CN108118363A - A kind of CO2The preparation of electrochemical reduction electrode and its electrode and application - Google Patents
A kind of CO2The preparation of electrochemical reduction electrode and its electrode and application Download PDFInfo
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- CN108118363A CN108118363A CN201611056706.5A CN201611056706A CN108118363A CN 108118363 A CN108118363 A CN 108118363A CN 201611056706 A CN201611056706 A CN 201611056706A CN 108118363 A CN108118363 A CN 108118363A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
Abstract
The present invention relates to a kind of CO2The preparation of electrochemical reduction electrode and its electrode and application carry out decontamination processing to base material first；Secondly, base material is immersed in the electrode precursor for obtaining that surface is nano thread structure in the chemical pretreatment solution of oxidisability；3rd, electrode precursor is subjected to electrochemical reduction processing, obtaining surface attachment has the electrode of nano thread structure layer.Compared with existing bulk metal electrode fabrication, electrode of the invention can provide more active sites for CO2Electrochemical reducting reaction, improve the yield of target product；The surface roughness of the nano thread structure layer of electrode surface attachment is big, can change combine between the intermediate product CO* and electrode surface of ERC reaction committed steps can, the subsequent reactions course of modulation CO*, and then change to the selectivity of target product.
Description
Technical field
The invention belongs to Carbon dioxide electrochemical reduction technical field, more particularly to a kind of high specific surface electrode and its preparation
Technology.
Background technology
Electrochemical reduction CO2(ERC) technology is to utilize electric energy by CO2Target product is reduced to, realizes CO2It converts and effective
A kind of technology utilized.With other CO2Transformation technology is compared, the outstanding advantages of ERC technologies be it is easy to operate, it is of low cost,
Using hydrogen source of the water as protonation, CO can be realized at normal temperatures and pressures2Efficient Conversion, therefore chemical conversion is not required
The energy expenditure caused by hydrogen manufacturing and heating, pressurization needed for technology, equipment investment are few.
At present, the principal element that ERC technologies develop slowly includes：(1) it is high to react overpotential；(2) catalytic activity is low；(3)
Target product selectivity is poor.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, so as to form 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 response area of ERC electrodes, researcher attempts nano metal particles being supported on supporting body surface,
Reacted as Reske et al. uses the nano Cu particle being supported on glass-carbon electrode catalysis ERC (J.Am.Chem.Soc.2014,
136,13319-13325), target product CH4Divide the high-purity copper foil electrode of current density ratio four times high, and faradic efficiency reaches
To 80%.Qiao etc. prepares nanofibrous structures using the method that heat treatment and electroreduction are combined on smooth Cu paper tinsels surface
Cu electrodes, obtained electrode reaction area and the ratio of geometric electrode area be up to 458cm2/cm2(geometric area), the electrode
Stability under ERC reaction conditions is up to 19h, primary product HCOOH.Above two expands the side of electrochemical reaction area
Method is usually directed to cumbersome nano-particle preparation and storage procedure or high-temperature heat treatment process, adds electrode production process
Complexity, while reappearance is poor, is poorly suited for preparing the electrode of large-size.
The content of the invention
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows,
A kind of CO2The preparation of electrochemical reduction electrode carries out decontamination processing to base material first；Secondly, by base
Bottom material is immersed in the electrode precursor for obtaining that surface is nano thread structure in the chemical pretreatment solution of oxidisability；3rd, by electrode
Presoma carries out electrochemical reduction processing, and obtaining surface attachment has the electrode of nano thread structure layer.
Base material is one kind in Cu, Ag, Au, Pd, Pb, and ground state is paper tinsel, piece, block or supports in conductive base
On above-mentioned metal in one kind or two kinds, the conductive base be carbon material, including one in carbon paper, charcoal cloth or charcoal felt
Kind.
The chemical pretreatment solution of oxidisability is the alkaline aqueous solution of persulfate, mistake in the chemical pretreatment solution of the oxidisability
The cation of sulfate include alkali metal ion or ammonium ion, anion be over cure acid group and hydroxyl, over cure acid group concentration
For 0.05M~0.5M, optimum concentration range is 0.1M~0.3M；PH scopes are 9~14.
