CN108654623A - Carbon dioxide electrochemical reduction catalyst and preparation method thereof and the gas-diffusion electrode for loading the catalyst - Google Patents
Carbon dioxide electrochemical reduction catalyst and preparation method thereof and the gas-diffusion electrode for loading the catalyst Download PDFInfo
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- CN108654623A CN108654623A CN201810385388.XA CN201810385388A CN108654623A CN 108654623 A CN108654623 A CN 108654623A CN 201810385388 A CN201810385388 A CN 201810385388A CN 108654623 A CN108654623 A CN 108654623A
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- carbon dioxide
- electrochemical reduction
- reduction catalyst
- oxide
- dioxide electrochemical
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 97
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 95
- 230000009467 reduction Effects 0.000 title claims abstract description 93
- 238000009792 diffusion process Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000011068 loading method Methods 0.000 title claims abstract description 10
- 241000446313 Lamella Species 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 21
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 21
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229920000557 Nafion® Polymers 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000002091 nanocage Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- 230000005518 electrochemistry Effects 0.000 claims 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 13
- 239000005751 Copper oxide Substances 0.000 abstract description 9
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 238000011946 reduction process Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000005764 inhibitory process Effects 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical group [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to electrochemical reduction catalyst technical fields, and in particular to a kind of carbon dioxide electrochemical reduction catalyst and preparation method thereof and the gas-diffusion electrode for loading the catalyst.Carbon dioxide electrochemical reduction catalyst provided by the invention is nanocatalyst, specially the nickel tin lamella bimetallic oxide of the ambrose alloy lamella bimetallic oxide or nickel oxide of the compound lamellar structure of nickel oxide and copper oxide and the compound lamellar structure of tin oxide.The nanocatalyst of the structure has high catalytic activity, greatly reduces the overpotential in electro-reduction process, while evolving hydrogen reaction adjoint during effective inhibition carbon dioxide reduction.The present invention also provides the gas-diffusion electrodes of the preparation method of the catalyst and the load catalyst, can not only solve the problems, such as that reduction current is too low, and effectively raise the faradic efficiency during Carbon dioxide electrochemical reduction.
Description
Technical field
The present invention relates to electrochemical reduction catalyst technical fields, and in particular to a kind of Carbon dioxide electrochemical reduction catalysis
Agent and preparation method thereof and the gas-diffusion electrode for loading the catalyst.
Background technology
The large-scale application of fossil fuel causes the excessive emissions of carbon dioxide, since carbon dioxide increases in air
And lead to global warming.To solve the above-mentioned problems, people utilize renewable resource such as solar energy, wind energy, tide energy institute
Electric energy of generation etc. by carbon dioxide excessive in air through electrochemical reduction, be converted into the valuable raw material of industry such as methane,
Methanol, formic acid etc..Therefore electrochemically reducing carbon dioxide method be it is a kind of cleaning, efficiently, environmental protection method.
However, since carbon dioxide is one of the carbon compound of thermodynamicaHy most stable, it is translated into other carbon
Compound needs high energy reducing agent or external energy source.Have been reported carbon dioxide can by a variety of different metals for example copper, silver,
The electrochemical reductions such as tin prepare carbon monoxide, methane, methanol, formic acid etc..Such as：Metallic tin has very strong selectivity, first to formic acid
Sour yield can be up to 95%, and however as the progress of reduction reaction, sheet tin electrode surface can generate metal organic complex, accelerate
Liberation of hydrogen rate reduces the yield of formic acid.For another example silver catalyst, which is carbon monoxide to carbon dioxide reduction, has higher selectivity,
However shortcoming is to need higher overpotential.It is well known that ideal elctro-catalyst needs to meet in lower overpotential
Under, single product is generated with higher current efficiency, therefore a kind of new structural catalyst can be developed to meet above-mentioned want
Asking just seems most important.
