CN107177862A - One kind is used for electro-catalysis and reduces CO2Prepare the electrode structure and preparation method of ethene - Google Patents

One kind is used for electro-catalysis and reduces CO2Prepare the electrode structure and preparation method of ethene Download PDF

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CN107177862A
CN107177862A CN201710321714.6A CN201710321714A CN107177862A CN 107177862 A CN107177862 A CN 107177862A CN 201710321714 A CN201710321714 A CN 201710321714A CN 107177862 A CN107177862 A CN 107177862A
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ethene
copper
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electrode
deposition
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毛庆
景维云
黄延强
刘松
杜兆龙
肖宇
刘灵惠
陈孝东
石越
银光照
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Dalian University of Technology
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Dalian University of Technology
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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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

It is used for electro-catalysis the present invention relates to one kind and reduces CO2Prepare the electrode structure and preparation method of ethene.The Cu Cu that electrode is mainly inlayed by conductive support layer and top layer2O is constituted, wherein Cu Cu2O is prepared using electro-deposition mode.Its synthesis material mol ratio is 1:5~20 copper sulphate and lactic acid, by modulation electro-deposition parameter, is realized to CO2The control of reduzate ethene.The embedding cathode construction feature of the copper is that it can not only lift CO2The selectivity of ethene in electro-catalysis reduzate, but also the stability of electrode operation can be improved.Preparation method of the present invention is simple, and the electrode of preparation possesses higher ethylene selectivity, is adapted to large-scale production.

Description

One kind is used for electro-catalysis and reduces CO2Prepare the electrode structure and preparation method of ethene
Technical field
Converted the present invention relates to the circulation of carbon resource and energy, it is specifically a kind of to be used for electro-catalysis reduction CO2Prepare The electrode structure and preparation method of ethene.
Background technology
At this stage, with the development of society and economy, energy and environment are just more and more paid close attention to by people.Due to CO2Excess emissions caused by greenhouse effects turn into one of most concerned environmental issue in the whole world.In order to reduce in air CO2Content, " negative carbon economy " as a kind of Sustainable Development pattern based on sorption enhanced carbon dioxide, in CO2Recycle During progressively approved.Around CO2Recycling, electro-catalysis technology is due to system architecture is simple, environment is friendly The advantage such as good, reaction condition is gentle, and receive significant attention.CO2Under electric field action, generation CO, CH can be reduced4、C2H4Deng The liquid product such as gas-phase product and formic acid, ethanol, wherein ethene due to its higher volumes specific energy density and economic value added, By common concern in research.Around the research of product ethylene, Hori (Chemistry Letters, 1985,14 (11): 1695-1698) find that Ni metal paper tinsel surface has the conversion ratio of higher ethene.But Ni metal paper tinsel is in catalysis CO2Deposited in electroreduction Stability is poor, selectivity low and higher overpotential the problems such as, limit its and further develop.