Optimum PH range is 12~13；
Described is 10min~600min by processing time of the base material in the chemical pretreatment solution of oxidisability, most preferably
Processing time is 30min~180min；
The described treatment temperature by base material in the chemical pretreatment solution of oxidisability is room temperature~60 DEG C, optimization process
Temperature is 30 DEG C~50 DEG C；
The base material is Cu, Ag, Au, one kind in Pd, Pb, and ground state is paper tinsel, piece, block or is supported in conduction
One kind in above-mentioned metal on Carbon Materials.
The base material decontamination processing, including chemical treatment or electrochemical treatments.Wherein, it is chemically treated as in matter
Amount concentration is to be impregnated in 36%~38% dense HCl acid solutions, and soaking time is 5min~30min, with inertia after cleaning up
Gas dries up.Electrochemical treatments be using mass concentration as 85% H3PO4Liquid is dealt with, processing current potential is 1V~4V (compared with full
And calomel electrode), optimization process current potential is 2V~3V, and treatment temperature is room temperature.
The electrochemical reduction treatment conditions are：Treatment fluid is molten for the alkalescent salt that high pure nitrogen or high-purity argon gas are protected
Liquid；Processing current density is -5~-50mA cm-2, optimization process current density is 20~40mAcm-2；Processing time is 5min
~60min, optimization process time are 10~30min.
The alkalescent salting liquid be bicarbonate solution or carbonate solution, metal therein be alkali metal, solution
PH be 8~9.
The electrode is attached with the electrode of nano thread structure layer for substrate material surface, the density of nano wire for 100~
1000/cm2, the length of nano wire is 2-20 μm, a diameter of 30-500nm.
Application of electrode is in Carbon dioxide electrochemical reduction reaction.
Advantages of the present invention and advantageous effect：
The present invention provides a kind of preparation method of Carbon dioxide electrochemical reduction high specific surface electrode, the preparation methods
The technology being combined using chemical impregnation with electrochemical reduction has easy to operate, repeatable strong advantage, prepared electricity
Has nano thread structure, the diameter and length of nano wire are adjustable, are suitable for the preparation of large-size electrode.
It is simple using preparation method proposed by the present invention, controllability and workable.With existing bulk metal electrode
Technology of preparing compare, using the electrode prepared by the method for the present invention, there are following features：1) nanowire-junction can effectively be kept
Structure by controlling reduction potential and reduction current density, makes the reduction process of nanowire precursor slowly carry out, can avoid due to
Nano thread structure caused by presoma dehydration caves in；
2) CO is increased considerably2The response area of electrochemical reduction, so as to reduce CO2The overpotential of electrochemical reaction.With body
Phase metal electrode compares, and has the electrode of nano thread structure since the nanowire density in unit geometric area and surface area are equal
It is very big, it is possible to provide more active sites are used for CO2Electrochemical reducting reaction, so as to improve the yield of target product；Electrode
The surface roughness of the nano thread structure layer of surface attachment is big, can change the intermediate product CO* and electrode of ERC reaction committed steps
Energy, the subsequent reactions course of modulation CO* are combined between surface, and then changes the selectivity to target product.
Description of the drawings
Fig. 1 is CuNW structure electrode presomas surface SEM figures prepared by embodiment 1；
Fig. 2 is that the electrode surface SEM that surface attachment prepared by embodiment 1 has CuNW structure sheafs schemes.
Specific embodiment
Embodiment 1
1. base material pre-processes：It it is 50 microns using thickness, area 10cm2Copper foil as base material, exist first
At room temperature, it is soaked in the concentrated hydrochloric acid that volume fraction is 36%~38% and handles 10min, removal surface scale etc. is miscellaneous
Matter then with a large amount of deionized water rinsings to neutrality, is dried up with high-purity argon gas；
The preparation of 2.Cu nanowire precursors：Chemical pretreatment solution is prepared, the wherein concentration of ammonium persulfate is 0.1M, and NaOH is dense
It spends for 0.1M.After bubble-free in solution is overflowed, the copper foil substrate obtained by step 1 processing is soaked in the chemistry configured
In treatment fluid, in 30 DEG C of waters bath with thermostatic control after sealing dipping 30min, take out, then with a large amount of deionized water rinsings to neutrality, use
High-purity argon gas dries up.Obtained nanowire precursor is black, and pattern is as shown in Figure 1.
