CN107841760A - Electrochemical reduction CO2The gas-diffusion electrode preparation method of hydrocarbon processed - Google Patents

Electrochemical reduction CO2The gas-diffusion electrode preparation method of hydrocarbon processed Download PDF

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CN107841760A
CN107841760A CN201610830275.7A CN201610830275A CN107841760A CN 107841760 A CN107841760 A CN 107841760A CN 201610830275 A CN201610830275 A CN 201610830275A CN 107841760 A CN107841760 A CN 107841760A
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CN107841760B (en
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邱艳玲
张华民
钟和香
李先锋
张桃桃
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a kind of electrochemical reduction CO2The gas-diffusion electrode preparation method of hydrocarbon processed, this method includes porous carbon material heat treatment successively, the deposition of Cu Catalytic Layers, concentrated hydrochloric acid solution soak, and is dried up after cleaning with inert gas.The gas-diffusion electrode prepared with this method has the characteristics of Catalytic Layer particle fine uniform, electrochemical reaction area can significantly be expanded, simultaneously to the product methane of Carbon dioxide electrochemical reduction reaction, there is high selectivity, especially suitable in Carbon dioxide electrochemical reduction technology.

Description

Electrochemical reduction CO2The gas-diffusion electrode preparation method of hydrocarbon processed
Technical field
The invention belongs to Carbon dioxide electrochemical reduction technical field, the preparation skill of more particularly to a kind of gas-diffusion electrode Art.
Background technology
Electrochemical reduction CO2(ERC) technology is that one kind realizes CO2The technology of recycling, its prominent features are to utilize electricity Can be by CO2It is reduced to various organic chemicals.With other CO2Transformation technology is compared, and the outstanding advantages of ERC technologies is available Hydrogen source of the water as reaction, can be achieved CO at normal temperatures and pressures2Efficient Conversion, therefore do not need chemical conversion technology needed for Hydrogen manufacturing and heating, pressurization caused by energy expenditure, equipment investment is few.
At present, restricting the principal element of ERC technologies development includes：(1) it is high to react overpotential；(2) conversion ratio is low；(3) produce Thing poor selectivity.Wherein, in the ERC reaction systems using the aqueous solution as supporting electrolyte, usually using flat board (such as sheet, Foil-like and bulk) metal carrys out catalysis electrode course of reaction.The prominent defect of one of this kind of metal electrode is that electrode reaction area is small, The surface being in contact with supporting electrolyte is concentrated merely on, so as to form ERC reaction overpotential height and CO2The low important original of conversion ratio Cause；In addition, ERC courses of reaction are related to multiple electronic transfer process, therefore product distribution is wide, to the selectivity of specific product It is relatively low..
To expand in ERC reactions the electrode area used, researcher is by constructing the electrode surface of special appearance, increasing Active crystal grain boundary significantly expands electrochemical reaction area.Xie Yi etc. is in document Electrochimica Angew.Chem.Int.Ed.2016, report in 55,698~702, it is only 1.72 to receive that thickness is synthesized by way of quickly heating Rice and 3.51 nanometers of Co3O4Atomic layer, abundant active sites are obtained, ensure CO2A large amount of absorption, thickness be 1.72nm original 20h can be used continuously more than 20% in the faradic efficiency of sublayer catalysis generation formic acid..
Gas-diffusion electrode (GDE) is a kind of conductive composite material based on porous material structure, and it is most obvious special Sign is with abundant hole, is particularly suitable for building three-phase reaction interface, response area is expanded, in fuel cell, energy-storage battery Field is widely used, and researcher was also once introduced into Carbon dioxide electrochemical reduction field.Such as Hara is in document J.Electrochem.Soc.,1995,142(4):Reported in L57-L59, GDE is prepared using Pt nano particle as active component, CO2Pressure<Under the conditions of 50atm, Pt-GDE reduction CO2Current density reach 900mA cm-2, current efficiency 46%.But The generally spherical metal nanoparticle of catalyst used during GDE is built, and many non-noble metal nano particles are in sky Stability is bad in gas, and surface easily aoxidizes (such as red nano Cu is oxidized to black CuO), seriously reduces the catalysis of catalyst Effect, while also change product distribution.To maintain the high catalytic activity of metal nanoparticle, it usually needs to the GDE of preparation Activation process is carried out, process is cumbersome, and whard to control.