It is presently used for CO2The preparation of electroreduction ethene electrode, research work surrounds Cu and Cu base electrodes all the time.CN 105420751 A disclose a kind of electrochemical reduction CO2The method for preparing hydrocarbon, if proposing, electrolyte solution uses nothing Machine salt and organic solvent double solvents, Cu electrode surfaces CO2Electrochemical reduction prepares hydrocarbon (CH4、C2H4、C2H6) Transformation efficiency can improve 10%~50%.The same A of CN 105304910 disclose a kind of CO2Electroreduction produces hydrocarbon Electrode and its technology of preparing.Using basalis, Porous Cu nanometer layer and there is copper whisker layer to constitute electrode.Control above-mentioned three layers Thickness, can improve CO2The selectivity of reduzate methane.The A of CN 102284293 disclose a kind of for CO2Photoelectrocatalysis is also Former Cu/Cu2O membrane electrodes.Electrochemistry anodic oxidation is respectively adopted and chemical " boiling " (reducing process) is made on Cu substrates Obtain p-type and n-type Cu2O films.Both combination electrode materials are respectively used to CO2Photo catalytic reduction, electro-catalysis reduction and Photoelectricity is catalyzed reduction altogether.For the yield of ethene, research shows：Fine copper is under electro-catalysis reduction, and the output of ethene is 159.8ppm, and n-type Cu-Cu2O and p-type Cu-Cu2O ethylene yield can be respectively increased to 174.1ppm under electro-catalysis reduction And 330.8ppm, and under photoelectricity altogether catalytic condition, the yield of ethene can be respectively increased to 471.3ppm and 501.4ppm.CN 103566934 A disclose a kind of preparation for the carbon dioxide electric reduction catalyst that nano cuprous oxide wire is synthesized by hydro-thermal method Technique, raw material by different volumes than copper acetate and aminoanisole constitute.In CO2In electro-reduction process, CO is improved2Electricity is urged Change reactivity, and effectively suppress liberation of hydrogen process.To point out that above-mentioned composite electrode catalyst needs to be supported on carbon-based for patent simultaneously Gas-diffusion electrode surface, its catalytic effect can just obtain maximum performance.In order to solve the monistic problem of base material, CN 105322183 A disclose a kind of for CO2Electrochemical reduction synthesizes method for preparing composite electrode with hydro-thermal method, and the electrode is to steep Foam copper, copper mesh, copper foil, copper coin, titanium net and titanium plate are base material.With various concentrations Cu presomas (nitrate, carbonate, Sulfate etc.) and template (CTAB, CTAC, SDS etc.) be used as mixed solution.Combination electrode is through being heat-treated a period of time in oxygen Afterwards, the electroreduction and in acidic electrolyte solution, obtaining has nano whisker, the Cu combination electrodes of nanometer flower structure, the electrode To CO2The selectivity of reduzate methane is significantly improved.For CO2Study of electrocatalysis work it is more, but for production Thing ethene, detailed research and probe is not carried out in above-mentioned work.
The present invention proposes a kind of by electro-deposition acquisition conductive support layer surface C u-Cu2The preparation method of O films.With biography Unite Cu2O preparation scheme is compared, and is trace p-type Cu-Cu obtained by preparation of the invention2O composite constructions.It is not only in CO2Reduction Product ethylene selectivity is more protruded, and can keep in long-time electro-reduction process good stability.
The content of the invention
Critical problem to be solved by this invention is to provide one kind and can ensured in long-time electrolytic reduction process The electrode structure and technology of preparing of Reductive stability are improved while high conversion of ethylene.Using electro-deposition method, using Cu as Main conductive support layer surface deposits trace (coulomb amount) Cu-Cu2O membrane structures.By changing electro-deposition parameter, modulation support Layer surface Cu2The electrode structure of O films.
Concrete technical scheme is：
One kind is used for electro-catalysis and reduces CO2The electrode structure of ethene is prepared, the electrode structure includes conductive support layer and electricity Chemical deposition layer, in conductive support layer outside deposition electrochemical deposition layer, wherein, conductive support layer for slab construction copper, Carbon, Au, Pt, Ag, Zn or loose structure carbon paper, foam copper, nickel foam, titanium foam；Wherein electrochemical deposition layer is Cu- Cu2O membrane structure, it is 0.5C/cm that it, which deposits coulomb amount,2~4C/cm2。
Above-mentioned electrode structure preparation method, comprises the following steps：
A, conductive support layer pretreatment
1. conductive support layer in the phosphoric acid of volumetric concentration 85% with current density 50mA/cm2~250mA/cm2Carry out electricity After polishing, deionized water rinsing is used；
2. it is placed in ultrasonically treated in absolute ethyl alcohol after taking out, and uses deionized water rinsing, drying for standby；
B, electrochemical deposition
Added in H type cathode of electrolytic tank room by mantoquita presoma and lactic acid mixed solution, mantoquita presoma and lactic acid Mol ratio is 1:5~20, pH value of solution scope is 9~12；Wherein Pt is as auxiliary electrode, and working electrode is that step a pre-processes it Conductive support layer afterwards；Reference electrode uses saturation calomel；Deposition process includes the following two kinds pattern：
1. constant current mode：Depositing temperature is controlled at 40 DEG C~80 DEG C；Depositing current density is 2mA/cm2~40mA/cm2、 Coulomb amount is deposited in 0.5C/cm2~4C/cm2；
2. potentiostatic mode：Depositing temperature is controlled at 40 DEG C~80 DEG C；Control sedimentation potential interval -0.2V~-0.4V, sink Product coulomb amount is in 0.5C/cm2~4C/cm2。
Further, described conductive supporting layer material is the copper of slab construction, carbon, Au, Ag, Zn or loose structure Carbon paper, foam copper, nickel foam, titanium foam.
