CN106876722A - A kind of Carbon dioxide electrochemical reduction gas-diffusion electrode and its preparation and application - Google Patents
A kind of Carbon dioxide electrochemical reduction gas-diffusion electrode and its preparation and application Download PDFInfo
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- CN106876722A CN106876722A CN201510924113.5A CN201510924113A CN106876722A CN 106876722 A CN106876722 A CN 106876722A CN 201510924113 A CN201510924113 A CN 201510924113A CN 106876722 A CN106876722 A CN 106876722A
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Abstract
The present invention relates to a kind of Carbon dioxide electrochemical reduction gas-diffusion electrode and its preparation and application, electrode includes the Sn catalyst and organic additive mixed layer that adhere on basalis and basalis, and the ratio between both Sn catalyst and organic additive mole are 100:1-30:1, the loading of Sn catalyst is 0.1mg/cm in electrode-2-5mg/cm-2.During Carbon dioxide electrochemical reduction, basalis plays a part of supporter, conduction, forms liquids and gases transmission channel, Sn catalyst carbon dioxide reductions, and organic additive can stablize intermediate reaction thing CO2·-, improve CO2Concentration, so as to reduce the overpotential of carbon dioxide electrochemical reaction, improves its current density and efficiency.Additionally, Sn catalyst is also anchored on carbon-based basal surface by auxiliary agent in the electrode, the electrode has stability very high.
Description
Technical field
The present invention relates to Carbon dioxide electrochemical reduction electrode and its application, belong to Resources of Carbon Dioxide and utilize and store up
Can technical field.
Background technology
In the last few years, with economic fast development, environmental problem and energy shortage problem are on the rise.Wherein, the whole world
Warming also has turned into countries in the world problem urgently to be resolved hurrily, and CO2A large amount of discharges be global warming one of the main reasons.Cause
And, how effectively to utilize CO2And reduce CO2Discharge cause the extensive concern of people.
Consider from energy consumption and cost, electrochemical reducing has can react in normal temperature and pressure, energy consumption is low and conversion
The advantages of efficiency is higher, is CO2One of more feasible approach in transformation technology.ERC technologies are to utilize electric energy by CO2It is reduced to
Various organic molecules or chemical products, effectively realize greenhouse gases CO2A kind of technology of recycling.With renewable energy
Source generation technology is developed rapidly, and the cost of generation technology is expected to significantly decline.Using renewable energy power generation, electricity is recycled
Electric energy can be realized to chemical transformation of energy and storage carbon dioxide synthesis of organic substance.ERC technologies can not only save oil, day
The right fossil energy such as gas and coal, and turn waste into wealth, make CO2It is utilized effectively, reduces CO2The environmental pollution for causing.Cause
This, ERC technologies have potential economic benefit and environmental benefit.
Sn base catalyst is catalysis CO2One of effective catalyst of electrochemical reduction.Because Sn metals are largely present in ground
In shell, less expensive, for large-scale commercial Application, it will substantially reduce cost.Finally, it is used for relative to other
Reduction CO2The catalyst (Pb, Cd, Hg etc.) of organic acid processed, Sn metals are also very little for the pollution of environment, are a kind of environment
Friendly metallic catalyst.Therefore Sn base catalyst is a kind of ERC catalyst with very big Research Prospects.But current Sn catalysis
The performance of agent is also than relatively low.
Many people recycle PTFE as binding agent by using catalyst such as chemical method synthesizing tin oxide, tin, are sprayed
Diffusion layer surface is coated onto, electrode is obtained.But this preparation method is more complicated, and electrode the relatively low (faradic efficiency of performance
Less than 60%).Additionally, above-mentioned electrode be mainly by various methods by Sn catalyst preparations on tinfoil paper and glassy carbon electrode,
, it is necessary to the catalyst of preparation is scraped off on electrode in actual application, then by adhesive coated to carbon-based basal surface,
So as to cause electrode fabrication process cumbersome, and catalyst is prepared due to the cladding of binding agent, active specific surface declines, so as to cause
Activity is reduced.In addition Sn bases catalyst is easily decomposed and poisons during long-term electrolysis, under making the performance of electrode
Drop.
