CN106876722B - 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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- CN106876722B CN106876722B CN201510924113.5A CN201510924113A CN106876722B CN 106876722 B CN106876722 B CN 106876722B CN 201510924113 A CN201510924113 A CN 201510924113A CN 106876722 B CN106876722 B CN 106876722B
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Abstract
The present invention relates to a kind of Carbon dioxide electrochemical reduction gas-diffusion electrode and its preparations and application, electrode includes the Sn catalyst and organic additive mixed layer adhered on basal layer and basal layer, the ratio between both Sn catalyst and organic additive mole are 100:1-30:1, and the loading of Sn catalyst is 0.1mg/cm in electrode‑2‑5mg/cm‑2.During Carbon dioxide electrochemical reduction, basal layer plays the role of supporter, conduction, forms liquids and gases transmission channel, Sn catalyst carbon dioxide reduction, and organic additive can stablize intermediate reaction object CO2·‑, improve CO2Concentration improves its current density and efficiency to reduce the overpotential of carbon dioxide electrochemical reaction.In addition, Sn catalyst is also anchored on carbon-based bottom surface by auxiliary agent in the electrode, which has very high stability.
Description
Technical field
The present invention relates to Carbon dioxide electrochemical reduction electrode and its applications, belong to Resources of Carbon Dioxide and utilize and store up
It can technical field.
Background technique
In recent years, with the rapid development of economy, environmental problem and energy shortage problem are on the rise.Wherein, global
It warms and also has become countries in the world problem urgently to be resolved, and CO2One of a large amount of discharge the main reason for being global warming.Cause
And how to efficiently use CO2And reduce CO2Discharge cause the extensive concern of people.
Comprehensively consider from energy consumption and cost, electrochemical reducing have can normal temperature and pressure react, low energy consumption and conversion
The advantages that efficiency is higher is CO2One of more feasible approach in transformation technology.ERC technology is to utilize electric energy by CO2It is reduced to
Various small organic molecules or chemical products effectively realize greenhouse gases CO2A kind of technology of resource utilization.With renewable energy
The cost of the rapid development of source generation technology, generation technology is expected to sharp fall.Using renewable energy power generation, electricity is recycled
Carbon dioxide synthesis of organic substance can be realized conversion and storage of the electric energy to chemical energy.ERC technology can not only save petroleum, day
The right fossil energies such as gas and coal, and turn waste into wealth, make CO2It is utilized effectively, reduces CO2Caused by environmental pollution.Cause
This, ERC technology has potential economic benefit and environmental benefit.
Sn base catalyst is catalysis CO2One of effective catalyst of electrochemical reduction.Since Sn metal is largely present in ground
In shell, less expensive, for large-scale industrial application, it will substantially reduce cost.Finally, being used for relative to other
Restore CO2The catalyst (Pb, Cd, Hg etc.) of organic acid processed, Sn metal 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 relatively low.
Many people are by recycling PTFE as binder, being sprayed using catalyst such as chemical method synthesizing tin oxide, tin
It is coated onto diffusion layer surface, obtains electrode.However this preparation method is more complicated, and the lower (faradic efficiency of performance of electrode
Lower than 60%).In addition, above-mentioned electrode mainly by various methods by Sn catalyst preparation on tinfoil paper and glassy carbon electrode,
It in actual application, needs on the electrode to scrape off the catalyst of preparation, then by adhesive coated to carbon-based bottom surface,
It is cumbersome so as to cause electrode fabrication process, and cladding of the catalyst due to binder is prepared, active specific surface decline, so as to cause
Activity reduces.Furthermore Sn base catalyst is easily decomposed and poisons, make under the performance of electrode during long-term electrolysis
Drop.