Further, described Cu salt precursors body is copper sulphate, copper acetate, copper nitrate or copper chloride.
Beneficial effects of the present invention are：
(1) electrode material is prepared and mainly obtained by electrochemical deposition.Plating solution composition is common inorganic salts and organic molten Agent, and all there is good dispersiveness in water, not only preparation process is relatively simple but also possesses preferable ethene output.
(2) in electrodeposition process, when conductive supporting layer surface deposits Cu2O-Cu thin layer coulomb amounts are in 0.5C/cm2~4C/ cm2Between, the faradic efficiency of product ethylene can reach more than 30%.
Brief description of the drawings
Fig. 1 is electrochemical deposition Cu2O-Cu film apparatus.In figure：1 conductive support layer；2 waters bath with thermostatic control；3 platinum electrodes；4 electricity Chem workstation；5 saturated calomel electrodes, 6Nafion films (115)
Fig. 2 be 25 DEG C at, 0.1M KHCO3Solution, copper foil and the embedding Cu foil electrodes of Cu are in CO2It is different in reduction process also to originate in Thing ethene changes with time trend.
Fig. 3 is the embedding Cu foil electrodes XRD pictures of copper foil surface crystal face Cu at 60 DEG C.
Fig. 4 be 25 DEG C at, 0.1M KHCO3Solution, depositing temperature and the embedding Cu foil electrodes CO of Cu2Electro-catalysis reduces ethylene process processed Draw the contact of efficiency.
Fig. 5 be 25 DEG C at, 0.1M KHCO3Solution, the embedding carbon papers of Cu and carbon paper electrode are in CO2Electro-catalysis reduces ethene farad processed The contact of efficiency.
Fig. 6 be 25 DEG C at, 0.1M KHCO3Solution, the embedding foam coppers of Cu and foam copper electrode are in CO2It is different in reduction process to go back Former product ethylene changes with time trend.
Fig. 7 be 25 DEG C at, 0.1M KHCO3Solution, deposition coulomb amount and the embedding Cu paper tinsels negative electrode CO of Cu2Electro-catalysis reduces ethene processed Faradic efficiency changes with time trend.
Fig. 8 be 25 DEG C at, 0.1M KHCO3Solution, depositing current density and the embedding Cu paper tinsels negative electrode CO of Cu2Electro-catalysis reduces second processed Alkene performance changes with time trend；(a)2mA/cm2；(b)20mA/cm2；(c)40mA/cm2。
Fig. 9 be 25 DEG C at, 0.1M KHCO3Solution, mantoquita presoma prepares the embedding Cu paper tinsels negative electrode CO of Cu to electro-deposition2Electro-catalysis Reduction ethene performance processed changes with time trend；(a) copper acetate；(b) copper chloride.
Figure 10 be 25 DEG C at, 0.1M KHCO3Solution, sedimentation potential and the embedding Cu paper tinsels negative electrode CO of Cu2It is different in reduction process to go back Original thing changes with time trend；(a)-0.2V；(b)-0.25V；(c)-0.4V.
Figure 11 be 25 DEG C at, 0.1M KHCO3Solution, electroplate liquid material molar ratio (lactic acid:Copper sulphate) it is cloudy with the embedding Cu paper tinsels of Cu Pole CO2Electro-catalysis reduces ethene performance processed and changed with time trend；(a)5:1；(b)10:1；(c)20:1.