The preparation of 3.Cu nano line electrodes：0.1MNaHCO is prepared using the ultra-pure water that resistivity is 18.2M Ω3Aqueous solution
(pH=8.2) it is used as electrochemical reduction treatment fluid.High-purity N is passed through into solution2After about 40min, using platinized platinum as to electrode, saturation
Calomel electrode makees reference electrode, makees working electrode with the copper foil of surface growth nanowire precursor, potentiostat as power supply,
Current density is 20mAcm-2Under the conditions of to nanowire precursor reduce 30min after, take out working electrode, obtain Cu nano wires electricity
Pole, surface are red, and pattern is as shown in Figure 2.Cu nanowire lengths are about 2~5 μm, diameter about 50nm.
4.Cu nano line electrodes are catalyzed the electrochemical reducting reaction of carbon dioxide：In improved H-type electrolytic cell, anode and cathode
200ml 0.5M NaHCO are separately added into chamber3Aqueous solution and 50ml 0.1M NaHCO3Aqueous solution is produced using DuPont
Membranes of the NF115 as anode and cathode chamber.Before test, high-purity N is passed through into cathode cavity first21h, then passing to purity is
99.995% CO2Gas, CO2Flow control be 60sccm.After 30min, Cu nano line electrodes are working electrode, and Pt pieces are
To electrode, saturated calomel electrode is reference electrode.Electrochemical reducting reaction 30min is carried out under -1.7V operating voltages, reacts tail
Gas is passed through the quantitative detection that gas-chromatography carries out gaseous product, and product liquid carries out quantitative analysis using ion chromatography.
Product analysis result is：The faradic efficiency of HCOOH is 16%, gaseous product C2H4Faradic efficiency be
11.9%, C2H6Faradic efficiency be 21.8%, CO faradic efficiency be 8.9%.Embodiment 2
1. prepared by the Cu electrodes that porous carbon paper supports：Using thickness as 0.19mm, area 3cm2TGP-H-090 carbon papers make
For porous conductive material, in 60 DEG C, 0.5M CuSO4In solution, in 60mAcm-2, deposit one on carbon paper surface under the conditions of 30min
Thin layer Cu particles, it is spare after high-purity Ar drying with a large amount of deionized water rinsing surfaces after taking-up；
2.Cu electrodes pre-process：The Cu electrodes supported in porous carbon paper surface that step 1 is obtained are soaked in volume fraction
To handle the impurity such as 5min, removal surface scale in 36%~38% concentrated hydrochloric acid, then with a large amount of deionized water rinsings extremely
Neutrality is dried up with high-purity argon gas；
The preparation of 3.Cu nanowire precursors：Chemical pretreatment solution is prepared, the wherein concentration of sodium peroxydisulfate is 0.05M, NaOH
Concentration is 0.01M.After bubble-free in solution is overflowed, process step 1 and 2 are handled to the Cu electrodes that obtained porous carbon paper supports
It is soaked in the chemical pretreatment solution configured, in 50 DEG C of waters bath with thermostatic control after sealing dipping 600min, takes out, then with largely going
Ionized water is rinsed to neutrality, is dried up with high-purity argon gas.
The preparation of 4.Cu nano line electrodes：0.5M KHCO are prepared using the ultra-pure water that resistivity is 18.2M Ω3Aqueous solution
(pH=9) it is used as electrochemical reduction treatment fluid.High-purity N is passed through into solution2After about 40min, using platinized platinum as to electrode, saturation is sweet
Mercury electrode makees reference electrode, makees working electrode by the copper foil with surface growth nanowire precursor, potentiostat as power supply,
It is 5mAcm in current density-2Under the conditions of to nanowire precursor reduce 60min after, take out working electrode, obtain supporting in porous
The Cu nano line electrodes on carbon paper surface, surface are red, and pattern is as shown in Figure 2.Cu nanowire lengths are about 2~5 μm, diameter
About 30nm.
