CN117987869A - Bimetal alloy modified carbon nano sheet material and preparation method and application thereof - Google Patents
Bimetal alloy modified carbon nano sheet material and preparation method and application thereof Download PDFInfo
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- CN117987869A CN117987869A CN202211362308.1A CN202211362308A CN117987869A CN 117987869 A CN117987869 A CN 117987869A CN 202211362308 A CN202211362308 A CN 202211362308A CN 117987869 A CN117987869 A CN 117987869A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 50
- 239000000956 alloy Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000002135 nanosheet Substances 0.000 title claims abstract description 37
- 150000001721 carbon Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 21
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 53
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008098 formaldehyde solution Substances 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 62
- 239000001569 carbon dioxide Substances 0.000 abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 27
- 238000006722 reduction reaction Methods 0.000 abstract description 17
- 239000003792 electrolyte Substances 0.000 abstract description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 9
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- -1 carbon dioxide saturated potassium chloride Chemical class 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 22
- 239000000047 product Substances 0.000 description 16
- 239000001103 potassium chloride Substances 0.000 description 11
- 235000011164 potassium chloride Nutrition 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000002064 nanoplatelet Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 150000002829 nitrogen Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241000124033 Salix Species 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910003336 CuNi Inorganic materials 0.000 description 1
- 239000012919 MOF-derived carbon material Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Catalysts (AREA)
Abstract
The application discloses a bimetal alloy modified carbon nano sheet material, and a preparation method and application thereof. The material is a copper-nickel alloy modified nitrogen-doped ultrathin nanosheet electrocatalyst (CuNi-N-CNS), has an ultrathin willow-shaped two-dimensional sheet structure, is used for electrocatalytic carbon dioxide reduction reaction (CO 2 RR) under an acidic condition, and has the characteristics of ultrahigh electrocatalytic activity, good conductivity, high selectivity and excellent stability. The flow cell device comprises an anode electrode plate, a cathode electrode plate, a proton exchange membrane, anode chamber electrolyte, cathode chamber electrolyte and a carbon dioxide gas chamber; the cathode catalyst is CuNiN-CNS coated on carbon paper, and the catholyte is carbon dioxide saturated potassium chloride solution; the anode catalyst is a commercial RuIrTi net, the anolyte is potassium hydroxide solution, and the device realizes high-selectivity conversion of carbon dioxide under high current.
Description
Technical Field
The application relates to a bimetal alloy modified carbon nano sheet material, a preparation method and application thereof, belonging to the technical field of inorganic catalyst materials and electrochemical reduction of CO 2.
Background
The large carbon dioxide emissions generated by the overuse of fossil fuels lead to a series of environmental problems. In addition to the method of reducing emissions of carbon dioxide from sources, current biological and chemical processes for reducing carbon dioxide to chemicals/fuels have been well studied, wherein the electroreduction of CO 2 provides a viable and convenient route to the production of valuable carbon-based chemical feedstocks. However, the extremely stable c=o bond (806 KJ mol -1) in CO 2 and the competing aqueous hydrogen evolution reaction limit the activation of CO 2. In addition, CO 2 can be electrochemically converted to a variety of products due to differences in the number of transferred electrons and the catalytic mechanism, which presents great difficulties in the selection of the orientation. To date, various nanostructured Ag, au and pd-based electrocatalysts have been studied because of their high selectivity in aqueous solutions, low overpotential for carbon dioxide, but at high cost. Therefore, it is critical to develop a catalyst material that is low cost, has high activity, high selectivity, and has good stability.
On the other hand, optimization of electrolytic devices is the most critical strategy in practical application, and a flow cell based on a GDE structure is generally adopted at present, so that stable operation under ultra-high current density is difficult to realize in most cases. The influencing factors comprise the type of electrolyte, the concentration of the electrolyte, the pH value, the spacing between the anode and cathode plates and the like, and different influencing factors determine the current density and the type of products. The common electrolyte system adopts neutral or alkaline solution, because the alkaline environment is favorable for the activation of carbon dioxide and inhibits hydrogen evolution, but the carbon dioxide inevitably reacts with the electrolyte in diffusion to generate carbonate, so that the carbonate is difficult to fully utilize.
Disclosure of Invention
Substitution of the noble metal catalyst with a non-noble metal-carbon material is a promising step in achieving sustainable CO 2 RR. The MOF-derived carbon material has wide application prospect in electrochemical carbon dioxide reduction reaction due to the extremely high specific surface area, flexible electronic structure, various active sites and designable morphology. Through nitrogen atom doping and specific metal modification, the number of active sites in the catalytic process can be effectively increased, and charge transfer and specific selection of products are promoted.