The content of the invention
The present invention proposes the gas-diffusion electrode preparation side that a kind of electrochemically reducing carbon dioxide produces hydrocarbon Method, effective catalyst component of the gas-diffusion electrode --- Cu particles are attached in a manner of pulse electrodeposition in gas diffusion base On bottom, electrochemical reaction area has significantly been expanded, has improved CO2The speed of electrochemical reaction, and the generation tool to hydrocarbon There is high selectivity, especially suitable in Carbon dioxide electrochemical reduction reactor.
To achieve the above object, technical scheme is as follows：
Electrochemical reduction CO2The gas-diffusion electrode preparation method of hydrocarbon processed, comprises the following steps：
1) porous carbon material is heat-treated：Porous carbon material is heated in atmosphere, the glued membrane of the carbon fiber surface of removal, increased Add its affinity to the aqueous solution, obtain gas diffusion substrate；
2) deposition of Cu Catalytic Layers：Under inert atmosphere protection, using the acid copper salt solution containing additive as plating solution, control Bath temperature processed, Cu particles are attached to the gas diffusion substrate of step 1) processing under stirring in a manner of pulse electrodeposition Surface, obtain gas-diffusion electrode；
3) gas-diffusion electrode prepared by step 2) is soaked in the concentrated hydrochloric acid solution that concentration is 36%~38%, cleaned Dried up after clean with inert gas.
The porous carbon material includes one kind in the carbon paper or charcoal cloth of braiding or non-woven, charcoal felt；At described heat It is 300 DEG C~800 DEG C to manage temperature, and processing time is 2~6h.
The porosity 70-90% of porous carbon material.
The Static water contact angular region of gas diffusion substrate is 60~130 degree.
Described acid copper salt solution is CuSO4、CuCl2、Cu(NO3)2In one kind, the concentration of copper ion for 0.05M~ 1.5M；Use 0.5M H2SO4Adjust the pH to 0.1~1.0 of copper salt solution.
Contain additive in described acid copper salt solution, additive be inorganic salts NaCl, KBr containing halogen, One kind in KI, or the organic matter containing one or both of N, O, S, Br above element, such as cetyl trimethyl Ammonium bromide (CTAB), polyvinyl alcohol (PEG), thiocarbamide (TU), one kind in amion acetic acid, the concentration of additive for 0.1mM~ 3.0mM。
In step 2), one kind for high pure nitrogen or in high-purity argon gas of gas that the inert atmosphere uses or two kinds with On, gas flow rate is 20~100ml min-1, optimum gas velocity is 40~70ml min-1；Described plating solution control temperature is Room temperature~80 DEG C, optimum temperature range are 30~60 DEG C；Described mixing speed is 100rpm~1000rpm, optimal stirring speed Spend for 300~600rpm.
Described pulse electrodeposition, depositional mode are that pulse current deposits or pulse potential deposits；
Described pulse current deposition, depositing current density is 10~200mAcm-2, optimal deposition electric current be 60~ 120mAcm-2；Oxide etch current density is 1~50mAcm-2, the optimal electric current that etches is 5~30mAcm-2；Pulse period is 1000~10000, the optimum pulse cycle is 3000~6000；Dutycycle be 20%~90%, optimum taking air ratio be 40%~ 75%；
Described pulse potential deposition, sedimentation potential is -0.5V~0V (relative to standard hydrogen electrode (SHE)), optimal heavy Product current potential is -0.3V~-0.1V；Oxidizing potential is 0.35V~0.6V (relative to standard hydrogen electrode (SHE)), and optimum oxidation is electric Position is 0.4V~0.5V；Pulse period is 1000~10000, and the optimum pulse cycle is 3000~6000；Dutycycle be 20%~ 90%, optimum taking air ratio is 40%~75%.
Described pulse electrodeposition, the auxiliary electrode in deposition process is using one kind in Cu pieces or Cu blocks, and its purity is not Less than 99.9%.
Described gas-diffusion electrode sample soaks in concentrated hydrochloric acid solution, and soaking temperature is normal temperature, soak time 10 ~30min, optimal soak time are 15~25min.
Compared with existing electro-deposition techniques, beneficial effects of the present invention are as follows：
1) the invention provides a kind of preparation method of Carbon dioxide electrochemical reduction gas-diffusion electrode, this method is used The gas-diffusion electrode of preparation has Catalytic Layer particle fine uniform, effective catalyst component-Cu particles of the gas-diffusion electrode It is attached in a manner of pulse electrodeposition in gas diffusion substrate, has significantly expanded electrochemical reaction area, improves CO2Electrification Learn reaction speed, while to Carbon dioxide electrochemical reduction reaction product-methane, there is high selectivity, especially suitable for In Carbon dioxide electrochemical reduction technology.
