CN106868538A - A kind of Carbon dioxide electrochemical reduction electrode, preparation method and applications - Google Patents

A kind of Carbon dioxide electrochemical reduction electrode, preparation method and applications Download PDF

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CN106868538A
CN106868538A CN201510924130.9A CN201510924130A CN106868538A CN 106868538 A CN106868538 A CN 106868538A CN 201510924130 A CN201510924130 A CN 201510924130A CN 106868538 A CN106868538 A CN 106868538A
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CN106868538B (en
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钟和香
张华民
邱艳玲
邓呈维
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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • 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
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • 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 invention discloses the Sn catalyst nanos layer adhered in a kind of Carbon dioxide electrochemical reduction electrode and its preparation and application, including basalis and basalis, the loading of Sn catalyst is 1mg/cm in electrode-2-6mg/cm-2, the Sn in electrode is made up of one or two or more kinds in nano wire, nanometer rods, the nanofiber of 1nm-500nm.The present invention has the Sn nanometer rods of abundant edge active position by the growth in situ in substrate, significantly improves the specific surface area and active area of electrode, and the electrochemical reduction that improve electrode pair carbon dioxide is the faradic efficiency of formic acid.

Description

A kind of Carbon dioxide electrochemical reduction electrode, preparation method and applications
Technical field
The present invention relates to Carbon dioxide electrochemical reduction electrode, preparation method and applications, belong to two Carbonoxide recycling field.
Background technology
In the last few years, with economic fast development, environmental problem and energy shortage problem are on the rise. Wherein, global warming has also turned into countries in the world problem urgently to be resolved hurrily, and CO2A large amount of discharges be The one of the main reasons of global warming.Thus, how effectively to utilize CO2And reduce CO2Discharge cause The extensive concern of people.
At present, people reduce CO using various methods2Discharge, including CO2Capture is fixed and turns Change and utilize.CO2Trans-utilization include catalytic hydrogenation, catalytic reforming, electrochemistry or electronation conversion Deng to realize CO2Activation synthesizes the organic compounds such as methane, methyl alcohol, formic acid or macromolecule chemical combination Thing.Consider from energy consumption and cost, electrochemical reducing has can be in normal temperature and pressure reaction, energy The advantages of consumption is low higher with transformation efficiency, is CO2One of more feasible approach in transformation technology, It is current hot research problem.ERC technologies are to utilize electric energy by CO2It is reduced to various organic small points Son or chemical products, effectively realize greenhouse gases CO2A kind of technology of recycling.With can be again Developing rapidly for energy source utilizing electricity generating techn is given birth to, the cost of generation technology is expected to significantly decline.Using can be again The raw energy generates electricity, and recycles electric energy by carbon dioxide synthesis of organic substance, realizes electric energy turning to chemical energy Change, will so form circulation and the energy conversion cycles of carbon.ERC technologies can not only save oil, The fossil energy such as natural gas and coal, and turn waste into wealth, make CO2It is utilized effectively, reduces CO2 The environmental pollution for causing.Therefore, ERC technologies have potential economic benefit and environmental benefit.
Electrochemical reduction CO2(ERC) technology is to utilize electric energy by CO2It is reduced to various organic molecules Or chemical products, effectively realize greenhouse gases CO2A kind of technology of recycling.With renewable Energy source utilizing electricity generating techn is developed rapidly, and the cost of generation technology is expected to significantly decline.Using renewable The energy generates electricity, and recycles electric energy by carbon dioxide synthesis of organic substance, realizes electric energy to chemical transformation of energy, Circulation and the energy conversion cycles of carbon will so be formed.ERC technologies can not only save oil, day The right fossil energy such as gas and coal, and turn waste into wealth, make CO2It is utilized effectively, reduces CO2 The environmental pollution for causing.Therefore, ERC technologies have potential economic benefit and environmental benefit.Someone It is expected, following CO2Chemical turns into new organic chemical industry's system, and its development is to solving people The energy and environmental problem that class faces are significant.
CO2Electrochemical reduction prepares organic acid such as formic acid, acetic acid, and to be that in ERC technologies is important grind Study carefully direction.The organic acid of preparation, can be used for medicine, agricultural chemicals, organic synthesis etc., therefore with very Application value and economic worth high.Be presently used for preparing the catalyst of organic acid mainly have In, Hg, Pb, Sn, Zn, Cu etc., electrochemical reduction CO2Activity order：In>Hg>Pb>Sn>Zn≈Cu. In is comparing high in the efficiency of catalysis carbon dioxide reduction generation organic acid, and such as K Ito utilize metal In does negative electrode and CO is reduced in water-soluble medium2Formic acid processed, faradic efficiency reaches as high as 80%, but Because In, Bi belong to rare metal, global reserves are little, therefore its cost of material is expensive, Limit its development prospect.The metals such as Pb, Hg belong to heavy metal, and toxicity is limited in fact than larger Apply on border.
