mixture on the surface of porous carbon paper from which the grease is removed in the first step, and controlling the areal density of the nano Cu particles to be 5mg cm -2 Drying in a vacuum oven at 60 ℃ with the vacuum degree of-0.1 MPa, and the thickness of the dried catalytic layer is about 200nm.
(3) Electrochemical reduction treatment of gas diffusion electrode: firstly, preparing NaHCO with the concentration of 0.1M by taking analytically pure sodium bicarbonate as a raw material and ultrapure water with the resistivity of 18.2M omega as a solvent 3 200ml of an aqueous solution; then high-purity N is introduced 2 1h, using the GDE prepared in 2 as a working electrode, pt sheetThe saturated calomel electrode is used as a reference electrode. At-2 mAcm -2 Electrochemical reduction is carried out for 120min under the condition, then the mixture is taken out, rinsed by a large amount of deionized water, dried by high-purity argon, and stored in an inert environment for standby.
(4) Electrochemical catalytic reduction of CO 2 : in the flow cell, 20ml of 1.0M KOH aqueous solution was added to each of the anode and cathode chambers, and NF115 produced by DuPont was used as a membrane of the anode and cathode chambers. The electrode in 3 is used as a working electrode, ag/AgCl (saturated KCl) is used as a reference electrode, and the Pt sheet is used as a counter electrode. Controlling the flow speed of the cathode electrolyte to be 3ml min -1 CO with a purity of 99.995% 2 Gas enters the cathode cavity from the surface of GDE without catalyst, CO 2 Is controlled to 20sccm. Electrochemical reduction reaction is carried out for 35min under the working voltage of-1.4V, reaction tail gas is introduced into gas chromatography for quantitative detection of gas products, and liquid products are quantitatively analyzed by ion chromatography.
After 30min of reaction, GDE was broken and ERC reaction was terminated.
The results of the product analysis within 30min were: c (C) 2 H 4 The Faraday efficiency of (2) is 40%, and the current density is 15mA cm < -2 >; the faraday efficiency of CO was 21%; the Faraday efficiency of HCOOH is 2%; h 2 The faraday efficiency of these four products was 38% and the total faraday efficiency of these four products was 99%, indicating that the other undetected products were produced in very little amount.
Comparative example 2
(1) Pretreatment of a flexible substrate: taking a porous polytetrafluoroethylene film with the thickness of 40 mu m, the porosity of 75% and the pore diameter of 0.22 mu m, cutting the porous polytetrafluoroethylene film into 4cm x 4cm, soaking the porous polytetrafluoroethylene film in deionized water, spreading the porous polytetrafluoroethylene film completely, spreading the porous polytetrafluoroethylene film on the surface of clean filter paper, and sucking water.
(2) Preparing a microporous conducting layer: preparing slurry by using Vulcan X-72 active carbon with the particle size of 1 mu m, polyvinylidene fluoride (PCDF) and N, N-dimethyl pyrrolidone, controlling the mass ratio of the active carbon to PVDF to be 8:2, and controlling the viscosity of the slurry to be 1000MPas; spreading the porous polytetrafluoroethylene film in step 1 on a clean glass plate, uniformly spraying the slurry on the surface of the porous PTFE, and controlling the surface density of the activated carbon to be 1.0mg cm -2 The sprayed assembly was dried in an oven at 120 c to give a sprayed coating thickness of about 100nm.
(3) Preparing a catalytic layer: mixing Cu particles with the particle size of 20nm, a perfluorosulfonic acid resin (Nafion) solution and isopropanol, wherein the mass ratio of the Cu particles to the perfluorosulfonic acid resin is 7:3, the mass ratio of the isopropanol to the perfluorosulfonic acid resin solution is 8:1, performing ultrasonic dispersion on the mixture for 30min, and then spraying the mixture on the surface of the microporous conductive layer prepared in the step 2, wherein the areal density of the nano Cu particles is controlled to be 5mg cm -2 Drying in a vacuum oven at 60 ℃ with the vacuum degree of-0.1 MPa, and the thickness of the dried catalytic layer is about 200nm.