Figure 12 be 25 DEG C at, 0.1M KHCO3Solution, conductive support layer electropolishing current density (copper foil) and the embedding Cu paper tinsels of Cu Negative electrode CO2Electro-catalysis reduces ethene performance processed and changed with time trend；(a)50mA/cm2；(b)125mA/cm2；(c)250mA/ cm2
Figure 13 be 25 DEG C at, 0.1M KHCO3Solution, the electroplate liquid pH and embedding Cu paper tinsels negative electrode CO of Cu2Electro-catalysis reduces ethene processed Performance changes with time trend；(a) pH=9；(b) pH=11；(b) pH=12.
Embodiment
In order to further illustrate the present invention, enumerate following examples and introduce CO2The preparation and application of electro-catalysis reducing electrode, It is not intended to limit the scope of invention.
Embodiment 1：The preparation of the embedding Cu foil electrodes of Cu and its CO2Electro-catalysis reduces ethene performance processed
CO is prepared using electro-deposition method2Electro-catalysis reduces the embedding Cu foil constructions negative electrodes of Cu, prepares constant temperature electrolytic cell used such as Shown in Fig. 1.It is made up of anode chamber, cathode chamber and dielectric film.Cathode chamber is built-in with plating catholyte solution, the Cu as working electrode Paper tinsel and saturated calomel electrode are used as reference electrode；Dielectric film be PEM (such as：Nafion membrane)；Anode chamber place by The auxiliary electrode that inertia oxygen-absorbing material is constituted.Wherein, negative electrode plating solution is mixed with by Cu salt precursors body and lactic acid, and adjust pH to 9~12.Fig. 2 is provided with electro-deposition Cu2O-Cu is working electrode, CO with Cu paper tinsels2Hydro carbons reduzate ethene faradic efficiency is at any time Between variation tendency, wherein copper foil surface Cu2O-Cu deposition coulomb amounts are 1C/cm2, depositing temperature is 60 DEG C.Can be obvious from figure Find out, copper foil surface deposition modification Cu2After O-Cu, CO2The faradic efficiency of ethene is gradually promoted to by 18% in reduzate 40%, while the undamped phenomenon in 120min electrolytic reduction process.Fig. 3, which is provided, deposits the embedding Cu foil electrodes XRD of Cu at 60 DEG C Image, as can be seen from the figure：2 θ values all correspond to for the diffraction maximum at 43.7 °, 50.7 ° and 74.8 ° belongs to Ni metal, and 29.8 °, 37.4 ° and 61.8 ° respectively pair and Cu2O (110), (111), (220).Under said temperature scope deposition, it was demonstrated that Cu2O- The presence of Cu structures.
Embodiment 2：Depositing temperature is with the embedding Cu foil electrodes of Cu in CO2Electro-catalysis reduces the relation of ethene performance processed
Depositing current density is 2mA/cm2Under, control sedimentation time be 500s, depositing temperature is changed to respectively 40 DEG C, 60 DEG C and 80 DEG C, prepare the embedding Cu foil electrodes of Cu.Fig. 4 gives CO2Electro-reduction process product ethylene faradic efficiency is with heavy Product temperature changing trend.Its electroreduction temperature control is at 25 DEG C, and reduction potential is -1.90V (vs.SCE).When depositing temperature is 40 DEG C when, the faradic efficiency of product ethylene is up to 35%, when further improving depositing temperature to 60 DEG C, and the FE of ethene is carried in product Rise to 40%.And after temperature reaches 80 DEG C, the FE of ethene ranges up to 41%.Compared to Cu paper tinsel surface Cs O2Electro-catalysis is reduced The faradic efficiency 18% of ethene, is obviously improved.