Sn base catalyst is catalysis CO2One of effective catalyst of reduction generation organic acid.Due to Sn gold Category is largely present in the earth's crust, less expensive, for large-scale commercial Application, it will make into Originally substantially reduce.Finally, it is used to reduce CO relative to other2Organic acid processed catalyst (Pb, Cd, Hg etc.), Sn metals are also very little for the pollution of environment, are a kind of environment-friendly metal catalytics Agent.Therefore Sn base catalyst is a kind of ERC catalyst with very big Research Prospects.But current Sn The performance of catalyst is also than relatively low.
Many people recycle PTFE as viscous by using catalyst such as chemical method synthesizing tin oxide, tin Knot agent, is sprayed to diffusion layer surface, obtains electrode.But this preparation method is more complicated, And the performance of electrode is relatively low (faradic efficiency is less than 60%).Additionally, above-mentioned electrode is mainly passing through Various methods by Sn catalyst preparations on tinfoil paper and glassy carbon electrode, in actual application, it is necessary to The catalyst of preparation is scraped off on electrode, then by adhesive coated to carbon-based basal surface, so that Cause electrode fabrication process cumbersome, and prepare catalyst due to the cladding of binding agent, under active specific surface Drop, so as to cause active reduction.
The content of the invention
The present invention is in order to solve the above technical problems, by electrochemical method, the in-situ deposition Sn in substrate Nanorods Catalyst, prepare Sn catalyst porous gas diffusive electrode set up stabilization gas/liquid/ Gu three phase boundary, shortening gas diffusion path, raising electrode reaction speed, can not only simplify catalysis The preparation process of agent, it is possible to the advantage crystal face and pattern of catalyst are effectively controlled, so as to regulate and control electrode Performance.
To achieve the above object, the concrete technical scheme that the present invention is used is as follows：
A kind of Carbon dioxide electrochemical reduction electrode, including the Sn adhered on basalis and basalis Catalyst nano layer, the loading of Sn catalyst is 1mg/cm-2-6mg/cm in electrode-2, in electrode Sn by one or two or more kinds group in nano wire, nanometer rods, the nanofiber of 1nm-500nm Into.
A kind of Carbon dioxide electrochemical reduction electrode preparation method,
1) charcoal felt, carbon paper or carbon slab are carried out into treatment 6-24 hours at 200~600 DEG C in atmosphere, then As substrate after oil removal treatment cleaning being carried out in ethanol or acetone；
2) it is 0.01M-0.5M SnSO by concentration4Solution, with 0.05M-3M H2SO4With 0.01M~1.0M Additive, be 50 with Sn and additive mol ratio：1~1：30 and SnSO4With H2SO4's Mol ratio is 1:1~1：50 well mixed obtain mixture solution as electrolyte solution；
3) in electrolyte solution, constant current density or constant potential are carried out under inert atmosphere protection in substrate Upper deposition Sn 10s~5000s；
4) substrate with depositing Sn layers is reduced in 0.05-0.8M post processing electrolyte in -0.8V~-1.1V 30s-900s；
5) electrode with Sn Nanorods Catalysts is prepared after washing, drying.
Step 2) SnSO in the electrolyte solution4With H2SO4Preferred molar ratio example be 1:1-1:10； Additive is 20 with the preferred molar ratio example of Sn salt:1-1:10.
Step 3) constant current be -5mA/cm2~-200mA/cm2, preferably -20mA/cm2~ -100mA/cm2；Constant potential is -0.2V~-4V, preferably -0.3V~-1.5V；
The additive be octyl phenyl polyoxyethylene ether (trixton-100), polysorbas20 (TWEEN-20), Tween 21 (TWEEN-21), polysorbate40 (TWEEN-40), polysorbate60 (TWEEN-60), tween 61 (TWEEN-61), Tween 80 (TWEEN-80), sorbimacrogol oleate100 (TWEEN-81), tween 85(TWEEN-85)；Sapn；Gelatin；Polyethylene glycol, polyalkylene glycol alkyl alcohol ether, polyethylene glycol One or two or more kinds in propane diols block copolymer, OP (APES).
Step 3) sedimentation time is preferably 30s-2500s..
Step 4) it is described post processing electrolyte for 0.05M-0.5M HCl, H3PO4Or NaHCO3、 NaOH、NaCl、KCl、KHCO3, one kind in KOH.
