CN107841760B - 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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CN107841760B
CN107841760B CN201610830275.7A CN201610830275A CN107841760B CN 107841760 B CN107841760 B CN 107841760B CN 201610830275 A CN201610830275 A CN 201610830275A CN 107841760 B CN107841760 B CN 107841760B
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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 successively include porous carbon material heat treatment, the immersion of the deposition of Cu Catalytic Layer, concentrated hydrochloric acid solution, are dried up after cleaning with inert gas.Has the characteristics that Catalytic Layer particle fine uniform with gas-diffusion electrode prepared by this method, electrochemical reaction area can significantly be expanded, simultaneously to Carbon dioxide electrochemical reduction reaction product methane, have it is highly selective, 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, in particular to the preparation skill of a kind of gas-diffusion electrode Art.
Background technique
Electrochemical reduction CO2(ERC) technology is a kind of realization CO2The technology of resource utilization, prominent features are to utilize electricity It can be by CO2It is reduced to various organic chemicals.With other CO2Transformation technology is compared, and the outstanding advantage of ERC technology is available Hydrogen source of the water as reaction, can be realized CO at normal temperatures and pressures2Efficient Conversion, therefore do not need needed for chemical conversion technology Hydrogen manufacturing and heating, pressurization caused by energy consumption, equipment investment is few.
Currently, the principal element for restricting the development of ERC technology includes: that (1) reaction overpotential is high；(2) conversion ratio is low；(3) it produces Object poor selectivity.Wherein, in the ERC reaction system using aqueous solution as supporting electrolyte, usually using plate (such as sheet, Foil-like and bulk) metal carrys out catalysis electrode reaction process.The prominent defect of one of this kind of metal electrode is that electrode reaction area is small, The surface being in contact with supporting electrolyte is concentrated merely on, to constitute ERC reaction overpotential height and CO2The low important original of conversion ratio Cause；In addition, ERC reaction process is related to multiple electronic transfer process, therefore product distribution is wide, to the selectivity of specific product It is lower.
To expand electrode area used in ERC reaction, researcher is by constructing the electrode surface of special appearance, increasing Active crystal grain boundary substantially expands electrochemical reaction area.Xie Yi etc. is in document Electrochimica Angew.Chem.Int.Ed.2016 reports in 55,698~702, and it is only 1.72 to receive that thickness is synthesized by way of quickly heating Rice and 3.51 nanometers of Co3O4Atomic layer obtains active sites abundant, guarantees CO2A large amount of absorption, with a thickness of the original of 1.72nm It is more than 20% that sublayer catalysis, which generates the faradic efficiency of formic acid, and 20h can be used continuously.
Gas-diffusion electrode (GDE) is a kind of conductive composite material based on porous material building, most apparent special Sign is that have hole abundant, 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): reporting in L57-L59, prepares GDE for Pt nano particle as active component, CO2Under the conditions of pressure < 50atm, Pt-GDE restores CO2Current density reach 900mA cm-2, current efficiency 46%.But The generally spherical metal nanoparticle of catalyst used in building GDE process, 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 changing product distribution.For the high catalytic activity for maintaining metal nanoparticle, it usually needs to the GDE of preparation It is activated, process is cumbersome, and not easy to control.
Summary of the invention
The invention proposes the gas-diffusion electrode preparation sides that a kind of electrochemically reducing carbon dioxide produces hydrocarbon Method, effective catalyst component of the gas-diffusion electrode --- Cu particle is attached in gas diffusion base in a manner of pulse electrodeposition On bottom, electrochemical reaction area has substantially been expanded, has improved CO2The speed of electrochemical reaction, and have to the generation of hydrocarbon Have it is highly selective, 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, includes the following steps:
1) porous carbon material is heat-treated: porous carbon material being heated, the glue film of the carbon fiber surface of removal in air, is increased It is added to obtain gas diffusion substrate to the affinity of aqueous solution；
2) deposition of Cu Catalytic Layer: under inert atmosphere protection, using the acid copper salt solution containing additive as plating solution, control Cu particle is attached to the gas diffusion base of step 1) processing by bath temperature processed under stirring in a manner of pulse electrodeposition Bottom surface obtains gas-diffusion electrode；
3) gas-diffusion electrode by step 2) preparation is impregnated in the concentrated hydrochloric acid solution that concentration is 36%~38%, is cleaned It is dried up after clean with inert gas.