Embodiment 3：Carbon paper and the embedding carbon paper negative electrodes of Cu, foam copper and the embedding foam cathode CO of Cu2Electro-catalysis reduces ethene processed The comparison of performance
Fig. 5 is provided with the embedding carbon paper of copper and carbon paper electrode surface C O2Reduzate changes over time trend.The wherein embedding carbon paper of copper Surface C u2O deposition coulomb amounts are 0.5C/cm2.From the graph, it is apparent that carbon paper surface modification is with Cu2After O-Cu, also originate in The amount of ethene can be promoted to 25% by 0% in thing.
Fig. 6 is provided with the embedding foam copper of copper and foam copper electrode surface CO2Reduzate changes over time trend.Wherein, copper Embedding foam copper surface C u2O deposition coulomb amounts are 0.5C/cm2.It can be seen that after the embedding foam copper electrode structures of Cu are formed The faradic efficiency of electrode surface ethene is obviously improved to 18% from 12%.
Embodiment 4：Deposit coulomb amount and the embedding Cu paper tinsels negative electrode CO of Cu2Electro-catalysis reduces the contact of ethene performance processed
Fig. 7 provides deposition respectively 0.5C/cm respectively2~4C/cm2The embedding Cu foil electrodes of Cu for CO2Electrochemistry is also The faradic efficiency of former product ethylene is changed over time.As can be seen that when reduction potential is -1.90V (vs.SCE), deposition For 0.5C/cm2The embedding Cu foil electrodes ethene of Cu faradic efficiency be 38%.Deposition is 4C/cm2The embedding Cu foil electrodes second of Cu The faradic efficiency of alkene is 32%.Compared to Cu paper tinsel surface Cs O2Electro-catalysis reduces the faradic efficiency 18% of ethene, has significantly Lifting.The faradic efficiency of ethene is still significantly higher than Cu paper tinsels after 120min is electrolysed stability test process.
Embodiment 5：Depositing current density and the embedding Cu paper tinsels negative electrode CO of Cu2Electro-catalysis reduces the contact of ethene performance processed
At 60 DEG C, current density is respectively adopted for 2mA/cm2、20mA/cm2And 40mA/cm2In Cu paper tinsels surface electro-deposition system The embedding Cu foil electrodes of standby Cu, deposition electricity is all 1C/cm2.In 25 DEG C, 0.1M KHCO3In solution, the faraday of electrode surface ethene Efficiency is as shown in Figure 8.As can be seen that in depositing current density in 2mA/cm2When, the initial faradic efficiency of product ethylene can be with 40% is reached, its activity of conversion is without obvious relaxation phenomenon in 120min electrolysis test process.When being in depositing current density 20mA/cm2When, within initial electrolysis 30min, the faradic efficiency of reduzate ethene was up to 23%, in reaction 120 minutes Afterwards, ethene faradic efficiency is 20%, is decayed up to 13%.It is 40mA/cm in depositing current density2When, reduzate ethene Initial faradic efficiency is 25%, after reaction 120 minutes, ethene faradic efficiency decay 20%.
Embodiment 6：Mantoquita presoma prepares the embedding Cu paper tinsels negative electrode CO of Cu to electro-deposition2Electro-catalysis reduces the shadow of ethene performance processed Ring.
It is 2mA/cm in current density using Cu paper tinsels as substrate at 60 DEG C2Under the conditions of copper acetate and chlorination copper is respectively adopted The embedding Cu paper tinsels negative electrodes of standby Cu, deposition coulomb amount is 1C/cm2。CO2The faradic efficiency of electro-catalysis reduzate ethene is changed over time Curve is respectively as shown in Fig. 9 (a) and (b).As can be seen that preparing the embedding Cu foil electrodes of Cu by presoma of copper acetate, it originates second Alkene faradic efficiency is 39%；Ethene faradic efficiency is 36% after 120min is electrolysed.Second is originated compared to Cu foil electrodes The 18% of alkene faradic efficiency and 15% after 120min is electrolysed, it is significantly improved.Prepared by presoma of copper chloride copper The embedding Cu foil electrodes of Cu, it is 41% that it, which originates ethene faradic efficiency,；Ethene faradic efficiency is 42% after 120min is electrolysed. The same ethene faradic efficiency compared to Cu foil electrodes is significantly improved.