The inert atmosphere is one or two or more kinds mixing in nitrogen, argon gas or helium atmosphere.
The negative electrode that the electrode can react as Carbon dioxide electrochemical reduction.
Using
By made electrode, as carbon dioxide reduction formic acid negative electrode.And by three-electrode system Carry out electro-chemical test：Working electrode is obtained electrode；It is Pt pieces to electrode, reference electrode is Hg/Hg2Cl2/ saturation KCl.The distance between WE and RE is 0.5cm, uses salt bridge to connect electricity to reduce liquid Gesture.Catholyte is 0.5M NaHCO3Aq.sol., electrolyte volume is 180ml.Anode electrolysis Liquid is 0.1M H2SO4aq.sol.
Compared with prior art, the beneficial effects of the invention are as follows：
There is provided a kind of electrode structure without binding agent, this kind of electrode need not additionally add binding agent, And can holding surface catalyst completely pattern, it is to avoid because the active sites that addition binding agent causes Loss；
It is coated with base on tinfoil paper and glassy carbon electrode and after the Sn catalyst that is directly synthesized compared to above-mentioned The method that electrode is prepared on bottom, has excellent method using the gas-diffusion electrode for preparing in situ of the invention Draw efficiency and the selectivity to carboxylic acid product.Prepared gas-diffusion electrode can not only improve electricity The effective active area of pole, can also improve the transmission of reactant, so as to reduce mass transfer polarization, improve Its performance, is more beneficial for the practical application of ERC.In addition method provided by the present invention is simple, easily-controllable, Beneficial to large-scale production.
There is provided a kind of new CO2The preparation method of electrochemical reduction electrode, i.e., with one kind with octyl group Phenyl APEO (trixton-100), polysorbas20 (TWEEN-20), tween 21 (TWEEN-21), Polysorbate40 (TWEEN-40), polysorbate60 (TWEEN-60), Tween61 (TWEEN-61), tween 80 (TWEEN-80), sorbimacrogol oleate100 (TWEEN-81), polysorbate85 (TWEEN-85)；Sapn；It is bright Glue；Polyethylene glycol, polyalkylene glycol alkyl alcohol ether, polyethylene glycol propane diols block copolymer, OP (alkane Base phenol polyethenoxy ether) it is additive, ordered structure electrode is prepared by electrochemical deposition, i.e., Growth in situ has the Sn nanometer rods of advantage crystal face in substrate, significantly improves the specific surface area of electrode With effective active area, electrochemical reduction activity of the catalyst to carbon dioxide is improve, and to organic The selectivity of acid；
The method can not only improve the effective active area of electrode with prepared gas-diffusion electrode, The transmission of reactant can also be improved, so as to reduce mass transfer polarization, its performance is improved, ERC is more beneficial for Practical application；Preparation method of the present invention simply, is easily grasped, conventional production device, is adapted to extensive life Produce, the electrode specific surface area of preparation is big, with carbon dioxide hydrogen reduction catalytic performance very high.
Brief description of the drawings
Fig. 1 embodiments 1,2,3 and comparative example 1 prepare the XRD spectra of electrode
The SEM photograph of electrode prepared by Fig. 2 embodiments 2；
The SEM photograph of electrode prepared by Fig. 3 embodiments 4；
The SEM photograph of electrode prepared by Fig. 4 comparative examples 1；
Fig. 5 embodiments 1 and comparative example 1 prepare the faradic efficiency of electrode.
Specific embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
Carbon paper is processed in atmosphere at 550 DEG C, is then carried out at oil removing in ethanol, acetone Clear after washing as substrate；It is 0.25M SnSO by concentration4Solution, with 0.7M H2SO4And 0.06M Trix100, it is well mixed to obtain mixture solution as electrolyte solution；In electrolyte solution, In N2Constant current density -60mA cm are carried out under atmosphere protection-2Potentiostatic electrodeposition 2000s；In post processing 0.5M NaHCO in electrolyte3In electrolyte solution 900s is reduced with -1.2V；Made after washing, drying It is standby to obtain Sn Nanorods Catalysts.Show from Fig. 5 relative to comparative example 1, electrode in embodiment 1 Performance is significantly improved.
Embodiment 2
Carbon paper is processed in atmosphere at 550 DEG C, is then carried out at oil removing in ethanol, acetone Clear after washing as substrate；It is 0.25M SnSO by concentration4Solution, with 0.8M H2SO4With 0.06 2 The OP of M, it is well mixed to obtain mixture solution as electrolyte solution；In electrolyte solution, In N2Constant current density -60mA cm are carried out under atmosphere protection-2Potentiostatic electrodeposition 2000s；In post processing 0.5M NaHCO in electrolyte3In electrolyte solution 900s is reduced with -1.2V；After washing, drying Prepare Sn Nanorods Catalysts.