The porous carbon material includes one of carbon paper or charcoal cloth, charcoal felt of braiding or non-woven；At the heat Managing temperature is 300 DEG C~800 DEG C, and the 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.
The acid copper salt solution is CuSO4、CuCl2、Cu(NO3)2One of, the concentration of copper ion be 0.05M~ 1.5M；Use 0.5M H2SO4Adjust the pH to 0.1~1.0 of copper salt solution.
Contain additive in the acid copper salt solution, additive be inorganic salts NaCl, KBr containing halogen elements, One of KI, or the organic matter containing one or more of N, O, S, Br element, such as cetyl trimethyl Ammonium bromide (CTAB), polyvinyl alcohol (PEG), thiocarbamide (TU), one of amion acetic acid, the concentration of additive be 0.1mM~ 3.0mM。
In step 2), gas that the inert atmosphere uses be one of high pure nitrogen or high-purity argon gas or two kinds with On, gas flow rate is 20~100ml min-1, optimum gas velocity is 40~70ml min-1；The plating solution control temperature For room temperature~80 DEG C, optimum temperature range is 30~60 DEG C；The mixing speed is 100rpm~1000rpm, best to stir Speed is 300~600rpm.
The pulse electrodeposition, depositional mode are that pulse current deposits or pulse potential deposits；
The pulse current deposition, depositing current density are 10~200mAcm-2, optimal deposition electric current be 60~ 120mAcm-2；Oxide etch current density is 1~50mAcm-2, the best electric current that etches is 5~30mAcm-2；Pulse period is 1000~10000, the optimum pulse period is 3000~6000；Duty ratio be 20%~90%, optimum taking air ratio be 40%~ 75%；
The pulse potential deposition, sedimentation potential are -0.5V~0V (relative to standard hydrogen electrode (SHE)), best heavy Product current potential is -0.3V~-0.1V；Oxidizing potential is 0.35V~0.6V (relative to standard hydrogen electrode (SHE)), optimum oxidation electricity Position is 0.4V~0.5V；Pulse period is 1000~10000, and the optimum pulse period is 3000~6000；Duty ratio be 20%~ 90%, optimum taking air ratio is 40%~75%.
The pulse electrodeposition, the auxiliary electrode in deposition process use one of Cu piece or Cu block, and purity is not Lower than 99.9%.
The gas-diffusion electrode sample impregnates in concentrated hydrochloric acid solution, and soaking temperature is room temperature, soaking 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 present 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 particle of the gas-diffusion electrode It is attached in gas diffusion substrate in a manner of pulse electrodeposition, has substantially expanded electrochemical reaction area, improve CO2Electrification Learn reaction speed, while to Carbon dioxide electrochemical reduction reaction product-methane, have it is highly selective, 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； It is also able to maintain the porous structure of supporter simultaneously, guarantees that gas diffusion substrate quickly transmits gas and discharge liquor to electrode catalyst position The function of body, to improve carbon dioxide electrochemical reaction speed.
3) additive has structure-directing effect in electrodeposition process, it is ensured that catalyst particle is raw according to specific direction It is long, 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 Layer prepared using the method for the present invention is to CH4FE efficiency be up to 85%, be that current open report is neutral One of optimal Cu catalyst of energy.
Detailed description of the invention
The crystal structure schematic diagram of the gas-diffusion electrode Catalytic Layer of Fig. 1 pulse current deposition.
Specific embodiment
Below with reference to preferred embodiment, technical solution of the present invention is described further, but technology contents of the invention It is not limited only to the range.
Comparative example 1
1. gas diffusion substrate is heat-treated: being passed through air in tube furnace, area is by air velocity 100mlmin-1 25cm2, with a thickness of 0.2mm, porosity be 78% TGP-H-060 carbon paper after 500 DEG C of heat treatment 3h, be down to room temperature naturally, Measuring Static water contact angles is 90 degree.