The present invention is directed to disadvantages mentioned above, by electrochemical method, the in-situ deposition Sn Nanorods Catalysts in substrate, and
Its Dispersion on surface organic additive, the porous gas diffusive electrode for preparing Sn catalyst sets up the phase boundary of gas liquid solid three of stabilization
Face, shortening gas diffusion path, raising electrode reaction speed, can not only simplify the preparation process of catalyst, it is possible to effectively
The advantage crystal face and pattern of catalyst are controlled, so as to regulate and control the performance of electrode.During Carbon dioxide electrochemical reduction, substrate
Layer plays a part of supporter, conduction, forms liquids and gases transmission channel, Sn catalyst carbon dioxide reductions, and has
Machine aided agent can stablize intermediate reaction thing CO2. -, improve CO2Concentration, so that the overpotential of carbon dioxide electrochemical reaction is reduced,
Improve its current density and efficiency.Additionally, Sn catalyst is also anchored on carbon-based basal surface by auxiliary agent in the electrode, the electrode has
Stability very high.It is coated with substrate on tinfoil paper and glassy carbon electrode and after the Sn catalyst that is directly synthesized compared to above-mentioned
The method for preparing electrode, has excellent faradic efficiency and formic acid is produced using the of the invention in situ gas-diffusion electrode for preparing
The selectivity of thing.Prepared gas-diffusion electrode can not only improve the effective active area of electrode, can also improve reaction
The transmission of thing, so as to reduce mass transfer polarization, improves its performance, is more beneficial for the practical application of ERC.In addition it is provided by the present invention
Method is simple, easily-controllable, beneficial to large-scale production.
The content of the invention
The present invention is in order to solve the above technical problems, by electrochemical method, in-situ deposition Sn nanometer rods are catalyzed in substrate
Agent, and in its Dispersion on surface organic additive, prepare Sn catalyst porous gas diffusive electrode set up the gas/liquid of stabilization/
Gu three phase boundary, shortening gas diffusion path, raising electrode reaction speed, can not only simplify the preparation process of catalyst, and
The advantage crystal face and pattern of catalyst can be effectively controlled, so as to regulate and control the performance of electrode.
To achieve the above object, the concrete technical scheme that the present invention is used is as follows：
A kind of Carbon dioxide electrochemical reduction gas-diffusion electrode, electrode includes what is adhered on basalis and basalis
The ratio between Sn catalyst and organic additive mixed layer, both Sn catalyst and organic additive mole are 100:1-30:1, Sn in electrode
The loading of catalyst is 0.1mg/cm-2-5mg/cm-2。
The organic additive includes ethylenediamine, hexamethylene diamine, phenol, resorcinol, imidazoles, aniline, thiophene, polyaniline, poly-
In thiophene, polypyrrole, polysulfones, polyketone, polyimides, polybenzimidazoles, polyvinyl pyridine, polyacrylonitrile, triphenylphosphine one
Plant or more than two kinds.
The electrode is prepared from according to the following procedure：
1) using the charcoal felt or carbon paper after gas diffusion layers or treatment as basalis：Charcoal felt or carbon paper processing procedure are：
200~600 DEG C are processed in atmosphere, and oil removal treatment cleaning is then carried out in ethanol, acetone；
2) the Sn catalyst layers described in are by the method for constant current, constant potential or scan round in above-mentioned substrate surface electrification
Learn tin plating obtaining；During electrochemistry is tin plating, plating solution is that concentration is 30-95g/L sodium stannates Na2SnO3·3H2O solution, 1.0-
20g/L inorganic alkali solutions and 1-10g/L cushioning liquid mixed liquors；Solute in the cushioning liquid is in sodium acetate or potassium acetate
A kind of or two kinds, sodium stannate is with the mass ratio of inorganic base:20:1-1：1, the mass ratio of solute in sodium stannate and cushioning liquid
For:20:1-1：1；The constant current is -5mA/cm2~-200mA/cm2, preferably -20mA/cm2~-100mA/cm2；Permanent electricity
Position be -0.2V~-6V, be preferably -0.3V~-, 2.0V；Scan round scope is -0.3V-2V；The tin plating time is 10s
~20000s, preferably time are 3000s-15000s；
3) be dissolved in organic additive in mixed solvent by, mixed solvent by DMSO, DMF, DMAC, in one kind or two kinds
Above with THF or n-hexane in one kind or two kinds mix, temperature be 25~50 degrees Celsius under stir to organic additive
It is completely dissolved, forms the solution that mass concentration is 5~40%；The mass content of THF or n-hexane is 5-40% in mixed solvent；
4) using the mode of spraying, by above-mentioned organic additive solution spraying to step 2) the Sn catalyst tables that prepare
Face；
5) is by above-mentioned steps 4) electrode for preparing takes out and dried in room temperature, after 40-100 degrees Celsius of drying of vacuum drying oven,
Electrode needed for being obtained；
Or, above-mentioned electrode is immersed in organic solvent, at least 1 hour is stood, take out and dried in room temperature, dried after vacuum
40-100 degrees Celsius of drying of case, electrode needed for being obtained.
