CN106521544B - Carbon dioxide electrochemical reduction porous electrode complex and its preparation and application - Google Patents
Carbon dioxide electrochemical reduction porous electrode complex and its preparation and application Download PDFInfo
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Abstract
The present invention provides a kind of Carbon dioxide electrochemical reduction porous electrode complex structures and preparation method thereof, including the gas diffusion substrate layer and porous metal electrode layer being layered on top of each other, and further include the cyclic annular frame that two shape and size are identical, hollow；The edge of two cyclic annular frames is mutually adhered to by adhesive, and gas diffusion substrate layer and porous metal electrode layer are between two cyclic annular frames with being layered on top of each other, and constitute porous electrode complex.The porous electrode complex can either utilize porous gas diffusion substrates quickly to transmit gas and the function that liquid is discharged to electrode catalyst position, electrode reaction interfacial area can be expanded using metal electrode longitudinal hole again, to improve carbon dioxide electrochemical reaction speed, the carbon dioxide electrochemical reactor at electrode reaction interface is vertically flowed through especially suitable for reaction gas.
Description
Technical field
The invention belongs to Carbon dioxide electrochemical reduction technical field, more particularly to a kind of porous electrode complex and its system
Standby technology.
Background technology
Electrochemical reduction CO2(ERC) technology is to utilize electric energy by CO2Various organic chemicals are reduced to, realize CO2Resource
Change a kind of technology utilized.With other CO2Transformation technology is compared, and the outstanding advantage of ERC technologies is using water as reaction
Hydrogen source, CO can be realized at normal temperatures and pressures2Efficient Conversion, therefore do not need the hydrogen manufacturing needed for chemical conversion technology and add
Energy expenditure caused by temperature, pressurization, equipment investment are few.
Currently, the principal element for restricting the development of ERC technologies includes：(1) reaction overpotential is high；(2) conversion ratio is low；(3) it produces
Object poor selectivity.Wherein, in the ERC reaction systems using aqueous solution as supporting electrolyte, usually using tablet (such as sheet,
Foil-like and bulk) metal carrys out catalysis electrode reaction process.The prominent defect of one of this kind of metal electrode is that electrode reaction area is small,
The surface being in contact with supporting electrolyte is concentrated merely on, to constitute ERC reaction overpotential height and CO2The low important original of conversion ratio
Cause；In addition, covering and poisoning effect of the intermediate product to electrode in ERC reaction process, make the fast prompt drop of electrode effective affecting acreage
Low, electrode can lose activity quickly.
To expand the electrode area used in ERC reactions, researcher is by constructing the electrode surface of special appearance, increasing
Active crystal grain boundary substantially expands electrochemical reaction area.Xie etc. is in document Electrochimica Acta, and 2014,139:
It is reported in 137-144, the progress line pulse anodic oxidation of Cu foils is obtained into CuO nanofibers, then its electrochemical reduction is obtained
Three-dimensional flower-shaped Cu nanofibers.The reaction overpotential of ERC can be reduced 400mV by this Cu nano flowers, by H2Faradic efficiency
25% is down to hereinafter, up in more than 9 hours electrolysis times, Cu nano flowers are still kept to CO2The high catalysis of reduction is lived
Property.
Gas-diffusion electrode (GDE) is a kind of conductive composite material built based on porous material, most apparent special
Sign is that have abundant hole, is particularly suitable for structure three-phase reaction interface, response area is expanded, in fuel cell, energy-storage battery
Field is widely used, and researcher was also once introduced into Carbon dioxide electrochemical reduction field.Such as Hara is in document
J.Electrochem.Soc.,1995,142(4):It is reported in L57-L59, GDE is prepared using Pt nano particle as active component,
CO2Pressure<Under the conditions of 50atm, Pt-GDE restores CO2Current density reach 900mA cm-2, current efficiency 46%.But
The generally spherical metal nanoparticle of catalyst used during building GDE, and many non-noble metal nano particles are in sky
Stability is bad in gas, and surface easily aoxidizes (such as red nano Cu is oxidized to black CuO), seriously reduces the catalysis of catalyst
Effect, while also changing product distribution.To maintain the high catalytic activity of metal nanoparticle, it usually needs to the GDE of preparation
Activation process is carried out, process is cumbersome, and not easy to control.
Invention content
In order to solve the above technical problems, the present invention provides a kind of Carbon dioxide electrochemical reduction porous electrode complexs
Structure and preparation method thereof, the porous electrode complex combine gas-diffusion electrode and substantially expand response area and flat metal
The double dominant of electrode efficient catalytic Carbon dioxide electrochemical reduction reaction, electrode table is vertically flowed through especially suitable for reaction gas
In the Carbon dioxide electrochemical reduction reactor in face.