5.Cu nano line electrodes are catalyzed the electrochemical reducting reaction of carbon dioxide：In improved H-type electrolytic cell, anode and cathode
200ml 0.5M NaHCO are separately added into chamber3Aqueous solution and 50ml 0.1M NaHCO3Aqueous solution is produced using DuPont
Membranes of the NF115 as anode and cathode chamber.Before test, high-purity N is passed through into cathode cavity first21h, then passing to purity is
99.995% CO2Gas, CO2Flow control be 60sccm.After 30min, to support in the Cu nano wires on porous carbon paper surface
Electrode is working electrode, and Pt pieces are to electrode, and saturated calomel electrode is reference electrode.Electrification is carried out under -1.7V operating voltages
Reduction reaction 30min is learned, reaction end gas is passed through the quantitative detection that gas-chromatography carries out gaseous product, and product liquid uses ion color
Spectrum carries out quantitative analysis.
Product analysis result is：The faradic efficiency of HCOOH is 4.3%, gaseous product C2H4Faradic efficiency be
10.8%, C2H6Faradic efficiency be 10.0%, CO faradic efficiency be 12.6%, CH4Faradic efficiency be 0.4%.
Embodiment 3
1. base material pre-processes：It it is 100 microns using thickness, area 5cm2Palladium piece as base material, exist first
At room temperature, it is soaked in the phosphoric acid that mass fraction is 85% and is made as working electrode, Pt pieces to electrode, saturated calomel electrode
As reference electrode.Using potentiostat, decomposition voltage is controlled to handle the impurity such as 5min, removal surface scale for 2V, then
With a large amount of deionized water rinsings to neutrality, dried up with high-purity argon gas；
The preparation of 2.Pd nanowire precursors：Chemical pretreatment solution is prepared, the wherein concentration of sodium peroxydisulfate is 0.3M, uses 2M
NaOH adjust pH to 9.After bubble-free in solution is overflowed, the copper foil substrate obtained by step 1 processing is soaked in configuration
In good chemical pretreatment solution, in room-temperature water bath after sealing dipping 120min, take out, then with a large amount of deionized water rinsings into
Property, it is dried up with high-purity argon gas.Obtained nanowire precursor is black.
The preparation of 3.Pd nano line electrodes：0.1M KHCO are prepared using the ultra-pure water that resistivity is 18.2M Ω3Aqueous solution
(pH=8.2) it is used as electrochemical reduction treatment fluid.High-purity N is passed through into solution2After about 40min, using platinized platinum as to electrode, saturation
Calomel electrode makees reference electrode, makees working electrode with the Pd pieces of surface growth Pd nanowire precursors, potentiostat as power supply,
It is 50mAcm in current density-2Under the conditions of to nanowire precursor reduce 5min after, take out working electrode, obtain Pd nano wires electricity
Pole, surface are black, and Pd nanowire lengths are about 10~20 μm, diameter about 100~300nm.
4. nano line electrode is catalyzed the electrochemical reducting reaction of carbon dioxide：In improved H-type electrolytic cell, anode and cathode chamber
In be separately added into 200ml 0.5M NaHCO3Aqueous solution and 50ml 0.1M NaHCO3Aqueous solution is produced using DuPont
Membranes of the NF115 as anode and cathode chamber.Before test, high-purity N is passed through into cathode cavity first21h, then passing to purity is
99.995% CO2Gas, CO2Flow control be 60sccm.After 30min, using Pd nano line electrodes as working electrode, Pt pieces
For to electrode, saturated calomel electrode is reference electrode.Electrochemical reducting reaction is carried out under -1.2V operating voltages
30min, reaction end gas are passed through the quantitative detection that gas-chromatography carries out gaseous product, and product liquid uses ion chromatography
Carry out quantitative analysis.
Product analysis result is：The faradic efficiency that the faradic efficiency of HCOOH is 15%, CO is 63%.