Inorganic base be NaOH, KOH, CsOH in one or more；Organic solvent is in ethanol, isopropanol, NMP
One or two or more kinds.
The gas diffusion layers can be prepared from according to the following procedure:Conductive porous material and binding agent are blended in solvent
In, electrode slurry is obtained, wherein solid matter and solvent ratios is 10~200mg solids/ml solvents；Using blade coating, spraying or
The mode of roll-in, treated carbon-based basal surface is coated on by slurry, and electrode is obtained in 40-80 degrees Celsius of drying, is prepared
Gas diffusion layers；The conductive porous material be particle diameter the KB600 of 10-100nm, KB300, BP2000, XC-72,
In Acetylene black, Alkaline-activated carbon, carbon aerogels or carbon xerogel, CNT, carbon receives
Rice fiber, one or two or more kinds in Graphene；Wherein the loading of conductive porous material is 0.5mg/cm-2-3.0mg/cm-2, binding agent shared mass fraction in diffusion layer is 10-30%；
Carbon substrate is charcoal felt or carbon paper, and charcoal felt or carbon paper processing procedure are：Processed in atmosphere at 200~600 DEG C,
Then oil removal treatment cleaning is carried out in ethanol, acetone；
Wherein, described binding agent is PTFE or PVDF；
During using PTFE as binding agent, solvent is alcohol, water or alcohol-water mixture, alcohol and water quality ratio in alcohol-water mixture
It is 1:4~4:1；The alcohol includes one or more in ethanol, isopropanol, ethylene glycol or glycerine；
During using PVDF as binding agent, solvent be 1-METHYLPYRROLIDONE, dimethylacetylamide, dimethylformamide,
One or more in carbonic acid triethyl, dimethyl sulfoxide (DMSO) or acetone.
The negative electrode that the electrode can react as Carbon dioxide electrochemical reduction.
Beneficial effects of the present invention：
1., the invention provides a kind of Carbon dioxide electrochemical reduction gas-diffusion electrode, it includes basalis and base
The Sn catalyst and organic additive mixed layer adhered on bottom, this kind of structure can effectively improve Sn catalyst to carbon dioxide also
Originally it was the kinetic current density of chemicals, improved its faradic efficiency.This kind of electrode structure need not be suppressed, therefore avoid biography
During system electrode fabrication, the structure of catalyst, pattern, active specific surface is set to change due to suppressing electrolysis, so as to influence
Its performance.
2. the present invention is by electrochemical method, the in-situ deposition Sn Nanorods Catalysts in substrate, and in its Dispersion on surface
Organic additive, the porous gas diffusive electrode for preparing Sn catalyst sets up the gas liquid solid three phase boundary of stabilization, shortens gas
Body diffusion path, raising electrode reaction speed, can not only simplify the preparation process of catalyst, it is possible to effectively control catalyst
Advantage crystal face and pattern, so as to regulate and control the performance of electrode.During Carbon dioxide electrochemical reduction, basalis plays support
Body, conduction, the effect for forming liquids and gases transmission channel, Sn catalyst carbon dioxide reductions, and organic additive can be with
Stabilization intermediate reaction thing CO2. -, improve CO2Concentration, so as to reduce the overpotential of carbon dioxide electrochemical reaction, improves its electric current
Density and efficiency.
3. ethylenediamine, hexamethylene diamine, phenol, resorcinol, imidazoles, aniline, thiophene, polyaniline, poly- thiophene are added in the electrodes
Fen, polypyrrole, polysulfones, polyketone, polyimides, polyphenyl and miaow
The medium auxiliary agent of azoles, polyvinyl pyridine, polyacrylonitrile, can be by the hetero atom (N, P, S, O) on its surface as metal
The characteristic of surface with electrons, has regulated and controled the electronic structure of metal surface, so as to regulate and control its surface and CO2And CO2The phase of free radical
Interreaction force, so as to regulate and control its selectivity.