According to one aspect of the present application, there is provided a bimetal alloy modified carbon nanoplatelet material comprising nitrogen doped carbon nanoplatelets and copper nickel alloy particles grown in situ on the surface of the nitrogen doped carbon nanoplatelets;
The copper-nickel alloy particles are coated by a carbon layer;
the copper-nickel alloy particles are coated by a carbon layer, and the thickness of the carbon layer is 4-6 nm;
optionally, the thickness of the carbon layer is any value or range between any two of 4nm, 5nm, 6 nm.
The content of the copper-nickel alloy particles in the bimetal alloy modified carbon nano sheet material is 2.0 to 8.0 weight percent;
Optionally, the content of the copper-nickel alloy particles in the bimetal alloy modified carbon nano sheet material is any value or a range of values between any two of 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, and 8 wt%.
Wherein the content of copper element is 1.0 to 4.0wt%, optionally, the content of copper element is any value or range between any two of 1wt%, 2wt%, 3wt%, 4 wt%.
The content of nickel element is 1.0-4.0 wt%, optionally, the content of nickel element is any value or range value between any two of 1wt%, 2wt%, 3wt% and 4 wt%.
The particle size of the copper-nickel alloy particles is 30-60 nm;
Optionally, the particle size of the copper nickel alloy particles is any value or range between any two values of 30nm, 40nm, 50nm, 60 nm.
The specific surface area of the bimetal alloy modified carbon nano sheet material is 984.21-1466.95 m 2/g;
optionally, the specific surface area of the bimetal alloy modified carbon nano sheet material is any value or a range value between any two of 984.21m2/g、1000m2/g、1100m2/g、1200m2/g、1300m2/g、1400m2/g、1466.95m2/g.
The single-point adsorption total pore volume of the bimetal alloy modified carbon nano-sheet material is 0.60-0.90 cm 3/g;
optionally, the single point adsorption total pore volume of the bimetallic alloy modified carbon nanomaterial is any value or range of values between any two of 0.6cm 3/g、0.7cm3/g、0.8cm3/g、0.9cm3/g.
The micropore aperture of the nitrogen-doped carbon nano sheet is 0.5 nm-2.0 nm.
Optionally, the microporous pore size of the nitrogen-doped carbon nanoplatelets is any value or range of values between any two of 0.5nm, 1nm, 1.5nm, 2 nm.
The bimetal alloy nano particles are coated by a carbon layer and are decorated on the salix leaf-shaped ultrathin carbon nano sheet.
According to another aspect of the present application, there is provided a method for preparing the above-mentioned bimetal alloy modified carbon nano sheet material, comprising the steps of:
a) Mixing a solution containing phenolic resin with an F127 surfactant aqueous solution, and reacting to obtain Resol-F127 solution;
b) Mixing raw materials containing zinc nitrate, nickel nitrate, copper nitrate, 2-methylimidazole and water to obtain a metal ZIF-8 suspension;
c) Mixing the Resol-F127 solution obtained in a) with the metal ZIF-8 suspension obtained in b), performing hydrothermal reaction, and performing pyrolysis to obtain the bimetal alloy modified carbon nano sheet material.
The solution containing phenolic resin is obtained by mixing phenol, 37 weight percent formaldehyde solution and 0.1M sodium hydroxide solution;
Wherein the content of the phenol is 0.01-0.08 g/ml;
Alternatively, the phenol content is any value or range of values between any two of 0.01g/ml, 0.02g/ml, 0.03g/ml, 0.04g/ml, 0.05g/ml, 0.06g/ml, 0.07g/ml, 0.08 g/ml.
The volume ratio of the 37wt% formaldehyde solution to the 0.1M sodium hydroxide solution is 0.07-0.28;
Alternatively, the volume ratio of the 37wt% formaldehyde solution to the 0.1M sodium hydroxide solution is any value or range of values between any two of 0.07, 0.1, 0.15, 0.2, 0.25, 0.28.
In the F127 surfactant aqueous solution, the content of the F127 surfactant is 0.009-0.22 g/ml;
Optionally, in the aqueous solution of the F127 surfactant, the content of the F127 surfactant is any value or a range of values between any two of 0.009g/ml, 0.01g/ml, 0.05g/ml, 0.1g/ml, 0.15g/ml, 0.2g/ml, 0.22 g/ml.
The temperature of the reaction is 60-80 ℃;
Alternatively, the temperature of the reaction is any value or range of values between any two of 60 ℃, 70 ℃, 80 ℃.
The reaction time is 12-20 h.
