CN106521544A - Porous electrode complex for carbon dioxide electrochemical reduction as well as preparation and application thereof - Google Patents
Porous electrode complex for carbon dioxide electrochemical reduction as well as preparation and application thereof Download PDFInfo
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- CN106521544A CN106521544A CN201510589121.9A CN201510589121A CN106521544A CN 106521544 A CN106521544 A CN 106521544A CN 201510589121 A CN201510589121 A CN 201510589121A CN 106521544 A CN106521544 A CN 106521544A
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Abstract
The invention provides a porous electrode complex structure for carbon dioxide electrochemical reduction and a preparing method thereof. The porous electrode complex structure comprises a gas diffusion base layer and a porous metal electrode layer which are laminated with each other and further comprises two hollow annular edge frames with the same shape and size, wherein the circumferential edges of the two annular edge frames are glued through an adhesive, and the gas diffusion base layer and the porous metal electrode layer are located between the two annular edge frames in the mutually laminated manner, forming a porous electrode complex. The porous electrode complex not only can utilize a porous gas diffusion base to rapidly transmit gas towards an electrode catalysis station and discharge liquid, but also can utilize metal electrode longitudinal holes to increase the area of an electrode reaction interface, so that the carbon dioxide electrochemical reduction rate is increased. The porous electrode complex structure is particularly suitable for a carbon dioxide electrochemical reactor in which reacting gas vertically flows across the electrode reaction interface.
Description
Technical field
The invention belongs to Carbon dioxide electrochemical reduction technical field, more particularly to a kind of porous electrode complex and its
Technology of preparing.
Background technology
Electrochemical reduction CO2(ERC) technology is by CO using electric energy2Various organic chemicals are reduced to, CO is realized2
A kind of technology of recycling.With other CO2Transformation technology is compared, and the outstanding advantage of ERC technologies is can profit
With water as the hydrogen source of reaction, CO is capable of achieving at normal temperatures and pressures2Efficient Conversion, therefore need not chemistry turn
The energy expenditure caused by hydrogen manufacturing and heating, pressurization needed for change technology, equipment investment are few.
At present, the principal element for restricting the development of ERC technologies includes：(1) react overpotential high；(2) conversion ratio is low；
(3) selectivity of product is poor.Wherein, in the ERC reaction systems using aqueous solution as supporting electrolyte, generally make
With flat board (such as lamellar, foil-like and bulk) metal come catalysis electrode course of reaction.One of this kind of metal electrode dashes forward
It is that electrode reaction area is little to go out defect, concentrates merely on the surface contacted with supporting electrolyte, anti-so as to constitute ERC
Answer overpotential high and CO2The low major reason of conversion ratio；Additionally, intermediate product is to electrode in ERC courses of reaction
Cover and poisoning effect, electrode effective affecting acreage is quickly reduced, electrode can be lost activity quickly.
For expand ERC reaction used in electrode area, research worker by construct special appearance electrode surface,
Increase active crystal grain boundary significantly to expand electrochemical reaction area.Xie etc. in document Electrochimica Acta,
2014,139:Report in 137-144, Cu paper tinsels are carried out into line pulse anodic oxidation and obtains CuO nanofibers, then
Its electrochemical reduction is obtained into three-dimensional flower-shaped Cu nanofibers.This Cu nano flowers can will be the reaction of ERC excessively electric
The low 400mV of potential drop, by H2Faradic efficiency be down to less than 25%, up to the electrolysis time of more than 9 hours
Interior, Cu nano flowers are still kept to CO2The high catalytic activity of reduction.
Gas-diffusion electrode (GDE) is a kind of conductive composite material built based on porous material, and which is most obvious
Be characterized in that with abundant hole, be particularly suitable for build three-phase reaction interface, expand response area, fuel cell,
Energy-storage battery field is widely used, and research worker was also once introduced into Carbon dioxide electrochemical reduction field.
Such as Hara etc. in document J.Electrochem.Soc., 1995,142 (4):In L57-L59 report, using Pt nano particle as
Active component prepares GDE, in CO2Pressure<Under the conditions of 50atm, Pt-GDE reduction CO2Electric current density reach
900mA cm-2, current efficiency is 46%.But, the catalyst used during GDE is built is generally spherical
Metal nanoparticle, and many non-noble metal nano particles property stable in the air is not good, surface easily aoxidizes (such as
Red nano Cu is oxidized to black CuO), the catalytic effect of catalyst is seriously reduced, while also changing product
Distribution.For maintaining the high catalytic activity of metal nanoparticle, it usually needs the GDE to preparing carries out activation processing,
Process is loaded down with trivial details, and wayward.
The content of the invention
For solving above-mentioned technical problem, the invention provides a kind of Carbon dioxide electrochemical reduction is compound with porous electrode
Body structure and preparation method thereof, the porous electrode complex combine gas-diffusion electrode significantly expand response area and
The double dominant of flat metal electrode efficient catalytic Carbon dioxide electrochemical reduction reaction, is particularly well-suited to reacting gas
Vertically flow through in the Carbon dioxide electrochemical reduction reactor of electrode surface.