2) impulse electrodeposition technology for controlling technological parameter is applied to the preparation of gas-diffusion electrode, it can be ensured that each Root gas-diffusion electrode supporter fiber surface uniformly coats one layer of tiny catalyst particle, expands electrochemical reaction area； The loose structure of supporter can also be kept simultaneously, ensure that gas diffusion substrate quickly transmits gas and discharge liquor to electrode catalyst position The function of body, so as to improve carbon dioxide electrochemical reaction speed.
3) additive has structure-directing effect in electrodeposition process, it is ensured that catalyst particle is given birth to according to specific direction It is long, so as to obtain the Catalytic Layer with specific lattice orientation, and then the selectivity of product of carbon dioxide electrochemical reaction is carried out Control, the Cu Catalytic Layers prepared using the inventive method are to CH4FE efficiency be up to 85%, be that current open report is neutral One of Cu catalyst that can be optimal.
Brief description of the drawings
The crystal structure schematic diagram of the gas-diffusion electrode Catalytic Layer of Fig. 1 pulse currents deposition.
Embodiment
With reference to preferred embodiment, technical scheme is described further, but the technology contents of the present invention It is not limited only to described scope.
Comparative example 1
1. gas diffusion substrate is heat-treated：Air is passed through in tube furnace, air velocity 100mlmin-1, is by area 25cm2, thickness 0.2mm, porosity be 78% TGP-H-060 carbon papers after 500 DEG C are heat-treated 3h, be down to room temperature naturally, It is 90 degree to determine Static water contact angles.
2. galvanostatic deposition Cu Catalytic Layers：CuSO is prepared using deionized water4·5H2O content is 0.5M electroplate liquid, is added Enter 2M H2SO4The pH for adjusting plating solution is 0.5, using 0.6mM KBr as additive.First with 60ml min-1Speed to plating solution In be passed through high-purity N240min, to control bath temperature be 60 DEG C, stirring rotor speed is 500rpm, then to be handled by step 1 TGP-H-060 carbon papers be working electrode, the Cu pieces that Cu contents are 99.90% are that saturated calomel electrode is as reference to electrode Electrode, constant current electro-deposition is carried out using the potentiostats of VersaSTAT 3 (production of Princeton companies of the U.S.).Coordination electrode Effective area is 3cm2, depositing current density is 90mA cm-2, sedimentation time 3600s.After deposition process terminates, with largely going The Cu catalysis layer surfaces of ionized water cleaning TGP-H-060 carbon paper supports, are then dried up with Ar, obtain gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface will pass through step 1 and 2 processing obtain gas-diffusion electrode in room 20min is soaked in the dense HCl acid solutions of temperature, with a large amount of deionized water cleaning electrode surfaces.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H type electrolytic cells, 100ml 0.5M NaHCO are separately added into anode and cathode chamber3The aqueous solution and 50ml 0.1M KHCO3The aqueous solution, the barrier film using the NF115 that DuPont produces as anode and cathode chamber.Before test, first into cathode cavity It is passed through high-purity N240min, then pass to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.40min Afterwards, using gas-diffusion electrode as working electrode, Pt pieces are that saturated calomel electrode is reference electrode to electrode.Worked in -2.5V electric Pressure carries out electrochemical reducting reaction 16min, and reaction end gas is passed through the online quantitative detection that gas-chromatography carries out gaseous product, liquid Body product carries out quantitative analysis using chromatography of ions.
Liquid product HCOOH concentration is 2ppm, gaseous product CH4Concentration be 425ppm, C2H4Concentration is 10ppm, hydrocarbon Total faradic efficiency of compound is 35.8%.
Comparative example 2
1. gas diffusion substrate is heat-treated：Air is passed through in tube furnace, air velocity is 100ml min-1, is by area 25cm2, thickness 0.19mm, porosity be 78% TGP-H-060 carbon papers after 600 DEG C are heat-treated 2h, be down to room temperature naturally, It is 80 degree to determine Static water contact angles.