4. the method can not only improve the effective active area of electrode with prepared gas-diffusion electrode, can also carry
The transmission of reactant high, so as to reduce mass transfer polarization, improves its performance, is more beneficial for the practical application of ERC；Preparation side of the invention
Method is simple, easily behaviour, conventional production device, is adapted to large-scale production, and the electrode specific surface area of preparation is big, with titanium dioxide very high
Carbon hydrogen reduction catalytic performance；
5. additive coating is catalyzed layer surface in Sn, and interaction is produced with Sn catalyst, to a certain extent can be to it
Grappling effect is produced, so as to improve its stability.
6. it is coated with being made in substrate compared to tradition on tinfoil paper and glassy carbon electrode and after the Sn catalyst that is directly synthesized
The method of standby electrode, has excellent faradic efficiency and to carboxylic acid product using the gas-diffusion electrode for preparing in situ of the invention
Selectivity.Prepared gas-diffusion electrode can not only improve the effective active area of electrode, can also improve reactant
Transmission so that reduce mass transfer polarization, improve its performance, be more beneficial for the practical application of ERC.In addition side provided by the present invention
Method is simple, easily-controllable, beneficial to large-scale production.
Using
By made electrode, as carbon dioxide reduction formic acid negative electrode.And electrification is carried out by three-electrode system
Learn test：Working electrode is obtained electrode；It is Pt pieces to electrode, reference electrode is Hg/Hg2Cl2/ saturation KCl.WE and RE it
Between distance be 0.5cm, salt bridge is used to reduce liquid potential.Catholyte is 0.5M NaHCO3Aq.sol., electrolyte
Volume is 180ml.Anolyte is 0.1M H2SO4aq.sol.
Brief description of the drawings
Fig. 1 electrode structure schematic diagrames
The faradic efficiency of electrode prepared by Fig. 2 embodiments 1,2,4.
Specific embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
Processed in atmosphere at 550 DEG C with carbon paper, oil removal treatment cleaning is then carried out in acetone；
Obtained above-mentioned substrate surface electrochemistry is tin plating by constant current process；During electrochemistry is tin plating, plating solution is
Concentration is 30g/L sodium stannates Na2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L cushioning liquid mixed liquors；The permanent electricity
Flow for -60mA/cm2, the tin plating time is 10000s；Phenol is dissolved in DMF and THF mixed solvents, is 25~50 in temperature
Stirred to organic additive under degree Celsius and be completely dissolved, form the solution that mass concentration is 10%；The quality of THF contains in mixed solvent
Measure is 20%；Using the mode of spraying, by above-mentioned organic additive solution spraying to the Sn catalyst surfaces for obtaining；By above-mentioned step
The rapid electrode for 4) preparing takes out and is dried in room temperature, after 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being obtained；
Embodiment 2
Processed in atmosphere at 550 DEG C with carbon paper, oil removal treatment cleaning is then carried out in acetone；
Obtained above-mentioned substrate surface electrochemistry is tin plating by constant current process；During electrochemistry is tin plating, plating solution is
Concentration is 30g/L sodium stannates Na2SnO3·3H2O solution, 15g/L KOH solutions and 5g/L cushioning liquid mixed liquors；The permanent electricity
Flow for -40mA/cm2, the tin plating time is 10000s；Phenol is dissolved in DMF and THF mixed solvents, is 25~50 in temperature
Stirred to organic additive under degree Celsius and be completely dissolved, form the solution that mass concentration is 20%；The quality of THF contains in mixed solvent
Measure is 30%；Using the mode of spraying, by above-mentioned organic additive solution spraying to the Sn catalyst surfaces for obtaining；By above-mentioned step
The rapid electrode for 4) preparing takes out and is dried in room temperature, after 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being obtained；
Embodiment 3
Processed in atmosphere at 450 DEG C with carbon paper, oil removal treatment cleaning is then carried out in acetone；
Obtained above-mentioned substrate surface electrochemistry is tin plating by constant voltage method；During electrochemistry is tin plating, plating solution is
