CN107916433B - The preparation of micro nano structure zinc electrode and zinc electrode and application - Google Patents

The preparation of micro nano structure zinc electrode and zinc electrode and application Download PDF

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CN107916433B
CN107916433B CN201610880149.2A CN201610880149A CN107916433B CN 107916433 B CN107916433 B CN 107916433B CN 201610880149 A CN201610880149 A CN 201610880149A CN 107916433 B CN107916433 B CN 107916433B
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zinc
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zinc metal
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CN107916433A (en
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张华民
张桃桃
钟和香
邱艳玲
李先锋
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Dalian Institute of Chemical Physics of CAS
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • 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
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • 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
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide

Abstract

The present invention relates to the preparation of micro nano structure zinc electrode and zinc electrode and applications, zinc electrode preparation process dissolves part zinc metal sheet including the use of malic acid under hydrothermal conditions, zinc hydroxide is formed on zinc metal sheet surface in temperature-fall period again, then drying and dehydrating obtains the zinc oxide of three-decker on zinc metal sheet surface.Zinc electrode of the invention has the characteristics that surface texture size adjustable and specific surface area are high, is used for Carbon dioxide electrochemical reduction, has excellent selectivity and catalytic activity to target product.

Description

The preparation of micro nano structure zinc electrode and zinc electrode and application
Technical field
The present invention relates to Resources of Carbon Dioxide to utilize field, the in particular to micro-nano knot of Carbon dioxide electrochemical reduction The preparation method of structure zinc electrode.
Background technique
CO2As a kind of potential carbon resource, there is very high utility value, can be recycled by many methods, It is converted to useful resource.CO in atmosphere can be reduced in this way2Content, turn bane into boon, slow down " greenhouse effects ", and can mitigate The consumption of current fossil fuel, double at one stroke.The method mainly used at present has: high temperature, high-pressure catalytic hydrogenization method；Bioconversion Method；Optical electro-chemistry conversion method；Electrochemical reducing etc..Electrochemical reduction is conversion CO2For the most effective of valuable compounds therefrom One of approach.CO can be realized in it at normal temperatures and pressures2Efficient Conversion, equipment investment is few.CO2Electrochemical reduction is current pole Attractive research topic.
Select suitable catalyst can be by CO2CO, CO and H are converted to by electrochemical reduction2It is the main original for preparing methanol Material, H2It can be obtained by electrolysis water.Liquid methanol can be used as energy storage vehicles and cleaning substitution new energy, be subtracted with this Oil gas energy crisis and global warming pressure during light socio-economic development.It is in this way the energy in oil gas epoch after solution Source problem and environmental protection provide an effective way.
Currently, the catalyst of high yield CO is mainly both noble metals of Au and Ag, selectivity is very high, is obtaining identical electricity When current density, both metal overpotentials are minimum.However its cost is very high, is easily poisoned, the lost of life, also this is to hinder its application One of the main reason for；And catalyst need to be prepared into micro nano structure to improve catalytic activity and utilization rate, conventionally used liquid Phase synthesi, electro-deposition, anodizing etc. are difficult to realize be mass produced.The preparation method being simple and efficient is developed, is developed honest and clean The catalyst of valence can with high selectivity, expeditiously promote CO2It is reduced to CO, is the weight of the renewable carbon-based liquid fuel of production Want a step.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of Carbon dioxide electrochemical reduction micro nano structure zinc electrode Preparation method.
To achieve the above object, the specific technical solution that the present invention uses is as follows:
1) preparation method of Carbon dioxide electrochemical reduction micro nano structure zinc electrode includes the following steps: successively use Water and ethyl alcohol are cleaned by ultrasonic zinc metal sheet, and are being dried under inert gas protection；2) washed zinc metal sheet is placed in interior In the reaction kettle for thering is polytetrafluoroethylene (PTFE) to cover, and concentration is added to be the aqueous solution of malic acid of 10~500ppm, liquor capacity accounts for autoclave The 5~40% of volume；Room temperature is naturally cooling to after reacting 6~24 hours at 160~200 DEG C；3) by zinc metal sheet from reaction kettle Middle taking-up, after washing with water, dry 2~12h at 120~150 DEG C.