(4) Electrochemical catalytic reduction of CO 2 : in the flow cell, 20ml of 1.0M KOH aqueous solution was added to each of the anode and cathode chambers, and NF115 produced by DuPont was used as a membrane of the anode and cathode chambers. The electrode in 3 is used as a working electrode, ag/AgCl (saturated KCl) is used as a reference electrode, and the Pt sheet is used as a counter electrode. Controlling the flow speed of the cathode electrolyte to be 3ml min -1 CO with a purity of 99.995% 2 Gas enters the cathode cavity from the surface of GDE without catalyst, CO 2 Is controlled to 20sccm. Electrochemical reduction reaction is carried out for 5h under the working voltage of-1.4V, the reaction tail gas is introduced into gas chromatography for quantitative detection of gas products, and the liquid products are quantitatively analyzed by NMR.
And the ERC reaction current is stable within 5 hours of reaction, and the appearance of the flexible gas diffusion electrode is good.
The product analysis results were: c (C) 2 H 4 The Faraday efficiency of (C) was 43%, and the partial current density was 29mA cm -2 (II), (III), (V), (; the faraday efficiency of CO is 12%; c (C) 2 H 5 The Faraday efficiency of OH is 6.3%; the Faraday efficiency of HCOOH is 3%; h 2 The faraday efficiency of 35.1% and the total faraday efficiency of these four products was 99.4%, indicating that the other undetected products were produced in very little amount.
In this comparative example, the gas diffusion electrode containing no interface layer and no polymer layer had no expansion in reaction area, a small number of reactive sites, and no CO presence 2 In-plane diffusion coefficient is improved, CO2 easily enters the electrolyte, ERC is reversedThe rate should be low.
Comparative examples 3 to 7, the preparation and test procedures were similar to comparative example 2, and the relevant main parameters are shown in Table 1.
Example 1
(1) Pretreatment of a flexible substrate: taking a porous polytetrafluoroethylene film with the thickness of 40 mu m, the porosity of 75% and the pore diameter of 0.22 mu m, cutting the porous polytetrafluoroethylene film into 4cm x 4cm, soaking the porous polytetrafluoroethylene film in deionized water, spreading the porous polytetrafluoroethylene film completely, spreading the porous polytetrafluoroethylene film on the surface of clean filter paper, and sucking water.
(2) Preparing a microporous conducting layer: preparing slurry by using Vulcan X-72 active carbon with the particle size of 1 mu m, polyvinylidene fluoride (PCDF) and N, N-dimethyl pyrrolidone, controlling the mass ratio of the active carbon to PVDF to be 8:2, and controlling the viscosity of the slurry to be 1000MPas; spreading the porous polytetrafluoroethylene film in step 1 on a clean glass plate, uniformly spraying the slurry on the surface of the porous PTFE, and controlling the surface density of the activated carbon to be 1.0mg cm -2 The sprayed assembly was dried in an oven at 120 c to give a sprayed coating thickness of about 100nm.
(3) Preparing a catalytic layer: mixing Cu particles with the particle size of 20nm, a perfluorosulfonic acid resin (Nafion) solution and isopropanol, wherein the mass ratio of the Cu particles to the perfluorosulfonic acid resin is 7:3, the mass ratio of the isopropanol to the perfluorosulfonic acid resin solution is 8:1, performing ultrasonic dispersion on the mixture for 30min, and then spraying the mixture on the surface of the microporous conductive layer prepared in the step 2, wherein the areal density of the nano Cu particles is controlled to be 5mg cm -2 Drying in a vacuum oven at 60 ℃ with the vacuum degree of-0.1 MPa, and the thickness of the dried catalytic layer is about 200nm.
(4) Preparation of the polymer layer: the surface of the catalytic layer prepared by spraying a perfluorosulfonic acid resin solution with the exchange equivalent of 1100 and the concentration of 1 percent on the surface of the catalytic layer prepared in 3, and controlling the surface density of the perfluorosulfonic acid resin to be 0.2mg cm -2 The corresponding thickness is about 20nm.
(5) Preparing an interface layer: and (3) spraying an interface layer on the surface of the polymer layer prepared in the step (4). Controlling the mass ratio of Cu particles to perfluorinated sulfonic acid resin to be 1:5, wherein the surface density of the nano Cu particles is 1mg cm -2 The thickness of the interface layer after drying was about 100nm.