Concentration is 30g/L sodium stannates Na2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L cushioning liquid mixed liquors；The permanent electricity
It is -1.2V to press, and the tin plating time is 10000s；Polyacrylonitrile is dissolved in DMF and THF mixed solvents, is 25~50 in temperature
Stirred to organic additive under degree Celsius and be completely dissolved, form the solution that mass concentration is 10%；The quality of THF contains in mixed solvent
Measure is 20%；Using the mode of spraying, by above-mentioned organic additive solution spraying to the Sn catalyst surfaces for obtaining；By above-mentioned steps
4) electrode for preparing takes out and is dried in room temperature, after 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being obtained；
Embodiment 4
XC-72 and PTFE are blended in water and ethanol with 1:In 3 mixed solvent, electrode slurry, wherein solids are obtained
Matter is 50mg solids/ml solvents with solvent ratios；By the way of roll-in, slurry is coated on to be carried out in atmosphere at 550 DEG C
Carbon paper surface after treatment；The loading of XC-72 is 1.5mg/cm-2, PTFE binding agents shared mass fraction in diffusion layer is
30%.Obtained above-mentioned substrate surface electrochemistry is tin plating by constant current process；During electrochemistry is tin plating, plating solution is concentration
It is 25g/L sodium stannates Na2SnO3·3H2O solution, 10g/LNaOH solution and 8g/L cushioning liquid mixed liquors；The constant current for-
80mA/cm2, the tin plating time is 10000s；Phenol is dissolved in DMF and THF mixed solvents, is 25~50 degrees Celsius in temperature
Lower stirring is completely dissolved to organic additive, forms the solution that mass concentration is 10%；The mass content of THF is in mixed solvent
20%；Using the mode of spraying, by above-mentioned organic additive solution spraying to the Sn catalyst surfaces for obtaining；By above-mentioned steps 4)
The electrode of preparation takes out and is dried in room temperature, after 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being obtained；
Embodiment 5
XC-72 and PTFE are blended in water and ethanol with 1:In 3 mixed solvent, electrode slurry, wherein solids are obtained
Matter is 50mg solids/ml solvents with solvent ratios；By the way of roll-in, slurry is coated on to be carried out in atmosphere at 550 DEG C
Carbon paper surface after treatment；The loading of XC-72 is 1.5mg/cm-2, PTFE binding agents shared mass fraction in diffusion layer is
30%.During electrochemistry is tin plating, plating solution is that concentration is 30g/L sodium stannates Na2SnO3·3H2O solution, 15g/L NaOH are molten
Liquid and 5g/L cushioning liquid mixed liquors；The constant potential is -0.8V vs.SCE, and the tin plating time is 10000s；By polyphenyl amine solvent
In DMF and THF mixed solvents, stirred to organic additive under being 25~50 degrees Celsius in temperature and be completely dissolved, form quality dense
Spend the solution for 10%；The mass content of THF is 20% in mixed solvent；It is using the mode of spraying, above-mentioned organic additive is molten
Liquid sprays to the Sn catalyst surfaces for obtaining；By above-mentioned steps 4) electrode for preparing takes out and dried in room temperature, after vacuum drying oven
80 degrees Celsius of dryings, electrode needed for being obtained；
Embodiment 6
XC-72 and PTFE are blended in water and ethanol with 1:In 2 mixed solvent, electrode slurry, wherein solids are obtained
Matter is 80mg solids/ml solvents with solvent ratios；By the way of roll-in, slurry is coated on to be carried out in atmosphere at 550 DEG C
Carbon paper surface after treatment；The loading of XC-72 is 2.0mg/cm-2, PTFE binding agents shared mass fraction in diffusion layer is
30%.Obtained above-mentioned substrate surface electrochemistry is tin plating by cyclic voltammetric method；During electrochemistry is tin plating, plating solution is dense
It is 30g/L sodium stannates Na to spend2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L cushioning liquid mixed liquors；The circulation is swept
It is -0.3-2.0V vs.SCE to retouch, and the tin plating time is 500s；Polyaniline is dissolved in DMF and THF mixed solvents, is in temperature
Stirred to organic additive under 25~50 degrees Celsius and be completely dissolved, form the solution that mass concentration is 10%；THF in mixed solvent