Invention content
The object of the present invention is to provide a kind of carbon dioxide electrochemical reduction catalysts and preparation method thereof to urge with this is loaded
The gas-diffusion electrode of agent, the catalyst have high catalytic activity, greatly reduce the mistake in electro-reduction process
Current potential, while evolving hydrogen reaction adjoint during effective inhibition carbon dioxide reduction.
To achieve the goals above, technical scheme of the present invention is specific as follows：
A kind of carbon dioxide electrochemical reduction catalyst is that nanocatalyst, specially nickel oxide and copper oxide are compound
Lamellar structure ambrose alloy lamella bimetallic oxide or nickel oxide and the compound lamellar structure of tin oxide the double gold of nickel tin lamella
Belong to oxide.
In the above-mentioned technical solutions, the molar ratio of the nickel oxide and copper oxide is：9:1~1:9, the nickel oxide and oxygen
Change tin molar ratio be：9:1~1:9.
In the above-mentioned technical solutions, the molar ratio of the nickel oxide and copper oxide is：8:2.
A kind of preparation method of carbon dioxide electrochemical reduction catalyst, includes the following steps：
Copper chloride or stannic chloride and nickel chloride are dissolved in deionized water, stirred, instilling ammonium hydroxide adjusting pH value of solution dropwise makes
Above-mentioned metal ion is co-precipitated, and is centrifuged, and is washed to neutrality with deionized water and absolute ethyl alcohol, dry, is heat-treated
To ambrose alloy lamella bimetallic oxide or nickel tin lamella bimetallic oxide.
In the above-mentioned technical solutions, the molar concentration ratio of the copper chloride and nickel chloride is：1:9~9:1, the chlorination
The molar concentration ratio of tin and nickel chloride is：1:9~9:1.
In the above-mentioned technical solutions, the molar concentration ratio of the copper chloride and nickel chloride is：2:8.
In the above-mentioned technical solutions, the pH is 7.5~14, and the temperature of the heat treatment is 250 DEG C~750 DEG C, at heat
The time of reason is -4 hours 0.5 hour.
In the above-mentioned technical solutions, the pH is 9, and the temperature of the heat treatment is 350 DEG C~450 DEG C, heat treatment when
Between be 3 hours.
A kind of gas-diffusion electrode of the above-mentioned carbon dioxide electrochemical reduction catalyst of load, the gas-diffusion electrode
Size is 0.4cm × 0.4cm~6cm × 6cm, the weight of the carbon dioxide electrochemical reduction catalyst of load be 5 μ g~
20mg。
In the above-mentioned technical solutions, the gas-diffusion electrode of the above-mentioned carbon dioxide electrochemical reduction catalyst of load,
It is prepared by following methods：
The carbon dioxide electrochemical reduction catalyst is distributed in ethyl alcohol, the perfluorinated sulfonic acid of 1wt%~5wt% is added
Resin Nafion solution, stirring ultrasound, makes carbon dioxide electrochemical reduction catalyst be uniformly dispersed, then by the mixed liquor of gained
It is coated in gas-diffusion electrode, dries, you can obtain loading the gas diffusion of above-mentioned carbon dioxide electrochemical reduction catalyst
Electrode；
Or mix the carbon dioxide electrochemical reduction catalyst with carbon material, mixture is distributed in ethyl alcohol,
The perfluorinated sulfonic resin Nafion solution of 1wt%~5wt% is added, stirring ultrasound makes carbon dioxide electrochemical reduction catalyst
It is uniformly dispersed, then the mixed liquor of gained is coated in gas-diffusion electrode, dry, you can obtain loading above-mentioned carbon dioxide
The gas-diffusion electrode of electrochemical reduction catalyst；
The gas-diffusion electrode is glass carbon plate, carbon paper, carbon cloth or carbon felt；The ethanol consumption is 500 μ L~10mL；Institute
The carbon material stated is activated carbon VLCAN X-72, BP200, carbon nanotube, carbon nano-fiber, nano cages, graphene, graphene
Quantum dot or graphene oxide, dosage are 10 μ g~100mg.