2. galvanostatic deposition Cu Catalytic Layer: preparing CuSO using deionized water4·5H2O content is the electroplate liquid of 0.5M, is added Enter 2M H2SO4The pH for adjusting plating solution is 0.5, using the KBr of 0.6mM as additive.First with 60ml min-1Speed to plating solution In be passed through high-purity N240min, control bath temperature is 60 DEG C, stirring rotor speed is 500rpm, then to handle by step 1 TGP-H-060 carbon paper be working electrode, the Cu piece that Cu content is 99.90% is to electrode, and saturated calomel electrode is as reference Electrode carries out constant current electro-deposition using 3 potentiostat of VersaSTAT (production of Princeton company, the U.S.).Coordination electrode Effective area is 3cm2, depositing current density is 90mA cm-2, sedimentation time 3600s.After deposition process, with largely going The Cu that ionized water cleans the support of TGP-H-060 carbon paper is catalyzed layer surface, is then dried up with Ar, obtains gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface will obtain gas-diffusion electrode in room by step 1 and 2 processing 20min is impregnated in the dense HCl acid solution of temperature, with a large amount of deionized water cleaning electrodes surface.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H-type electrolytic cell, 100ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Before test, first to cathode cavity In be passed through high-purity N240min then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm. After 40min, using gas-diffusion electrode as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -2.5V Electrochemical reducting reaction 16min is carried out under operating voltage, reaction end gas is passed through gas-chromatography and carries out the online quantitative of gaseous product Detection, product liquid carry out quantitative analysis using ion chromatography.
Liquid product HCOOH concentration is 2ppm, gaseous product CH4Concentration be 425ppm, C2H4Concentration is 10ppm, carbon Total faradic efficiency of hydrogen compound is 35.8%.
Comparative example 2
1. gas diffusion substrate is heat-treated: being passed through air in tube furnace, air velocity is 100ml min-1, is by area 25cm2, with a thickness of 0.19mm, porosity be 78% TGP-H-060 carbon paper after 600 DEG C of heat treatment 2h, be down to room temperature naturally, Measuring Static water contact angles is 80 degree.
2. constant voltage deposits Cu Catalytic Layer: preparing Cu (NO using deionized water3)2Content is the electroplate liquid of 0.35M, is added 2M H2SO4The pH for adjusting plating solution is 0.8, using the amion acetic acid of 1.5mM as additive, first with 100ml min-1Speed to High-purity N is passed through in plating solution240min, control bath temperature is 60 DEG C, stirring rotor speed is 500rpm, then to pass through step 1 The TGP-H-060 carbon paper of processing is working electrode, and the Cu piece that Cu content is 99.90% is to electrode, saturated calomel electrode conduct Reference electrode carries out potentiostatic electrodeposition using 3 potentiostat of VersaSTAT (production of Princeton company, the U.S.).Control electricity Very effective area is 3cm2, sedimentation potential is -0.3V (relative to SHE), sedimentation time 3600s.After deposition process, use A large amount of deionized water cleaning electrode surfaces, it is then dry with Ar air-blowing, 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 impregnated in the dense HCl acid solution of room temperature, with a large amount of deionized water cleaning electrodes surface.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H-type electrolytic cell, 100ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Before test, first to cathode cavity In be passed through high-purity N240min then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm. After 40min, using gas-diffusion electrode as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -2.5V Electrochemical reducting reaction 16min is carried out under operating voltage, reaction end gas is passed through gas-chromatography and carries out the online quantitative of gaseous product Detection, product liquid carry out quantitative analysis using ion chromatography.
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: being passed through air in tube furnace, area is by air velocity 100mlmin-1 25cm2, with a thickness of 0.2mm, porosity be 78% TGP-H-060 carbon paper after 500 DEG C of heat treatment 3h, be down to room temperature naturally, Measuring Static water contact angles is 90 degree.