Embodiment 4
1. prepared by the Au electrodes that porous carbon paper supports：Using thickness as 0.19mm, area 3cm2TGP-H-090 carbon papers make
For porous conductive material, containing 5mM HAuCl4、0.5M H2SO4Electroplate liquid in, in 5mAcm-2, under the conditions of 30min in charcoal
Paper surface deposits a thin layer Au particles, spare after high-purity Ar drying with a large amount of deionized water rinsing surfaces after taking-up；
2.Au electrodes pre-process：At room temperature, the Au electrodes that step 1 obtains are soaked in the phosphoric acid that mass fraction is 85%
Middle to be used as working electrode, Pt pieces are made to electrode, and saturated calomel electrode is as reference electrode.Use potentiostat, control electrolysis electricity
It presses and handles 5min for 4V, remove surface impurity, then with a large amount of deionized water rinsings to neutrality, dried up with high-purity argon gas；
The preparation of 3.Au nanowire precursors：Chemical pretreatment solution is prepared, the wherein concentration of potassium peroxydisulfate is 0.5M, uses 2M
KOH adjust pH to 10.0.After bubble-free in solution is overflowed, the porous carbon paper obtained by step 1 and 2 processing is supported
Au electrodes are soaked in the chemical pretreatment solution configured, at room temperature sealing dipping 10min after, take out, then with largely go from
Sub- water is rinsed to neutrality, is dried up with high-purity argon gas, obtains the Au nano line electrode presomas supported in carbon paper surface.
The preparation of 4.Au nano line electrodes：0.1MNaHCO is prepared using the ultra-pure water that resistivity is 18.2M Ω3Aqueous solution
(pH=8.2) it is used as electrochemical reduction treatment fluid.High-purity N is passed through into solution2After about 40min, using platinized platinum as to electrode, saturation
Calomel electrode makees reference electrode, makees working electrode with the carbon paper of surface growth Au nanowire precursors, potentiostat as power supply,
It is 40mAcm in current density-2Under the conditions of to nanowire precursor reductase 12 0min after, take out working electrode, obtain supporting in charcoal
The Au nano line electrodes on paper surface, Au nanowire surfaces are in black, and nanowire length is about 5~10 μm, and diameter about 30~
100nm。
5.Au nano line electrodes are catalyzed the electrochemical reducting reaction of carbon dioxide：In improved H-type electrolytic cell, anode and cathode
200ml 0.5M NaHCO are separately added into chamber3Aqueous solution and 50ml 0.1M NaHCO3Aqueous solution is produced using DuPont
Membranes of the NF115 as anode and cathode chamber.Before test, high-purity N is passed through into cathode cavity first21h, then passing to purity is
99.995% CO2Gas, CO2Flow control be 60sccm.After 30min, to support the Au nano wires in carbon paper surface as work
Make electrode, Pt pieces are to electrode, and saturated calomel electrode is reference electrode.It is anti-that electrochemical reduction is carried out under -1.0V operating voltages
30min is answered, reaction end gas is passed through the quantitative detection that gas-chromatography carries out gaseous product, and product liquid is determined using ion chromatography
Amount analysis.
Product analysis result is：The faradic efficiency of CO is 86%, and HCOOH is not detected.
Embodiment 5
1.Pb base materials pre-process：It it is 1 millimeter using thickness, area 6cm2Lead as base material, exist first
At room temperature, it is soaked in the concentrated hydrochloric acid that volume fraction is 36%~38% and handles 30min, removal surface scale etc. is miscellaneous
Matter then with a large amount of deionized water rinsings to neutrality, is dried up with high-purity argon gas；The preparation of 2.Pb nanowire precursors：Preparation
Treatment fluid is learned, the wherein concentration of potassium peroxydisulfate is 0.2M, and pH to 14 is adjusted using the NaOH of 4M.Treat that bubble-free is overflowed in solution
Afterwards, the lead substrate obtained by step 1 processing is soaked in the chemical pretreatment solution configured, leaching is sealed in 60 DEG C of water-baths
After stain 180min, take out, then with a large amount of deionized water rinsings to neutrality, dried up with high-purity argon gas.Obtained Pb nano wires
Presoma is black.
The preparation of 3.Pb nano line electrodes：0.1M KHCO are prepared using the ultra-pure water that resistivity is 18.2M Ω3Aqueous solution
(pH=8.2) it is used as electrochemical reduction treatment fluid.High-purity N is passed through into solution2After about 40min, using platinized platinum as to electrode, saturation
Calomel electrode makees reference electrode, makees working electrode by the Pb blocks with surface growth nanowire precursor, potentiostat is as electricity
Source is 50mAcm in current density-2Under the conditions of to nanowire precursor reduce 60min after, take out working electrode, obtain surface life
The Pb block electrodes of long Pb nano wires, surface are black, and Pb nanowire lengths are about 10~20 μm, diameter about 400~500nm.