A kind of Carbon dioxide electrochemical reduction porous electrode complex, including the gas diffusion substrate layer being layered on top of each other
With porous metal electrode layer, also including two shape and size identicals, hollow ring-type frame；Gas diffusion base
The edge of bottom adheres to a side surface of a ring-type frame by binding agent, and gas diffusion substrate layer
Distance is left between the edge of edge and ring-type frame hollow region；The edge of porous metal electrode layer leads to
Cross the side surface that binding agent adheres to another ring-type frame, and edge and the ring-type of porous metal electrode layer
Distance is left between the edge of frame hollow region；The edge of two ring-type frames is mutually adhered to by binding agent,
And gas diffusion substrate layer and porous metal electrode layer are between two ring-type frames with being layered on top of each other, and constitute porous
Electrode complex.
The material of the ring-type frame is the one kind in polypropylene, polyester, Merlon or polyimides；Described
Binding agent is pressure sensitive adhesive, including the one kind in acrylic compounds, silicone or polyurethaness pressure sensitive adhesive；
Described gas diffusion substrate is used for transmitting reacting gas and liquid, and porous metal electrode is used for being catalyzed titanium dioxide
Carbon electrochemical reducting reaction.
Described gas diffusion substrate, is nonmetallic materials, is the good conductor of electricity, including braiding or non-woven charcoal
The non-woven fabrics of base carbon paper or charcoal cloth, charcoal felt or dual coating Carbon Materials.
Described gas diffusion substrate, porosity are 50%～95%, and optimal porosity is 70%～90%；
Described gas diffusion substrate, its thickness are 0.08mm～3.0mm, and optimum thickness is 0.1mm～1.5mm；
For guaranteeing that gas diffusion substrate has a good gas transmission property, the Static water contact of described gas diffusion substrate
Angle range is 60～130 degree.
Described porous metal electrode, is metal plate material, including piece or paper tinsel；Thickness is 5 μm～2.0mm, most
Good thickness is 0.01mm～1.0mm；
Described porous metal electrode, porosity are 0.1%～5%, and optimal porosity is 0.5%～2%.
Described porous metal electrode, average pore size scope are 50 μm～2mm, and optimum aperture is 100 μm
～500 μm；
Porous metal electrode layer is provided with collection ear, and collection ear is stretched out from the outward flange of two ring-type frames.
Described porous metal electrode, the effective metal content for being catalyzed ERC reactions are not less than 99.0%；
Effective metal in described porous metal electrode, including one or two or more kinds in following metals, i.e.,
Metallic element In, Tl, Sn in IIIA～VA, Pb, Sb, Bi, Cu, Ag, the Au in IB, and VIIIB
In Pd, Pt, Ru, Rh, Ir.
Preparation process is comprised the following steps：
1) gas diffusion substrate is carried out into oil removing pretreatment；2) porous metal electrode is carried out oil removing, goes the removal of impurity
Pretreatment；3) gas diffusion substrate and porous metal electrode are adhered to the two rings of side application of adhesive respectively
On shape plastic frame, the side that two panels frame is scribbled binding agent is relative, make the two edge respectively with corresponding edge inframe
The spacing of ring is impartial, finally that the binding agent side of two frames is relative, constitutes porous electrode complex preload component；
4) porous electrode complex preload component is placed in flat board tablet machine, porous is obtained under room temperature, pressurized conditions
Electrode complex.
The pressurized equipment be flat board tablet machine, flatness requirement ± 20 μm.
It is 1MPa～10MPa to the pressure of combination electrode, optimum pressure is 5MPa～20MPa；Pressing time is
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) it is porous metal electrode is compound with gas diffusion substrate, can either be using porous gas diffusion substrates to electricity
Pole catalytic sites quickly transmit the function of gas and drain, and can be anti-to expand electrode using metal electrode longitudinal hole
Interfacial area is answered, so as to improve carbon dioxide electrochemical reaction speed, reacting gas is particularly well-suited to and is vertically flowed through electricity
The carbon dioxide electrochemical reactor of pole reaction interface.Compared with plate electrode, the porous effect of porous electrode complex
Gas transport path and transmission means should be changed, the reactant holdup time in the electrodes is increased, thus to suppression
The generation of liberation of hydrogen side reaction processed and raising reaction efficiency have facilitation, with raising CO2Conversion ratio it is potential excellent
Gesture.
2) as electrochemically reducing carbon dioxide is the compound of interfacial reaction, porous metal electrode and gas diffusion substrate
Body, it is possible to reduce the consumption of metal electrode, reduces the electrode material cost of carbon dioxide electrochemical reaction；Additionally,
For foil-like electrode, as its rigidity is poor, gas diffusion substrate can strengthen complex as its supporter
Mechanical strength, such that it is able to make broad-area electrode, improves ERC response speeds.
Description of the drawings
Fig. 1 porous electrode complex structure schematic diagrams.
The ring-shaped plastics frame of 1 side coated with adhesive
2 gas diffusion substrates
3 porous metal electrodes.
Specific embodiment
With reference to preferred embodiment, technical scheme is described further, but in the technology of the present invention
Appearance is not limited only to described scope.