Embodiment 3
Carbon paper is processed in atmosphere at 550 DEG C, is then carried out at oil removing in ethanol, acetone Clear after washing as substrate；It is 0.25M SnSO by concentration4Solution, with 0.8M H2SO4And 0.06M Gelatin, it is well mixed to obtain mixture solution as electrolyte solution；In electrolyte solution, N2Constant current density -60mA cm are carried out under atmosphere protection-2Potentiostatic electrodeposition 2000s；It is electrolysed in post processing 0.5M NaHCO in liquid3In electrolyte solution 900s is reduced with -1.2V；Prepared after washing, drying Obtain Sn Nanorods Catalysts.
Embodiment 4
Carbon paper is processed in atmosphere at 550 DEG C, is then carried out at oil removing in ethanol, acetone Clear after washing as substrate；It is 0.25M SnSO by concentration4Solution, with 0.8M H2SO4And 0.06M Tween-80, it is well mixed to obtain mixture solution as electrolyte solution；In electrolyte solution, In N2Constant current density -60mA cm are carried out under atmosphere protection-2Potentiostatic electrodeposition 2000s；In post processing electricity 0.5M NaHCO in solution liquid3In electrolyte solution 900s is reduced with -0.9V；Prepared after washing, drying Obtain Sn Nanorods Catalysts.From figure 3, it can be seen that the electrode surface catalyst for preparing is in Polygon flechette-type nanorod structure.
Embodiment 5
Carbon paper is processed in atmosphere at 550 DEG C, is then carried out at oil removing in ethanol, acetone Clear after washing as substrate；It is 0.25M SnSO by concentration4Solution, with 1.0M H2SO4And 0.03M Gelatin -80, it is well mixed to obtain mixture solution as electrolyte solution；In electrolyte solution, Constant current density -20mA cm are carried out under Ar atmosphere protections-2Potentiostatic electrodeposition 2000s；In post processing 0.5M NaHCO in electrolyte3In electrolyte solution 900s is reduced with -0.9V；Made after washing, drying It is standby to obtain Sn Nanorods Catalysts.
Embodiment 6
Carbon paper is processed in atmosphere at 450 DEG C, is then carried out at oil removing in ethanol, acetone Clear after washing as substrate；It is 0.5M SnSO by concentration4Solution, with 1.5M H2SO4And 0.02M OP, it is well mixed to obtain mixture solution as electrolyte solution；In electrolyte solution, N2Constant current density -150mA cm are carried out under atmosphere protection-2Potentiostatic electrodeposition 200s；It is electrolysed in post processing 0.8M KHCO in liquid3In electrolyte solution 100s is reduced with -1.0V；It is prepared into after washing, drying To Sn Nanorods Catalysts.
Embodiment 7
Carbon paper is processed in atmosphere at 300 DEG C, is then carried out at oil removing in ethanol, acetone Clear after washing as substrate；It is 0.4M SnSO by concentration4Solution, with 1.0M H2SO4And 0.10M TW-20, it is well mixed to obtain mixture solution as electrolyte solution；In electrolyte solution, Constant potential -0.5V Vs.SCE depositions 4000s is carried out under He atmosphere protections；In electrolyte is post-processed In 0.1M NaOH electrolyte solutions 500s is reduced with -0.7V；Sn is prepared after washing, drying Nanorods Catalyst.
Embodiment 8
Carbon paper is processed in atmosphere at 300 DEG C, is then carried out at oil removing in ethanol, acetone Clear after washing as substrate；It is 0.25M SnSO by concentration4Solution, with 0.7M H2SO4And 0.15M Sapn, it is well mixed to obtain mixture solution as electrolyte solution；In electrolyte solution, Constant potential -1.25V Vs.SCE depositions 500s is carried out under He atmosphere protections；0.1 in electrolyte is post-processed In M HCl electrolyte solutions 700s is reduced with -0.8V；Sn nanometer rods are prepared after washing, drying Catalyst.
Comparative example 1
Carbon paper is processed in atmosphere at 550 DEG C, is then carried out at oil removing in ethanol, acetone Clear after washing as substrate；It is 0.25M SnSO by concentration4Solution, with 0.8M H2SO4, mixing is The even mixture solution that obtains is used as electrolyte solution；In electrolyte solution, in N2Enter under atmosphere protection Row constant current density -60mA cm-2Potentiostatic electrodeposition 2000s；The 0.5M in electrolyte is post-processed NaHCO3In electrolyte solution 900s is reduced with -0.9V；Sn nanometers is prepared after washing, drying Rod catalyst.