2. constant voltage deposits Cu Catalytic Layers：Cu (NO are prepared using deionized water3)2Content is 0.35M electroplate liquid, is added 2M H2SO4The pH for adjusting plating solution is 0.8, using 1.5mM amion acetic acid as additive, first with 100ml min-1Speed to High-purity N is passed through in plating solution240min, to control bath temperature be 60 DEG C, stirring rotor speed is 500rpm, then with by step 1 place The TGP-H-060 carbon papers of reason are working electrode, and the Cu pieces that Cu contents are 99.90% are that saturated calomel electrode is as ginseng to electrode Than electrode, potentiostatic electrodeposition is carried out using the potentiostats of VersaSTAT 3 (production of Princeton companies of the U.S.).Coordination electrode Effective area is 3cm2, sedimentation potential is -0.3V (relative to SHE), sedimentation time 3600s.After deposition process terminates, with big Deionized water cleaning electrode surface is measured, is then done with Ar air-blowings, obtains gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface exists the gas-diffusion electrode obtained by step 1 and 2 processing 5min is soaked in the dense HCl acid solutions of room temperature, with a large amount of deionized water cleaning electrode surfaces.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H type electrolytic cells, 100ml 0.5M NaHCO are separately added into anode and cathode chamber3The aqueous solution and 50ml 0.1M KHCO3The aqueous solution, the barrier film using the NF115 that DuPont produces as anode and cathode chamber.Before test, first into cathode cavity It is passed through high-purity N240min, then pass to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.40min Afterwards, using gas-diffusion electrode as working electrode, Pt pieces are that saturated calomel electrode is reference electrode to electrode.Worked in -2.5V electric Pressure carries out electrochemical reducting reaction 16min, and reaction end gas is passed through the online quantitative detection that gas-chromatography carries out gaseous product, liquid Body product carries out quantitative analysis using chromatography of ions.
Liquid product HCOOH concentration is 3.8ppm, gaseous product CH4Concentration be 350ppm, C2H4Concentration is 4ppm, carbon Total faradic efficiency of hydrogen compound is 28.5%.
Embodiment 1
1. gas diffusion substrate is heat-treated：Air is passed through in tube furnace, air velocity 100mlmin-1, is by area 25cm2, thickness 0.2mm, porosity be 78% TGP-H-060 carbon papers after 500 DEG C are heat-treated 3h, be down to room temperature naturally, It is 90 degree to determine Static water contact angles.
2. pulse current deposits Cu Catalytic Layers：CuSO is prepared using deionized water4·5H2O content is 0.5M electroplate liquid, Add 2M H2SO4The pH for adjusting plating solution is 0.5, using 0.6mM KBr as additive.First with 60ml min-1Speed to plating High-purity N is passed through in liquid240min, to control bath temperature be 60 DEG C, stirring rotor speed is 500rpm, then with by step 1 place The TGP-H-060 carbon papers of reason are working electrode, and the Cu pieces that Cu contents are 99.90% are that saturated calomel electrode is as ginseng to electrode Than electrode, pulse current deposition is carried out using the potentiostats of VersaSTAT 3 (production of Princeton companies of the U.S.).Control electricity Very effective area is 3cm2, depositing current density is 90mA cm-2, oxide etch current density is 20mAcm-2, dutycycle is 50%, pulse period 4000cycles.After deposition process terminates, clean TGP-H-060 carbon papers with a large amount of deionized waters and support Cu catalysis layer surface, then dried up with Ar, obtain gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface will pass through step 1 and 2 processing obtain gas-diffusion electrode in room 20min is soaked in the dense HCl acid solutions of temperature, with a large amount of deionized water cleaning electrode surfaces.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H type electrolytic cells, 100ml 0.5M NaHCO are separately added into anode and cathode chamber3The aqueous solution and 50ml 0.1M KHCO3The aqueous solution, the barrier film using the NF115 that DuPont produces as anode and cathode chamber.Before test, first into cathode cavity It is passed through high-purity N240min, then pass to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.40min Afterwards, using gas-diffusion electrode as working electrode, Pt pieces are that saturated calomel electrode is reference electrode to electrode.Worked in -2.5V electric Pressure carries out electrochemical reducting reaction 16min, and reaction end gas is passed through the online quantitative detection that gas-chromatography carries out gaseous product, liquid Body product carries out quantitative analysis using chromatography of ions.
Liquid product HCOOH concentration is 3.6ppm, gaseous product CH4Concentration be 1564ppm, C2H4Concentration is 45ppm, Total faradic efficiency of hydrocarbon is up to 85%, is 2.37 times of comparative example 1, illustrates the Cu that pulse current sedimentation obtains Catalytic Layer produces hydrocarbon (particularly CH to catalysis4) there is very high catalytic activity and selectivity.
As can be seen from Figure 1, the crystal grain of the Cu Catalytic Layers of pulse current deposition is more tiny, and the texture of each main crystal face Coefficient changes, and the ratio increase of (200) crystal face exposure, the electrodeposition method for illustrating to add additive can change catalysis Each crystal face ratio of layer, and then influence product distribution.