A kind of Carbon dioxide electrochemical reduction porous electrode complex, including the gas diffusion substrate layer that is layered on top of each other and
Porous metal electrode layer further includes the cyclic annular frame that two shape and size are identical, hollow；The surrounding of gas diffusion substrate layer
Edge is adhered to a side surface of a cyclic annular frame, and the edge of gas diffusion substrate layer and cyclic annular side by adhesive
There are distances between the edge of frame hollow region；The edge of porous metal electrode layer is adhered to another ring by adhesive
One side surface of shape frame, and between the edge of porous metal electrode layer and the edge of cyclic annular frame hollow region there are away from
From；The edge of two cyclic annular frames is mutually adhered to by adhesive, and gas diffusion substrate layer and porous metal electrode layer phase
Mutually stacking is located between two cyclic annular frames, constitutes porous electrode complex.
The material of the ring-type frame is one kind in polypropylene, polyester, makrolon or polyimides；The bonding
Agent is one kind in pressure sensitive adhesive, including acrylic compounds, organic silicon or polyurethanes pressure sensitive adhesive；
The gas diffusion substrate is used for transmission reaction gas and liquid, and porous metal electrode is for being catalyzed carbon dioxide
Electrochemical reducting reaction.
The gas diffusion substrate is nonmetallic materials, is the good conductor of electricity, including braiding or non-woven charcoal base charcoal
The non-woven fabrics of paper or charcoal cloth, charcoal felt or dual coating Carbon Materials.
The gas diffusion substrate, porosity are 50%~95%, and optimal porosity is 70%~90%；
The gas diffusion substrate, thickness are 0.08mm~3.0mm, and optimum thickness is 0.1mm~1.5mm；It is true
Protecting gas diffusion substrate has good gas transmission property, the Static water contact angles ranging from 60 of the gas diffusion substrate
~130 degree.
The porous metal electrode is metal plate material, including piece or foil；Thickness is 5 μm~2.0mm, best thick
Degree is 0.01mm~1.0mm；
The porous metal electrode, porosity are 0.1%~5%, and optimal porosity is 0.5%~2%.
The porous metal electrode, average pore size scope are 50 μm~2mm, and optimum aperture is 100 μm~500 μm；
Porous metal electrode layer is equipped with collection ear, and collection ear is stretched out from the outer edge of two cyclic annular frames.
The porous metal electrode, the effective metal content for being catalyzed ERC reactions are not less than 99.0%；
One or two or more kinds in effective metal in the porous metal electrode, including following metals, i.e. IIIA
Metallic element In, Tl, Sn in~VA, Pb, Sb, Bi, Pd, Pt in Cu, Ag, Au and VIIIB in IB, Ru, Rh, Ir.
Preparation process includes the following steps：
1) gas diffusion substrate is subjected to oil removing pretreatment；2) by porous metal electrode carry out oil removing, go it is deimpurity pre-
Processing；3) gas diffusion substrate and porous metal electrode are adhered to the two panels ring-type plastic frame of side application of adhesive respectively
On, the side that two panels frame is coated with to adhesive is opposite, keeps the two edge impartial with the spacing of corresponding frame inner ring respectively, finally
The adhesive side of two frames is opposite, constitute porous electrode complex preload component；4) by porous electrode complex precompressed
Component is placed in tablet tablet press machine, and porous electrode complex is obtained under room temperature, pressurized conditions.
The pressurized equipment is tablet tablet press machine, flatness requirement ± 20 μm.
Pressure to combination electrode is 1MPa~10MPa, and optimum pressure is 5MPa~20MPa；Pressing time be 30s~
5min, optimum pressurized time are 1min~3min.
Porous electrode complex is applied in Carbon dioxide electrochemical reduction.
Compared with prior art, beneficial effects of the present invention are as follows：
1) by the compound of porous metal electrode and gas diffusion substrate, porous gas diffusion substrates can either be utilized to electrode
Catalytic sites quickly transmit gas and the function of liquid are discharged, and can expand electrode reaction interface face using metal electrode longitudinal hole
Product, to improve carbon dioxide electrochemical reaction speed, the two of electrode reaction interface is vertically flowed through especially suitable for reaction gas
Carbonoxide electrochemical reactor.Compared with plate electrode, the porous effect of porous electrode complex changes gas transport path
And transmission mode, the residence time of reactant in the electrodes is increased, thus to inhibiting the generation of liberation of hydrogen side reaction and improving anti-
It answers efficiency that there is facilitation, has and improve CO2The potential advantages of conversion ratio.
2) since electrochemically reducing carbon dioxide is interfacial reaction, porous metal electrode and gas diffusion substrate it is compound
Body, it is possible to reduce the dosage of metal electrode reduces the electrode material cost of carbon dioxide electrochemical reaction；In addition, for foil-like
Electrode, since its rigidity is poor, gas diffusion substrate can be used as its supporter, enhance the mechanical strength of complex, so as to
To make broad-area electrode, ERC reaction speeds are improved.
Description of the drawings
Fig. 1 porous electrode complex structure schematic diagrames.
The ring-shaped plastics frame of 1-side coated with adhesive
2-gas diffusion substrates
3-porous metal electrodes.
Specific implementation mode
With reference to preferred embodiment, technical scheme of the present invention is described further, but the technology contents of the present invention
It is not limited only to the range.