4.Pb nano line electrodes are catalyzed the electrochemical reducting reaction of carbon dioxide：In improved H-type electrolytic cell, in anode and cathode chamber respectively
Add in 200ml 0.5M NaHCO3Aqueous solution and 50ml 0.1M NaHCO3Aqueous solution, the NF115 produced using DuPont
Membrane as anode and cathode chamber.Before test, high-purity N is passed through into cathode cavity first21h then passes to purity as 99.995%
CO2Gas, CO2Flow control be 60sccm.After 30min, using the Pb blocks of surface growth Pb nano wires as working electrode, Pt
Piece is to electrode, and saturated calomel electrode is reference electrode.Electrochemical reducting reaction 30min is carried out under -1.5V operating voltages, instead
Tail gas is answered to be passed through the quantitative detection that gas-chromatography carries out gaseous product, product liquid carries out quantitative analysis using ion chromatography.
Product analysis result is：The faradic efficiency of HCOOH is 92%.
Embodiment 6
1. base material pre-processes：It it is 0.5 millimeter using thickness, area 5cm2Silver strip as base material, in room temperature
Under, it is soaked in the phosphoric acid that mass fraction is 85% and is made as working electrode, Pt pieces to electrode, saturated calomel electrode conduct
Reference electrode.Using potentiostat, decomposition voltage is controlled to handle 10min for 1V, surface impurity is removed, then with a large amount of deionizations
Water is rinsed to neutrality, is dried up with high-purity argon gas；The preparation of 2.Ag nanowire precursors：Prepare chemical pretreatment solution, wherein persulfuric acid
The concentration of ammonium is 0.1M, and pH to 11 is adjusted using the NaOH of 3M.After bubble-free in solution is overflowed, it will be handled by step 1
To silver strip substrate be soaked in the chemical pretreatment solution configured, in 25 DEG C of water-baths sealing dipping 60min after, take out, then
With a large amount of deionized water rinsings to neutrality, dried up with high-purity argon gas.Obtained Ag nanowire precursors are black.
The preparation of 3.Ag nano line electrodes：0.1M KHCO are prepared using the ultra-pure water that resistivity is 18.2M Ω3Aqueous solution
(pH=8.2) it is used as electrochemical reduction treatment fluid.High-purity N is passed through into solution2After about 40min, using platinized platinum as to electrode, saturation
Calomel electrode makees reference electrode, makees working electrode by the Ag pieces with surface growth nanowire precursor, potentiostat is as electricity
Source is 10mAcm in current density-2Under the conditions of to Ag nanowire precursors reduce 10min after, take out working electrode, obtain Ag and receive
Rice noodles electrode, surface are black, and Ag nanowire lengths are about 5~10 μm, diameter about 30~80nm.
4.Ag nano line electrodes are catalyzed the electrochemical reducting reaction of carbon dioxide：In improved H-type electrolytic cell, anode and cathode
200ml 0.5M NaHCO are separately added into chamber3Aqueous solution and 50ml 0.1M NaHCO3Aqueous solution is produced using DuPont
Membranes of the NF115 as anode and cathode chamber.Before test, high-purity N is passed through into cathode cavity first21h, then passing to purity is
99.995% CO2Gas, CO2Flow control be 60sccm.After 30min, using the Ag pieces of surface growth Ag nano wires as work
Electrode, Pt pieces are to electrode, and saturated calomel electrode is reference electrode.Electrochemical reducting reaction is carried out under -1.2V operating voltages
30min, reaction end gas are passed through the quantitative detection that gas-chromatography carries out gaseous product, and product liquid is quantified using ion chromatography
Analysis.
Product analysis result is：The faradic efficiency of CO is 75%.