The beneficial effects of the invention are as follows：
Carbon dioxide electrochemical reduction catalyst provided by the invention is nanocatalyst, specially nickel oxide and copper oxide
The nickel tin lamella of the compound lamellar structure of ambrose alloy lamella bimetallic oxide or nickel oxide and tin oxide of compound lamellar structure
Bimetallic oxide.The nanocatalyst of the structure has high catalytic activity, greatly reduces electro-reduction process
In overpotential, while effective inhibiting evolving hydrogen reaction adjoint during carbon dioxide reduction.
The preparation method of carbon dioxide electrochemical reduction catalyst provided by the invention, using coprecipitation, by effective
The preparation condition for regulating and controlling catalyst, obtains ambrose alloy lamella bimetallic oxide or nickel tin lamella bimetallic oxide, the structure
Catalyst have more active sites, greatly reduce the overpotential in electrochemical catalysis reduction process, it is effective to drop
Low energy consumption.The effective evolving hydrogen reaction inhibited in carbon dioxide electrochemical catalysis reduction process simultaneously, greatly improves method
Draw efficiency.
The gas-diffusion electrode of the load carbon dioxide electrochemical reduction catalyst provided by the invention, can not only solve
Reduction current too low problem, and effectively raise the faradic efficiency during Carbon dioxide electrochemical reduction.
Description of the drawings
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the carbon dioxide electrochemical reduction catalyst in embodiment 1-3 in CO2The 0.1M Na of saturation2SO4In solution
Cyclic voltammetry curve figure；
Fig. 2 is the carbon dioxide electrochemical reduction catalyst in embodiment 1-3 in CO2It is followed in the 0.1M KCl solution of saturation
Ring volt-ampere curve figure；
The transmission electron microscope figure (TEM) of carbon dioxide electrochemical reduction catalyst in Fig. 3 embodiments 2；
The X-ray diffraction spectrum figure (XRD) of carbon dioxide electrochemical reduction catalyst in Fig. 4 embodiments 1-3.
Specific implementation mode
The present invention invention thought be：The present invention changes copper, tin and nickle atom ratio, pH value and Re Chu by coprecipitation
The temperature and time of reason, to obtain the bi-metal oxide catalyst of lamellar structure, gained catalyst is to carbon dioxide electricity
Catalyst of the chemical catalysis reduction with high catalytic activity, and the overpotential in electro-reduction process is greatly reduced,
Evolving hydrogen reaction adjoint during effective inhibition carbon dioxide reduction simultaneously, improves the reduction of carbon dioxide electrochemical catalysis
Faradic efficiency.Simultaneously as raw material rich reserves, nontoxic, process for synthetic catalyst used in the catalyst of the present invention
It is simple and environmentally-friendly, it is suitable for commercial Application.
The present invention provides a kind of carbon dioxide electrochemical reduction catalyst, is nanocatalyst, specially ambrose alloy lamella
Bimetallic oxide or nickel tin lamella bimetallic oxide.The structure of the ambrose alloy lamella bimetallic oxide be nickel oxide and
The compound lamellar structure of copper oxide, the structure of the nickel tin lamella bimetallic oxide are nickel oxide and the compound lamella of tin oxide
Structure.It is preferred that the molar ratio of the nickel oxide and copper oxide is：9:1~1:9, the molar ratio of the nickel oxide and tin oxide is：
9:1~1:9.The molar ratio of the most preferably described nickel oxide and copper oxide is：8:2.