Comparative example 1
1. metal electrode pretreatment：Under room temperature, it is 20 μm, purity that length and width is respectively 4cm and 5cm, thickness
For 99.9% Cu paper tinsels respectively in acetone and 0.1M H2SO4Middle ultrasound immersion 30min, carries out oil removing, at oxide film dissolving
Reason, then with washes of absolute alcohol, ultrasound immersion 15min, it is finally dry with Ar air-blowings；
3. the polycarbonate plastic of two panels One-sided coatings acrylate pressure sensitive adhesive is tailored into into hollow rectangular shaped rim, housing size
For 6cm*7cm, the size of hollow space (referred to as internal ring) is 3.4cm*4.4cm (i.e. 14.96cm2), then
Cu paper tinsels after step 1 is processed are placed on into the side centre position that two frames coat pressure sensitive adhesive, Cu paper tinsels side is made
Edge is impartial with the spacing of corresponding edge inframe ring.Finally pre-bonded is carried out by the pressure sensitive adhesive side of two frames relative, obtain
To Cu foil electrode preload components；
4. Cu foil electrode preload components are transferred between two pieces of flat boards of flat board tablet machine that maximum pressure is 50MPa, are applied
Pressure, the pressure for making preload component surface is 12MPa, suppresses 1min at ambient pressure, obtains Cu foil electrodes.
5. ERC performance evaluations of metal electrode
In H type electrolyzers, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and 50ml 0.1
M KHCO3Aqueous solution, using the NF115 of DuPont production as cathode cavity and the barrier film of anode cavities.Survey
Before examination, high-purity N is passed through in cathode cavity first21h, then passes to the CO that purity is 99.995%2Gas, CO2
Flow speed control be 60sccm.After 30min, using Cu foil electrodes as working electrode, Pt pieces are, to electrode, to satisfy
It is reference electrode with calomel electrode.Electrochemical reducting reaction 30min, reaction end gas are carried out under -2.0V running voltages
Being passed through gas chromatogram carries out the detection by quantitative of gaseous product, and product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, in the present embodiment, gaseous product CH4Concentration be 850ppm, C2H4Concentration is 24ppm,
HCOOH concentration is 25ppm, CO2Conversion ratio is 8%.
Comparative example 2
1. metal electrode pretreatment：Under room temperature, it is 0.2mm, the circle that purity is 99.5% by a diameter of 2.0cm, thickness
Pd pieces are respectively in acetone and 0.1M H2SO4Middle ultrasound immersion 30min, carries out oil removing, oxide film dissolving process, then uses
Washes of absolute alcohol, ultrasound immersion 15min, it is finally dry with Ar air-blowings；
3. the polyester plasticses of two panels One-sided coatings organic pressure-sensitive gel are tailored into into hollow circular frame, the external diameter of frame is
Then Pd pieces after step 1 is processed are put by 3.0cm, a diameter of 1.6cm of hollow space (referred to as internal ring)
The side centre position for coating pressure sensitive adhesive in two frames is put, makes Pd pieces edge impartial with the spacing of frame internal ring.Most
Bond the binding agent side of two frames relative afterwards, obtain Pd plate electrode preload components；
4. Pd plate electrode preload components are transferred between two pieces of flat boards of flat board tablet machine that maximum pressure is 10MPa, are applied
Pressure, the pressure for making preload component surface is 2MPa, suppresses 30s at ambient pressure, obtains Pd plate electrodes.
5. ERC performance evaluations of metal electrode
In H type electrolyzers, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and 50ml 0.1
M KHCO3Aqueous solution, using DuPont produce NF115 as anode and cathode chamber barrier film.Before test,
High-purity N is passed through in cathode cavity first21h, then passes to the CO that purity is 99.995%2Gas, CO2Flow velocity
It is controlled to 60sccm.After 30min, with Pd plate electrodes as working electrode, Pt pieces are made to electrode, saturation calomel electricity
Extremely reference electrode.Electrochemical reducting reaction 30min is carried out under -1.5V running voltages, and reaction end gas are passed through gas phase
Chromatograph carries out the detection by quantitative of gaseous product, and product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, in the present embodiment, the concentration of gaseous product CO is 365ppm, and HCOOH concentration is 50ppm,
CO2Conversion ratio is 6%.
Embodiment 1
1. gas diffusion substrate oil removing pretreatment：Under room temperature, length and width is respectively 4cm and 5cm, thickness is
0.2mm, porosity are 78% TGP-H-060 carbon papers in acetone after ultrasound immersion 20min, then use anhydrous second
Alcohol cleaning, ultrasound immersion 15min, it is finally dry with Ar air-blowings, in 6M HNO350 DEG C of immersion 3h in aqueous solution,
Deionized water is cleaned, and after Ar air-blowings are dry, it is 100 degree to determine Static water contact angles；
2. porous metal electrode pretreatment：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 0.1mm,
Purity is 99.5%, average pore size is 0.5mm, porosity is 1% porous C u piece is respectively in acetone and 0.5M
H2SO4Middle ultrasound immersion 20min, carries out oil removing, oxide film dissolving process, then is soaked with washes of absolute alcohol, ultrasound
15min, it is finally dry with Ar air-blowings；
3. the polycarbonate plastic of two panels One-sided coatings acrylate pressure sensitive adhesive is tailored into into hollow rectangular shaped rim, housing size
For 6cm*7cm, the size of hollow space (referred to as internal ring) is 3.4cm*4.4cm (i.e. 14.96cm2), then
The carbon paper and porous C u piece after step 1 and 2 are processed is placed on into two frame coating pressure sensitive adhesive sides respectively
Centre position, makes the two edge impartial with the spacing of corresponding edge inframe ring respectively.Finally by the pressure sensitive adhesive of two frames
Side is relative to bond, and 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 flat boards of flat board tablet machine it
Between, applying pressure, the pressure for making preload component surface is 10MPa, suppresses 2min at ambient pressure, obtains porous electricity
Pole complex.