Embodiment 7：Sedimentation potential and the embedding Cu paper tinsels negative electrode CO of Cu2Electro-catalysis reduces the contact of ethene performance processed
At 60 DEG C, -0.2V, -0.25V is respectively adopted and -0.4V potentiostatic electrodepositions prepare the embedding Cu foil electrodes of Cu, its surface CO2Electro-catalysis is converted into shown in faradic efficiency such as Figure 10 (a), (b) and (c) of ethene.It can be seen that when deposition electricity When position is -0.2V, the faradic efficiency of product ethylene is 39% after initial launch 30min, in 120min stability test The faradic efficiency decay of middle product ethylene is only 5%.When sedimentation potential is -0.25V, the faradic efficiency of product ethylene exists 39% is also can reach after initial launch 30min, the faradic efficiency decay of product ethylene can in 120min stability test Up to 13%.Compared to Cu paper tinsels in 120min electrolysis test process, the faradic efficiency decay 17% of ethene has clear improvement.Heavy When product current potential is -0.4V, the faradic efficiency of ethene is reachable 37% within the 30min of initial electrolysis, but performance degradation is more Significantly.After operation 120min, the decay of ethene faradic efficiency is up to 35%.
Embodiment 8：Electroplate liquid material molar ratio and the embedding Cu paper tinsels negative electrode CO of Cu2Electro-catalysis reduces the contact of ethene performance processed
It is 2mA/cm in current density using Cu paper tinsels as substrate at 60 DEG C2Under the conditions of n is respectively adoptedLactic acid：nCopper sulphate=5:1、 10:1 and 20:1 prepares the embedding Cu paper tinsels negative electrodes of Cu, and deposition coulomb amount is 1C/cm2。CO2Faraday's effect of electro-catalysis reduzate ethene Rate changes over time curve respectively as shown in Figure 11 (a), (b) and (c).As can be seen that raw material compares nLactic acid：nCopper sulphate=5:1 prepares Cu Embedding Cu foil electrodes, it is 39.8% that it, which originates ethene faradic efficiency,；Ethene faradic efficiency is after 120min is electrolysed 40.8%.Compared to Cu foil electrodes originate ethene faradic efficiency 18% and after 120min is electrolysed 15%, have substantially Improve.N is equally being compared with raw materialLactic acid：nCopper sulphate=10:1 prepares the embedding Cu foil electrodes of Cu, and its starting ethene faradic efficiency is 39.4%；Ethene faradic efficiency is 40.5% after 120min is electrolysed.N is compared with raw materialLactic acid：nCopper sulphate=20:1 time preparation Cu Embedding Cu foil electrodes, it is 38.4% that it, which originates ethene faradic efficiency,；Ethene faradic efficiency is after 120min is electrolysed 39.9%.The same ethene faradic efficiency compared to Cu foil electrodes is significantly improved.
Embodiment 9：Conductive support layer electropolishing current density and the embedding Cu paper tinsels negative electrode CO of Cu2Electro-catalysis reduces ethene performance processed Contact
Under room temperature condition, by conductive support layer in phosphoric acid (v%=85) respectively with current density 50mA/cm2、125mA/ cm2And 250mA/cm2Carry out electropolishing processing.At 60 DEG C, using current density as 2mA/cm2Under the conditions of prepare the embedding Cu paper tinsels negative electrodes of Cu, It is 1C/cm to deposit coulomb amount2。CO2The faradic efficiency of electro-catalysis reduzate ethene changes over time curve respectively such as Figure 12 (a), shown in (b) and (c).As can be seen that polishing current density is 50mA/cm2The embedding Cu foil electrodes of lower preparation Cu, it originates ethene Faradic efficiency is 36.2%；Ethene faradic efficiency is 38.5% after 120min is electrolysed.Compared to the starting of Cu foil electrodes The 18% of ethene faradic efficiency and 15% after 120min is electrolysed, it is significantly improved.It is same to polish current density For 125mA/cm2The embedding Cu foil electrodes of lower preparation Cu, it is 39.2% that it, which originates ethene faradic efficiency,；The second after 120min is electrolysed Alkene faradic efficiency is 39.4%.To polish current density as 250mA/cm2The embedding Cu foil electrodes of Cu are prepared, it originates ethene farad Efficiency is 36.9%；Ethene faradic efficiency is 39.2% after 120min is electrolysed.The same second compared to Cu foil electrodes Alkene faradic efficiency is significantly improved.