The present invention is directed to disadvantages mentioned above, by electrochemical method, the in-situ deposition Sn Nanorods Catalyst in substrate, and
Its Dispersion on surface organic additive, the porous gas diffusive electrode that Sn catalyst is prepared establish stable three phase boundary of gas liquid solid
Face shortens gas diffusion path, improves electrode reaction rate, not only can simplify the preparation process of catalyst, and can be effective
The advantage crystal face and pattern for controlling catalyst, to regulate and control the performance of electrode.During Carbon dioxide electrochemical reduction, substrate
Layer plays the role of supporter, conduction, forms liquids and gases transmission channel, Sn catalyst carbon dioxide reduction, and has
Machine aided agent can stablize intermediate reaction object CO2. -, improve CO2Concentration, so that the overpotential of carbon dioxide electrochemical reaction is reduced,
Improve its current density and efficiency.In addition, Sn catalyst is also anchored on carbon-based bottom surface by auxiliary agent in the electrode, which has
Very high stability.Compared to re-coating after the above-mentioned Sn catalyst on tinfoil paper and glassy carbon electrode and directly synthesized in substrate
The method for preparing electrode has excellent faradic efficiency using the gas-diffusion electrode that the present invention is prepared in situ and produces to formic acid
The selectivity of object.The effective active area of electrode not only can be improved in prepared gas-diffusion electrode, can also improve reaction
The transmission of object improves its performance, is more advantageous to the practical application of ERC to reduce mass transfer polarization.Furthermore provided by the present invention
Method is simple, easily-controllable, is conducive to large-scale production.
Summary of the invention
The present invention is in order to solve the above technical problems, by electrochemical method, and in-situ deposition Sn nanometer rods are catalyzed in substrate
Agent, and in its Dispersion on surface organic additive, be prepared Sn catalyst porous gas diffusive electrode establish stable gas/liquid/
Gu three phase boundary shortens gas diffusion path, improves electrode reaction rate, the preparation process of catalyst not only can simplify, and
The advantage crystal face and pattern that catalyst can effectively be controlled, to regulate and control the performance of electrode.
To achieve the above object, the specific technical solution that the present invention uses is as follows:
A kind of Carbon dioxide electrochemical reduction gas-diffusion electrode, electrode include adhering on basal layer and basal layer
Sn catalyst and organic additive mixed layer, the ratio between 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, gathers
Thiophene, polypyrrole, polysulfones, polyketone, polyimides, polybenzimidazoles, polyvinyl pyridine, polyacrylonitrile, one in triphenylphosphine
Kind or two kinds or more.
The electrode is prepared according to the following procedure:
1) using gas diffusion layers or treated charcoal felt or carbon paper as basal layer: charcoal felt or carbon paper treatment process are as follows:
200~600 DEG C are handled in air, and oil removal treatment cleaning is then carried out in ethyl alcohol, acetone；
2) the Sn catalyst layer described in is by constant current, constant potential or the method for scan round in above-mentioned substrate surface electrification
Learn tin plating obtain；During electrochemistry is tin plating, plating solution is that concentration is 30-95g/L sodium stannate Na2SnO3·3H2O solution, 1.0-
20g/L inorganic alkali solution and 1-10g/L buffer solution mixed liquor；Solute in the buffer solution is in sodium acetate or potassium acetate
It is a kind of or two kinds, the mass ratio of sodium stannate and inorganic base are as follows: the mass ratio of solute in 20:1-1:1, sodium stannate and buffer solution
Are as follows: 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 range is -0.3V-2V；The tin plating time is 10s
~20000s, preferably time are 3000s-15000s；
3) organic additive is dissolved in the mixed solvent by, mixed solvent by DMSO, DMF, DMAC, one of or two kinds
It mixes with one of THF or n-hexane or two kinds, stirs under being 25~50 degrees Celsius in temperature to organic additive above
It is completely dissolved, forms the solution that mass concentration is 5~40%；The mass content of in the mixed solvent THF or n-hexane is 5-40%；
4) in the way of spraying, Sn catalyst table that above-mentioned organic additive solution spraying to step 2) is prepared
Face；
5) is by above-mentioned steps 4) electrode of preparation takes out and dries in room temperature, after in 40-100 degrees Celsius of drying of vacuum drying oven,
Electrode needed for being made；
Alternatively, by above-mentioned electrode immerse organic solvent in, stand at least 1 hour, taking-up dried in room temperature, after in vacuum dry
40-100 degrees Celsius of drying of case, electrode needed for being made.