2. pulse current deposits Cu Catalytic Layer: preparing CuSO using deionized water4·5H2O content is the electroplate liquid of 0.5M, 2M H is added2SO4The pH for adjusting plating solution is 0.5, using the KBr of 0.6mM as additive.First with 60ml min-1Speed to plating High-purity N is passed through in liquid240min, control bath temperature is 60 DEG C, stirring rotor speed is 500rpm, then to pass through step 1 place The TGP-H-060 carbon paper of reason is working electrode, and the Cu piece that Cu content is 99.90% is to electrode, and saturated calomel electrode is as ginseng Than electrode, pulse current deposition is carried out using 3 potentiostat of VersaSTAT (production of Princeton company, the U.S.).Control electricity Very effective area is 3cm2, depositing current density is 90mA cm-2, oxide etch current density is 20mAcm-2, duty ratio is 50%, pulse period 4000cycles.After deposition process, the support of TGP-H-060 carbon paper is cleaned with a large amount of deionized waters Cu be catalyzed layer surface, then dried up with Ar, obtain gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface will obtain gas-diffusion electrode in room by step 1 and 2 processing 20min is impregnated in the dense HCl acid solution of temperature, with a large amount of deionized water cleaning electrodes surface.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H-type electrolytic cell, 100ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Before test, first to cathode cavity In be passed through high-purity N240min then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm. After 40min, using gas-diffusion electrode as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -2.5V Electrochemical reducting reaction 16min is carried out under operating voltage, reaction end gas is passed through gas-chromatography and carries out the online quantitative of gaseous product Detection, product liquid carry out quantitative analysis using ion chromatography.
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 what pulse current sedimentation obtained Cu Catalytic Layer generates hydrocarbon (especially 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 Layer of pulse current deposition is more tiny, and the texture of each main crystal face Coefficient changes, and the ratio of (200) crystal face exposure increases, and illustrates that the electrodeposition method that additive is added can change catalysis Each crystal face ratio of layer, and then influence product distribution.
Embodiment 2
1. gas diffusion substrate is heat-treated: being passed through air in tube furnace, air velocity is 100ml min-1, is by area 25cm2, with a thickness of 0.10mm, porosity be 82% TGP-H-030 carbon paper after 300 DEG C of heat treatment 6h, be down to room temperature naturally, Measuring Static water contact angles is 130 degree.
2. pulse potential deposits Cu Catalytic Layer: preparing CuCl using deionized water2Content is the electroplate liquid of 1.0M, is added 2M H2SO4The pH for adjusting plating solution is 0.2, using the NaCl of 0.3mM as additive, first with 100ml min-1Speed to plating solution In be passed through high-purity Ar 40min, control bath temperature is 30 DEG C, stirring rotor speed is 1000rpm, then to pass through step 1 place The TGP-H-030 carbon paper of reason is working electrode, and the Cu block that Cu content is 99.5% is to electrode, and saturated calomel electrode is as reference Electrode carries out pulse potential deposition using 3 potentiostat of VersaSTAT (production of Princeton company, the U.S.).Coordination electrode Effective area is 3cm2, sedimentation potential is -0.3V (relative to SHE), and oxide etch current potential is 0.4V, duty ratio 60%, arteries and veins Rushing the period is 6000cycles.It is then dry with Ar air-blowing with a large amount of deionized water cleaning electrodes surface after deposition process, 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 30min is impregnated in the dense HCl acid solution of room temperature, with a large amount of deionized water cleaning electrodes surface.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H-type electrolytic cell, 100ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Before test, first to cathode cavity In be passed through high-purity N240min then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm. After 40min, using gas-diffusion electrode as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -2.5V Electrochemical reducting reaction 16min is carried out under operating voltage, reaction end gas is passed through gas-chromatography and carries out the online quantitative of gaseous product Detection, product liquid carry out quantitative analysis using ion chromatography.
Liquid product HCOOH concentration is 8pm, gaseous product CH4Concentration be 930ppm, C2H4Concentration is 9ppm, hydrocarbon Total faradic efficiency of compound is 67%, is 2.35 times of comparative example 2, illustrates the Cu catalysis that pulse potential sedimentation obtains Layer generates hydrocarbon (especially CH to catalysis4) catalytic activity and selectivity with higher.
Embodiment 3
1. gas diffusion substrate is heat-treated: being passed through air in tube furnace, area is by air velocity 100mlmin-1 25cm2, with a thickness of 0.3mm, charcoal cloth that porosity is 80% after 600 DEG C of heat treatment 2h, be down to room temperature naturally, measurement Static Water Contact angle is 60 degree.