Mass content is 20%；Using the mode of spraying, by above-mentioned organic additive solution spraying to the Sn catalyst surfaces for obtaining；Will
Above-mentioned steps 4) electrode for preparing takes out and dried in room temperature, after 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being obtained；
Embodiment 7
Graphene and PTFE are blended in water and ethanol with 1:In 3 mixed solvent, electrode slurry, wherein solids are obtained
Matter is 30mg solids/ml solvents with solvent ratios；By the way of roll-in, slurry is coated on to be carried out in atmosphere at 450 DEG C
Carbon paper surface after treatment；The loading of Graphene is 0.5mg/cm-2, PTFE binding agents shared mass fraction in diffusion layer is
10%.During electrochemistry is tin plating, plating solution is that concentration is 30g/L sodium stannates Na2SnO3·3H2O solution, 15g/LNaOH solution
And 5g/L cushioning liquid mixed liquors；The constant potential is -1.5V vs.SCE, and the tin plating time is 500s；Polyaniline is dissolved in
In DMF and THF mixed solvents, stirred to organic additive under being 25~50 degrees Celsius in temperature and be completely dissolved, form mass concentration
It is 10% solution；The mass content of THF is 20% in mixed solvent；Using the mode of spraying, by above-mentioned organic additive solution
Spray to the Sn catalyst surfaces for obtaining；By above-mentioned steps 4) electrode for preparing takes out and dried in room temperature, after vacuum drying oven 80
Degree Celsius drying, electrode needed for being obtained；
Embodiment 8
CNT and PTFE are blended in water and ethanol with 1:In 3 mixed solvent, electrode slurry, wherein solid are obtained
Material is 50mg solids/ml solvents with solvent ratios；By the way of roll-in, slurry is coated on to enter in atmosphere at 550 DEG C
Carbon paper surface after row treatment；The loading of nanotube is 1.5mg/cm-2, PTFE binding agents shared mass fraction in diffusion layer
It is 30%.Obtained above-mentioned substrate surface electrochemistry is tin plating by constant current process；During electrochemistry is tin plating, plating solution is dense
It is 30g/L sodium stannates Na to spend2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L cushioning liquid mixed liquors；The constant potential
It is -0.8V vs.SCE, the tin plating time is 10000s；Polyaniline is dissolved in DMF and THF mixed solvents, temperature be 25~
Stirred to organic additive under 50 degrees Celsius and be completely dissolved, form the solution that mass concentration is 10%；The quality of THF in mixed solvent
Content is 20%；Using the mode of spraying, by above-mentioned organic additive solution spraying to the Sn catalyst surfaces for obtaining；Will be above-mentioned
Step 4) electrode for preparing takes out and dried in room temperature, after 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being obtained；
Comparative example 1
Processed in atmosphere at 550 DEG C with carbon paper, oil removal treatment cleaning is then carried out in acetone；By constant current
Method is obtained above-mentioned substrate surface electrochemistry is tin plating；During electrochemistry is tin plating, plating solution is that concentration is 30g/L sodium stannates
Na2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L cushioning liquid mixed liquors；The constant current is -60mA/cm2, it is tin plating
Time is 10000s；The electrode of above-mentioned preparation is taken out and is dried in room temperature, after 80 degrees Celsius of dryings of vacuum drying oven, needed for being obtained
Electrode；Show in Fig. 2, relative to comparative example 1, embodiment 1,2, electrode performance is significantly improved in 4.
Claims (7)
1. a kind of Carbon dioxide electrochemical reduction gas-diffusion electrode, it is characterised in that electrode includes basalis and basalis
The ratio between the Sn catalyst and organic additive mixed layer of upper attachment, both Sn catalyst and organic additive mole are 100:1-30:1,
The loading of Sn catalyst is 0.1mg/cm in electrode-2-5mg/cm-2。
2. according to Carbon dioxide electrochemical reduction gas-diffusion electrode described in claim 1, it is characterised in that：It is described to have machine aided
Agent includes ethylenediamine, hexamethylene diamine, phenol, resorcinol, imidazoles, aniline, thiophene, polyaniline, polythiophene, polypyrrole, polysulfones, poly-
One or two or more kinds in ketone, polyimides, polybenzimidazoles, polyvinyl pyridine, polyacrylonitrile, triphenylphosphine.