5. ERC performance evaluations of porous electrode complex
In improved H types electrolyzer, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and
50ml 0.1M KHCO3Aqueous solution, using DuPont produce NF115 as anode and cathode chamber barrier film.
Wherein, the gas of cathode cavity is entered from electrolyzer lower end, flows through porous electrode and CO occurs2Electrochemical reducting reaction
Afterwards, discharge from the upper end outlet of cathode cavity.Before test, high-purity N is passed through in cathode cavity first21h, Ran Houtong
Enter the CO that purity is 99.995%2Gas, CO2Flow speed control be 60sccm.After 30min, with porous electrode
Complex is working electrode, and Pt pieces are that, to electrode, saturated calomel electrode is reference electrode.In -2.0V running voltages
Under carry out electrochemical reducting reaction 30min, reaction end gas are passed through gas chromatogram and carry out the detection by quantitative of gaseous product,
Product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, gaseous product CH4Concentration be 1680ppm, C2H4Concentration is 20ppm, C2H6's
Concentration is 2ppm, and HCOOH concentration is 100ppm, C2H5OH concentration is 15ppm, CO2Conversion ratio is 15%,
It is 1.875 times of comparative example 1.
Embodiment 2
1. gas diffusion substrate oil removing pretreatment：Under room temperature, length and width is respectively 4cm and 5cm, thickness is
2.0mm, porosity are 80% charcoal cloth in acetone after ultrasound immersion 30min, then with washes of absolute alcohol, super
Sound soaks 15min, finally dry with Ar air-blowings；In 6M HNO350 DEG C of immersion 1h in aqueous solution, deionized water are clear
Wash, after Ar air-blowings are dry, it is 130 degree to determine Static water contact angles；
2. porous metal electrode pretreatment：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 50 μm,
Purity is 99.0%, average pore size is 50 μm, porosity is 0.5% porous Ag paper tinsel respectively in acetone and 0.5M
H2SO4Middle ultrasound immersion 30min, carries out surface degreasing, goes oxide film dissolving to process, then with washes of absolute alcohol, super
Sound soaks 15min, finally dry with Ar air-blowings；
3. the polypropylene plastics of two panels One-sided coatings polyurethaness pressure sensitive adhesive are tailored into into hollow rectangular shaped rim, housing size
For 6cm*7cm, the size of hollow space (referred to as internal ring) is 3.4cm*4.4cm (i.e. 14.96cm2), then
The charcoal cloth and porous Ag paper tinsel after step 1 and 2 are processed is placed on into two frame coating pressure sensitive adhesive sides respectively
Centre position, makes the two edge equal with the spacing of corresponding edge inframe ring respectively.Finally by the pressure sensitive adhesive of two frames
Side is relative to bond, and obtains the preload component of porous electrode complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 50MPa two pieces of flat boards of flat board tablet machine it
Between, applying pressure, the pressure for making preload component surface is 30MPa, suppresses 3min at ambient pressure, obtains porous electricity
Pole complex.
5. ERC performance evaluations of porous electrode complex
In improved H types electrolyzer, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and
50ml 0.1M KHCO3Aqueous solution, using DuPont produce NF115 as anode and cathode chamber barrier film.
Wherein, the gas of cathode cavity is entered from electrolyzer lower end, flows through porous electrode and CO occurs2Electrochemical reducting reaction
Afterwards, discharge from the upper end outlet of cathode cavity.Before test, high-purity N is passed through in cathode cavity first21h, Ran Houtong
Enter the CO that purity is 99.995%2Gas, CO2Flow speed control be 60sccm.After 30min, with porous electrode
Complex is working electrode, and Pt pieces are that, to electrode, saturated calomel electrode is reference electrode.In -2.0V running voltages
Under carry out electrochemical reducting reaction 30min, reaction end gas are passed through gas chromatogram and carry out the detection by quantitative of gaseous product,
Product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, the concentration of gaseous product CO is 5500ppm, and HCOOH concentration is 100ppm,
C2H5OH concentration is 200ppm, CO2Conversion ratio is 30%.