The present invention also provides a kind of preparation methods of carbon dioxide electrochemical reduction catalyst, include the following steps：
Copper chloride or stannic chloride and nickel chloride are dissolved in deionized water, stirred, instilling ammonium hydroxide adjusting pH value of solution dropwise is
7.5~14, so that above-mentioned metal ion is co-precipitated, centrifuge, washed to neutrality with deionized water and absolute ethyl alcohol, does
It is dry, it is thermally treated resulting in ambrose alloy lamella bimetallic oxide or nickel tin lamella bimetallic oxide, the temperature of heat treatment is 250 DEG C
~750 DEG C, the time of heat treatment is -4 hours 0.5 hour；It is 9 that most preferably reaction condition, which is the pH, the temperature of the heat treatment
Degree is 350 DEG C~450 DEG C, and the time of heat treatment is 3 hours.It is preferred that the molar concentration ratio of the copper chloride and nickel chloride is：
1:9~9:1, the molar concentration ratio of the stannic chloride and nickel chloride is：1:9~9:1.The most preferably described copper chloride and nickel chloride
Molar concentration ratio be：2:8.
The present invention also provides a kind of gas-diffusion electrode of the above-mentioned carbon dioxide electrochemical reduction catalyst of load, the gas
The size of body diffusion electrode is 0.4cm × 0.4cm~6cm × 6cm, the carbon dioxide electrochemical reduction catalyst of load
Weight is 5 μ g~20mg.
The gas-diffusion electrode of the above-mentioned carbon dioxide electrochemical reduction catalyst of load, is prepared by following methods
It obtains：
The carbon dioxide electrochemical reduction catalyst is distributed in ethyl alcohol, the perfluorinated sulfonic acid of 1wt%~5wt% is added
Resin Nafion solution, stirring ultrasound, makes carbon dioxide electrochemical reduction catalyst be uniformly dispersed, then by the mixed liquor of gained
It is coated in gas-diffusion electrode, dries, you can obtain loading the gas diffusion of above-mentioned carbon dioxide electrochemical reduction catalyst
Electrode；
Or mix the carbon dioxide electrochemical reduction catalyst with carbon material, mixture is distributed in ethyl alcohol,
The perfluorinated sulfonic resin Nafion solution of 1wt%~5wt% is added, stirring ultrasound makes carbon dioxide electrochemical reduction catalyst
It is uniformly dispersed, then the mixed liquor of gained is coated in gas-diffusion electrode, dry, you can obtain loading above-mentioned carbon dioxide
The gas-diffusion electrode of electrochemical reduction catalyst.
Above-mentioned gas diffusion electrode is glass carbon plate, carbon paper, carbon cloth or carbon felt；Above-mentioned ethanol consumption is 500 μ L~10mL；On
It is activated carbon VLCAN X-72, BP200, carbon nanotube, carbon nano-fiber, nano cages, graphene, graphene amount to state carbon material
Son point or graphene oxide, dosage are 10 μ g~100mg.
The present invention is described in detail below in conjunction with the accompanying drawings.
Carbon dioxide electrochemical reduction catalyst prepares embodiment：
Embodiment 1
A kind of carbon dioxide electrochemical reduction catalyst, including ambrose alloy lamella bimetallic oxide, the ambrose alloy lamella
Bimetallic oxide is obtained by Co deposited synthesis, and preparation method is：2mmol Copper dichloride dihydrates, 8mmol six is taken to be hydrated chlorine
Change nickel and be dissolved in 40mL deionized waters in beaker, concentrated ammonia liquor 5mL is dissolved in 45mL deionized waters, is added drop-wise to dropwise in beaker to pH
Value is 9, stirs 4h, centrifuges, is washed to neutrality with deionized water and absolute ethyl alcohol, be placed in 60 DEG C of dryings in drying box, obtain
To solid powder.It will be put into after powder mull in tube furnace and heat 3h in air at 350 DEG C, obtain the oxidation of ambrose alloy lamella bimetallic
(molar ratio of NiO/CuO is 8 to object:2), as carbon dioxide electrochemical reduction catalyst.