Embodiment 2
1. gas diffusion substrate is heat-treated：Air is passed through in tube furnace, air velocity is 100ml min-1, is by area 25cm2, thickness 0.10mm, porosity be 82% TGP-H-030 carbon papers after 300 DEG C are heat-treated 6h, be down to room temperature naturally, It is 130 degree to determine Static water contact angles.
2. pulse potential deposits Cu Catalytic Layers：CuCl is prepared using deionized water2Content is 1.0M electroplate liquid, adds 2M H2SO4The pH for adjusting plating solution is 0.2, using 0.3mM NaCl as additive, first with 100ml min-1Speed into plating solution lead to Enter high-purity Ar 40min, to control bath temperature be 30 DEG C, stirring rotor speed is 1000rpm, then to be handled by step 1 TGP-H-030 carbon papers are working electrode, and the Cu blocks that Cu contents are 99.5% are that saturated calomel electrode is as reference electricity to electrode Pole, pulse potential deposition is carried out using the potentiostats of VersaSTAT 3 (production of Princeton companies of the U.S.).Coordination electrode has Effect area is 3cm2, sedimentation potential is -0.3V (relative to SHE), and oxide etch current potential is 0.4V, dutycycle 60%, pulse Cycle is 6000cycles.After deposition process terminates, with a large amount of deionized water cleaning electrode surfaces, then done, obtained with Ar air-blowings To gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface exists the gas-diffusion electrode obtained by step 1 and 2 processing 30min is soaked in the dense HCl acid solutions of room temperature, with a large amount of deionized water cleaning electrode surfaces.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H type electrolytic cells, 100ml 0.5M NaHCO are separately added into anode and cathode chamber3The aqueous solution and 50ml 0.1M KHCO3The aqueous solution, the barrier film using the NF115 that DuPont produces as anode and cathode chamber.Before test, first into cathode cavity It is passed through high-purity N240min, then pass to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.40min Afterwards, using gas-diffusion electrode as working electrode, Pt pieces are that saturated calomel electrode is reference electrode to electrode.Worked in -2.5V electric Pressure carries out electrochemical reducting reaction 16min, and reaction end gas is passed through the online quantitative detection that gas-chromatography carries out gaseous product, liquid Body product carries out quantitative analysis using chromatography of ions.
Liquid product HCOOH concentration is 8pm, gaseous product CH4Concentration be 930ppm, C2H4Concentration is 9ppm, hydrocarbonization Total faradic efficiency of compound is 67%, is 2.35 times of comparative example 2, illustrates the Cu Catalytic Layers pair that pulse potential sedimentation obtains Catalysis produces hydrocarbon (particularly CH4) there is higher catalytic activity and selectivity..
Embodiment 3
1. gas diffusion substrate is heat-treated：Air is passed through in tube furnace, air velocity 100mlmin-1, is by area 25cm2, thickness 0.3mm, porosity be 80% charcoal cloth after 600 DEG C are heat-treated 2h, be down to room temperature naturally, determine Static Water Contact angle is 60 degree.
2. pulse current deposits Cu Catalytic Layers：Cu (NO are prepared using deionized water3)2Content is 0.05M electroplate liquid, is added Enter 2M H2SO4The pH for adjusting plating solution is 1, with 0.1mM cetyl trimethylammonium bromide (CTAB) for additive.First with 20ml min-1Speed high-purity Ar 40min is passed through into plating solution, it is 200rpm to control speed of agitator, then with pass through step 1 The TGP-H-060 carbon papers of processing are working electrode, and the Cu pieces that Cu contents are 99.999% are to electrode, saturated calomel electrode conduct Reference electrode, pulse current is carried out in room temperature using the potentiostats of VersaSTAT 3 (production of Princeton companies of the U.S.) and sunk Product.Coordination electrode effective area is 3cm2, depositing current density is 100mA cm-2, oxide etch current density is 5mAcm-2, account for Sky is than being 90%, pulse period 10000cycles.After deposition process terminates, with a large amount of deionized water cleaning electrode surfaces, so Dried up afterwards with Ar, obtain gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface will pass through step 1 and 2 processing obtain gas-diffusion electrode in room 10min is soaked in the dense HCl acid solutions of temperature, with a large amount of deionized water cleaning electrode surfaces.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H type electrolytic cells, 100ml 0.5M NaHCO are separately added into anode and cathode chamber3The aqueous solution and 50ml 0.1M KHCO3The aqueous solution, the barrier film using the NF115 that DuPont produces as anode and cathode chamber.Before test, first into cathode cavity It is passed through high-purity N240min, then pass to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.40min Afterwards, using gas-diffusion electrode as working electrode, Pt pieces are that saturated calomel electrode is reference electrode to electrode.Worked in -2.5V electric Pressure carries out electrochemical reducting reaction 16min, and reaction end gas is passed through the online quantitative detection that gas-chromatography carries out gaseous product, liquid Body product carries out quantitative analysis using chromatography of ions.