Embodiment 3
1. gas diffusion substrate oil removing pretreatment：Under room temperature, it is that 3.0mm, porosity are by a diameter of 2.0cm, thickness
95% circular charcoal felt in acetone ultrasound immersion 30min after, then with washes of absolute alcohol, ultrasound immersion 15min,
Finally dry with Ar air-blowings, it is 130 degree to determine Static water contact angles；
2. porous metal electrode pretreatment：Under room temperature, by a diameter of 2.0cm, thickness be 0.2mm, purity be 99.5%,
Ultrasound soaks 30min to the rounded porous Pd pieces that average pore size is 1.0mm, porosity is 0.1% in acetone, carries out table
Face oil removal treatment, then with washes of absolute alcohol, ultrasound immersion 15min, it is finally dry with Ar air-blowings；
3. the polyimides of two panels One-sided coatings acrylate pressure-sensitive adhesive are tailored into into circular frame, the external diameter of frame is
3.0cm, a diameter of 1.6cm of hollow space (referred to as internal ring), then by the charcoal after step 1 and 2 are processed
Felt and porous Pd piece are individually positioned in the centre position of two frames coating pressure sensitive adhesive sides, make the two edge with it is corresponding
The spacing of frame internal ring is impartial.Finally bond the binding agent side of two frames relative, obtain porous electrode and be combined
The preload component of body；
4. by porous electrode complex preload component be transferred to maximum pressure be 10MPa two pieces of flat boards of flat board tablet machine it
Between, applying pressure, the pressure for making preload component surface is 2MPa, suppresses 30s at ambient pressure, obtains porous electrode
Complex.
5. ERC performance evaluations of porous electrode complex
In improved H types electrolyzer, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and
50ml 0.1M KHCO3Aqueous solution, using DuPont produce NF115 as anode and cathode chamber barrier film.
Wherein, the gas of cathode cavity is entered from electrolyzer lower end, flows through porous electrode and CO occurs2Electrochemical reducting reaction
Afterwards, discharge from the upper end outlet of cathode cavity.Before test, high-purity N is passed through in cathode cavity first21h, Ran Houtong
Enter the CO that purity is 99.995%2Gas, CO2Flow speed control be 60sccm.After 30min, with porous electrode
Complex is working electrode, and Pt pieces are that, to electrode, saturated calomel electrode is reference electrode.In -1.5V running voltages
Under carry out electrochemical reducting reaction 30min, reaction end gas are passed through gas chromatogram and carry out the detection by quantitative of gaseous product,
Product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, the concentration of gaseous product CO is 800ppm, and HCOOH concentration is 20ppm, CO2Conversion
Rate is 14%, is 2.33 times of comparative example 2.
Embodiment 4
1. gas diffusion substrate oil removing pretreatment：Under room temperature, length and width is respectively 4cm and 5cm, thickness is
0.15mm, porosity be 80% non-woven fabrics in acetone ultrasound immersion 30min after, then with washes of absolute alcohol,
Ultrasound immersion 15min, it is finally dry with Ar air-blowings；
2. gas diffusion substrate coats Carbon Materials：Using Cabot companies production Vulcan XC-72 charcoals as conductive material,
PVDF makees binding agent, and it is 9 to control the two ratio:1, charcoal slurry is prepared as dispersant with dehydrated alcohol.At normal temperatures,
The mixed slurry of charcoal and PVDF is coated uniformly on into the two sides of non-woven fabrics, is dried in 160 DEG C of baking ovens, determine static
Contact angle is 90 degree, and porosity is 65%.
3. porous metal electrode pretreatment：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 10 μm,
Purity is the porous Sn paper tinsel ultrasound immersion in acetone that 99.9%, average pore size is 100 μm, porosity is 0.3%
30min, carries out surface degreasing process, then with washes of absolute alcohol, ultrasound immersion 15min, it is finally dry with Ar air-blowings；
3. the polyimides of two panels One-sided coatings polyacrylate binder are tailored into into hollow rectangular shaped rim, housing size
For 6cm*7cm, the size of hollow space (referred to as internal ring) is 3.4cm*4.4cm (i.e. 14.96cm2), then
The nonwoven fabric base bottom after step 1 and 2 are processed and porous Sn paper tinsel are placed on into two frame coating pressure sensitive adhesives respectively
The centre position of side, makes the two edge equal with the spacing of corresponding edge inframe ring respectively.Finally by two frames
Pressure sensitive adhesive side is relative to bond, and obtains the preload component of porous electrode complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 30MPa two pieces of flat boards of flat board tablet machine it
Between, applying pressure, the pressure for making preload component surface is 15MPa, suppresses 2min at ambient pressure, obtains porous electricity
Pole complex.
5. ERC performance evaluations of porous electrode complex
In improved H types electrolyzer, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and
50ml 0.1M KHCO3Aqueous solution, using DuPont produce NF115 as anode and cathode chamber barrier film.
Wherein, the gas of cathode cavity is entered from electrolyzer lower end, flows through porous electrode and CO occurs2Electrochemical reducting reaction
Afterwards, discharge from the upper end outlet of cathode cavity.Before test, high-purity N is passed through in cathode cavity first21h, Ran Houtong
Enter the CO that purity is 99.995%2Gas, CO2Flow speed control be 60sccm.After 30min, with porous electrode
Complex is working electrode, and Pt pieces are that, to electrode, saturated calomel electrode is reference electrode.In -1.5V running voltages
Under carry out electrochemical reducting reaction 30min, reaction end gas are passed through gas chromatogram and carry out the detection by quantitative of gaseous product,
Product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, without CO2The gaseous product of reduction reaction, product liquid HCOOH concentration are 500ppm,
CO2Conversion ratio is 18%.