2. pulse current deposits Cu Catalytic Layer: preparing Cu (NO using deionized water3)2Content is the electroplate liquid of 0.05M, is added Enter 2M H2SO4The pH for adjusting plating solution is 1, with the cetyl trimethylammonium bromide (CTAB) of 0.1mM for additive.First with 20ml min-1Speed be passed through high-purity Ar 40min into plating solution, control speed of agitator is 200rpm, then to pass through step 1 The TGP-H-060 carbon paper of processing is working electrode, and the Cu piece that Cu content is 99.999% is to electrode, and saturated calomel electrode is made For reference electrode, pulse current is carried out in room temperature using 3 potentiostat of VersaSTAT (production of Princeton company, the U.S.) and is sunk Product.Coordination electrode effective area is 3cm2, depositing current density is 100mA cm-2, oxide etch current density is 5mAcm-2, Duty ratio is 90%, pulse period 10000cycles.After deposition process, with a large amount of deionized water cleaning electrodes surface, Then it is dried up with Ar, obtains gas-diffusion electrode.
3. the removal of gas-diffusion electrode oxide on surface will obtain gas-diffusion electrode in room by step 1 and 2 processing 10min is impregnated in the dense HCl acid solution of temperature, with a large amount of deionized water cleaning electrodes surface.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H-type electrolytic cell, 100ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Before test, first to cathode cavity In be passed through high-purity N240min then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm. After 40min, using gas-diffusion electrode as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -2.5V Electrochemical reducting reaction 16min is carried out under operating voltage, reaction end gas is passed through gas-chromatography and carries out the online quantitative of gaseous product Detection, product liquid carry out quantitative analysis using ion chromatography.
Liquid product HCOOH concentration is 3ppm, gaseous product CH4Concentration be 705ppm, C2H4Concentration is 25ppm, carbon Total faradic efficiency of hydrogen compound is 54%, is 1.5 times of comparative example 1, illustrates the Cu catalysis that pulse current sedimentation obtains Layer generates hydrocarbon (especially CH to catalysis4) catalytic activity and selectivity with higher.
Embodiment 4
1. gas diffusion substrate is heat-treated: being passed through air in tube furnace, air velocity is 100ml min-1, is by area 25cm2, with a thickness of 0.10mm, charcoal cloth that porosity is 80% after 500 DEG C of heat treatment 3h, be down to room temperature naturally, measurement static state Water contact angle is 80 degree.
2. pulse potential deposits Cu Catalytic Layer: preparing CuSO using deionized water4Content is the electroplate liquid of 0.3M, is added 2M H2SO4The pH for adjusting plating solution is 0.1, with the polyvinyl alcohol (PEG, the degree of polymerization 6000) of 3.0mM for additive.First with 80ml min-1Speed high-purity N is passed through into plating solution240min, control bath temperature is 80 DEG C, stirring rotor speed is 100rpm, so Afterwards using the charcoal cloth handled by step 1 as working electrode, the Cu block that Cu content is 99.99% is to electrode, saturated calomel electrode As reference electrode, pulse potential deposition is carried out using 3 potentiostat of VersaSTAT (production of Princeton company, the U.S.). Coordination electrode effective area is 3cm2, sedimentation potential is -0.5V (relative to SHE), and oxide etch current potential is 0.6V, duty ratio It is 30%, pulse period 1000cycles.After deposition process, with a large amount of deionized water cleaning electrodes surface, then use Ar air-blowing is dry, 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 impregnated in the dense HCl acid solution of room temperature, with a large amount of deionized water cleaning electrodes surface.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H-type electrolytic cell, 100ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Before test, first to cathode cavity In be passed through high-purity N240min then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm. After 40min, using gas-diffusion electrode as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -2.5V Electrochemical reducting reaction 16min is carried out under operating voltage, reaction end gas is passed through gas-chromatography and carries out the online quantitative of gaseous product Detection, product liquid carry out quantitative analysis using ion chromatography.