Comparative example 1
1. metal electrode pre-processes：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 20 μm, purity is
99.9% Cu foils are respectively in acetone and 0.1M H2SO4Middle ultrasound impregnates 30min, carries out oil removing, oxide film dissolving processing, then use nothing
Water-ethanol cleaning, ultrasound impregnate 15min, finally use Ar air-blowings dry；
3. the polycarbonate plastic of two panels One-sided coatings acrylate pressure sensitive adhesive is tailored into hollow rectangular shaped rim, outline border ruler
Very little is 6cm*7cm, and the size of hollow space (referred to as inner ring) is 3.4cm*4.4cm (i.e. 14.96cm2), it then will pass through step
The side centre position of rapid 1 treated Cu foils are placed on two frames coating pressure sensitive adhesives, make Cu foil edges in corresponding frame
The spacing of ring is impartial.The pressure sensitive adhesive side of two frames is finally subjected to pre-bonded relatively, obtains Cu foil electrode preload components；
4. Cu foil electrode preload components are transferred between two pieces of tablets of tablet tablet press machine that maximum pressure is 50MPa, apply
Plus-pressure, it is 12MPa to make the pressure on preload component surface, suppresses 1min under normal pressure, obtains Cu foil electrodes.
5. the ERC performance evaluations of metal electrode
In H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M
KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of cathode cavity and anode cavities.Before test, first to the moon
It is passed through high-purity N in the chamber of pole21h then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.30min
Afterwards, using Cu foil electrodes as working electrode, Pt pieces are to electrode, and saturated calomel electrode is reference electrode.In -2.0V operating voltages
Lower progress electrochemical reducting reaction 30min, reaction end gas are passed through the quantitative detection that gas-chromatography carries out gaseous product, product liquid
Quantitative analysis is carried out using ion chromatography.
In the present embodiment, in the present embodiment, gaseous product CH4A concentration of 850ppm, C2H4A concentration of 24ppm, HCOOH
A concentration of 25ppm, CO2Conversion ratio is 8%.
Comparative example 2
1. metal electrode pre-processes：Under room temperature, the circle for being 99.5% by a diameter of 2.0cm, thickness 0.2mm, purity
Pd pieces are respectively in acetone and 0.1M H2SO4Middle ultrasound impregnates 30min, carries out oil removing, oxide film dissolving processing, then clear with absolute ethyl alcohol
It washes, ultrasound immersion 15min, finally uses Ar air-blowings dry；
3. the polyester plastics of two panels One-sided coatings organic pressure-sensitive gel to be tailored into hollow round frame, the outer diameter of frame
For 3.0cm, a diameter of 1.6cm of hollow space (referred to as inner ring) then will pass through step 1 treated that Pd pieces are placed on two
The side centre position of a frame coating pressure sensitive adhesive keeps Pd pieces edge and the spacing of frame inner ring impartial.Finally by two frames
Binder side relatively bond, obtain Pd plate electrode preload components；
4. Pd plate electrode preload components are transferred between two pieces of tablets of tablet tablet press machine that maximum pressure is 10MPa, apply
Plus-pressure, it is 2MPa to make the pressure on preload component surface, suppresses 30s under normal pressure, obtains Pd plate electrodes.
5. the ERC performance evaluations of metal electrode
In H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M
KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of anode and cathode chamber.Before test, first into cathode cavity
It is passed through high-purity N21h then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.After 30min, with
Pd plate electrodes are working electrode, and Pt pieces are made to electrode, and saturated calomel electrode is reference electrode.It is carried out under -1.5V operating voltages
Electrochemical reducting reaction 30min, reaction end gas be passed through gas-chromatography carry out gaseous product quantitative detection, product liquid use from
Sub- chromatography carries out quantitative analysis.
In the present embodiment, in the present embodiment, a concentration of 365ppm of gaseous product CO, HCOOH a concentration of 50ppm, CO2Turn
Rate is 6%.
Embodiment 1
1. gas diffusion substrate oil removing pre-processes：It is respectively that 4cm and 5cm, thickness are by length and width under room temperature
0.2mm, porosity be 78% TGP-H-060 carbon papers in acetone ultrasound impregnate 20min after, then with washes of absolute alcohol, surpass
Sound impregnates 15min, finally uses Ar air-blowings dry, in 6M HNO350 DEG C of immersion 3h in aqueous solution, deionized water cleaning, Ar air-blowings are dry
Afterwards, it is 100 degree to measure Static water contact angles；
2. porous metal electrode pre-processes：By length and width it is respectively 4cm and 5cm, thickness 0.1mm, pure under room temperature
Degree for 99.5%, average pore size 0.5mm, porosity be 1% porous C u pieces respectively in acetone and 0.5M H2SO4Middle ultrasound
20min is impregnated, oil removing, oxide film dissolving processing is carried out, then 15min is impregnated with washes of absolute alcohol, ultrasound, finally uses Ar air-blowings
It is dry；
3. the polycarbonate plastic of two panels One-sided coatings acrylate pressure sensitive adhesive is tailored into hollow rectangular shaped rim, outline border ruler
Very little is 6cm*7cm, and the size of hollow space (referred to as inner ring) is 3.4cm*4.4cm (i.e. 14.96cm2), it then respectively will be through
Both it crosses step 1 and 2 treated carbon papers and porous C u pieces is placed on the centre position of two frames coating pressure sensitive adhesive sides, make
Edge is impartial with the spacing of corresponding frame inner ring respectively.Finally the pressure sensitive adhesive side of two frames is bonded relatively, is obtained porous
The preload component of electrode complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 20MPa two pieces of tablets of tablet tablet press machine it
Between, apply pressure, it is 10MPa to make the pressure on preload component surface, suppresses 2min under normal pressure, obtains porous electrode complex.