Embodiment 5
1. gas diffusion substrate oil removing pretreatment：Under room temperature, length and width is respectively 4cm and 5cm, thickness is
0.09mm, porosity are 82% TGP-H-030 carbon papers in acetone after ultrasound immersion 20min, then with anhydrous
Ethanol purge, ultrasound immersion 15min, finally dry with Ar air-blowings, it is 126 degree to determine Static water contact angles；
2. porous metal electrode pretreatment：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 0.5mm,
Purity is 99.5%, average pore size is 1.5mm, porosity is 2% porous In piece is respectively in acetone and 0.1M
H2SO4Middle ultrasound immersion 20min, carries out oil removing, oxide film dissolving process, then is soaked with washes of absolute alcohol, ultrasound
15min, it is finally dry with Ar air-blowings；
3. the polycarbonate plastic of two panels One-sided coatings organic pressure-sensitive gel is tailored into into hollow rectangular shaped rim, housing size
For 6cm*7cm, the size of hollow space (referred to as internal ring) is 3.4cm*4.4cm (i.e. 14.96cm2), then
Respectively the carbon paper and porous In piece after step 1 and 2 are processed is placed in two frame coating pressure sensitive adhesive sides
Between position, make the two edge equal with the spacing of internal ring respectively.Finally the pressure sensitive adhesive side of two frames is glued relatively
Knot, 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 flat boards of flat board tablet machine it
Between, applying pressure, the pressure for making preload component surface is 8MPa, suppresses 5min at ambient pressure, obtains porous electrode
Complex.
5. ERC performance evaluations of porous electrode complex
In improved H types electrolyzer, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and
50ml 0.1M KHCO3Aqueous solution, using DuPont produce NF115 as anode and cathode chamber barrier film.
Wherein, the gas of cathode cavity is entered from electrolyzer lower end, flows through porous electrode and CO occurs2Electrochemical reducting reaction
Afterwards, discharge from the upper end outlet of cathode cavity.Before test, high-purity N is passed through in cathode cavity first21h, Ran Houtong
Enter the CO that purity is 99.995%2Gas, CO2Flow speed control be 60sccm.After 30min, with porous electrode
Complex is working electrode, and Pt pieces are that, to electrode, saturated calomel electrode is reference electrode.In -1.3V running voltages
Under carry out electrochemical reducting reaction 30min, reaction end gas are passed through gas chromatogram and carry out the detection by quantitative of gaseous product,
Product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, liquid product HCOOH concentration is 300ppm, C2H5OH concentration is 30ppm, CO2Conversion ratio
For 14%.
Embodiment 6
1. gas diffusion substrate oil removing pretreatment：Under room temperature, length and width is respectively 4cm and 5cm, thickness is
0.05mm, porosity are 70% charcoal cloth in acetone after ultrasound immersion 30min, then with washes of absolute alcohol, super
Sound soaks 15min, finally dry with Ar air-blowings；In 6M HNO360 DEG C of immersion 6h in aqueous solution, deionized water are clear
Wash, after Ar air-blowings are dry, it is 80 degree to determine Static water contact angles；
2. porous metal electrode pretreatment：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 2.0mm,
It is 2.0mm, porous Pb piece that porosity is 1.6% respectively in acetone and 0.1M that purity is 99.0%, average pore size
H2SO4Middle ultrasound immersion 30min, carries out surface degreasing, goes oxide film dissolving to process, then with washes of absolute alcohol, super
Sound soaks 15min, finally dry with Ar air-blowings；
3. the polypropylene plastics of two panels One-sided coatings polyurethane-type pressure sensitive adhesive are tailored into into hollow rectangular shaped rim, housing size
For 6cm*7cm, the size of hollow space (referred to as internal ring) is 3.4cm*4.4cm (i.e. 14.96cm2), then
The charcoal cloth and porous Pb piece after step 1 and 2 are processed is placed on into two frame coating pressure sensitive adhesive sides respectively
Centre position, makes the two edge equal with the spacing of corresponding edge inframe ring respectively.Finally by the pressure sensitive adhesive of two frames
Side is relative to bond, and obtains the preload component of electrode complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 50MPa two pieces of flat boards of flat board tablet machine it
Between, applying pressure, the pressure for making preload component surface is 20MPa, suppresses 30s at ambient pressure, obtains porous electrode
Complex.
5. ERC performance evaluations of porous electrode complex
In improved H types electrolyzer, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and
50ml 0.1M KHCO3Aqueous solution, using DuPont produce NF115 as anode and cathode chamber barrier film.
Wherein, the gas of cathode cavity is entered from electrolyzer lower end, flows through porous electrode and CO occurs2Electrochemical reducting reaction
Afterwards, discharge from the upper end outlet of cathode cavity.Before test, high-purity N is passed through in cathode cavity first21h, Ran Houtong
Enter the CO that purity is 99.995%2Gas, CO2Flow speed control be 60sccm.After 30min, with porous electrode
Complex is working electrode, and Pt pieces are that, to electrode, saturated calomel electrode is reference electrode.In -2.0V running voltages
Under carry out electrochemical reducting reaction 30min, reaction end gas are passed through gas chromatogram and carry out the detection by quantitative of gaseous product,
Product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, liquid product HCOOH concentration is 700ppm, C2H5OH concentration is 32ppm, CO2
Conversion ratio is 15%.