For the zinc metal sheet with a thickness of 0.01~1mm, optimum thickness is 0.08~0.2mm；
The inert atmosphere is that one of nitrogen, argon gas or helium atmosphere or two kinds or more mix.
The zinc metal sheet floods 80% or more that surface area in the solution accounts for its total total surface area, and aqueous solution of malic acid is most Suitable concentration is 30~200ppm.
The optimum reacting time is 8~12h, and during which, malic acid whole consumptive use dissolves zinc metal sheet, and the salt for forming zinc is molten Liquid；Baking oven stops heat supply in temperature-fall period, reaction kettle Temperature fall in an oven, and zinc salt forms hydrogen-oxygen on zinc metal sheet surface in solution Change zinc；The concentration of zinc salt reduces in solution in temperature-fall period and temperature reduces, so that zinc metal sheet surface forms double-layer structure.
The optimum drying time range is 3~6h, and complete dehydration obtains oxygen to the zinc hydroxide on zinc metal sheet surface in air Change zinc；
The electrode has the three-decker of outer layer, intermediate permeable formation, internal layer, and the electrode surface, outer layer is laminated structure ZnO is constituted, and laminated structure area is 0.1-5 μm2, laminated structure thickness 1-15nm, 5-15 μm of outer layer thickness, laminated structure ZnO Projection at the electrode surface accounts for the 10-80% of electrode surface area；Internal layer is the column structure perpendicular to electrode surface, column knot Structure diameter is 5nm~5 μm, and with a thickness of 1~50 μm, volume and the internal layer of columnar structured material are taken up space total columnar structure layer Volume is 40-90%；Laminated structure ZnO part inlay forms intermediate permeable formation, intermediate permeation layer thickness in columnar structure layer 1-5 μm, the totality that the sum of laminated structure and the volume of columnar structured material are taken up space by intermediate permeable formation in intermediate permeable formation Product is 60-95%；The micro nano structure zinc electrode can be used for being catalyzed the electrochemical reducting reaction of carbon dioxide.
The advantages of the present invention are as follows:
Zinc electrode preparation process of the invention dissolves part zinc metal sheet including the use of malic acid under hydrothermal conditions, then is cooling down Zinc hydroxide is formed on zinc metal sheet surface in the process, then drying and dehydrating obtains the zinc oxide of three-decker on zinc metal sheet surface.
1) preparation process height at low cost, easy to operate, repeated is suitble to large-scale production.
2) micro-nano zinc electrode surface has sheet and column structure, and the size and column structure of these laminated structures Diameter it is adjustable, so that zinc electrode is had the characteristics that specific surface area is high.
3) high specific surface area increases electrode and electrolyte and CO2The contact area of gas effectively increases reaction Active area, to improve CO2Transformation efficiency；
4) micro-and nano-structural surface has the unsaturated atom of more coordinations, can expose more advantage crystal faces；For CO2Electrochemical reduction has excellent selectivity and catalytic activity to target product.
5) zinc is a kind of abundant and cheap element, can satisfy the demand of large-scale commercial applications application.
Using
By made electrode, as carbon dioxide reduction CO cathode.And electrochemistry survey is carried out by three-electrode system Examination: working electrode is electrode obtained；It is Pt piece, reference electrode Hg/Hg to electrode2Cl2/ saturation KCl.Salt bridge is used to drop Low liquid potential.Catholyte is 0.5M NaHCO3aq.sol.Electrolyte volume is 180ml；CO2Flow mass flowmenter Control, flow velocity 60ml/min；Anolyte is 0.1M H2SO4aq.sol。
Detailed description of the invention
The SEM photograph of electrode prepared by Fig. 1 embodiment of the present invention 1 under different amplification, 5000 times of (a) (b) 20000 times.
Electrode XRD diagram prepared by Fig. 2 embodiment of the present invention 1.
The chemical property of electrode and comparative sample prepared by Fig. 3 embodiment of the present invention 1.