Inorganic base is one or more of NaOH, KOH, CsOH；Organic solvent is ethyl alcohol, in isopropanol, NMP
It is one or two or more kinds of.
The gas diffusion layers can be prepared according to the following procedure: conductive porous material is blended with binder in solvent
In, electrode slurry is obtained, wherein solid matter and solvent ratios are 10~200mg solid/ml solvent；Using blade coating, spraying or
Slurry is coated on processed carbon-based bottom surface by the mode of roll-in, dries in 40-80 degrees Celsius and electrode is made, be prepared
Gas diffusion layers；The conductive porous material be partial size KB600, KB300 of 10-100nm, BP2000, XC-72,
In Acetylene black, Alkaline-activated carbon, carbon aerogels or carbon xerogel, carbon nanotube, carbon receives
Rice fiber, one of graphene or two kinds or more；Wherein the loading of conductive porous material is 0.5mg/cm-2-3.0mg/cm-2, binder shared mass fraction in diffusion layer is 10-30%；
Carbon substrate is charcoal felt or carbon paper, charcoal felt or carbon paper treatment process are as follows: it is handled in air at 200~600 DEG C,
Then oil removal treatment cleaning is carried out in ethyl alcohol, acetone；
Wherein, the binder is PTFE or PVDF；
When using PTFE as binder, solvent is alcohol, water or alcohol-water mixture, alcohol and water quality ratio in alcohol-water mixture
For 1:4~4:1；The alcohol includes one of ethyl alcohol, isopropanol, ethylene glycol or glycerine or a variety of；
When using PVDF as binder, solvent be N-Methyl pyrrolidone, dimethyl acetamide, dimethylformamide,
One of carbonic acid triethyl, dimethyl sulfoxide or acetone are a variety of.
The electrode can be used as the cathode of Carbon dioxide electrochemical reduction reaction.
Beneficial effects of the present invention:
1. the present invention provides a kind of Carbon dioxide electrochemical reduction gas-diffusion electrodes comprising basal layer 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, and improved its faradic efficiency.This kind of electrode structure does not need to suppress, therefore avoids biography
It unites during electrode fabrication, changes since compacting is electrolysed the structure for making catalyst, pattern, active specific surface, to influence
Its performance.
2. the present invention is by electrochemical method, the in-situ deposition Sn Nanorods Catalyst in substrate, and in its Dispersion on surface
Organic additive, the porous gas diffusive electrode that Sn catalyst is prepared establish stable gas liquid solid three phase boundary, shorten gas
Body diffusion path improves electrode reaction rate, not only can simplify the preparation process of catalyst, and can effectively control catalyst
Advantage crystal face and pattern, to regulate and control the performance of electrode.During Carbon dioxide electrochemical reduction, basal layer plays support
Body, conduction, the effect for forming liquids and gases transmission channel, Sn catalyst carbon dioxide reduction, and organic additive can be with
Stablize intermediate reaction object CO2. -, improve CO2Concentration improves its electric current to reduce the overpotential of carbon dioxide electrochemical reaction
Density and efficiency.
3. adding ethylenediamine, hexamethylene diamine, phenol, resorcinol, imidazoles, aniline, thiophene, polyaniline, poly- thiophene in the electrodes
Pheno, 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, to regulate and control its surface and CO2And CO2The phase of free radical
Interreaction force, to regulate and control its selectivity.