Liquid product HCOOH concentration is 3ppm, gaseous product CH4Concentration be 705ppm, C2H4Concentration is 25ppm, hydrocarbon Total faradic efficiency of compound is 54%, is 1.5 times of comparative example 1, illustrates the Cu Catalytic Layers that pulse current sedimentation obtains Hydrocarbon (particularly CH is produced to catalysis4) there is higher catalytic activity and selectivity..
Embodiment 4
1. gas diffusion substrate is heat-treated：Air is passed through in tube furnace, air velocity is 100ml min-1, is by area 25cm2, thickness 0.10mm, porosity be 80% charcoal cloth after 500 DEG C are heat-treated 3h, be down to room temperature naturally, measure is static Water contact angle is 80 degree.
2. pulse potential deposits Cu Catalytic Layers：CuSO is prepared using deionized water4Content is 0.3M electroplate liquid, adds 2M H2SO4The pH for adjusting plating solution is 0.1, with 3.0mM polyvinyl alcohol (PEG, the degree of polymerization 6000) for additive.First with 80ml min-1Speed high-purity N is passed through into plating solution240min, to control bath temperature be 80 DEG C, stirring rotor speed is 100rpm, then Using the charcoal cloth handled by step 1 as working electrode, the Cu blocks that Cu contents are 99.99% are that electrode, saturated calomel electrode are made For reference electrode, pulse potential deposition is carried out using the potentiostats of VersaSTAT 3 (production of Princeton companies of the U.S.).Control Electrode effective area processed is 3cm2, sedimentation potential is -0.5V (relative to SHE), and oxide etch current potential is 0.6V, and dutycycle is 30%, pulse period 1000cycles.After deposition process terminates, with a large amount of deionized water cleaning electrode surfaces, Ar is then used Air-blowing is done, and obtains gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface exists the gas-diffusion electrode obtained by step 1 and 2 processing 30min is soaked in the dense HCl acid solutions of room temperature, with a large amount of deionized water cleaning electrode surfaces.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H type electrolytic cells, 100ml 0.5M NaHCO are separately added into anode and cathode chamber3The aqueous solution and 50ml 0.1M KHCO3The aqueous solution, the barrier film using the NF115 that DuPont produces as anode and cathode chamber.Before test, first into cathode cavity It is passed through high-purity N240min, then pass to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.40min Afterwards, using gas-diffusion electrode as working electrode, Pt pieces are that saturated calomel electrode is reference electrode to electrode.Worked in -2.5V electric Pressure carries out electrochemical reducting reaction 16min, and reaction end gas is passed through the online quantitative detection that gas-chromatography carries out gaseous product, liquid Body product carries out quantitative analysis using chromatography of ions.
Liquid product HCOOH concentration is 2.4ppm, gaseous product CH4Concentration be 1100ppm, C2H4Concentration is 12ppm, Total faradic efficiency of hydrocarbon is 75%, is 2.63 times of comparative example 2, illustrates that the Cu that pulse potential sedimentation obtains is urged Change layer and hydrocarbon (particularly CH is produced to catalysis4) there is very high catalytic activity and selectivity..
Embodiment 5
1. gas diffusion substrate is heat-treated：Air is passed through in tube furnace, air velocity 100mlmin-1, is by area 25cm2, thickness 0.5mm, porosity be 80% charcoal felt after 400 DEG C are heat-treated 4.5h, be down to room temperature naturally, measure is static Water contact angle is 90 degree.