5. the ERC performance evaluations of porous electrode complex
In improved H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml
0.1M KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity
Body enters from electrolytic cell lower end, flows through porous electrode and CO occurs2After electrochemical reducting reaction, arranged from the upper end outlet of cathode cavity
Go out.Before test, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow velocity
Control is 60sccm.After 30min, using porous electrode complex as working electrode, Pt pieces are to electrode, and saturated calomel electrode is ginseng
Compare electrode.Electrochemical reducting reaction 30min is carried out under -2.0V operating voltages, reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
In the present embodiment, gaseous product CH4A concentration of 1680ppm, C2H4A concentration of 20ppm's, C2H6 is a concentration of
2ppm, HCOOH a concentration of 100ppm, C2H5OH a concentration of 15ppm, CO2Conversion ratio is 15%, is 1.875 times of comparative example 1.
Embodiment 2
1. gas diffusion substrate oil removing pre-processes：It is respectively that 4cm and 5cm, thickness are by length and width under room temperature
2.0mm, porosity be 80% charcoal cloth in acetone ultrasound impregnate 30min after, then with washes of absolute alcohol, ultrasound immersion
15min finally uses Ar air-blowings dry；In 6M HNO350 DEG C of immersion 1h in aqueous solution, deionized water cleaning after Ar air-blowings are dry, measure
Static water contact angles are 130 degree；
2. porous metal electrode pre-processes：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 50 μm, it is pure
The porous Ag foils that degree is 99.0%, average pore size is 50 μm, porosity is 0.5% are respectively in acetone and 0.5M H2SO4Middle ultrasound
30min is impregnated, surface degreasing is carried out, oxide film dissolving is gone to handle, then 15min is impregnated with washes of absolute alcohol, ultrasound, finally uses Ar
Air-blowing is dry；
3. the polypropylene plastics of two panels One-sided coatings polyurethanes pressure sensitive adhesive is tailored into hollow rectangular shaped rim, outline border ruler
Very little is 6cm*7cm, and the size of hollow space (referred to as inner ring) is 3.4cm*4.4cm (i.e. 14.96cm2), it then respectively will be through
Both it crosses step 1 and 2 treated charcoal cloth and porous Ag foils is placed on the centre position of two frames coating pressure sensitive adhesive sides, make
Edge is equal with the corresponding spacing of frame inner ring respectively.Finally the pressure sensitive adhesive side of two frames is bonded relatively, is obtained porous
The preload component of electrode complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 50MPa two pieces of tablets of tablet tablet press machine it
Between, apply pressure, it is 30MPa to make the pressure on preload component surface, suppresses 3min under normal pressure, obtains porous electrode complex.
5. the ERC performance evaluations of porous electrode complex
In improved H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml
0.1M KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity
Body enters from electrolytic cell lower end, flows through porous electrode and CO occurs2After electrochemical reducting reaction, arranged from the upper end outlet of cathode cavity
Go out.Before test, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow velocity
Control is 60sccm.After 30min, using porous electrode complex as working electrode, Pt pieces are to electrode, and saturated calomel electrode is ginseng
Compare electrode.Electrochemical reducting reaction 30min is carried out under -2.0V operating voltages, reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
In the present embodiment, a concentration of 5500ppm of gaseous product CO, HCOOH a concentration of 100ppm, C2H5OH is a concentration of
200ppm, CO2Conversion ratio is 30%.
Embodiment 3
1. gas diffusion substrate oil removing pre-processes：Under room temperature, it is by a diameter of 2.0cm, thickness 3.0mm, porosity
95% round charcoal felt in acetone ultrasound impregnate 30min after, then with washes of absolute alcohol, ultrasound immersion 15min, finally use Ar
Air-blowing is dry, and it is 130 degree to measure Static water contact angles；
2. porous metal electrode pre-processes：Under room temperature, by a diameter of 2.0cm, thickness 0.2mm, purity 99.5%, put down
Ultrasound impregnates 30min to the rounded porous Pd pieces that aperture is 1.0mm, porosity is 0.1% in acetone, carries out at surface degreasing
Reason, then 15min is impregnated with washes of absolute alcohol, ultrasound, finally use Ar air-blowings dry；
3. the polyimides of two panels One-sided coatings acrylate pressure-sensitive adhesive is tailored into round frame, the outer diameter of frame is
3.0cm, a diameter of 1.6cm of hollow space (referred to as inner ring) then will pass through step 1 and 2 treated charcoal felts and porous
Pd pieces are individually positioned in the centre position of two frame coating pressure sensitive adhesive sides, make the spacing at the two edge and corresponding frame inner ring
It is impartial.Finally the binder side of two frames is bonded relatively, obtains the preload component of porous electrode complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 10MPa two pieces of tablets of tablet tablet press machine it
Between, apply pressure, it is 2MPa to make the pressure on preload component surface, suppresses 30s under normal pressure, obtains porous electrode complex.