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, the Cu for illustrating that pulse potential sedimentation obtains is urged Change layer and hydrocarbon (especially CH is generated to catalysis4) there is very high catalytic activity and selectivity.
Embodiment 5
1. gas diffusion substrate is heat-treated: being passed through air in tube furnace, area is by air velocity 100mlmin-1 25cm2, with a thickness of 0.5mm, charcoal felt that porosity is 80% after 400 DEG C of heat treatment 4.5h, be down to room temperature naturally, measurement static state Water contact angle is 90 degree.
2. pulse current deposits Cu Catalytic Layer: preparing CuCl using deionized water2Content is the electroplate liquid of 0.8M, is added 2M H2SO4The pH for adjusting plating solution is 0.3, with the thiocarbamide (TU) of 0.1mM for additive.First with 60ml min-1Speed to High-purity Ar 40min is passed through in plating solution, control speed of agitator is 800rpm, then using the charcoal felt handled by step 1 as work electricity Pole, the Cu block that Cu content is 99.9% are to electrode, and saturated calomel electrode is as reference electrode, using the permanent electricity of VersaSTAT 3 Position instrument (production of Princeton company, 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, duty ratio 75%, the pulse period is 1000cycles.It after deposition process, with a large amount of deionized water cleaning electrodes surface, is then dried up with Ar, obtains gas expansion Dissipate electrode.
3. the removal of gas-diffusion electrode oxide on surface will obtain gas-diffusion electrode in room by step 1 and 2 processing 25min is impregnated in the dense HCl acid solution of temperature, with a large amount of deionized water cleaning electrodes surface.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H-type electrolytic cell, 100ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Before test, first to cathode cavity In be passed through high-purity N240min then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm. After 40min, using gas-diffusion electrode as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -2.5V Electrochemical reducting reaction 16min is carried out under operating voltage, reaction end gas is passed through gas-chromatography and carries out the online quantitative of gaseous product Detection, product liquid carry out quantitative analysis using ion chromatography.
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, the Cu for illustrating that pulse current sedimentation obtains is urged Change layer and hydrocarbon (especially CH is generated to catalysis4) there is very high catalytic activity and selectivity.
Embodiment 6
1. gas diffusion substrate is heat-treated: being passed through air in tube furnace, air velocity is 100ml min-1, is by area 25cm2, with a thickness of 0.10mm, charcoal felt that porosity is 80% after 600 DEG C of heat treatment 2h, be down to room temperature naturally, measurement static state Water contact angle is 60 degree.
2. pulse potential deposits Cu Catalytic Layer: preparing Cu (NO using deionized water3)2Content is the electroplate liquid of 0.35M, is added Enter 2M H2SO4The pH for adjusting plating solution is 0.8, using the amion acetic acid of 1.5mM as additive.First with 100ml min-1Speed High-purity N is passed through into plating solution240min, control bath temperature is 50 DEG C, stirring rotor speed is 300rpm, then by step The charcoal felt of rapid 1 processing is working electrode, and the Cu block that Cu content is 99.9% is to electrode, and saturated calomel electrode is as reference electricity Pole carries out pulse potential deposition using 3 potentiostat of VersaSTAT (production of Princeton company, the U.S.).Coordination electrode has Effect area is 3cm2, sedimentation potential is 0V (relative to SHE), and oxide etch current potential is 0.5V, duty ratio 20%, pulse period For 10000cycles.It is then dry with Ar air-blowing with a large amount of deionized water cleaning electrodes surface after deposition process, obtain gas Body 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 impregnated in the dense HCl acid solution of room temperature, with a large amount of deionized water cleaning electrodes surface.
4. gas-diffusion electrode is to CO2The performance evaluation of electrochemical reducting reaction
In H-type electrolytic cell, 100ml 0.5M NaHCO is separately added into anode and cathode chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses the NF115 of DuPont production as the diaphragm of anode and cathode chamber.Before test, first to cathode cavity In be passed through high-purity N240min then passes to the CO that purity is 99.995%2Gas, CO2Flow control be 60sccm. After 40min, using gas-diffusion electrode as working electrode, Pt piece is to electrode, and saturated calomel electrode is reference electrode.In -2.5V Electrochemical reducting reaction 16min is carried out under operating voltage, reaction end gas is passed through gas-chromatography and carries out the online quantitative of gaseous product Detection, product liquid carry out quantitative analysis using ion chromatography.