3. the electrode preparation method described in a kind of claim 1 or 2, it is characterised in that the electrode prepare according to the following procedure and
Into：
1) using the charcoal felt or carbon paper after gas diffusion layers or treatment as basalis：Charcoal felt or carbon paper processing procedure are：200~
600 DEG C are processed in atmosphere, and oil removal treatment cleaning is then carried out in ethanol, acetone；
2) the Sn catalyst layers described in are by the method for constant current, constant potential or scan round in above-mentioned substrate surface electrochemical plating
Tin is obtained；During electrochemistry is tin plating, plating solution is that concentration is 30-95g/L sodium stannates Na2SnO3·3H2O solution, 1.0-20g/
L inorganic alkali solutions and 1-10g/L cushioning liquid mixed liquors；Solute in the cushioning liquid is a kind of in sodium acetate or potassium acetate
Or two kinds, sodium stannate is 20 with the mass ratio of inorganic base:1-1：1, sodium stannate is with the mass ratio of solute in cushioning liquid:20:
1-1：1；The constant current is -5mA/cm2~-200mA/cm2, preferably -20mA/cm2~-100mA/cm2；Constant potential for-
0.2V~-6V, is preferably -0.3V~-2.0V；Scan round scope is -0.3V-2.0V；The tin plating time be 10s~
20000s, preferably time are 3000s-15000s.；
3) organic additive is dissolved in mixed solvent, mixed solvent by DMSO, DMF, DMAC, in one or two or more kinds with
One kind in THF or n-hexane or two kinds are mixed, and stir completely molten to organic additive under being 25~50 degrees Celsius in temperature
Solution, forms the solution that mass concentration is 5~40%；The mass content of THF or n-hexane is 5-40% in mixed solvent；
4) using the mode of spraying, by above-mentioned organic additive solution spraying to step 2) the Sn catalyst surfaces that prepare；
5) by above-mentioned steps 4) electrode for preparing takes out and dried in room temperature, after 40-100 degrees Celsius of drying of vacuum drying oven, be obtained
Required electrode；
Or, above-mentioned electrode is immersed in organic solvent, at least 1 hour is stood, take out and dried in room temperature, after vacuum drying oven
40-100 degrees Celsius of drying, electrode needed for being obtained.
4. preparation method according to claim 3, it is characterised in that：Inorganic base be NaOH, KOH, CsOH in one kind or
It is two or more；Organic solvent is one or two or more kinds in ethanol, isopropanol, NMP.
5. preparation method according to claim 3, it is characterised in that：Described organic additive include ethylenediamine, hexamethylene diamine,
Phenol, resorcinol, imidazoles, aniline, thiophene, polyaniline, polythiophene, polypyrrole, polysulfones, polyketone, polyimides, polyphenyl and miaow
One or two or more kinds in azoles, polyvinyl pyridine, polyacrylonitrile, triphenylphosphine.
6. preparation method according to claim 3, it is characterised in that：The gas diffusion layers can prepare according to the following procedure and
Into:Conductive porous material and binding agent are blended in solvent, electrode slurry is obtained, wherein solid matter and solvent ratios is 10
~200mg solids/ml solvents；By the way of blade coating, spraying or roll-in, slurry is coated on treated charcoal felt or carbon paper table
Face, electrode is obtained in 40-80 degrees Celsius of drying, prepares gas diffusion layers；The conductive porous material is particle diameter in 10-
KB600, KB300, BP2000, XC-72, Acetylene black, Alkaline-activated carbon of 100nm, carbon
One or two or more kinds in aeroge or carbon xerogel, in CNT, carbon nano-fiber, Graphene；It is wherein conductive porous
The loading of material is 0.5mg/cm-2-3.0mg/cm-2, binding agent shared mass fraction in diffusion layer is 10-30%；
Carbon substrate is charcoal felt or carbon paper, and charcoal felt or carbon paper processing procedure are：Processed in atmosphere at 200~600 DEG C, then
Oil removal treatment cleaning is carried out in ethanol, acetone；
Wherein, described binding agent is PTFE or PVDF；
During using PTFE as binding agent, solvent is alcohol, water or alcohol-water mixture, and alcohol and water quality ratio are 1 in alcohol-water mixture:
4~4:1；The alcohol includes one or more in ethanol, isopropanol, ethylene glycol or glycerine；
During using PVDF as binding agent, solvent is 1-METHYLPYRROLIDONE, dimethylacetylamide, dimethylformamide, carbonic acid
One or more in triethyl, dimethyl sulfoxide (DMSO) or acetone.
7. the application of electrode described in a kind of claim 1 or 2, it is characterised in that：The electrode can be used as carbon dioxide electrochemistry
The negative electrode of reduction reaction.
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| CN107158895B (en) * | 2017-07-13 | 2020-07-28 | 斯养武 | Carbon dioxide absorbent |
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| CN111519207B (en) * | 2020-05-19 | 2021-06-29 | 大连大学 | Preparation and application of Sn electrode for electrochemical reduction of carbon dioxide |
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