5. the ERC performance evaluations of porous electrode complex
In improved H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml
0.1M KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity
Body enters from electrolytic cell lower end, flows through porous electrode and CO occurs2After electrochemical reducting reaction, arranged from the upper end outlet of cathode cavity
Go out.Before test, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow velocity
Control is 60sccm.After 30min, using porous electrode complex as working electrode, Pt pieces are to electrode, and saturated calomel electrode is ginseng
Compare electrode.Electrochemical reducting reaction 30min is carried out under -1.5V operating voltages, reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
In the present embodiment, a concentration of 800ppm of gaseous product CO, HCOOH a concentration of 20ppm, CO2Conversion ratio is 14%,
It is 2.33 times of comparative example 2.
Embodiment 4
1. gas diffusion substrate oil removing pre-processes：It is respectively that 4cm and 5cm, thickness are by length and width under room temperature
0.15mm, porosity be 80% non-woven fabrics in acetone ultrasound impregnate 30min after, then with washes of absolute alcohol, ultrasound immersion
15min finally uses Ar air-blowings dry；
2. gas diffusion substrate coats Carbon Materials：Using the Vulcan XC-72 charcoals that Cabot companies produce as conductive material,
PVDF makees binder, and both control ratio is 9:1, charcoal slurry is prepared as dispersant with absolute ethyl alcohol.At normal temperatures, by charcoal and PVDF
Mixed slurry be coated uniformly on the two sides of non-woven fabrics, dried in 160 DEG C of baking ovens, it is 90 degree to measure static contact angle, porosity
It is 65%.
3. porous metal electrode pre-processes：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 10 μm, it is pure
Ultrasound impregnates 30min to the porous Sn foils that degree is 99.9%, average pore size is 100 μm, porosity is 0.3% in acetone, carries out
Surface degreasing processing, then 15min is impregnated with washes of absolute alcohol, ultrasound, finally use Ar air-blowings dry；
3. the polyimides of two panels One-sided coatings polyacrylate binder is tailored into hollow rectangular shaped rim, outline border ruler
Very little is 6cm*7cm, and the size of hollow space (referred to as inner ring) is 3.4cm*4.4cm (i.e. 14.96cm2), it then respectively will be through
It crosses step 1 and 2 treated nonwoven fabric base bottoms and porous Sn foils is placed on the centre position of two frames coating pressure sensitive adhesive sides,
Keep the two edge equal with the corresponding spacing of frame inner ring respectively.Finally the pressure sensitive adhesive side of two frames is bonded relatively, is obtained
To the preload component of porous electrode complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 30MPa two pieces of tablets of tablet tablet press machine it
Between, apply pressure, it is 15MPa to make the pressure on preload component surface, suppresses 2min under normal pressure, obtains porous electrode complex.
5. the ERC performance evaluations of porous electrode complex
In improved H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml
0.1M KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity
Body enters from electrolytic cell lower end, flows through porous electrode and CO occurs2After electrochemical reducting reaction, arranged from the upper end outlet of cathode cavity
Go out.Before test, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow velocity
Control is 60sccm.After 30min, using porous electrode complex as working electrode, Pt pieces are to electrode, and saturated calomel electrode is ginseng
Compare electrode.Electrochemical reducting reaction 30min is carried out under -1.5V operating voltages, reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
In the present embodiment, no CO2The gaseous product of reduction reaction, product liquid HCOOH a concentration of 500ppm, CO2Conversion ratio
It is 18%.
Embodiment 5
1. gas diffusion substrate oil removing pre-processes：It is respectively that 4cm and 5cm, thickness are by length and width under room temperature
0.09mm, porosity be 82% TGP-H-030 carbon papers in acetone ultrasound impregnate 20min after, then with washes of absolute alcohol, surpass
Sound impregnates 15min, finally uses Ar air-blowings dry, and it is 126 degree to measure Static water contact angles；
2. porous metal electrode pre-processes：By length and width it is respectively 4cm and 5cm, thickness 0.5mm, pure under room temperature
Degree for 99.5%, average pore size 1.5mm, porosity be 2% porous In pieces respectively in acetone and 0.1M H2SO4Middle ultrasound
20min is impregnated, oil removing, oxide film dissolving processing is carried out, then 15min is impregnated with washes of absolute alcohol, ultrasound, finally uses Ar air-blowings
It is dry；
3. the polycarbonate plastic of two panels One-sided coatings organic pressure-sensitive gel is tailored into hollow rectangular shaped rim, outline border ruler
Very little is 6cm*7cm, and the size of hollow space (referred to as inner ring) is 3.4cm*4.4cm (i.e. 14.96cm2), it then respectively will be through
Both it crosses step 1 and 2 treated carbon papers and porous In pieces is placed on the centre position of two frames coating pressure sensitive adhesive sides, make
Edge is equal with the spacing of inner ring respectively.Finally the pressure sensitive adhesive side of two frames is bonded relatively, it is compound to obtain porous electrode
The preload component of body；
4. by porous electrode complex preload component be transferred to maximum pressure be 20MPa two pieces of tablets of tablet tablet press machine it
Between, apply pressure, it is 8MPa to make the pressure on preload component surface, suppresses 5min under normal pressure, obtains porous electrode complex.