Specific embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Comparative example
1. zinc metal sheet pre-processes: will be with a thickness of 0.1mm, area 9cm2, zinc metal sheet that Zn content is 99.99%, process is ultrapure After water cleaning, ethyl alcohol cleaning, transposition is in 85% H3PO4In solution, with 10mA cm-2Current density carry out leveling 300s, most It is cleaned up with ultrapure water, after inert gas drying, is placed on spare in drier afterwards；
2. zinc metal sheet electrode is to CO2The performance evaluation of electrochemical reducting reaction:
In H-type electrolytic cell, 180ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M H2SO4Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity is from electricity The lower end Xie Chi enters, and CO occurs in working electrode surface2After electrochemical reducting reaction, it is discharged from the upper end outlet of cathode cavity.It surveys Before examination, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow control For 60sccm.After 30min, using zinc metal sheet as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -1.8V Electrochemical reducting reaction 15min is carried out under operating voltage, reaction end gas is passed through the quantitative detection that gas-chromatography carries out gaseous product, Product liquid carries out quantitative analysis using ion chromatography.
Liquid product HCOOH concentration is 0.3ppm, and the concentration of gaseous product CO is 50.35ppm；H2Concentration is The selectivity of 249.94ppm, CO are 16.3%, H2Selectivity be 81.3%.
Embodiment 1
1. the preparation of micro nano structure zinc electrode:
1) successively zinc metal sheet is cleaned by ultrasonic with ultrapure water and ethyl alcohol, and is dried in the case where argon gas is protected, Zinc metal sheet purity is 99.99%, with a thickness of 0.1mm, area 9cm2；
2) washed zinc metal sheet is placed in the interior reaction kettle for having polytetrafluoroethylene (PTFE) to cover, reaction kettle liner volume is 100ml, high Degree is 15cm, and the aqueous solution of malic acid that 30ml concentration is 100ppm is added thereto, and liquor capacity accounts for the 30% of autoclave volume；
3) reaction kettle is put into temperature control oven, is naturally cooling to room temperature after reacting 8 hours at 190 DEG C；
4) zinc metal sheet is taken out, is put into temperature control oven after being cleaned with ultrapure water, dry 4 hours at 120 DEG C.
From figure 1 it appears that the electrode has the three-decker of outer layer, intermediate permeable formation, internal layer, the electrode table Face, outer layer are laminated structure ZnO composition, and laminated structure area is 1-5 μm2, laminated structure thickness 5-15nm, outer layer thickness 5-10 μm, the projection of laminated structure ZnO at the electrode surface accounts for the 40-60% of electrode surface area；Internal layer is perpendicular to electrode surface Column structure, column structure diameter are 500nm~4 μm, and columnar structure layer is with a thickness of 10~40 μm, the volume of columnar structured material It is 45-80% with the total volume that internal layer is taken up space；Laminated structure ZnO part inlay is in columnar structure layer into intermediate infiltration Layer, 2-5 μm of intermediate permeation layer thickness, the sum of laminated structure and the volume of columnar structured material are intermediate infiltration in intermediate permeable formation The total volume that layer is taken up space is 60-80%；
2. micro nano structure zinc electrode is to CO2The performance evaluation of electrochemical reducting reaction:
In H-type electrolytic cell, 180ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M H2SO4Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity is from electricity The lower end Xie Chi enters, and CO occurs in working electrode surface2After electrochemical reducting reaction, it is discharged from the upper end outlet of cathode cavity.It surveys Before examination, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow control For 60sccm.After 30min, using zinc metal sheet as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -1.3V Electrochemical reducting reaction 30min is carried out under operating voltage, restores electrode surface zinc oxide completely；Again in -1.3V operating voltage Lower carry out CO2Electrochemical reducting reaction 15min, reaction end gas are passed through the quantitative detection that gas-chromatography carries out gaseous product, liquid Product carries out quantitative analysis using ion chromatography.
Liquid product HCOOH concentration is 1ppm, and the concentration of gaseous product CO is 520.89ppm；H2Concentration is 99.43ppm. The selectivity of CO is 82.2%, about the 5.1 of comparative example times；The selectivity of H2 is 15.7%, about the 1/5 of comparative example.