(6) Electrochemical catalytic reduction of CO 2 : in the flow cell, 20ml of 1.0M KOH aqueous solution was added to each of the anode and cathode chambers, and NF115 produced by DuPont was used as a membrane of the anode and cathode chambers. The electrode in 5 is used as a working electrode, ag/AgCl (saturated KCl) is used as a reference electrode, and the Pt sheet is used as a counter electrode. Controlling the flow speed of the cathode electrolyte to be 3ml min -1 CO with a purity of 99.995% 2 Gas enters the cathode cavity from the surface of GDE without catalyst, CO 2 Is controlled to 20sccm. Electrochemical reduction reaction is carried out for 5h under the working voltage of-1.4V, the reaction tail gas is introduced into gas chromatography for quantitative detection of gas products, and the liquid products are quantitatively analyzed by NMR.
And the ERC reaction current is stable within 5 hours of reaction, and the flexible gas diffusion electrode is intact.
The product analysis results were: c (C) 2 H 4 The Faraday efficiency of (2) was 65% and 1.7 times that of the comparative example; the current density is 150mA cm -2 10 times that of the comparative example; the faraday efficiency of CO is 9%; c (C) 2 H 5 The Faraday efficiency of OH is 13.8%; h 2 The faraday efficiency of these four products was 12% and the total faraday efficiency of these four products was 99.8%, indicating that the other undetected products were produced in very little amount.
By comparing the test results with the test results of the comparative examples, the test results of the examples show that the electrode structure of the invention remarkably improves the reaction rate of ERC under the condition of taking 20nmCu particles as catalysts, and simultaneously improves the selectivity of C2 (+) products from 38% to 77%, and the improvement amplitude reaches 1 time.
Example 2
(1) Pretreatment of a flexible substrate: taking a porous polyvinylidene fluoride membrane with the thickness of 100 mu m and the pore diameter of 0.1 mu m, cutting the membrane into 4cm x 4cm, soaking the membrane in deionized water, spreading the membrane completely, spreading the membrane on the surface of clean filter paper, and sucking water.
(2) Preparing a microporous conducting layer: preparing slurry from graphite powder with the particle size of 2 mu m, polytetrafluoroethylene and N, N-dimethyl pyrrolidone, wherein the mass ratio of the graphite powder to the PTFE is controlled to be 9:1, and the viscosity of the slurry is 1500MPas; spreading the porous polytetrafluoroethylene film in step 1 on a clean glass plate, and uniformly spraying the slurryOn the surface of porous PVDF, the surface density of the activated carbon is controlled to be 3.0mg cm -2 The sprayed composition was dried in an oven at 70 c to give a sprayed layer having a thickness of about 500nm.
(3) Preparing a catalytic layer: mixing 40wt% Cu/C particles with the particle size of 5nm, a perfluorosulfonic acid resin (Nafion) solution and isopropanol, wherein the mass ratio of the Cu/C particles to the perfluorosulfonic acid resin is 2:1, the mass ratio of the isopropanol to the perfluorosulfonic acid resin solution is 10:1, ultrasonically dispersing the mixture for 30min, spraying the mixture on the surface of the microporous conductive layer prepared in the step 2, and controlling the areal density of the nano Cu/C particles to be 5mg cm -2 Drying in a vacuum oven at 60 ℃ with the vacuum degree of-0.1 MPa, and the thickness of the dried catalytic layer is about 500nm.
(4) Preparation of the polymer layer: the surface of the catalytic layer prepared by spraying a perfluorosulfonic acid resin solution having an exchange Equivalent (EW) of 900 and a concentration of 1% on 3 was controlled to have an areal density of 0.5mg cm -2 The corresponding thickness is about 50nm.
(5) Preparing an interface layer: and (3) spraying an interface layer on the surface of the polymer layer prepared in the step (4). The mass ratio of Cu/C particles to the perfluorinated sulfonic acid resin is controlled to be 1:7, and the surface density of the nano Cu/C particles is controlled to be 0.5mg cm -2 The thickness of the interface layer after drying was about 200nm.
(6) Electrochemical catalytic reduction of CO 2 : in the flow cell, 20ml of 1.0M KOH aqueous solution was added to each of the anode and cathode chambers, and NF115 produced by DuPont was used as a membrane of the anode and cathode chambers. The electrode in 5 is used as a working electrode, ag/AgCl (saturated KCl) is used as a reference electrode, and the Pt sheet is used as a counter electrode. Controlling the flow speed of the cathode electrolyte to be 3ml min -1 CO with a purity of 99.995% 2 Gas enters the cathode cavity from the surface of GDE without catalyst, CO 2 Is controlled to 20sccm. Electrochemical reduction reaction is carried out for 5h under the working voltage of-1.4V, the reaction tail gas is introduced into gas chromatography for quantitative detection of gas products, and the liquid products are quantitatively analyzed by NMR.