5. the ERC performance evaluations of porous electrode complex
In improved H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml
0.1M KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity
Body enters from electrolytic cell lower end, flows through porous electrode and CO occurs2After electrochemical reducting reaction, arranged from the upper end outlet of cathode cavity
Go out.Before test, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow velocity
Control is 60sccm.After 30min, using porous electrode complex as working electrode, Pt pieces are to electrode, and saturated calomel electrode is ginseng
Compare electrode.Electrochemical reducting reaction 30min is carried out under -1.3V operating voltages, reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
In the present embodiment, liquid product HCOOH a concentration of 300ppm, C2H5OH a concentration of 30ppm, CO2Conversion ratio is
14%.
Embodiment 6
1. gas diffusion substrate oil removing pre-processes：It is respectively that 4cm and 5cm, thickness are by length and width under room temperature
0.05mm, porosity be 70% charcoal cloth in acetone ultrasound impregnate 30min after, then with washes of absolute alcohol, ultrasound immersion
15min finally uses Ar air-blowings dry；In 6M HNO360 DEG C of immersion 6h in aqueous solution, deionized water cleaning after Ar air-blowings are dry, measure
Static water contact angles are 80 degree；
2. porous metal electrode pre-processes：By length and width it is respectively 4cm and 5cm, thickness 2.0mm, pure under room temperature
The porous Pb pieces that degree is 99.0%, average pore size 2.0mm, porosity are 1.6% are respectively in acetone and 0.1M H2SO4Middle ultrasound
30min is impregnated, surface degreasing is carried out, oxide film dissolving is gone to handle, then 15min is impregnated with washes of absolute alcohol, ultrasound, finally uses Ar
Air-blowing is dry；
3. the polypropylene plastics of two panels One-sided coatings polyurethane-type pressure sensitive adhesive is tailored into hollow rectangular shaped rim, outline border ruler
Very little is 6cm*7cm, and the size of hollow space (referred to as inner ring) is 3.4cm*4.4cm (i.e. 14.96cm2), it then respectively will be through
Both it crosses step 1 and 2 treated charcoal cloth and porous Pb pieces is placed on the centre position of two frames coating pressure sensitive adhesive sides, make
Edge is equal with the corresponding spacing of frame inner ring respectively.Finally the pressure sensitive adhesive side of two frames is bonded relatively, obtains electrode
The preload component of complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 50MPa two pieces of tablets of tablet tablet press machine it
Between, apply pressure, it is 20MPa to make the pressure on preload component surface, suppresses 30s under normal pressure, obtains porous electrode complex.
5. the ERC performance evaluations of porous electrode complex
In improved H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml
0.1M KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity
Body enters from electrolytic cell lower end, flows through porous electrode and CO occurs2After electrochemical reducting reaction, arranged from the upper end outlet of cathode cavity
Go out.Before test, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow velocity
Control is 60sccm.After 30min, using porous electrode complex as working electrode, Pt pieces are to electrode, and saturated calomel electrode is ginseng
Compare electrode.Electrochemical reducting reaction 30min is carried out under -2.0V operating voltages, reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
In the present embodiment, liquid product HCOOH a concentration of 700ppm, C2H5OH a concentration of 32ppm, CO2Conversion ratio is
15%.
Embodiment 7
1. gas diffusion substrate oil removing pre-processes：Under room temperature, it is by a diameter of 2.8cm, thickness 1.0mm, porosity
90% round charcoal felt in acetone ultrasound impregnate 30min after, then with washes of absolute alcohol, ultrasound immersion 15min, finally use Ar
Air-blowing is dry, and it is 70 degree to measure Static water contact angles；
2. porous metal electrode pre-processes：Under room temperature, by area be a diameter of 2.8cm, thickness is 30 μm, purity is
99.2%, ultrasound impregnates 30min to the rounded porous Bi foils that average pore size is 80 μm, porosity is 0.5% in acetone, carries out table
Face oil removal treatment, then 15min is impregnated with washes of absolute alcohol, ultrasound, finally use Ar air-blowings dry；
3. the polyester plastics of two panels One-sided coatings organic pressure-sensitive gel is tailored into round frame, the outer diameter of frame is
3.8cm, a diameter of 2.4cm of hollow space (referred to as inner ring) then will pass through step 1 and 2 treated charcoal felts and porous
Bi foils are placed on the side centre position of two frame coating pressure sensitive adhesives, make the two edge spacing with corresponding frame inner ring respectively
It is impartial.Finally the binder side of two frames is bonded relatively, obtains the preload component of porous electrode complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 20MPa two pieces of tablets of tablet tablet press machine it
Between, apply pressure, it is 10MPa to make the pressure on preload component surface, suppresses 1min under normal pressure, obtains porous electrode complex.