Comparative example 1
1. prepared by the Au electrodes that porous carbon paper supports：Using thickness as 0.19mm, area 3cm2TGP-H-090 carbon papers make
For porous conductive material, containing 5mM HAuCl4、0.5M H2SO4Electroplate liquid in, in 5mAcm-2, under the conditions of 30min in charcoal
Paper surface deposits a thin layer Au particles, spare after high-purity Ar drying with a large amount of deionized water rinsing surfaces after taking-up；；
2. the electrochemical reducting reaction for the Au electrode catalyst carbon dioxide that porous carbon paper supports：In improved H-type electrolytic cell
In, 200ml 0.5M NaHCO are separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M NaHCO3Aqueous solution uses
Membranes of the NF115 of DuPont production as anode and cathode chamber.Before test, high-purity N is passed through into cathode cavity first21h, so
The CO that purity is 99.995% is passed through afterwards2Gas, CO2Flow control be 60sccm.After 30min, prepared by step 1 more
The Au electrodes that hole carbon paper supports are working electrode, and Pt pieces are to electrode, and saturated calomel electrode is reference electrode.It works in -1.0V
Electrochemical reducting reaction 30min is carried out under voltage, reaction end gas is passed through the quantitative detection that gas-chromatography carries out gaseous product, liquid
Product carries out quantitative analysis using ion chromatography.
Product analysis result is：The faradic efficiency that the faradic efficiency of CO is 52%, HCOOH is 3.4%.
Comparative example 2
1. copper sheet pre-processes：At room temperature, it is 200 microns by thickness, area 10cm2Copper sheet be soaked in volume fraction
To handle the impurity such as 10min, removal surface scale in 36%~38% concentrated hydrochloric acid, then with a large amount of deionized water rinsings extremely
Neutrality is dried up with high-purity argon gas；
2. copper sheet is catalyzed the electrochemical reducting reaction of carbon dioxide：In improved H-type electrolytic cell, in anode and cathode chamber respectively
Add in 200ml 0.5M NaHCO3Aqueous solution and 50ml 0.1M NaHCO3Aqueous solution, the NF115 produced using DuPont
Membrane as anode and cathode chamber.Before test, high-purity N is passed through into cathode cavity first21h then passes to purity as 99.995%
CO2Gas, CO2Flow control be 60sccm.After 30min, the copper sheet handled by step 1 is working electrode, and Pt pieces are pair
Electrode, saturated calomel electrode are reference electrode.Electrochemical reducting reaction 30min, reaction end gas are carried out under -1.7V operating voltages
The quantitative detection that gas-chromatography carries out gaseous product is passed through, product liquid carries out quantitative analysis using ion chromatography.
Product analysis result is：CH4Faradic efficiency be 1.4%, HCOOH faradic efficiency be 2.5%.
Claims (10)
1. a kind of CO2The preparation method of electrochemical reduction electrode, it is characterised in that：Base material is carried out at decontamination first
Reason；Secondly, base material is immersed in the electrode precursor for obtaining that surface is nano thread structure in the chemical pretreatment solution of oxidisability；
3rd, electrode precursor is subjected to electrochemical reduction processing, obtaining surface attachment has the electrode of nano thread structure layer.
2. preparation method according to claim 1, which is characterized in that one in base material Cu, Ag, Au, Pd, Pb
Kind, ground state is paper tinsel, piece, block or supports one kind in the above-mentioned metal on conductive base or two kinds, the conductive base
Material is carbon material, including one kind in carbon paper, charcoal cloth or charcoal felt.
3. preparation method according to claim 1, which is characterized in that the chemical pretreatment solution of oxidisability is the alkali of persulfate
Property aqueous solution, the cation of persulfate includes alkali metal ion or ammonium ion in the chemical pretreatment solution of the oxidisability,
Anion is over cure acid group and hydroxyl, and over cure acid group concentration is 0.05M~0.5M, and optimum concentration range is 0.1M~0.3M；
PH scopes are 9~14.
4. preparation method according to claim 3, which is characterized in that optimum PH range is 12~13.
5. the preparation method according to claim 1 or 3, which is characterized in that it is described by base material oxidisability change
The processing time in treatment fluid is learned as 10min~600min, the optimization process time is 30min~180min；
Treatment temperature is room temperature~60 DEG C, and optimum treatmenting temperature is 30 DEG C~50 DEG C；After processing cleaning to after neutrality with nitrogen and/
Or Ar dryings.
6. preparation method according to claim 1, which is characterized in that the base material decontamination processing, including changing
Learn processing or electrochemical treatments；
Wherein, be chemically treated to be impregnated in the dense HCl acid solutions that mass concentration is 36%~38%, soaking time for 5min~
30min is dried up after cleaning to neutrality with nitrogen or Ar；
Electrochemical treatments are the H using mass concentration as 85-87%3PO4For treatment fluid, processing current potential is that 1-4V is (sweet compared with saturation
Mercury electrode), optimization process current potential is 2-3V, and processing time is 5min~30min, and treatment temperature is room temperature.