4. the effective active area of electrode not only can be improved with prepared gas-diffusion electrode for this method, can also mention
The transmission of high reactant improves its performance, is more advantageous to the practical application of ERC to reduce mass transfer polarization；Present invention preparation side
Method is simple, easily grasps, conventional production device, is suitble to large-scale production, the electrode specific surface area of preparation is big, has very high titanium dioxide
Carbon hydrogen reduction catalytic performance；
5. additive coating is catalyzed layer surface in Sn, interaction is generated with Sn catalyst, it to a certain extent can be to it
Anchoring effect is generated, to improve its stability.
6. re-coating is made in substrate after the Sn catalyst synthesized on tinfoil paper and glassy carbon electrode and directly compared to tradition
The method of standby electrode, the gas-diffusion electrode being prepared in situ using the present invention are had excellent faradic efficiency and to carboxylic acid products
Selectivity.The effective active area of electrode not only can be improved in prepared gas-diffusion electrode, can also improve reactant
Transmission, thus reduce mass transfer polarization, improve its performance, be more advantageous to the practical application of ERC.Furthermore side provided by the present invention
Method is simple, easily-controllable, is conducive to large-scale production.
Using
By made electrode, as carbon dioxide reduction formic acid cathode.And electrification is carried out by three-electrode system
Learn test: working electrode is electrode obtained；It is Pt piece, reference electrode Hg/Hg to electrode2Cl2/ saturation KCl.WE and RE it
Between distance be 0.5cm, use salt bridge to reduce liquid potential.Catholyte is 0.5M NaHCO3Aq.sol., electrolyte
Volume is 180ml.Anolyte is 0.1M H2SO4aq.sol.
Detailed description of the invention
Fig. 1 electrode structure schematic diagram
The faradic efficiency of electrode prepared by Fig. 2 embodiment 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
It is handled in air with carbon paper at 550 DEG C, then carries out oil removal treatment cleaning in acetone；
It is obtained by constant current process above-mentioned substrate surface electrochemistry is tin plating；During electrochemistry is tin plating, plating solution is
Concentration is 30g/L sodium stannate Na2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L buffer solution mixed liquor；The permanent electricity
Stream is -60mA/cm2, the tin plating time is 10000s；Phenol is dissolved in DMF and THF in the mixed solvent, is 25~50 in temperature
Stirring is completely dissolved to organic additive under degree Celsius, forms the solution that mass concentration is 10%；The quality of in the mixed solvent THF contains
Amount is 20%；In the way of spraying, by above-mentioned organic additive solution spraying to obtained Sn catalyst surface；By above-mentioned step
The electrode taking-up of rapid 4) preparation is dried in room temperature, after in 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being made；
Embodiment 2
It is handled in air with carbon paper at 550 DEG C, then carries out oil removal treatment cleaning in acetone；
It is obtained by constant current process above-mentioned substrate surface electrochemistry is tin plating；During electrochemistry is tin plating, plating solution is
Concentration is 30g/L sodium stannate Na2SnO3·3H2O solution, 15g/L KOH solution and 5g/L buffer solution mixed liquor；The permanent electricity
Stream is -40mA/cm2, the tin plating time is 10000s；Phenol is dissolved in DMF and THF in the mixed solvent, is 25~50 in temperature
Stirring is completely dissolved to organic additive under degree Celsius, forms the solution that mass concentration is 20%；The quality of in the mixed solvent THF contains
Amount is 30%；In the way of spraying, by above-mentioned organic additive solution spraying to obtained Sn catalyst surface；By above-mentioned step