5. the ERC performance evaluations of porous electrode complex
In improved H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml
0.1M KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity
Body enters from electrolytic cell lower end, flows through porous electrode and CO occurs2After electrochemical reducting reaction, arranged from the upper end outlet of cathode cavity
Go out.Before test, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow velocity
Control is 60sccm.After 30min, using porous electrode complex as working electrode, Pt pieces are to electrode, and saturated calomel electrode is ginseng
Compare electrode.Electrochemical reducting reaction 30min is carried out under -1.3V operating voltages, reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
In the present embodiment, product liquid HCOOH a concentration of 600ppm, CO2Conversion ratio is 20%.
Embodiment 8
1. gas diffusion substrate oil removing pre-processes：It is respectively that 4cm and 5cm, thickness are by length and width under room temperature
0.09mm, porosity be 82% TGP-H-030 carbon papers in acetone ultrasound impregnate 20min after, then with washes of absolute alcohol, surpass
Sound impregnates 15min, finally uses Ar air-blowings dry, in 6M HNO360 DEG C of immersion 4h in aqueous solution, deionized water cleaning, Ar air-blowings are dry
Afterwards, it is 90 degree that measurement Static water contact angles, which are 80 degree of measurement Static water contact angles,；
2. porous metal electrode pre-processes：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 20 μm, it is pure
Degree for 99.9%, average pore size 0.5mm, porosity be 1.3% porous C u foils respectively in acetone and 0.1M H2SO4In surpass
Sound impregnates 30min, carries out oil removing, oxide film dissolving processing, then impregnate 15min with washes of absolute alcohol, ultrasound, finally uses Ar air-blowings
It is dry；
3. the polyimide plastic of two panels One-sided coatings acrylate pressure-sensitive adhesive is tailored into hollow rectangular shaped rim, outline border
Size is 6cm*7cm, and the size of hollow space (referred to as inner ring) is 3.4cm*4.4cm (i.e. 14.96cm2), then respectively will
It is placed on the centre position of two frames coating pressure sensitive adhesive sides by step 1 and 2 treated carbon papers and porous C u pieces, makes two
Person edge is equal with the corresponding spacing of frame inner ring respectively.Finally the pressure sensitive adhesive side of two frames is bonded relatively, is obtained more
The preload component of pore electrod complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 50MPa two pieces of tablets of tablet tablet press machine it
Between, apply pressure, it is 12MPa to make the pressure on preload component surface, suppresses 1min under normal pressure, obtains porous electrode complex.
5. the ERC performance evaluations of porous electrode complex
In improved H-type electrolytic cell, 100ml 0.5M KHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml
0.1M KHCO3Aqueous solution, using the NF115 that DuPont produces as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity
Body enters from electrolytic cell lower end, flows through porous electrode and CO occurs2After electrochemical reducting reaction, arranged from the upper end outlet of cathode cavity
Go out.Before test, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow velocity
Control is 60sccm.After 30min, using porous electrode complex as working electrode, Pt pieces are to electrode, and saturated calomel electrode is ginseng
Compare electrode.Electrochemical reducting reaction 30min is carried out under -2.0V operating voltages, reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
In the present embodiment, in the present embodiment, gaseous product CH4A concentration of 2000ppm, C2H4A concentration of 50ppm, C2H6's
A concentration of 5ppm, HCOOH a concentration of 20ppm, C2H5OH a concentration of 15ppm, CO2Conversion ratio is 25%, is the 2.35 of comparative example 1
Times.
Claims (13)
1. Carbon dioxide electrochemical reduction porous electrode complex, it is characterised in that：Including the gas diffusion base being layered on top of each other
Bottom and porous metal electrode layer further include the cyclic annular frame that two shape and size are identical, hollow；Gas diffusion substrate layer
Edge be adhered to a side surface of a cyclic annular frame by adhesive, and the edge of gas diffusion substrate layer with
There are distances between the edge of cyclic annular frame hollow region；The edge of porous metal electrode layer is adhered to separately by adhesive
One side surface of one cyclic annular frame, and between the edge of porous metal electrode layer and the edge of cyclic annular frame hollow region
There are distances；The edge of two cyclic annular frames is mutually adhered to by adhesive, and gas diffusion substrate layer and porous metals electricity
Pole layer is between two cyclic annular frames with being layered on top of each other, and constitutes porous electrode complex.
2. according to porous electrode complex described in claim 1, it is characterised in that：It is described ring-type frame material be polypropylene,
One kind in polyester, makrolon or polyimides；The adhesive be pressure sensitive adhesive, including acrylic compounds, organic silicon or
One kind in polyurethanes pressure sensitive adhesive；The gas diffusion substrate is used for transmission reaction gas and liquid, porous metal electrode
For being catalyzed Carbon dioxide electrochemical reduction reaction.