Embodiment 10：The electroplate liquid pH and embedding Cu paper tinsels negative electrode CO of Cu2Electro-catalysis reduces the contact of ethene performance processed
It is 2mA/cm in current density using Cu paper tinsels as substrate at 60 DEG C2Under the conditions of electroplate liquid pH=9, pH=is respectively adopted 11 and pH=12 prepares the embedding Cu paper tinsels negative electrodes of Cu, and deposition coulomb amount is 1C/cm2。CO2The faraday of electro-catalysis reduzate ethene Efficiency changes over time curve respectively as shown in Figure 13 (a), (b) and (c).As can be seen that it is embedding that Cu is prepared under electroplate liquid pH=9 Cu foil electrodes, it is 39.8% that it, which originates ethene faradic efficiency,；Ethene faradic efficiency is 30.8% after 120min is electrolysed. Compared to Cu foil electrodes originate ethene faradic efficiency 18% and after 120min is electrolysed 15%, be significantly improved. To prepare the embedding Cu foil electrodes of Cu under electroplate liquid pH=11, it is 36.2% that it, which originates ethene faradic efficiency,；It is electrolysed by 120min Ethene faradic efficiency is 39.6% afterwards, is significantly improved compared to Cu foil electrode ethene faradic efficiencies.Equally with electroplate liquid pH =12 times preparation embedding Cu foil electrodes of Cu, it is 36.9% that it, which originates ethene faradic efficiency,；The ethene farad after 120min is electrolysed Efficiency is 39.2%.Ethene faradic efficiency compared to Cu foil electrodes is significantly improved.

Claims (4)

1. one kind, which is used for electro-catalysis, reduces CO2Prepare the electrode structure of ethene, it is characterised in that the electrode structure includes conductive prop up Layer and electrochemical deposition layer are supportted, in conductive support layer outside deposition electrochemical deposition layer, wherein, conductive support layer is flat board knot The copper of structure, carbon, the carbon paper of Au, Pt, Ag, Zn or loose structure, foam copper, nickel foam, titanium foam；Wherein electrochemical deposition layer For Cu-Cu2O membrane structure, it is 0.5C/cm that it, which deposits coulomb amount,2~4C/cm2。
2. one kind described in claim 1, which is used for electro-catalysis, reduces CO2The electrode structure preparation method of ethene is prepared, its feature exists In comprising the following steps：
A, conductive support layer pretreatment
1. conductive support layer in the phosphoric acid of volumetric concentration 85% with current density 50mA/cm2~250mA/cm2Carry out electropolishing After processing, deionized water rinsing is used；
2. it is placed in ultrasonically treated in absolute ethyl alcohol after taking out, and uses deionized water rinsing, drying for standby；
B, electrochemical deposition
Added in H type cathode of electrolytic tank room by mantoquita presoma and lactic acid mixed solution, mole of mantoquita presoma and lactic acid Than for 1:5~20, pH value of solution scope is 9~12；Wherein Pt is as auxiliary electrode, and working electrode is after step a is pre-processed Conductive support layer；Reference electrode uses saturation calomel；Deposition process includes the following two kinds pattern：
1. constant current mode：Depositing temperature is controlled at 40 DEG C~80 DEG C；Depositing current density is 2mA/cm2~40mA/cm2, deposition Coulomb amount is in 0.5C/cm2~4C/cm2；
2. potentiostatic mode：Depositing temperature is controlled at 40 DEG C~80 DEG C；Control sedimentation potential interval -0.2V~-0.4V, deposition storehouse Logical sequence amount is in 0.5C/cm2~4C/cm2。
3. preparation method according to claim 2, it is characterised in that described conductive supporting layer material is slab construction Copper, carbon, the carbon paper of Au, Ag, Zn or loose structure, foam copper, nickel foam, titanium foam.