2. pulse current deposits Cu Catalytic Layers：CuCl is prepared using deionized water2Content is 0.8M electroplate liquid, adds 2M H2SO4The pH for adjusting plating solution is 0.3, with 0.1mM thiocarbamide (TU) for additive.First with 60ml min-1Speed to plating solution In be passed through high-purity Ar 40min, it is 800rpm to control speed of agitator, then using by step 1 handle charcoal felt as working electrode, The Cu blocks that Cu contents are 99.9% are that saturated calomel electrode is as reference electrode, using the potentiostats of VersaSTAT 3 to electrode (production of Princeton companies of the U.S.) carries out pulse current deposition in room temperature.Coordination electrode effective area is 3cm2, deposition current Density is 120mA cm-2, oxide etch current density is 30mAcm-2, dutycycle 75%, pulse period 1000cycles. After deposition process terminates, with a large amount of deionized water cleaning electrode surfaces, then dried up with Ar, obtain gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface will pass through step 1 and 2 processing obtain gas-diffusion electrode in room 25min is soaked in the dense HCl acid solutions of temperature, with a large amount of deionized water cleaning electrode surfaces.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H type electrolytic cells, 100ml 0.5M NaHCO are separately added into anode and cathode chamber3The aqueous solution and 50ml 0.1M KHCO3The aqueous solution, the barrier film using the NF115 that DuPont produces as anode and cathode chamber.Before test, first into cathode cavity It is passed through high-purity N240min, then pass to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.40min Afterwards, using gas-diffusion electrode as working electrode, Pt pieces are that saturated calomel electrode is reference electrode to electrode.Worked in -2.5V electric Pressure carries out electrochemical reducting reaction 16min, and reaction end gas is passed through the online quantitative detection that gas-chromatography carries out gaseous product, liquid Body product carries out quantitative analysis using chromatography of ions.
Liquid product HCOOH concentration is 3.3ppm, gaseous product CH4Concentration be 1780ppm, C2H4Concentration is 20ppm, Total faradic efficiency of hydrocarbon is 83%, is 2.32 times of comparative example 1, illustrates that the Cu that pulse current sedimentation obtains is urged Change layer and hydrocarbon (particularly CH is produced to catalysis4) there is very high catalytic activity and selectivity..
Embodiment 6
1. gas diffusion substrate is heat-treated：Air is passed through in tube furnace, air velocity is 100ml min-1, is by area 25cm2, thickness 0.10mm, porosity be 80% charcoal felt after 600 DEG C are heat-treated 2h, be down to room temperature naturally, measure is static Water contact angle is 60 degree.
2. pulse potential deposits Cu Catalytic Layers：Cu (NO are prepared using deionized water3)2Content is 0.35M electroplate liquid, is added Enter 2M H2SO4The pH for adjusting plating solution is 0.8, using 1.5mM amion acetic acid as additive.First with 100ml min-1Speed High-purity N is passed through into plating solution240min, to control bath temperature be 50 DEG C, stirring rotor speed is 300rpm, then with by step The charcoal felt of 1 processing is working electrode, the Cu blocks that Cu contents are 99.9% be to electrode, saturated calomel electrode as reference electrode, Pulse potential deposition is carried out using the potentiostats of VersaSTAT 3 (production of Princeton companies of the U.S.).Coordination electrode significant surface Product is 3cm2, sedimentation potential is 0V (relative to SHE), and oxide etch current potential is 0.5V, dutycycle 20%, and the pulse period is 10000cycles.After deposition process terminates, with a large amount of deionized water cleaning electrode surfaces, then done with Ar air-blowings, obtain gas Diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface exists the gas-diffusion electrode obtained by step 1 and 2 processing 5min is soaked in the dense HCl acid solutions of room temperature, with a large amount of deionized water cleaning electrode surfaces.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H type electrolytic cells, 100ml 0.5M NaHCO are separately added into anode and cathode chamber3The aqueous solution and 50ml 0.1M KHCO3The aqueous solution, the barrier film using the NF115 that DuPont produces as anode and cathode chamber.Before test, first into cathode cavity It is passed through high-purity N240min, then pass to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm.40min Afterwards, using gas-diffusion electrode as working electrode, Pt pieces are that saturated calomel electrode is reference electrode to electrode.Worked in -2.5V electric Pressure carries out electrochemical reducting reaction 16min, and reaction end gas is passed through the online quantitative detection that gas-chromatography carries out gaseous product, liquid Body product carries out quantitative analysis using chromatography of ions.
Liquid product HCOOH concentration is 3.9ppm, gaseous product CH4Concentration be 850ppm, C2H4Concentration is 45ppm, carbon Total faradic efficiency of hydrogen compound is 63%, is 2.21 times of comparative example 2, illustrates the Cu catalysis that pulse current sedimentation obtains Layer produces hydrocarbon (particularly CH to catalysis4) there is higher catalytic activity and selectivity.

Claims (10)

1. electrochemical reduction CO2The gas-diffusion electrode preparation method of hydrocarbon processed, it is characterised in that comprise the following steps：
1) porous carbon material is heat-treated：Porous carbon material is heated in atmosphere, obtains gas diffusion substrate；
2) deposition of Cu Catalytic Layers：Under inert atmosphere protection, using the acid copper salt solution containing additive as plating solution, control plating Liquid temperature degree, Cu particles are attached to the gas diffusion substrate table of step 1) processing under stirring in a manner of pulse electrodeposition Face, obtain gas-diffusion electrode；
3) gas-diffusion electrode prepared by step 2) is soaked in the concentrated hydrochloric acid solution that concentration is 36%~38%, cleaned up Dried up afterwards with inert gas.