Embodiment 7
1. gas diffusion substrate oil removing pretreatment：Under room temperature, it is that 1.0mm, porosity are by a diameter of 2.8cm, thickness
90% circular charcoal felt in acetone ultrasound immersion 30min after, then with washes of absolute alcohol, ultrasound immersion 15min,
Finally dry with Ar air-blowings, it is 70 degree to determine Static water contact angles；
2. porous metal electrode pretreatment：Under room temperature, by area be a diameter of 2.8cm, thickness be 30 μm, purity be
99.2%th, ultrasound soaks 30min to the rounded porous Bi paper tinsels that average pore size is 80 μm, porosity is 0.5% in acetone,
Surface degreasing process is carried out, then with washes of absolute alcohol, ultrasound immersion 15min, it is finally dry with Ar air-blowings；
3. the polyester plasticses of two panels One-sided coatings organic pressure-sensitive gel are tailored into into circular frame, the external diameter of frame is 3.8cm,
A diameter of 2.4cm of hollow space (referred to as internal ring), then by the charcoal felt after step 1 and 2 are processed and porous
Bi paper tinsels are placed on the side centre position that two frames coat pressure sensitive adhesives, make the two edge respectively with corresponding edge inframe ring
Spacing it is impartial.Finally bond the binding agent side of two frames relative, obtain the precompressed of porous electrode complex
Component；
4. by porous electrode complex preload component be transferred to maximum pressure be 20MPa two pieces of flat boards of flat board tablet machine it
Between, applying pressure, the pressure for making preload component surface is 10MPa, suppresses 1min at ambient pressure, obtains porous electricity
Pole complex.
5. ERC performance evaluations of porous electrode complex
In improved H types electrolyzer, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and
50ml 0.1M KHCO3Aqueous solution, using DuPont produce NF115 as anode and cathode chamber barrier film.
Wherein, the gas of cathode cavity is entered from electrolyzer lower end, flows through porous electrode and CO occurs2Electrochemical reducting reaction
Afterwards, discharge from the upper end outlet of cathode cavity.Before test, high-purity N is passed through in cathode cavity first21h, Ran Houtong
Enter the CO that purity is 99.995%2Gas, CO2Flow speed control be 60sccm.After 30min, with porous electrode
Complex is working electrode, and Pt pieces are that, to electrode, saturated calomel electrode is reference electrode.In -1.3V running voltages
Under carry out electrochemical reducting reaction 30min, reaction end gas are passed through gas chromatogram and carry out the detection by quantitative of gaseous product,
Product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, product liquid HCOOH concentration is 600ppm, CO2Conversion ratio is 20%.
Embodiment 8
1. gas diffusion substrate oil removing pretreatment：Under room temperature, length and width is respectively 4cm and 5cm, thickness is
0.09mm, porosity are 82% TGP-H-030 carbon papers in acetone after ultrasound immersion 20min, then with anhydrous
Ethanol purge, ultrasound immersion 15min, it is finally dry with Ar air-blowings, in 6M HNO360 DEG C of immersion 4h in aqueous solution,
Deionized water is cleaned, and after Ar air-blowings are dry, determine Static water contact angles to determine Static water contact angles for 80 degree is 90 degree；
2. porous metal electrode pretreatment：Under room temperature, by length and width be respectively 4cm and 5cm, thickness be 20 μm,
Purity is 99.9%, average pore size is 0.5mm, porosity is 1.3% porous C u paper tinsel is respectively in acetone and 0.1M
H2SO4Middle ultrasound immersion 30min, carries out oil removing, oxide film dissolving process, then is soaked with washes of absolute alcohol, ultrasound
15min, it is finally dry with Ar air-blowings；
3. the polyimide plastic of two panels One-sided coatings acrylate pressure-sensitive adhesive is tailored into into hollow rectangular shaped rim, housing chi
It is very little for 6cm*7cm, the size of hollow space (referred to as internal ring) is 3.4cm*4.4cm (i.e. 14.96cm2), so
The carbon paper and porous C u piece after step 1 and 2 are processed is placed on into two frame coating pressure sensitive adhesive sides respectively afterwards
Centre position, make the two edge equal with the spacing of corresponding edge inframe ring respectively.Finally by the pressure-sensitive of two frames
Glue side is relative to bond, and obtains the preload component of porous electrode complex；
4. by porous electrode complex preload component be transferred to maximum pressure be 50MPa two pieces of flat boards of flat board tablet machine it
Between, applying pressure, the pressure for making preload component surface is 12MPa, suppresses 1min at ambient pressure, obtains porous electricity
Pole complex.
5. ERC performance evaluations of porous electrode complex
In improved H types electrolyzer, 100ml 0.5M KHCO in anode and cathode chamber, are separately added into3Aqueous solution and
50ml 0.1M KHCO3Aqueous solution, using DuPont produce NF115 as anode and cathode chamber barrier film.