The electrode taking-up of rapid 4) preparation is dried in room temperature, after in 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being made；
Embodiment 3
It is handled in air with carbon paper at 450 DEG C, then carries out oil removal treatment cleaning in acetone；
It is obtained by constant voltage method above-mentioned substrate surface electrochemistry is tin plating；During electrochemistry is tin plating, plating solution is
Concentration is 30g/L sodium stannate Na2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L buffer solution mixed liquor；The permanent electricity
Pressure is -1.2V, and the tin plating time is 10000s；Polyacrylonitrile is dissolved in DMF and THF in the mixed solvent, is 25~50 in temperature
Stirring is completely dissolved to organic additive under degree Celsius, forms the solution that mass concentration is 10%；The quality of in the mixed solvent THF contains
Amount is 20%；In the way of spraying, by above-mentioned organic additive solution spraying to obtained Sn catalyst surface；By above-mentioned steps
4) the electrode taking-up prepared is dried in room temperature, after in 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being made；
Embodiment 4
XC-72 is blended in water and ethyl alcohol with PTFE with the in the mixed solvent of 1:3, obtains electrode slurry, wherein solids
Matter and solvent ratios are 50mg solid/ml solvent；By the way of roll-in, slurry is coated on and is carried out in air at 550 DEG C
Treated carbon paper surface；The loading of XC-72 is 1.5mg/cm-2, PTFE binder shared mass fraction in diffusion layer is
30%.It is obtained by constant current process above-mentioned substrate surface electrochemistry is tin plating；During electrochemistry is tin plating, plating solution is concentration
For 25g/L sodium stannate Na2SnO3·3H2O solution, 10g/LNaOH solution and 8g/L buffer solution mixed liquor；The constant current be-
80mA/cm2, the tin plating time is 10000s；Phenol is dissolved in DMF and THF in the mixed solvent, 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 in the mixed solvent THF is
20%；In the way of spraying, by above-mentioned organic additive solution spraying to obtained Sn catalyst surface；By above-mentioned steps 4)
The electrode taking-up of preparation is dried in room temperature, after in 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being made；
Embodiment 5
XC-72 is blended in water and ethyl alcohol with PTFE with the in the mixed solvent of 1:3, obtains electrode slurry, wherein solids
Matter and solvent ratios are 50mg solid/ml solvent；By the way of roll-in, slurry is coated on and is carried out in air at 550 DEG C
Treated carbon paper surface；The loading of XC-72 is 1.5mg/cm-2, PTFE binder shared mass fraction in diffusion layer is
30%.During electrochemistry is tin plating, plating solution is that concentration is 30g/L sodium stannate Na2SnO3·3H2O solution, 15g/L NaOH are molten
Liquid and 5g/L buffer solution mixed liquor；The constant potential is -0.8V vs.SCE, and the tin plating time is 10000s；Polyaniline is dissolved
In DMF and THF in the mixed solvent, stirring to organic additive is completely dissolved under being 25~50 degrees Celsius in temperature, and it is dense to form quality
The solution that degree is 10%；The mass content of in the mixed solvent THF is 20%；It is in the way of spraying, above-mentioned organic additive is molten
The Sn catalyst surface that liquid sprays to；By above-mentioned steps 4) preparation electrode taking-up dried in room temperature, after in vacuum drying oven
80 degrees Celsius of dryings, electrode needed for being made；
Embodiment 6
XC-72 is blended in water and ethyl alcohol with PTFE with the in the mixed solvent of 1:2, obtains electrode slurry, wherein solids
Matter and solvent ratios are 80mg solid/ml solvent；By the way of roll-in, slurry is coated on and is carried out in air at 550 DEG C
Treated carbon paper surface；The loading of XC-72 is 2.0mg/cm-2, PTFE binder shared mass fraction in diffusion layer is