And the ERC reaction current is stable within 5 hours of reaction, and the flexible gas diffusion electrode is intact.
The product analysis results were: c (C) 2 H 4 The Faraday efficiency of (2) was 60% and 1.58 times that of the comparative example; the current density is 120mA cm -2 8 times that of the comparative example; the faraday efficiency of CO is 13%; c (C) 2 H 5 Faraday efficiency of OH 11%; h 2 The faraday efficiency of these four products was 15% and the total faraday efficiency of these four products was 99%, indicating that the other undetected products were produced in very little amount. Wherein the proportion of C2 (+) product is up to 84.52% of the total C product.
Example 3
(1) Pretreatment of a flexible substrate: and (3) taking a porous polyethylene film with the thickness of 5 mu m and the pore diameter of 0.5 mu m, cutting the porous polyethylene film into 4cm x 4cm, soaking the porous polyethylene film in deionized water, spreading the porous polyethylene film completely, spreading the porous polyethylene film on the surface of clean filter paper, and sucking water.
(2) Preparing a microporous conducting layer: preparing ink-state slurry by KJ-300 with the particle size of 0.5 mu m, perfluorosulfonic acid resin and isopropanol, controlling the mass ratio of carbon black to perfluorosulfonic acid resin to be 4:1, and controlling the viscosity of the slurry to be 500MPas; spreading the porous polyethylene film in step 1 on a clean glass plate, uniformly spraying the slurry on the surface of the porous PE, and controlling the surface density of the activated carbon to be 2.0mg cm -2 The sprayed assembly was dried in an oven at 60 c to give a sprayed coating having a thickness of about 700nm.
(3) Preparing a catalytic layer: mixing Zn particles with the particle size of 30nm, 20% PTFE emulsion and isopropanol, wherein the mass ratio of the Zn particles to the PTFE is 8:1, the mass ratio of the isopropanol to the PTFE emulsion is 8:1, performing ultrasonic dispersion on the mixture for 30min, spraying the mixture on the surface of the microporous conductive layer prepared in the step 2, and controlling the areal density of the nano Zn particles to be 2.5mg cm -2 Drying in a vacuum oven at 60 ℃ with the vacuum degree of-0.1 MPa, and the thickness of the dried catalytic layer is about 50nm.
(4) Preparation of the polymer layer: the surface of the catalytic layer prepared by spraying a perfluorinated sulfonic acid resin solution with exchange equivalent of 900 and concentration of 5% on the surface of the catalytic layer prepared in step 3, and controlling the surface density of the perfluorinated sulfonic acid resin to be 0.5mg cm -2 The corresponding thickness is about 50nm.
(5) Preparing an interface layer: and (3) spraying an interface layer on the surface of the polymer layer prepared in the step (4). Controlling the mass ratio of Zn particles to perfluorinated sulfonic acid resin to be1:9, the surface density of the nano Zn particles is 0.2mg cm -2 The thickness of the interface layer after drying was about 20nm.
(6) Electrochemical catalytic reduction of CO 2 : in the flow cell, 20ml of 1.0M KOH aqueous solution was added to each of the anode and cathode chambers, and NF115 produced by DuPont was used as a membrane of the anode and cathode chambers. The electrode in 5 is used as a working electrode, ag/AgCl (saturated KCl) is used as a reference electrode, and the Pt sheet is used as a counter electrode. Controlling the flow speed of the cathode electrolyte to be 3ml min -1 CO with a purity of 99.995% 2 Gas enters the cathode cavity from the surface of GDE without catalyst, CO 2 Is controlled to 20sccm. Electrochemical reduction reaction is carried out for 5h under the working voltage of-1.7V, the reaction tail gas is introduced into gas chromatography for quantitative detection of gas products, and the liquid products are quantitatively analyzed by NMR.
And the ERC reaction current is stable within 5 hours of reaction, and the flexible gas diffusion electrode is intact. The product analysis results were: c (C) 2 H 4 The Faraday efficiency of (2) is 4%; CH (CH) 4 The Faraday efficiency of (2) was 20%, and the split current density was 30mA cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The faraday efficiency of CO is 60%; c (C) 2 H 5 Faraday efficiency of OH 2%; h 2 The faraday efficiency of these five products was 12% and the total faraday efficiency of these five products was 99%, indicating that the other undetected products were produced in very little amount.