4. the preparation method according to Claims 2 or 3, it is characterised in that described Cu salt precursors body is copper sulphate, acetic acid Copper, copper nitrate or copper chloride.
CN201710321714.6A 2017-05-10 2017-05-10 One kind is used for electro-catalysis and reduces CO2Prepare the electrode structure and preparation method of ethene Pending CN107177862A (en)

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CN109811364A (en) * 2019-01-10 2019-05-28 北京化工大学 A kind of ruthenium/cuprous oxide electrocatalysis material and preparation method thereof
CN111378983A (en) * 2020-03-13 2020-07-07 大连理工大学 CO based on electrode solution system2Method for controlling electroreduction reaction
CN111850595A (en) * 2020-07-24 2020-10-30 中国科学技术大学 Photoelectrocatalysis system and preparation method thereof
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108400346A (en) * 2018-03-11 2018-08-14 浙江大学 A kind of preparation method of the overmolded carbon material of cuprous oxide
CN108588748A (en) * 2018-06-11 2018-09-28 浙江大学 A kind of method that Carbon dioxide electrochemical reduction prepares methane and ethylene
CN108823596A (en) * 2018-06-11 2018-11-16 浙江大学 Gas-diffusion electrode and preparation method thereof and the application in Carbon dioxide electrochemical reduction
CN108588748B (en) * 2018-06-11 2020-06-26 浙江大学 Method for preparing methane and ethylene by electrochemical reduction of carbon dioxide
CN109811364A (en) * 2019-01-10 2019-05-28 北京化工大学 A kind of ruthenium/cuprous oxide electrocatalysis material and preparation method thereof
CN112973398A (en) * 2019-12-13 2021-06-18 中国科学院大连化学物理研究所 An electrode with residual ions in CO2Application in electrochemical reduction reaction
CN111378983A (en) * 2020-03-13 2020-07-07 大连理工大学 CO based on electrode solution system2Method for controlling electroreduction reaction
CN111378983B (en) * 2020-03-13 2021-11-05 大连理工大学 CO based on electrode solution system2Method for controlling electroreduction reaction
CN111850595B (en) * 2020-07-24 2022-03-01 中国科学技术大学 Photoelectrocatalysis system and preparation method thereof
CN111850595A (en) * 2020-07-24 2020-10-30 中国科学技术大学 Photoelectrocatalysis system and preparation method thereof
CN112301375A (en) * 2020-10-10 2021-02-02 华东理工大学 Sulfur-modified Cu-based MOF material, preparation method and application thereof in electrocatalysis of CO2Application of reduction reaction
CN112323094A (en) * 2020-11-22 2021-02-05 赵玉平 Preparation method of sulfur-modified copper-based composite material and application of sulfur-modified copper-based composite material in electrocatalytic reduction of CO2
CN112323094B (en) * 2020-11-22 2024-02-27 德瑞宝(中国)复合材料有限公司 Preparation method and application of composite material
WO2022125831A1 (en) * 2020-12-10 2022-06-16 Saudi Arabian Oil Company Electrochemical reduction of carbon dioxide
US11447887B2 (en) 2020-12-10 2022-09-20 Saudi Arabian Oil Company Surface smoothing of copper by electropolishing
US11512400B2 (en) 2020-12-10 2022-11-29 Saudi Arabian Oil Company Electrochemical reduction of carbon dioxide
CN113968602A (en) * 2021-10-25 2022-01-25 中国科学院合肥物质科学研究院 Method for removing nitrified nitrogen in water through electro-catalysis
CN113968602B (en) * 2021-10-25 2023-11-24 中国科学院合肥物质科学研究院 Method for removing nitrified nitrogen in water by electrocatalytic treatment

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