Liquid product HCOOH concentration is 3.9ppm, gaseous product CH4Concentration be 850ppm, C2H4Concentration is 45ppm, Total faradic efficiency of hydrocarbon is 63%, is 2.21 times of comparative example 2, the Cu for illustrating that pulse current sedimentation obtains is urged Change layer and hydrocarbon (especially CH is generated to catalysis4) catalytic activity and selectivity with higher.

Claims (13)

1. electrochemical reduction CO2The gas-diffusion electrode preparation method of hydrocarbon processed, which comprises the steps of:
1) porous carbon material is heat-treated: porous carbon material being heated in air, obtains gas diffusion substrate；
2) deposition of Cu Catalytic Layer: under inert atmosphere protection, using the acid copper salt solution containing additive as plating solution, control plating Cu particle is attached to the gas diffusion substrate table of step 1) processing by liquid temperature under stirring in a manner of pulse electrodeposition Face obtains gas-diffusion electrode；
3) gas-diffusion electrode by step 2) preparation is impregnated in the concentrated hydrochloric acid solution that concentration is 36%~38%, is cleaned up It is dried up afterwards with inert gas.
2. preparation method according to claim 1, it is characterised in that: the porous carbon material is braiding or non-woven One of carbon paper or charcoal cloth, charcoal felt；The heat treatment temperature is 300 DEG C~800 DEG C, and the 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: the acid copper salt solution is CuSO4、CuCl2、 Cu(NO3)2One of, the concentration of copper ion is 0.05M~1.5M；Use H2SO4The pH to 0.1 of adjusting copper salt solution~ 1.0。
6. preparation method according to claim 1 or 5, it is characterised in that: contain addition in the acid copper salt solution Agent, additive be one of inorganic salts NaCl, KBr, KI containing halogen elements or cetyl trimethylammonium bromide, One of polyvinyl alcohol, thiocarbamide or amion acetic acid, the concentration of additive are 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 one of nitrogen or argon gas or two kinds, gas flow rate is 20~100ml min-1；The plating solution control temperature is room temperature ~80 DEG C；The mixing speed is 100rpm~1000rpm.
8. preparation method according to claim 7, it is characterised in that: in step 2), gas flow rate is 40~70ml min-1；30~60 DEG C of the plating solution control temperature；The mixing speed is 300~600rpm.
9. preparation method according to claim 1, it is characterised in that: the pulse electrodeposition, depositional mode are pulse Current deposits or pulse potential deposition；
The pulse current deposition, depositing current density are 10~200mAcm-2；Oxide etch current density be 1~ 50mAcm-2；Pulse period is 1000~10000；Duty ratio is 20%~90%；The pulse potential deposition, relative to mark Quasi- hydrogen electrode (SHE) sedimentation potential is -0.5V~0V；It is 0.35V~0.6V relative to standard hydrogen electrode (SHE) oxidizing potential； Pulse period is 1000~10000；Duty ratio is 20%~90%.
10. preparation method according to claim 9, it is characterised in that: the pulse current deposition, depositing current density For 60~120mAcm-2；Oxide etch current density is 5~30mAcm-2；Pulse period is 3000~6000；Duty ratio is 40%~75%；
The pulse potential deposition, is -0.3V~-0.1V relative to standard hydrogen electrode (SHE) sedimentation potential；Relative to standard Hydrogen electrode (SHE) oxidizing potential is 0.4V~0.5V；Pulse period is 3000~6000；Duty ratio is 40%~75%.
11. preparation method according to claim 9, it is characterised in that: the pulse electrodeposition, it is auxiliary in deposition process Help electrode using one of Cu piece or Cu block, purity is not less than 99.9%.
12. preparation method according to claim 1, it is characterised in that: the gas-diffusion electrode sample is in concentrated hydrochloric acid It is impregnated in solution, soaking temperature is room temperature, and soaking time is 10~30min.
13. preparation method according to claim 12, it is characterised in that: soaking time is 15~25min.
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