2. preparation method according to claim 1, it is characterised in that：The porous carbon material includes braiding or non-woven Carbon paper or charcoal cloth, charcoal felt in one kind；Described heat treatment temperature is 300 DEG C~800 DEG C, and processing time is 2~6h.
3. preparation method according to claim 1 or 2, it is characterised in that：The porosity 70-90% of porous carbon material.
4. preparation method according to claim 2, it is characterised in that：The Static water contact angular region of gas diffusion substrate is 60~130 degree.
5. preparation method according to claim 1, it is characterised in that：Described acid copper salt solution is CuSO4、CuCl2、 Cu(NO3)2In one kind, the concentration of copper ion is 0.05M~1.5M；Use H2SO4The pH to 0.1 of regulation copper salt solution~ 1.0。
6. preparation method according to claim 1 or 5, it is characterised in that：Contain addition in described acid copper salt solution Agent, additive be inorganic salts NaCl, KBr, KI containing halogen in one kind, or cetyl trimethylammonium bromide, One kind in polyvinyl alcohol, thiocarbamide or amion acetic acid, the concentration of additive is 0.1mM~3.0mM.
7. preparation method according to claim 1, it is characterised in that：In step 2), the gas of the inert atmosphere use For in one kind in nitrogen or argon gas or two kinds, gas flow rate is 20~100ml min-1, optimum gas velocity is 40~70ml min-1；Described plating solution control temperature is room temperature~80 DEG C, and optimum temperature range is 30~60 DEG C；Described mixing speed is 100rpm~1000rpm, optimal mixing speed are 300~600rpm.
8. preparation method according to claim 1, it is characterised in that：Described pulse electrodeposition, depositional mode are pulse Current deposits or pulse potential deposition；
Described pulse current deposition, depositing current density is 10~200mAcm-2, optimal deposition electric current is 60~120mAcm-2； Oxide etch current density is 1~50mAcm-2, the optimal electric current that etches is 5~30mAcm-2；Pulse period is 1000~10000, The optimum pulse cycle is 3000~6000；Dutycycle is 20%~90%, and optimum taking air ratio is 40%~75%；
Described pulse potential deposition, sedimentation potential are -0.5V~0V (relative to standard hydrogen electrode (SHE)), and optimal deposition is electric Position is -0.3V~-0.1V；Oxidizing potential is 0.35V~0.6V (relative to standard hydrogen electrode (SHE)), and optimum oxidation current potential is 0.4V~0.5V；Pulse period is 1000~10000, and the optimum pulse cycle is 3000~6000；Dutycycle is 20%~90%, Optimum taking air ratio is 40%~75%.
9. preparation method according to claim 8, it is characterised in that：Described pulse electrodeposition, it is auxiliary in deposition process Electrode is helped to be not less than 99.9% using one kind in Cu pieces or Cu blocks, its purity.
10. preparation method according to claim 1, it is characterised in that：Described gas-diffusion electrode sample is in concentrated hydrochloric acid Soaked in solution, soaking temperature is normal temperature, and soak time is 10~30min, and optimal soak time is 15~25min.
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CN110804750A (en) * 2018-08-06 2020-02-18 南京理工大学 Electrochemical preparation method of oriented carbon nano tube embedded with copper nano particles
CN110804750B (en) * 2018-08-06 2022-01-11 南京理工大学 Electrochemical preparation method of oriented carbon nano tube embedded with copper nano particles
CN109108279A (en) * 2018-09-13 2019-01-01 中南大学 A kind of poly-dopamine coated copper nanowire composite and its preparation method and application
CN110639488A (en) * 2019-08-30 2020-01-03 中国科学院广州能源研究所 Application of biomass-based carbon material in electrochemical reduction of carbon dioxide
CN111647909A (en) * 2020-07-01 2020-09-11 中国科学技术大学 Dendritic copper electrode with hydrophobic surface and preparation method and application thereof
CN114622234A (en) * 2020-12-10 2022-06-14 中国科学院大连化学物理研究所 Flexible gas diffusion electrode structure and application thereof in electrochemical reduction of carbon dioxide
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CN113637996A (en) * 2021-08-26 2021-11-12 合肥工业大学 Copper-based nano material for electrocatalytic reduction of carbon dioxide and preparation method thereof

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