Embodiment 2
A kind of carbon dioxide electrochemical reduction catalyst, including ambrose alloy lamella bimetallic oxide, the ambrose alloy lamella
Bimetallic oxide is obtained by Co deposited synthesis, and preparation method is：2mmol Copper dichloride dihydrates, 8mmol six is taken to be hydrated chlorine
Change nickel and be dissolved in 40mL deionized waters in beaker, concentrated ammonia liquor 5mL is dissolved in 45mL deionized waters, is added drop-wise to dropwise in beaker to pH
Value is 9, stirs 4h, centrifuges, is washed to neutrality with deionized water and absolute ethyl alcohol, be placed in 60 DEG C of dryings in drying box, obtain
To solid powder.It will be put into after powder mull in tube furnace and heat 3h in air at 450 DEG C, obtain the oxidation of ambrose alloy lamella bimetallic
(molar ratio of NiO/CuO is 8 to object:2), as carbon dioxide electrochemical reduction catalyst.
Embodiment 3
A kind of carbon dioxide electrochemical reduction catalyst, including ambrose alloy lamella bimetallic oxide, the ambrose alloy lamella
Bimetallic oxide is obtained by Co deposited synthesis, and preparation method is：2mmol Copper dichloride dihydrates, 8mmol six is taken to be hydrated chlorine
Change nickel and be dissolved in 40mL deionized waters in beaker, concentrated ammonia liquor 5mL is dissolved in 45mL deionized waters, is added drop-wise to dropwise in beaker to pH
Value is 9, stirs 4h, centrifuges, is washed to neutrality with deionized water and absolute ethyl alcohol, be placed in 60 DEG C of dryings in drying box, obtain
To solid powder.It will be put into after powder mull in tube furnace and heat 3h in air at 550 DEG C, obtain the oxidation of ambrose alloy lamella bimetallic
(molar ratio of NiO/CuO is 8 to object:2), as carbon dioxide electrochemical reduction catalyst.
Embodiment 4
A kind of carbon dioxide electrochemical reduction catalyst, including ambrose alloy lamella bimetallic oxide, the ambrose alloy lamella
Bimetallic oxide is obtained by Co deposited synthesis, and preparation method is：9mmol Copper dichloride dihydrates, 1mmol six is taken to be hydrated chlorine
Change nickel and be dissolved in 40mL deionized waters in beaker, concentrated ammonia liquor 5mL is dissolved in 45mL deionized waters, is added drop-wise to dropwise in beaker to pH
Value is 14, stirs 4h, centrifuges, is washed to neutrality with deionized water and absolute ethyl alcohol, be placed in 60 DEG C of dryings in drying box, obtain
To solid powder.It will be put into after powder mull in tube furnace and heat 4h in air at 750 DEG C, obtain the oxidation of ambrose alloy lamella bimetallic
(molar ratio of NiO/CuO is 1 to object:9), as carbon dioxide electrochemical reduction catalyst.
Prepared ambrose alloy lamella bimetallic oxide is nickel oxide and the compound lamellar structure nanocatalyst of copper oxide,
The nanocatalyst of the structure has high catalytic activity, can greatly reduce the overpotential in electro-reduction process,
Evolving hydrogen reaction adjoint during effective inhibition carbon dioxide reduction simultaneously.
Embodiment 5
A kind of carbon dioxide electrochemical reduction catalyst, including nickel tin lamella bimetallic oxide, the nickel tin lamella
Bimetallic oxide is obtained by Co deposited synthesis, and preparation method is：Tetra- hydrous tin chlorides of 1mmol, 9mmol six is taken to be hydrated chlorine
Change nickel and be dissolved in 40mL deionized waters in beaker, concentrated ammonia liquor 5mL is dissolved in 45mL deionized waters, is added drop-wise to dropwise in beaker to pH
Value is 7.5, stirs 4h, centrifuges, is washed to neutrality with deionized water and absolute ethyl alcohol, be placed in 60 DEG C of dryings in drying box,
Obtain solid powder.It will be put into after powder mull in tube furnace and heat 0.5h in air at 250 DEG C, obtain nickel tin lamella bimetallic
Oxide (NiO/SnO2Molar ratio be 9:1), as carbon dioxide electrochemical reduction catalyst.