From figure 2 it can be seen that the crystal structure of the target electrode restored by hydrothermal oxidization and the crystalline substance of zinc foil Body structure is significantly different.
From figure 3, it can be seen that the target electrode restored by hydrothermal oxidization is used to restore CO2At point electricity of CO Current density is 10 times of zinc foil at -1.8V, illustrates the catalysis CO of the micro nano structure zinc electrode of embodiment preparation2At CO's Activity is 10 times of common Zn foil.
Embodiment 2
1. the preparation of micro nano structure zinc electrode:
1) successively zinc metal sheet is cleaned by ultrasonic with ultrapure water and ethyl alcohol, and is dried in the case where argon gas is protected, Zinc metal sheet purity is 99.99%, with a thickness of 0.05mm, area 10cm2；
2) washed zinc metal sheet is placed in the interior reaction kettle for having polytetrafluoroethylene (PTFE) to cover, reaction kettle liner volume is 100ml, high Degree is 15cm, and the aqueous solution of malic acid that 40ml concentration is 50ppm is added thereto, and liquor capacity accounts for the 40% of autoclave volume；
3) reaction kettle is put into temperature control oven, is naturally cooling to room temperature after reacting 10 hours at 185 DEG C；
4) zinc metal sheet is taken out, is put into temperature control oven after being cleaned with ultrapure water, dry 6 hours at 130 DEG C.
The electrode has the three-decker of outer layer, intermediate permeable formation, internal layer, and the electrode surface, outer layer is laminated structure ZnO is constituted, and laminated structure area is 1-2 μm2, laminated structure thickness 5-10nm, 5-10 μm of outer layer thickness, laminated structure ZnO exists Projection on electrode surface accounts for the 40-60% of electrode surface area；Internal layer is the column structure perpendicular to electrode surface, column structure Diameter is 500nm~2 μm, columnar structure layer with a thickness of 10~50 μm, what the volume and internal layer of columnar structured material were taken up space Total volume is 60-90%；Laminated structure ZnO part inlay forms intermediate permeable formation, centre infiltration thickness in columnar structure layer 2-5 μm is spent, the sum of laminated structure and the volume of columnar structured material are taken up space total by intermediate permeable formation in intermediate permeable formation Volume is 80-95%；The micro nano structure zinc electrode can be used for being catalyzed the electrochemical reducting reaction of carbon dioxide.
2. micro nano structure zinc electrode is to CO2The performance evaluation of electrochemical reducting reaction:
In H-type electrolytic cell, 180ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M H2SO4Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity is from electricity The lower end Xie Chi enters, and CO occurs in working electrode surface2After electrochemical reducting reaction, it is discharged from the upper end outlet of cathode cavity.It surveys Before examination, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow control For 60sccm.After 30min, using zinc metal sheet as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -1.3V Electrochemical reducting reaction 30min is carried out under operating voltage, restores electrode surface zinc oxide completely；Again in -1.3V operating voltage Lower carry out CO2Electrochemical reducting reaction 15min, reaction end gas are passed through the quantitative detection that gas-chromatography carries out gaseous product, liquid Product carries out quantitative analysis using ion chromatography.
Liquid product HCOOH concentration is 1ppm, and the concentration of gaseous product CO is 600.34ppm；H2Concentration is 229.19ppm.The selectivity of CO is 64.35%, about the 4 of comparative example times；H2Selectivity be 24.57%, about comparative example 3/10.
Embodiment 3
1. the preparation of micro nano structure zinc electrode:
1) successively zinc metal sheet is cleaned by ultrasonic with ultrapure water and ethyl alcohol, and is dried in the case where argon gas is protected, Zinc metal sheet purity is 99.99%, with a thickness of 0.15mm, area 8cm2；
2) washed zinc metal sheet is placed in the interior reaction kettle for having polytetrafluoroethylene (PTFE) to cover, reaction kettle liner volume is 100ml, high Degree is 15cm, and the aqueous solution of malic acid that 20ml concentration is 30ppm is added thereto, and liquor capacity accounts for the 20% of autoclave volume；
3) reaction kettle is put into temperature control oven, is naturally cooling to room temperature after reacting 6 hours at 170 DEG C；
4) zinc metal sheet is taken out, is put into temperature control oven after being cleaned with ultrapure water, dry 4 hours at 140 DEG C.