The test result of example 3 shows that the electrode structure of the invention obviously improves the reaction rate of ERC under the condition of taking 30nm Zn particles as a catalyst, the sum of the partial current density of the C1 product is 120mA cm < -2 >, and the proportion of the C1 product to the total C product is as high as 93 percent.
Example 4
(1) Pretreatment of a flexible substrate: and (3) taking a porous polypropylene film with the thickness of 50 mu m and the pore diameter of 0.1 mu m, cutting the porous polypropylene film into 4cm x 4cm, soaking the porous polypropylene film in deionized water, spreading the porous polypropylene film completely, spreading the porous polypropylene film on the surface of clean filter paper, and sucking water.
(2) Preparing a microporous conducting layer: preparing slurry from KJ-600 carbon black with the particle size of 1.5 mu m, polyvinylidene fluoride and N, N-dimethyl pyrrolidone, controlling the mass ratio of active carbon to PVDF to be 2:1, and controlling the viscosity of the slurry to be 1000MPas; spreading the porous polypropylene film in step 1 on a clean glass plate, uniformly spraying the slurry on the surface of porous PP, and controlling the surface density of the activated carbon to be 2.0mg cm -2 The sprayed assembly was dried in an oven at 60 c to give a sprayed coating thickness of about 1000nm.
(3) Preparing a catalytic layer: mixing nitrogen doped hollow carbon spheres (N-HC) with the particle size of 5nm, a perfluorosulfonic acid resin (Nafion) solution and isopropanol, wherein the mass ratio of Cu particles to the perfluorosulfonic acid resin is 6:1, the mass ratio of isopropanol to the perfluorosulfonic acid resin solution is 8:1, ultrasonically dispersing the mixture for 30min, spraying the mixture on the surface of the microporous conductive layer prepared in the step 2, and controlling the areal density of nano N-HCS particles to be 0.2mg cm -2 Drying in a vacuum oven at 60 ℃ with the vacuum degree of-0.1 MPa, and the thickness of the dried catalytic layer is about 20nm.
(4) Preparation of the polymer layer: the surface of the catalytic layer prepared by spraying a perfluorinated sulfonic acid resin solution with exchange equivalent of 900 and concentration of 1% on the surface of the catalytic layer prepared in step 3, and controlling the surface density of the perfluorinated sulfonic acid resin to be 0.1mg cm -2 The corresponding thickness is about 10nm.
(5) Preparing an interface layer: and (3) spraying an interface layer on the surface of the polymer layer prepared in the step (4). The mass ratio of Cu particles to the perfluorinated sulfonic acid resin is controlled to be 1:8, and the surface density of N-HC particles is controlled to be 0.4mg cm -2 The thickness of the interface layer after drying was about 50nm.
(6) Electrochemical catalytic reduction of CO 2 : in the flow cell, 20ml of 1.0M KOH aqueous solution was added to each of the anode and cathode chambers, and NF115 produced by DuPont was used as a membrane of the anode and cathode chambers. The electrode in 5 is used as a working electrode, ag/AgCl (saturated KCl) is used as a reference electrode, and the Pt sheet is used as a counter electrode. Controlling the flow speed of the cathode electrolyte to be 3ml min -1 CO with a purity of 99.995% 2 Gas enters the cathode cavity from the surface of GDE without catalyst, CO 2 Is controlled to 20sccm. Electrochemical reduction reaction is carried out for 5h under the working voltage of-1.2V, the reaction tail gas is introduced into gas chromatography for quantitative detection of gas products, and the liquid products are quantitatively analyzed by NMR.
Within 5h of reaction, ERC reaction current is stable, and flexible gas expandsThe scattering electrode is intact. The product analysis results were: the Faraday efficiency of CO was 88%, and the partial current density of CO was 50mA cm -2 ；H 2 The faraday efficiency of (2) was 10% and the total faraday efficiency of both was 98%, indicating that the other undetected products were produced in very small amounts.
The test results of example 4 demonstrate that the sum of the partial current densities of the CO product is 50mA cm using the electrode structure of the present invention with 50nm N-hollow carbon spheres as catalyst -2 Its Faraday efficiency is as high as 88%.