30%.It is obtained by cyclic voltammetric method above-mentioned substrate surface electrochemistry is tin plating；During electrochemistry is tin plating, plating solution is dense
Degree is 30g/L sodium stannate Na2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L buffer solution mixed liquor；The circulation is swept
It retouches as -0.3-2.0V vs.SCE, the tin plating time is 500s；Polyaniline is dissolved in DMF and THF in the mixed solvent, is in temperature
Stirring is completely dissolved to organic additive under 25~50 degrees Celsius, forms the solution that mass concentration is 10%；In the mixed solvent THF's
Mass content is 20%；In the way of spraying, by above-mentioned organic additive solution spraying to obtained Sn catalyst surface；Will
Above-mentioned steps 4) the electrode taking-up of preparation dries in room temperature, after in 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being made；
Embodiment 7
Graphene is blended in water and ethyl alcohol with PTFE with the in the mixed solvent of 1:3, obtains electrode slurry, wherein solids
Matter and solvent ratios are 30mg solid/ml solvent；By the way of roll-in, slurry is coated on and is carried out in air at 450 DEG C
Treated carbon paper surface；The loading of graphene is 0.5mg/cm-2, PTFE binder shared mass fraction in diffusion layer is
10%.During electrochemistry is tin plating, plating solution is that concentration is 30g/L sodium stannate Na2SnO3·3H2O solution, 15g/LNaOH solution
And 5g/L buffer solution mixed liquor；The constant potential is -1.5V vs.SCE, and the tin plating time is 500s；Polyaniline is dissolved in
DMF and THF in the mixed solvent, stirring to organic additive is completely dissolved under being 25~50 degrees Celsius in temperature, forms mass concentration
For 10% solution；The mass content of in the mixed solvent THF is 20%；In the way of spraying, by above-mentioned organic additive solution
The Sn catalyst surface sprayed to；By above-mentioned steps 4) preparation electrode taking-up dried in room temperature, after in vacuum drying oven 80
Degree Celsius drying, electrode needed for being made；
Embodiment 8
Carbon nanotube is blended in water and ethyl alcohol with PTFE with the in the mixed solvent of 1:3, obtains electrode slurry, wherein solid
Substance and solvent ratios are 50mg solid/ml solvent；By the way of roll-in, by slurry be coated on 550 DEG C in air into
Row treated carbon paper surface；The loading of nanotube is 1.5mg/cm-2, PTFE binder shared mass fraction in diffusion layer
It is 30%.It is obtained by constant current process above-mentioned substrate surface electrochemistry is tin plating；During electrochemistry is tin plating, plating solution is dense
Degree is 30g/L sodium stannate Na2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L buffer solution mixed liquor；The constant potential
For -0.8V vs.SCE, the tin plating time is 10000s；Polyaniline is dissolved in DMF and THF in the mixed solvent, temperature be 25~
Stirring is completely dissolved to organic additive under 50 degrees Celsius, forms the solution that mass concentration is 10%；The quality of in the mixed solvent THF
Content is 20%；In the way of spraying, by above-mentioned organic additive solution spraying to obtained Sn catalyst surface；It will be above-mentioned
The electrode taking-up of step 4) preparation is dried in room temperature, after in 80 degrees Celsius of dryings of vacuum drying oven, electrode needed for being made；
Comparative example 1
It is handled in air with carbon paper at 550 DEG C, then carries out oil removal treatment cleaning in acetone；Pass through 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 stannate
Na2SnO3·3H2O solution, 15g/LNaOH solution and 5g/L buffer solution mixed liquor；The constant current is -60mA/cm2, tin plating
Time is 10000s；The electrode of above-mentioned preparation is taken out and is dried in room temperature, after in 80 degrees Celsius of dryings of vacuum drying oven, needed for being made
Electrode；Show in Fig. 2 relative to comparative example 1, electrode performance significantly improves in embodiment 1,2,4.