Prepared nickel tin lamella bimetallic oxide is nickel oxide and the compound lamellar structure nanocatalyst of tin oxide,
The nanocatalyst of the structure has high catalytic activity, can greatly reduce the overpotential in electro-reduction process,
Evolving hydrogen reaction adjoint during effective inhibition carbon dioxide reduction simultaneously.
Load the preparation of the gas-diffusion electrode of above-mentioned carbon dioxide electrochemical reduction catalyst：
Embodiment 6
Carbon dioxide electrochemical reduction catalyst 5mg in embodiment 1-3 is distributed to the absolute ethyl alcohol of 950 μ L respectively
In, 50 μ L 5wt%Nafion solution are added, ultrasonic disperse 5h obtains mixed liquor, takes 10 μ L mixed liquors to be applied to this diameter of
On the glass-carbon electrode of 4mm, drying, obtaining load has the gas-diffusion electrode of carbon dioxide electrochemical reduction catalyst, load capacity
398μg/cm2。
The weight of the carbon dioxide electrochemical reduction catalyst of the gas-diffusion electrode load can be in 5 μ g~20mg
It is arbitrarily chosen in range, the gas-diffusion electrode can also be carbon paper, carbon cloth or carbon felt；The ethanol consumption can for
It is arbitrarily chosen within the scope of 500 μ L~10mL.
The gas-diffusion electrode of the above-mentioned above-mentioned carbon dioxide electrochemical reduction catalyst of load can also pass through following methods
It prepares：The carbon dioxide electrochemical reduction catalyst is mixed with carbon material, mixture is distributed in ethyl alcohol, is added
The perfluorinated sulfonic resin Nafion solution of 1wt%~5wt%, stirring ultrasound, makes carbon dioxide electrochemical reduction catalyst disperse
Uniformly, then the mixed liquor of gained is coated in gas-diffusion electrode, is dried, you can obtain loading above-mentioned carbon dioxide electrification
Learn the gas-diffusion electrode of reducing catalyst.
The carbon material is activated carbon VLCAN X-72, BP200, carbon nanotube, carbon nano-fiber, nano cages, stone
Black alkene, graphene quantum dot or graphene oxide, dosage are arbitrarily chosen between 10 μ g~100mg.
Here it no longer enumerates.
Electrochemical property test is tested：
Embodiment 7
Electrochemical property test carries out in electrochemical workstation test system, respectively has load prepared by embodiment 6
The gas-diffusion electrode of carbon dioxide electrochemical reduction catalyst as working electrode, saturated calomel electrode as reference electrode,
Platinum electrode constitutes three-electrode system as auxiliary electrode.Electrolyte is the Na of 0.1M2SO4Solution.Electrochemical operation instrument is purchased
Hai Chenhua companies.
Embodiment 8
Electrochemical property test carries out in electrochemical workstation test system, respectively has load prepared by embodiment 6
The gas-diffusion electrode of carbon dioxide electrochemical reduction catalyst as working electrode, saturated calomel electrode as reference electrode,
Platinum electrode constitutes three-electrode system as auxiliary electrode.Electrolyte is the KCl solution of 0.1M.Electrochemical operation instrument purchases Shanghai
Chen Hua companies.
Such as attached drawing 1 of cyclic voltammetry scan curve at room temperature, shown in attached drawing 2.It is respectively to be born in embodiment 7 shown in Fig. 1
It is loaded with the cycle volt of embodiment 1, embodiment 2, the gas-diffusion electrode of carbon dioxide electrochemical reduction catalyst in embodiment 3
Pacify scanning curve.Fig. 1 illustrates that embodiment 1, the overpotential of embodiment 2 are minimum in 3 kinds of catalyst, and reduction current density is larger.