Wherein, the gas of cathode cavity is entered from electrolyzer lower end, flows through porous electrode and CO occurs2Electrochemical reducting reaction
Afterwards, discharge from the upper end outlet of cathode cavity.Before test, high-purity N is passed through in cathode cavity first21h, Ran Houtong
Enter the CO that purity is 99.995%2Gas, CO2Flow speed control be 60sccm.After 30min, with porous electrode
Complex is working electrode, and Pt pieces are that, to electrode, saturated calomel electrode is reference electrode.In -2.0V running voltages
Under carry out electrochemical reducting reaction 30min, reaction end gas are passed through gas chromatogram and carry out the detection by quantitative of gaseous product,
Product liquid carries out quantitative analyses using chromatography of ions.
In the present embodiment, in the present embodiment, gaseous product CH4Concentration be 2000ppm, C2H4Concentration is 50ppm,
C2H6Concentration be 5ppm, HCOOH concentration be 20ppm, C2H5OH concentration is 15ppm, CO2Conversion ratio is
25%, it is 2.35 times of comparative example 1.
Claims (10)
1. Carbon dioxide electrochemical reduction porous electrode complex, it is characterised in that：Including the gas being layered on top of each other
Diffusion substrates layer and porous metal electrode layer, also including two shape and size identicals, hollow ring-type frame；
The edge of gas diffusion substrate layer adheres to a side surface of a ring-type frame by binding agent, and gas expands
Distance is left between the edge of scattered basal layer and the edge of ring-type frame hollow region；Porous metal electrode layer
Edge adheres to a side surface of another ring-type frame, and the surrounding of porous metal electrode layer by binding agent
Distance is left between the edge of edge and ring-type frame hollow region；The edge of two ring-type frames is by bonding
Agent is mutually adhered to, and gas diffusion substrate layer and porous metal electrode layer are between two ring-type frames with being layered on top of each other,
Constitute porous electrode complex.
2. according to porous electrode complex described in claim 1, it is characterised in that：The material of the ring-type frame is
One kind in polypropylene, polyester, Merlon or polyimides；Described binding agent is pressure sensitive adhesive, including propylene
One kind in acids, silicone or polyurethaness pressure sensitive adhesive；
Described gas diffusion substrate is used for transmitting reacting gas and liquid, and porous metal electrode is used for being catalyzed titanium dioxide
Carbon electrochemical reducting reaction.
3. according to porous electrode complex described in claim 1, it is characterised in that：
Described gas diffusion substrate, is nonmetallic materials, is the good conductor of electricity, including braiding or non-woven charcoal
The non-woven fabrics of base carbon paper or charcoal cloth, charcoal felt or dual coating Carbon Materials.
4. according to porous electrode complex described in claim 1 or 3, it is characterised in that：
Described gas diffusion substrate, porosity are 50%～95%, and optimal porosity is 70%～90%；
Described gas diffusion substrate, its thickness are 0.08mm～3.0mm, and optimum thickness is 0.1mm～1.5mm；
For guaranteeing that gas diffusion substrate has a good gas transmission property, the Static water contact of described gas diffusion substrate
Angle range is 60～130 degree.
5. according to porous electrode complex described in claim 1, it is characterised in that：
Described porous metal electrode, is metal plate material, including piece or paper tinsel；Thickness is 5 μm～2.0mm, most
Good thickness is 0.01mm～1.0mm；
Described porous metal electrode, porosity are 0.1%～5%, and optimal porosity is 0.5%～2%；
Described porous metal electrode, average pore size scope are 50 μm～2mm, and optimum aperture is 100 μm
～500 μm；
Porous metal electrode layer is provided with collection ear, and collection ear is stretched out from the outward flange of two ring-type frames.
6. according to porous electrode complex described in claim 1 or 5, it is characterised in that：
Described porous metal electrode, the effective metal content for being catalyzed ERC reactions are not less than 99.0%；
Effective metal in described porous metal electrode, including one or two or more kinds in following metals, i.e.,
Metallic element In, Tl, Sn in IIIA～VA, Pb, Sb, Bi, Cu, Ag, the Au in IB, and VIIIB
In Pd, Pt, Ru, Rh, Ir.
7. the preparation method of the arbitrary porous electrode complex of a kind of claim 1-6, it is characterised in that：
Preparation process is comprised the following steps：
1) gas diffusion substrate is carried out into oil removing pretreatment；2) porous metal electrode is carried out oil removing, goes the removal of impurity
Pretreatment；3) gas diffusion substrate and porous metal electrode are adhered to the two rings of side application of adhesive respectively
On shape plastic frame, the side that two panels frame is scribbled binding agent is relative, make the two edge respectively with corresponding edge inframe
The spacing of ring is impartial, finally that the binding agent side of two frames is relative, constitutes porous electrode complex preload component；
4) porous electrode complex preload component is placed in flat board tablet machine, porous is obtained under room temperature, pressurized conditions
Electrode complex.
8. according to the preparation method of porous electrode complex described in claim 7, it is characterised in that：The pressurization
Equipment be flat board tablet machine, flatness requirement ± 20 μm.
9. according to the preparation method of porous electrode complex described in claim 7, it is characterised in that：To compound electric
The pressure of pole is 1MPa～10MPa, and optimum pressure is 5MPa～20MPa；Pressing time is 30s～5min, most preferably
Pressing time is 1min～3min.
10. a kind of arbitrary porous electrode complex of claim 1-6 is applied to Carbon dioxide electrochemical reduction
In.
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