3. according to porous electrode complex described in claim 1, it is characterised in that：The gas diffusion substrate is nonmetallic
Material is the good conductor of electricity, including the nonwoven of braiding or non-woven charcoal base carbon paper or charcoal cloth, charcoal felt or dual coating Carbon Materials
Cloth.
4. according to the porous electrode complex of claim 1 or 3, it is characterised in that：The gas diffusion substrate, hole
Rate is 50% ~ 95%；The gas diffusion substrate, thickness are 0.08mm ~ 3.0mm；To ensure that it is good that gas diffusion substrate has
Good gas transmission property, ranging from 60 ~ 130 degree of the Static water contact angles of the gas diffusion substrate.
5. according to porous electrode complex described in claim 4, it is characterised in that：The gas diffusion substrate, porosity are
70%~90%；The gas diffusion substrate, thickness are 0.1mm ~ 1.5mm.
6. according to porous electrode complex described in claim 1, it is characterised in that：The porous metal electrode is sheet metal
Shape material, including piece or foil；Thickness is 5 μm ~ 2.0mm；The porous metal electrode, porosity are 0.1% ~ 5%;Described
Porous metal electrode, average pore size scope are 50 μm ~ 2mm；Porous metal electrode layer is equipped with collection ear, collects ear from two ring-types
The outer edge of frame stretches out.
7. according to porous electrode complex described in claim 6, it is characterised in that：The porous metal electrode thickness is
0.01mm~1.0mm；The porous metal electrode porosity is 0.5% ~ 2%;The porous metal electrode aperture is 100 μ
m ~500µm。
8. according to porous electrode complex described in claim 6, it is characterised in that：The porous metal electrode, for being catalyzed
The effective metal content of ERC reactions is not less than 99.0%；Effective metal in the porous metal electrode, including following metals
In one or two or more kinds, i.e. Cu, Ag, Au in metallic element In, Tl, Sn, Pb, Sb, Bi, IB in IIIA ~ VA, with
And Pd, Pt, Ru, Rh, Ir in VIIIB.
9. a kind of preparation method of any porous electrode complexs of claim 1-8, it is characterised in that：Preparation process packet
Include following steps： 1）Gas diffusion substrate is subjected to oil removing pretreatment；2）Porous metal electrode is subjected to oil removing, removal impurity
Pretreatment；3）Gas diffusion substrate and porous metal electrode are adhered to the two panels ring-shaped plastics of side application of adhesive respectively
On frame, the side that two panels frame is coated with to adhesive is opposite, keeps the two edge impartial with the spacing of corresponding frame inner ring respectively,
It is finally that the adhesive side of two frames is opposite, constitute porous electrode complex preload component；
4）Porous electrode complex preload component is placed in tablet tablet press machine, porous electricity is obtained under room temperature, pressurized conditions
Pole complex.
10. according to the preparation method of porous electrode complex described in claim 9, it is characterised in that：The pressurized equipment is flat
Plate tablet press machine, flatness requirement ± 20 μm.
11. according to the preparation method of porous electrode complex described in claim 9, it is characterised in that：To the pressure of combination electrode
For 1MPa ~ 10MPa；Pressing time is 30s ~ 5min.
12. according to the preparation method of porous electrode complex described in claim 9, it is characterised in that：To the pressure of combination electrode
For 5MPa ~ 20MPa；Pressing time is 1min ~ 3min.
13. a kind of application of any porous electrode complexs of claim 1-8 in Carbon dioxide electrochemical reduction.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931168A (en) * | 1986-03-07 | 1990-06-05 | Masahiro Watanabe | Gas permeable electrode |
| CN101931081A (en) * | 2010-08-27 | 2010-12-29 | 西安交通大学 | Preparation method of air diffusion electrode for preparing methanol by electrochemically reducing carbon dioxide |
| CN103741164A (en) * | 2014-01-03 | 2014-04-23 | 南开大学 | Preparation method of gas diffusion electrode for producing formic acid by electrochemical reduction of CO2 |
| CN104428449A (en) * | 2012-03-03 | 2015-03-18 | 威思洛伊化工有限公司 | Electrolytic cell including a three-phase interface to react carbon-based gases in an aqueous electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0557131A (en) * | 1991-09-02 | 1993-03-09 | Hitachi Ltd | Carbon dioxide reducing electrode and carbon dioxide converting device |
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|---|---|---|---|---|
| US4931168A (en) * | 1986-03-07 | 1990-06-05 | Masahiro Watanabe | Gas permeable electrode |
| CN101931081A (en) * | 2010-08-27 | 2010-12-29 | 西安交通大学 | Preparation method of air diffusion electrode for preparing methanol by electrochemically reducing carbon dioxide |
| CN104428449A (en) * | 2012-03-03 | 2015-03-18 | 威思洛伊化工有限公司 | Electrolytic cell including a three-phase interface to react carbon-based gases in an aqueous electrolyte |
| CN103741164A (en) * | 2014-01-03 | 2014-04-23 | 南开大学 | Preparation method of gas diffusion electrode for producing formic acid by electrochemical reduction of CO2 |
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