It is respectively to load to have the Carbon dioxide electrochemical reduction in embodiment 1, embodiment 2, embodiment 3 to urge in embodiment 8 shown in Fig. 2
The cyclic voltammetry scan curve of the gas-diffusion electrode of agent.Fig. 2 illustrates that embodiment 1, embodiment 2 have relatively low in 3 kinds of catalyst
Overpotential, embodiment 1 have maximum reduction current density.Fig. 3 is the saturating of carbon dioxide electric reduction catalyst prepared by embodiment 2
Electron microscope picture TEM is penetrated, which illustrates that the catalyst of the present invention is nanocatalyst.Fig. 4 is embodiment 1, embodiment 2, reality
The X-ray diffracting spectrum of carbon dioxide electric reduction catalyst in example 3 is applied, obviously occurs ambrose alloy lamella bimetallic oxygen in spectrogram
The characteristic peak of compound.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of carbon dioxide electrochemical reduction catalyst, which is characterized in that it is nanocatalyst, specially nickel oxide and oxygen
Change the ambrose alloy lamella bimetallic oxide of the compound lamellar structure of copper or the nickel tin of nickel oxide and the compound lamellar structure of tin oxide
Lamella bimetallic oxide.
2. carbon dioxide electrochemical reduction catalyst according to claim 1, which is characterized in that the nickel oxide and oxidation
The molar ratio of copper is：9:1~1:9, the molar ratio of the nickel oxide and tin oxide is：9:1~1:9.
3. carbon dioxide electrochemical reduction catalyst according to claim 1, which is characterized in that the nickel oxide and oxidation
The molar ratio of copper is：8:2.
4. a kind of preparation method of carbon dioxide electrochemical reduction catalyst described in claim 1, which is characterized in that including with
Lower step：
Copper chloride or stannic chloride and nickel chloride are dissolved in deionized water, stirred, instillation ammonium hydroxide adjusting pH value of solution makes above-mentioned dropwise
Metal ion is co-precipitated, and is centrifuged, and is washed to neutrality with deionized water and absolute ethyl alcohol, dry, is thermally treated resulting in nickel
Copper sheet layer bimetallic oxide or nickel tin lamella bimetallic oxide.
5. the preparation method of carbon dioxide electrochemical reduction catalyst according to claim 4, which is characterized in that the chlorine
The molar concentration ratio for changing copper and nickel chloride is：1:9~9:1, the molar concentration ratio of the stannic chloride and nickel chloride is：1:9
~9:1.
6. the preparation method of carbon dioxide electrochemical reduction catalyst according to claim 5, which is characterized in that the chlorine
The molar concentration ratio for changing copper and nickel chloride is：2:8.
7. the preparation method of the carbon dioxide electrochemical reduction catalyst according to claim 4-6 any one, feature
It is, the pH is 7.5~14, and the temperature of the heat treatment is 250 DEG C~750 DEG C, and time of heat treatment is 0.5 hour -4 small
When.
8. the preparation method of carbon dioxide electrochemical reduction catalyst according to claim 7, which is characterized in that the pH
It is 9, the temperature of the heat treatment is 350 DEG C~450 DEG C, and the time of heat treatment is 3 hours.
9. a kind of gas-diffusion electrode of load carbon dioxide electrochemical reduction catalyst described in claim 1, feature exist
In the size of the gas-diffusion electrode is 0.4cm × 0.4cm~6cm × 6cm, and the carbon dioxide electrochemistry of load is also
The weight of raw catalyst is 5 μ g~20mg.