Example 5
(1) Pretreatment of a flexible substrate: and (3) taking a porous polytetrafluoroethylene film with the thickness of 5 mu m and the pore diameter of 0.1 mu m, cutting the porous polytetrafluoroethylene film into 4cm x 4cm, soaking the porous polytetrafluoroethylene film in deionized water, spreading the porous polytetrafluoroethylene film completely, spreading the porous polytetrafluoroethylene film on the surface of clean filter paper, and sucking water.
(2) Preparing a microporous conducting layer: preparing slurry by KJ-300 carbon black with the particle size of 0.5 mu m, polyvinylidene fluoride and N, N-dimethyl pyrrolidone, wherein the mass ratio of the activated carbon to PVDF is controlled to be 3:1, and the viscosity of the slurry is 1000MPas; spreading the porous polytetrafluoroethylene film in step 1 on a clean glass plate, uniformly spraying the slurry on the surface of the porous PTFE, and controlling the surface density of the activated carbon to be 0.1mg cm -2 The sprayed assembly was dried in an oven at 120 c to give a sprayed coating thickness of about 10nm.
(3) Preparing a catalytic layer: monodisperse ZnN with particle size of 30nm 4 -C, perfluorosulfonic acid resin (Nafion) solution, isopropanol mixture, znN 4 The mass ratio of the C particles to the perfluorinated sulfonic acid resin is 5:1, the mass ratio of the isopropanol to the perfluorinated sulfonic acid resin solution is 8:1, the mixture is dispersed for 30min by ultrasonic, and then the mixture is sprayed on the surface of the microporous conductive layer prepared in the step 2, so that the nano ZnN is controlled 4 The areal density of the C particles is 0.3mg cm -2 Drying in a vacuum oven at 60 ℃ with the vacuum degree of-0.1 MPa, and the thickness of the dried catalytic layer is about 5nm.
(4) Preparation of the polymer layer: spraying a perfluorinated sulfonic acid resin solution with exchange equivalent of 1100 and concentration of 1% on the surface of the catalytic layer prepared by 3, and controlling the surface density of the perfluorinated sulfonic acid resin to be 0.05mg cm -2 Corresponding to a thickness of about 2nm。
(5) Preparing an interface layer: and (3) spraying an interface layer on the surface of the polymer layer prepared in the step (4). Control of ZnN 4 The mass ratio of the-C particles to the perfluorinated sulfonic acid resin is 1:5, and the nano ZnN is adopted 4 The areal density of the C particles is 0.1mg cm -2 The thickness of the interface layer after drying was about 5nm.
(6) Electrochemical catalytic reduction of CO 2 : in the flow cell, 20ml of 1.0M KOH aqueous solution was added to each of the anode and cathode chambers, and NF115 produced by DuPont was used as a membrane of the anode and cathode chambers. The electrode in (5) is used as a working electrode, ag/AgCl (saturated KCl) is used as a reference electrode, and the Pt sheet is used as a counter electrode. Controlling the flow speed of the cathode electrolyte to be 3ml min -1 CO with a purity of 99.995% 2 Gas enters the cathode cavity from the surface of GDE without catalyst, CO 2 Is controlled to 20sccm. Electrochemical reduction reaction is carried out for 5h under the working voltage of-1.5V, the reaction tail gas is introduced into gas chromatography for quantitative detection of gas products, and the liquid products are quantitatively analyzed by NMR.
And the ERC reaction current is stable within 5 hours of reaction, and the flexible gas diffusion electrode is intact.
The product analysis results were: CH (CH) 4 The Faraday efficiency of (C) was 75%, and the partial current density was 60mA cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The Faraday efficiency of CO is 12%, the Faraday efficiency of HCOOH is 3%, H 2 The faraday efficiency of these three products was 8% and the total faraday efficiency of these three products was 99%, indicating that the other undetected products were produced in very little amount.