Claims (7)
1. a kind of Carbon dioxide electrochemical reduction gas-diffusion electrode, which is characterized in that electrode includes basal layer and basal layer
The Sn catalyst and organic additive mixed layer of upper attachment, the ratio between both Sn catalyst and organic additive mole are 100:1-30:1,
The loading of Sn catalyst is 0.1 mg/cm in electrode2-5 mg/cm2；
The organic additive include ethylenediamine, hexamethylene diamine, phenol, resorcinol, imidazoles, aniline, thiophene, polyaniline, polythiophene,
One of polypyrrole, polysulfones, polyketone, polyimides, polybenzimidazoles, polyvinyl pyridine, polyacrylonitrile, triphenylphosphine or two
Kind or more；
The electrode is prepared according to the following procedure:
1) using gas diffusion layers or treated charcoal felt or carbon paper as basal layer: charcoal felt or carbon paper treatment process are as follows: 200~
600oC is handled in air, and oil removal treatment cleaning is then carried out in ethyl alcohol, acetone；
2) the Sn catalyst layer described in is by constant current, constant potential or the method for scan round in above-mentioned substrate surface electrochemical plating
Tin obtains；During electrochemistry is tin plating, plating solution is that concentration is 30-95 g/L sodium stannate Na2SnO3·3H2O solution, 1.0- 20
G/L inorganic alkali solution and 1-10 g/L buffer solution mixed liquor；Solute in the buffer solution is in sodium acetate or potassium acetate
A kind of or two kinds, the mass ratio of sodium stannate and inorganic base is 20:1-1:1, the mass ratio of solute in sodium stannate and buffer solution are as follows:
20:1-1:1；The constant current is -5 mA/cm2~-200 mA/cm2, constant potential is -0.2 V of V~-6, scan round range
For -0.3V-2.0 V；The tin plating time is 10s~20000s；
3) organic additive is dissolved in the mixed solvent, mixed solvent by one of DMSO, DMF, DMAC or two kinds or more with
One of THF or n-hexane or two kinds mix, and stirring is 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 in the mixed solvent THF or n-hexane is 5-40%；
4) in the way of spraying, Sn catalyst surface that above-mentioned organic additive solution spraying to step 2 is prepared；
5) by above-mentioned steps 4) the electrode taking-up of preparation dries in room temperature, after in 40-100 degrees Celsius of drying of vacuum drying oven, be made
Required electrode；
Alternatively, by above-mentioned electrode immerse organic solvent in, stand at least 1 hour, taking-up dried in room temperature, after in vacuum drying oven
40-100 degrees Celsius of drying, electrode needed for being made.
2. a kind of preparation method of Carbon dioxide electrochemical reduction gas-diffusion electrode described in claim 1, feature exist
In the electrode is prepared according to the following procedure:
1) using gas diffusion layers or treated charcoal felt or carbon paper as basal layer: charcoal felt or carbon paper treatment process are as follows: 200~
600oC is handled in air, and oil removal treatment cleaning is then carried out in ethyl alcohol, acetone；
2) the Sn catalyst layer described in is by constant current, constant potential or the method for scan round in above-mentioned substrate surface electrochemical plating
Tin obtains；During electrochemistry is tin plating, plating solution is that concentration is 30-95 g/L sodium stannate Na2SnO3·3H2O solution, 1.0- 20
G/L inorganic alkali solution and 1-10 g/L buffer solution mixed liquor；Solute in the buffer solution is in sodium acetate or potassium acetate
A kind of or two kinds, the mass ratio of sodium stannate and inorganic base is 20:1-1:1, the mass ratio of solute in sodium stannate and buffer solution are as follows:
20:1-1:1；The constant current is -5 mA/cm2~-200 mA/cm2；Constant potential is -0.2 V of V~-6；Scan round range
For -0.3V-2.0 V；The tin plating time is 10s~20000s；
3) organic additive is dissolved in the mixed solvent, mixed solvent by one of DMSO, DMF, DMAC or two kinds or more with
One of THF or n-hexane or two kinds mix, and stirring is 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 in the mixed solvent THF or n-hexane is 5-40%；
4) in the way of spraying, Sn catalyst surface that above-mentioned organic additive solution spraying to step 2 is prepared；
5) by above-mentioned steps 4) the electrode taking-up of preparation dries in room temperature, after in 40-100 degrees Celsius of drying of vacuum drying oven, be made
Required electrode；
Alternatively, by above-mentioned electrode immerse organic solvent in, stand at least 1 hour, taking-up dried in room temperature, after in vacuum drying oven
40-100 degrees Celsius of drying, electrode needed for being made.