From figure 1 it appears that adding different additives to obtain the catalyst of different advantage crystal faces. Embodiment 1 prepares catalyst (220) and (211) face is advantage crystal face；And Sn-OP in embodiment 2.
As can be seen that the electrode surface catalyst for preparing is in gyroscope-like nanorod structure in Fig. 2.

Claims (9)

1. a kind of Carbon dioxide electrochemical reduction electrode, it is characterised in that：Including basalis and basalis The Sn catalyst nanos layer of upper attachment, the loading of Sn catalyst is 1mg/cm in electrode-2-6 mg/cm-2, the Sn in electrode is by nano wire, nanometer rods, the nanofiber of 1nm-500nm One or two or more kinds composition.
2. a kind of Carbon dioxide electrochemical reduction electrode preparation method described in claim 1, its feature exists In：
1) charcoal felt, carbon paper or carbon slab are carried out into treatment 6-24 hours at 200~600 DEG C in atmosphere, Then as substrate after carrying out oil removal treatment cleaning in ethanol or acetone；
2) it is 0.01M-0.5M SnSO by concentration4Solution, with 0.05M-3M H2SO4With 0.01 The additive of M~1.0M, is 50 with Sn and additive mol ratio：1~1：30 and SnSO4With H2SO4 Mol ratio be 1:1~1：50 well mixed obtain mixture solution as electrolyte solution；
3) in electrolyte solution, constant current density or constant potential are carried out under inert atmosphere protection In deposition Sn 10s~5000s in substrate；
4) with deposition Sn layer substrate 0.05-0.8M post-process electrolyte in -0.8V~-1.2 V reduces 30s-900s；
5) electrode with Sn Nanorods Catalysts is prepared after washing, drying.
3. according to the preparation method described in claim 2, it is characterised in that：Step 2) electrolysis SnSO in matter solution4With H2SO4Preferred molar ratio example be 1:1-1:10；Additive is excellent with Sn salt It is 20 to select molar ratio:1-1:10.
4. according to the preparation method described in claim 1, it is characterised in that：Step 3) constant current For -5mA/cm2~-200mA/cm2, preferably -20mA/cm2~-100mA/cm2；Constant potential is - 0.2V~-4V, preferably -0.3V~-1.5V.
5. according to the preparation method described in claim 1, it is characterised in that：The additive is octyl group benzene Base APEO (trixton-100), polysorbas20 (TWEEN-20), tween 21 (TWEEN-21), Polysorbate40 (TWEEN-40), polysorbate60 (TWEEN-60), Tween61 (TWEEN-61), tween 80 (TWEEN-80), sorbimacrogol oleate100 (TWEEN-81), polysorbate85 (TWEEN-85)；Sapn；It is bright Glue；Polyethylene glycol, polyalkylene glycol alkyl alcohol ether, polyethylene glycol propane diols block copolymer, OP (alkane Base phenol polyethenoxy ether) in one or two or more kinds.
6. according to the preparation method described in claim 1, it is characterised in that：Step 3) deposition when Between be preferably 30s-2500s..
7. according to the preparation method described in claim 1, it is characterised in that：Step 4) post processing Electrolyte is HCl, H of 0.05M-0.5M3PO4Or NaHCO3、NaOH、NaCl、KCl、 KHCO3, one kind in KOH.
8. according to the preparation method described in claim 1, it is characterised in that：The inert atmosphere be nitrogen, One or two or more kinds mixing in argon gas or helium atmosphere.
9. the application of electrode described in a kind of claim 1, it is characterised in that：The electrode can be used as dioxy Change the negative electrode of carbon electrochemical reducting reaction.
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CN109518214A (en) * 2017-09-19 2019-03-26 株式会社东芝 The reducing catalyst body and its manufacturing method of carbon dioxide, reducing electrode and reduction reaction device
CN109852990A (en) * 2017-11-30 2019-06-07 中国科学院大连化学物理研究所 A kind of CO2Electrochemical reduction electrode and its preparation and application
CN109972162A (en) * 2019-05-13 2019-07-05 中国人民解放军军事科学院防化研究院 A kind of electro-chemistry oxygen-producing method
CN111519207A (en) * 2020-05-19 2020-08-11 大连大学 Preparation and application of Sn electrode for electrochemical reduction of carbon dioxide
CN111519207B (en) * 2020-05-19 2021-06-29 大连大学 Preparation and application of Sn electrode for electrochemical reduction of carbon dioxide

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