7. preparation method according to claim 1, which is characterized in that the electrochemical reduction processing procedure is：To weak
N is passed through in alkaline salt solution2Or after Ar gas to saturation, using platinized platinum as to electrode, saturated calomel electrode makees reference electrode, with electrode
Presoma makees working electrode, and potentiostat is -5~-50mA cm in current density as power supply-2Under the conditions of to electrode precursor
After reducing 5min~60min, working electrode is taken out, obtains nano line electrode；Handle current density preferably 20~40mA cm-2；Place
Manage time preferably 10~30min.
8. preparation method according to claim 7, which is characterized in that the alkalescent salting liquid is bicarbonate solution
Or carbonate solution, metal therein are alkali metal, the pH of solution is 8~9.
9. electrode prepared by a kind of preparation method as described in claim 1-8, which is characterized in that the electrode is base material table
Face is attached with the electrode of nano thread structure layer, and the density of nano wire is 100~1000/cm2, the length of nano wire is 2-20 μ
M, a diameter of 30-500nm.
10. application of electrode described in a kind of claim 9 is in Carbon dioxide electrochemical reduction reaction.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111636074A (en) * | 2020-06-10 | 2020-09-08 | 大连大学 | Preparation and application of copper electrode for electrochemical reduction of carbon dioxide |
| CN111676482A (en) * | 2020-06-13 | 2020-09-18 | 大连大学 | Electrode for electrochemical reduction of carbon dioxide and application thereof |
| CN112813480A (en) * | 2021-01-07 | 2021-05-18 | 江苏大学 | In-situ grown silver nanocluster material, preparation method thereof and electro-catalytic reduction of CO2Applications of |
| CN113106472A (en) * | 2021-04-01 | 2021-07-13 | 南京理工大学 | For photoelectrocatalysis of CO2Super-structure plane photoelectrode for reduction reaction mechanism research |
| CN114032581A (en) * | 2021-08-31 | 2022-02-11 | 中国科学院过程工程研究所 | Method for electrochemically reconstructing metal surface by ionic liquid medium to electro-catalytically reduce carbon dioxide |
| CN114395778A (en) * | 2021-12-21 | 2022-04-26 | 南京理工大学 | Method for constructing stable three-phase interface, electrode and application thereof |
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2016
- 2016-11-26 CN CN201611056706.5A patent/CN108118363B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| MING MA等: ""Selective electrochemical reduction of CO2 to CO on CuO-derived Cu nanowires"", 《PHYS.CHEM.CHEM.PHYS.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111636074A (en) * | 2020-06-10 | 2020-09-08 | 大连大学 | Preparation and application of copper electrode for electrochemical reduction of carbon dioxide |
| CN111676482A (en) * | 2020-06-13 | 2020-09-18 | 大连大学 | Electrode for electrochemical reduction of carbon dioxide and application thereof |
| CN112813480A (en) * | 2021-01-07 | 2021-05-18 | 江苏大学 | In-situ grown silver nanocluster material, preparation method thereof and electro-catalytic reduction of CO2Applications of |
| CN113106472A (en) * | 2021-04-01 | 2021-07-13 | 南京理工大学 | For photoelectrocatalysis of CO2Super-structure plane photoelectrode for reduction reaction mechanism research |
| CN114032581A (en) * | 2021-08-31 | 2022-02-11 | 中国科学院过程工程研究所 | Method for electrochemically reconstructing metal surface by ionic liquid medium to electro-catalytically reduce carbon dioxide |
| CN114032581B (en) * | 2021-08-31 | 2023-03-07 | 中国科学院过程工程研究所 | Method for electrochemically reconstructing metal surface by ionic liquid medium to electro-catalytically reduce carbon dioxide |
| CN114395778A (en) * | 2021-12-21 | 2022-04-26 | 南京理工大学 | Method for constructing stable three-phase interface, electrode and application thereof |
| CN114395778B (en) * | 2021-12-21 | 2023-12-19 | 南京理工大学 | Method for constructing stable three-phase interface, electrode and application thereof |
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