3. preparation method according to claim 2, it is characterised in that: the constant current is -20 mA/cm2~-100 mA/
cm2；Constant potential is -0.3 V of V~-2.0；The tin plating time is 3000s-15000s.
4. preparation method according to claim 2, it is characterised in that: one of inorganic base NaOH, KOH, CsOH or
It is two or more；Organic solvent is one of ethyl alcohol, isopropanol, NMP or two kinds or more.
5. preparation method according to claim 2, it is characterised in that: the organic additive include ethylenediamine, hexamethylene diamine,
Phenol, resorcinol, imidazoles, aniline, thiophene, polyaniline, polythiophene, polypyrrole, polysulfones, polyketone, polyimides, polyphenyl and miaow
One of azoles, polyvinyl pyridine, polyacrylonitrile, triphenylphosphine or two kinds or more.
6. preparation method according to claim 2, it is characterised in that: the gas diffusion layers can prepare according to the following procedure and
At: conductive porous material is blended in solvent with binder, obtains electrode slurry, wherein solid matter is with solvent ratios
10 ~ 200 mg solids/ml solvent；By the way of blade coating, spraying or roll-in, slurry is coated on processed charcoal felt or carbon paper
Surface dries in 40-80 degrees Celsius and electrode is made, gas diffusion layers are prepared；The conductive porous material is partial size in 10-
KB600, KB300, BP2000, XC-72, Acetylene black, Alkaline-activated carbon, the carbon of 100 nm
One of aeroge or carbon xerogel, carbon nanotube, carbon nano-fiber, graphene or two kinds or more；Wherein conductive porous material
The loading of material is 0.5 mg/cm2- 3.0 mg/cm2, binder shared mass fraction in diffusion layer is 10-30%；
Basal layer is charcoal felt or carbon paper, charcoal felt or carbon paper treatment process are as follows: 200~600oC is handled in air, then
Oil removal treatment cleaning is carried out in ethyl alcohol, acetone；
Wherein, the binder is PTFE or PVDF；
When using PTFE as binder, 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 of ethyl alcohol, isopropanol, ethylene glycol or glycerine or a variety of；
When using PVDF as binder, solvent is N-Methyl pyrrolidone, dimethyl acetamide, dimethylformamide, diformazan
One of base sulfoxide or acetone are a variety of.
7. a kind of application of Carbon dioxide electrochemical reduction gas-diffusion electrode described in claim 1, it is characterised in that: institute
Stating electrode can be used as the cathode of Carbon dioxide electrochemical reduction reaction.
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| CN107158895B (en) * | 2017-07-13 | 2020-07-28 | 斯养武 | Carbon dioxide absorbent |
| CN108842162A (en) * | 2018-06-15 | 2018-11-20 | 重庆大学 | For electrochemical reduction CO2SnO2Nanometer sheet gas-diffusion electrode and method |
| CN111519207B (en) * | 2020-05-19 | 2021-06-29 | 大连大学 | Preparation and application of Sn electrode for electrochemical reduction of carbon dioxide |
| CN111575726B (en) * | 2020-05-27 | 2021-10-01 | 上海科技大学 | Electrochemical reactor for electrochemical reduction of carbon dioxide |
| CN111628183B (en) * | 2020-05-27 | 2022-12-13 | 先进储能材料国家工程研究中心有限责任公司 | Preparation method of fuel cell catalyst slurry |
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| CN116676615B (en) * | 2023-07-21 | 2024-05-17 | 深圳先进技术研究院 | For electrocatalytic CO2Gas-phase diffusion electrode for reducing formic acid, preparation method and application |
| CN117673379B (en) * | 2024-01-30 | 2024-04-12 | 江苏源氢新能源科技股份有限公司 | Preparation method of spinning type CNT (carbon nanotube) diffusion layer and preparation method of membrane electrode |
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