10. the gas-diffusion electrode of load carbon dioxide electrochemical reduction catalyst according to claim 9, feature exist
In being prepared by following methods：
The carbon dioxide electrochemical reduction catalyst is distributed in ethyl alcohol, the perfluorinated sulfonic resin of 1wt%~5wt% is added
Nafion solution, stirring ultrasound, makes carbon dioxide electrochemical reduction catalyst be uniformly dispersed, and then coats the mixed liquor of gained
Onto gas-diffusion electrode, drying, you can obtain loading the gas-diffusion electrode of above-mentioned carbon dioxide electrochemical reduction catalyst；
Or mix the carbon dioxide electrochemical reduction catalyst with carbon material, mixture is distributed in ethyl alcohol, is added
The perfluorinated sulfonic resin Nafion solution of 1wt%~5wt%, stirring ultrasound, makes carbon dioxide electrochemical reduction catalyst disperse
Uniformly, then the mixed liquor of gained is coated in gas-diffusion electrode, is dried, you can obtain loading above-mentioned carbon dioxide electrification
Learn the gas-diffusion electrode of reducing catalyst；
The gas-diffusion electrode is glass carbon plate, carbon paper, carbon cloth or carbon felt；The ethanol consumption is 500 μ L~10mL；Described
Carbon material is activated carbon VLCAN X-72, BP200, carbon nanotube, carbon nano-fiber, nano cages, graphene, graphene quantum
Point or graphene oxide, dosage are 10 μ g~100mg.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111229195A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Electro-reduction carbon dioxide catalytic material and preparation and application thereof |
| CN111519207A (en) * | 2020-05-19 | 2020-08-11 | 大连大学 | Preparation and application of Sn electrode for electrochemical reduction of carbon dioxide |
| CN112176359A (en) * | 2019-07-03 | 2021-01-05 | 中石化南京化工研究院有限公司 | Bimetal gas diffusion electrode and preparation method and application thereof |
| CN114438519A (en) * | 2022-01-28 | 2022-05-06 | 西安理工大学 | Construction of polycrystalline interface CuO for electrocatalysis of CO2Reduction preparation method |
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| CN101931081A (en) * | 2010-08-27 | 2010-12-29 | 西安交通大学 | Preparation method of air diffusion electrode for preparing methanol by electrochemically reducing carbon dioxide |
| CN103715436A (en) * | 2013-12-19 | 2014-04-09 | 东华大学 | Carbon dioxide electrochemical reduction catalyst as well as preparation method and application thereof |
| CN106868535A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | Electrochemically reducing carbon dioxide produces the gas-diffusion electrode preparation method of hydrocarbon |
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| CN101931081A (en) * | 2010-08-27 | 2010-12-29 | 西安交通大学 | Preparation method of air diffusion electrode for preparing methanol by electrochemically reducing carbon dioxide |
| CN103715436A (en) * | 2013-12-19 | 2014-04-09 | 东华大学 | Carbon dioxide electrochemical reduction catalyst as well as preparation method and application thereof |
| CN106868535A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | Electrochemically reducing carbon dioxide produces the gas-diffusion electrode preparation method of hydrocarbon |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111229195A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Electro-reduction carbon dioxide catalytic material and preparation and application thereof |
| CN112176359A (en) * | 2019-07-03 | 2021-01-05 | 中石化南京化工研究院有限公司 | Bimetal gas diffusion electrode and preparation method and application thereof |
| CN112176359B (en) * | 2019-07-03 | 2021-11-12 | 中石化南京化工研究院有限公司 | Bimetal gas diffusion electrode and preparation method and application thereof |
| CN111519207A (en) * | 2020-05-19 | 2020-08-11 | 大连大学 | Preparation and application of Sn electrode for electrochemical reduction of carbon dioxide |
| CN111519207B (en) * | 2020-05-19 | 2021-06-29 | 大连大学 | Preparation and application of Sn electrode for electrochemical reduction of carbon dioxide |
| CN114438519A (en) * | 2022-01-28 | 2022-05-06 | 西安理工大学 | Construction of polycrystalline interface CuO for electrocatalysis of CO2Reduction preparation method |
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