The electrode has the three-decker of outer layer, intermediate permeable formation, internal layer, and the electrode surface, outer layer is laminated structure ZnO is constituted, and laminated structure area is 2-5 μm2, laminated structure thickness 4-15nm, 8-15 μm of outer layer thickness, laminated structure ZnO exists Projection on electrode surface accounts for the 40-70% of electrode surface area；Internal layer is the column structure perpendicular to electrode surface, column structure Diameter is 100nm~4 μm, columnar structure layer with a thickness of 10~50 μm, what the volume and internal layer of columnar structured material were taken up space Total volume is 60-90%；Laminated structure ZnO part inlay forms intermediate permeable formation, centre infiltration thickness in columnar structure layer 2-5 μm is spent, the sum of laminated structure and the volume of columnar structured material are taken up space total by intermediate permeable formation in intermediate permeable formation Volume is 70-95%；The micro nano structure zinc electrode can be used for being catalyzed the electrochemical reducting reaction of carbon dioxide.
2. micro nano structure zinc electrode is to CO2The performance evaluation of electrochemical reducting reaction:
In H-type electrolytic cell, 180ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M H2SO4Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity is from electricity The lower end Xie Chi enters, and CO occurs in working electrode surface2After electrochemical reducting reaction, it is discharged from the upper end outlet of cathode cavity.It surveys Before examination, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow control For 60sccm.After 30min, using zinc metal sheet as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -1.3V Electrochemical reducting reaction 30min is carried out under operating voltage, restores electrode surface zinc oxide completely；Again in -1.3V operating voltage Lower carry out CO2Electrochemical reducting reaction 15min, reaction end gas are passed through the quantitative detection that gas-chromatography carries out gaseous product, liquid Product carries out quantitative analysis using ion chromatography.
Liquid product HCOOH concentration is 0.1ppm, and the concentration of gaseous product CO is 537.4ppm；H2Concentration is 127.2ppm.The selectivity of CO is 80.9%, about the 5 of comparative example times；H2Selectivity be 19.1%, about the 1/ of comparative example 4。
Embodiment 4
1. the preparation of micro nano structure zinc electrode:
1) successively zinc metal sheet is cleaned by ultrasonic with ultrapure water and ethyl alcohol, and is dried in the case where argon gas is protected, Zinc metal sheet purity is 99.99%, with a thickness of 0.2mm, area 7cm2；
2) washed zinc metal sheet is placed in the interior reaction kettle for having polytetrafluoroethylene (PTFE) to cover, reaction kettle liner volume is 100ml, high Degree is 15cm, and the aqueous solution of malic acid that 10ml concentration is 100ppm is added thereto, and liquor capacity accounts for the 10% of autoclave volume；
3) reaction kettle is put into temperature control oven, is naturally cooling to room temperature after reacting 12 hours at 160 DEG C；
4) zinc metal sheet is taken out, is put into temperature control oven after being cleaned with ultrapure water, dry 6 hours at 120 DEG C.
The electrode has the three-decker of outer layer, intermediate permeable formation, internal layer, and the electrode surface, outer layer is laminated structure ZnO is constituted, and laminated structure area is 1-4 μm2, laminated structure thickness 5-15nm, 5-10 μm of outer layer thickness, laminated structure ZnO exists Projection on electrode surface accounts for the 10-80% of electrode surface area；Internal layer is the column structure perpendicular to electrode surface, column structure Diameter is 200nm~4 μm, and with a thickness of 5~40 μm, volume and the internal layer of columnar structured material are taken up space total columnar structure layer Volume is 70-90%；Laminated structure ZnO part inlay forms intermediate permeable formation, intermediate permeation layer thickness in columnar structure layer 2-5 μm, the totality that the sum of laminated structure and the volume of columnar structured material are taken up space by intermediate permeable formation in intermediate permeable formation Product is 70-90%；The micro nano structure zinc electrode can be used for being catalyzed the electrochemical reducting reaction of carbon dioxide.