The test results of example 5 demonstrate that with the electrode structure of the present invention, C1 (CH) 4 +CO+HCOOH) product with a total Faraday efficiency of up to 91%, main product CH 4 The current density of the current is up to 60mA cm -2 。
TABLE 1 influence of primary control parameters on ERC reaction rate and primary product selectivity
Based on the above data, the comparative analysis:
1. in the electrode of the carbon-based support structure, the electrode is extremely easy to break under the action of pressure; in addition, the catalyst does not contain an interface layer and a polymer layer, the reaction area is not expanded, and the catalyst does not react with CO 2 In-plane diffusion coefficient enhancement, CO 2 The electrolyte is easy to enter, the ERC reaction rate is low, and the hydrogen evolution side reaction is serious;
2. in the flexible electrode, if the interface layer and the polymer layer are not constructed, the reaction area is not expanded, the number of the reactive sites is small, and the catalyst is not used for CO 2 The in-plane diffusion coefficient is improved, CO2 easily enters the electrolyte, and the ERC reaction rate is low;
3. in the flexible electrode structure, if the thickness of the catalytic layer is too high, the catalyst particles positioned in the flexible electrode structure cannot be used as places for electrochemical reduction, so that the catalytic effect is lost, the number of catalytic activity bits participating in ERC reaction is reduced, and the ERC reaction rate is reduced; the thickness of the polymer layer is too high, so that the proton transfer speed is reduced, the hydrogenation reduction speed of carbon dioxide is delayed, the reduction speed of the carbon dioxide is reduced, and the generation speed and the selectivity of a product are influenced; the interface layer is too high in thickness, and the catalyst particle density in the interface layer is insufficient, so that on one hand, the number of active sites is reduced, on the other hand, the proton transfer speed is also reduced, the hydrogenation reduction speed of carbon dioxide is delayed, the reduction speed of the carbon dioxide is reduced, and the generation speed and the selectivity of a product are affected.
Claims (11)
1. The gas diffusion electrode comprises a substrate layer, a catalytic layer, a polymer layer and an interface layer which are sequentially arranged, wherein the substrate layer comprises a porous high-molecular polymer film;
the porous high molecular polymer film has a thickness of any value between 5 μm and 100 μm;
the pore diameter of the porous high molecular polymer film is any value between 0.1 mu m and 5 mu m, and the porosity is any value between 60% and 90%;
the skeleton material of the porous high polymer film is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene and polypropylene;
the thickness of the catalytic layer is 5-500 nm, the thickness of the polymer layer is 2-50 nm, and the thickness of the interface layer is 5-200 nm;
the catalytic layer comprises a nano material with electrocatalytic activity on electrochemical reduction of carbon dioxide reaction and a binder;
the polymer layer comprises a porous high molecular polymer resin I;
the interface layer comprises a porous high molecular polymer resin II and catalyst particles.
2. The gas diffusion electrode according to claim 1, wherein the degree of polymerization of the porous high molecular polymer in the porous high molecular polymer film is not less than 10 3 。
3. A gas diffusion electrode according to claim 1, wherein,
the nano material in the catalytic layer is at least one selected from nano metal particles, supported nano metal particles, carbon materials doped with strong electronegative elements or monoatomic metal catalysts;
the binder is one of polyvinylidene fluoride or perfluorinated sulfonic acid resin;
the mass ratio of the nano material to the binder is 8:1-2:1.
4. The gas diffusion electrode according to claim 1, wherein a microporous conductive layer is provided between the base layer and the catalytic layer, and the microporous conductive layer has a thickness of 10nm to 1000nm;
the conductive microporous layer comprises highly conductive carbon and a binder;
the high-conductivity carbon in the conductive microporous layer is one of graphite powder and active carbon, and the particle size is 0.5-2 mu m; the binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride or perfluorinated sulfonic acid resin; the mass ratio of the high conductive carbon to the binder is 9:1-2:1.
5. A gas diffusion electrode according to claim 1, wherein,
in the interface layer, the mass ratio of the polymer resin II to the catalyst particles is 9:1-5:1.
6. The gas diffusion electrode of claim 1, wherein the catalyst particles in the interface layer are the same elements as the catalyst particles in the catalytic layer.
7. The gas diffusion electrode of claim 1, wherein the polymer resin II in the interface layer is the same as the polymer resin I in the polymer layer.
8. A gas diffusion electrode according to claim 1, wherein,
the polymer resin I in the polymer layer is an organic high polymer resin containing hydrophilic groups;
the hydrophilic group includes at least one of an acrylic group, a sulfonic group, an acryl sulfonic group, or a quaternary amine group.
9. The gas diffusion electrode according to claim 1, wherein CO 2 The gas has a gas diffusion coefficient within the interface layer that is greater than the diffusion coefficient in the catholyte.
10. A carbon dioxide electrochemical reduction cell comprising a gas diffusion electrode according to any one of claims 1 to 9.
11. The electrochemical reduction cell for carbon dioxide according to claim 10, wherein the resulting C is electrolyzed 2 The volume ratio of the product to the total reaction product is 60-80%.
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