2. micro nano structure zinc electrode is to CO2The performance evaluation of electrochemical reducting reaction:
In H-type electrolytic cell, 180ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M H2SO4Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Wherein, the gas of cathode cavity is from electricity The lower end Xie Chi enters, and CO occurs in working electrode surface2After electrochemical reducting reaction, it is discharged from the upper end outlet of cathode cavity.It surveys Before examination, high-purity N is passed through into cathode cavity first21h then passes to the CO that purity is 99.995%2Gas, CO2Flow control For 60sccm.After 30min, using zinc metal sheet as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -1.3V Electrochemical reducting reaction 30min is carried out under operating voltage, restores electrode surface zinc oxide completely；Again in -1.3V operating voltage Lower carry out CO2Electrochemical reducting reaction 15min, reaction end gas are passed through the quantitative detection that gas-chromatography carries out gaseous product, liquid Product carries out quantitative analysis using ion chromatography.
Liquid product HCOOH concentration is 0.2ppm, and the concentration of gaseous product CO is 480.9ppm；H2Concentration is 109.2ppm.The selectivity of CO is 81.2%, about the 5 of comparative example times；H2Selectivity be 18.4%, about the 1/ of comparative example 4。

Claims (8)

1. the preparation method of micro nano structure zinc electrode, which comprises the steps of:
1) successively zinc metal sheet is cleaned by ultrasonic respectively with water and ethyl alcohol, and is dried under inert atmosphere protection；
2) washed zinc metal sheet is placed in the interior reaction kettle for having polytetrafluoroethylene (PTFE) to cover, and the apple that concentration is 10 ~ 500ppm is added Aqueous acid is naturally cooling to room temperature after reacting 6~24 hours at 160~200 DEG C；Wherein aqueous solution volume accounts for reaction kettle The 5~40% of volume；
3) zinc metal sheet is taken out from reaction kettle, after washing with water, dry 2~12h, is made required micro-nano at 120~150 DEG C Rice structure zinc electrode.
2. preparation method described in accordance with the claim 1, it is characterised in that: the zinc metal sheet is with a thickness of 0.01 ~ 1mm；
The inert atmosphere is that one of nitrogen, argon gas or helium atmosphere or two kinds or more mix.
3. preparation method according to claim 2, it is characterised in that: the zinc metal sheet is with a thickness of 0.08 ~ 0.2mm.
4. preparation method described in accordance with the claim 1, it is characterised in that: zinc metal sheet described in step 2 floods depth in the solution Account for 80% or more of its total surface, aqueous solution of malic acid concentration preferably 30 ~ 200ppm.
5. preparation method described in accordance with the claim 1, it is characterised in that: the reaction time described in step 2 is preferably 8 ~ 12h.
6. preparation method described in accordance with the claim 1, it is characterised in that: the preferably 3~6h of drying time described in step 3).
7. a kind of micro nano structure zinc electrode of any preparation method preparation of claim 1-6, it is characterised in that: the electrode Surface, outer layer are laminated structure ZnO composition, and laminated structure area is 0.1-5 μm2, laminated structure thickness 1-15nm, outer layer thickness 5-15 μm, the projection of laminated structure ZnO at the electrode surface accounts for the 10-80% of electrode surface area；Internal layer is perpendicular to electrode surface Column structure, column structure diameter is 5nm ~ 5 μm, columnar structure layer with a thickness of 1 ~ 50 μm, the volume of columnar structured material with The total volume that internal layer is taken up space is 40-90%；Laminated structure ZnO part inlay forms intermediate permeable formation in columnar structure layer, 1-5 μm of intermediate permeation layer thickness, the sum of laminated structure and the volume of columnar structured material are intermediate permeable formation in intermediate permeable formation The total volume to be taken up space is 60-95%.
8. micro nano structure zinc electrode described in a kind of claim 7 can be used for being catalyzed the electrochemical reducting reaction of carbon dioxide.
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