Alternatively, the reaction time is any value or range of values between any two of 12h, 14h, 16h, 18h, 20 h.
The ratio of the total molar amount of nickel element in the nickel nitrate to copper element in the copper nitrate to the molar amount of zinc element in the zinc nitrate is 1: 20-1: 10;
Optionally, the ratio of the total molar amount of nickel element in the nickel nitrate to copper element in the copper nitrate to the molar amount of zinc element in the zinc nitrate is any value or a range of values between any two of 1:20, 1:15, 1:10.
The molar ratio of zinc element in the zinc nitrate to the 2-methylimidazole is 1:6-1:4;
optionally, the ratio of the molar amount of zinc element in the zinc nitrate to the 2-methylimidazole is any value or range of values between any two of 1:6, 1:5, 1:4.
The ratio of the molar quantity of zinc element in the zinc nitrate to the volume of water is 3mmol/60 mL-3 mmol/40mL;
optionally, the ratio of the molar amount of zinc element in the zinc nitrate to the volume of water is any value or a range of values between any two of 3mmol/60mL, 3mmol/50mL, 3mmol/40 mL.
A) The volume ratio of the Resol-F127 solution obtained in the step (a) to the metal ZIF-8 suspension obtained in the step (b) is 1:6-1:1;
Optionally, the volume ratio of the Resol-F127 solution obtained in a) to the metal ZIF-8 suspension obtained in b) is any value or a range of values between any two of 1:6, 1:5, 1:4, 1:3, 1:2, 1:1.
The temperature of the hydrothermal reaction is 120-160 ℃;
alternatively, the temperature of the hydrothermal reaction is any value or a range of values between any two of 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃.
The hydrothermal reaction time is 12-24 hours;
Optionally, the time of the hydrothermal reaction is any value or a range of values between any two of 12h, 18h, 24 h.
The pyrolysis comprises the following processes:
Raising the temperature to 300-400 ℃ at the speed of 2-4 ℃/min, keeping the temperature for 1-2 hours, raising the temperature to 900-950 ℃ at the speed of 2-4 ℃/min, and keeping the temperature for 1-2 hours.
The pyrolysis atmosphere is an inactive gas atmosphere;
The inert gas atmosphere is selected from at least one of nitrogen, argon or helium.
C) Drying before pyrolysis;
The drying is freeze drying;
The temperature of freeze drying is-40 to-10 ℃;
optionally, the freeze-drying temperature is any value or range of values between-40 ℃, -30 ℃, -20 ℃, -10 ℃.
The freeze drying time is 12-24 h.
Optionally, the freeze-drying time is any value or range of values between any two of 12h, 18h, 24 h.
Specifically, the method comprises the following steps:
1) Uniformly mixing the prepared Resol-F127 solution with the prepared bimetallic ZIF-8 suspension, and carrying out hydrothermal reaction;
2) Centrifugally washing the precipitate after the hydrothermal reaction with water, freeze-drying for 24 hours, and grinding to obtain a powdery precursor;
3) Placing the powdery precursor in a porcelain boat, and performing a two-step pyrolysis method (heat preservation for 1 hour at 350 ℃ and then heat preservation for 2 hours at 900 ℃) in a tube furnace under the argon atmosphere to obtain a nitrogen-doped carbon nano sheet material modified by the bimetal alloy;
Optionally, the volume ratio of Resol-F127 solution to bimetallic ZIF-8 suspension in 1) is 1:3;
optionally, adding 8mL Resol-F127 solution and 24mL bimetallic ZIF-8 suspension for ultrasonic dispersion;
optionally, the temperature of the hydrothermal reaction is 150 ℃ and the reaction time is 20 hours;
optionally, the heating rate in the step 3) is 3 ℃/min;
Optionally, the first stage cracking temperature in the step 3) is 250-350 ℃ and the holding time is 0.5-2 h;
optionally, the second-stage cracking temperature in the step 3) is 800-1000 ℃ and the holding time is 1-2 h;
Optionally, in step 3), the first stage cracking temperature is 350 ℃ and the holding time is 1h;
optionally, the second stage cracking temperature in step 3) is 900 ℃ and the holding time is 2h.
The phenolic resin is obtained through the following steps:
weighing a proper amount of phenol, formaldehyde and sodium hydroxide aqueous solution, and stirring under the condition of heating in an oil bath in a flask to obtain a solution containing phenolic resin.
According to another aspect of the present application, there is provided a cathode catalyst comprising the above-described bimetal alloy modified carbon nano sheet material or the bimetal alloy modified carbon nano sheet material prepared by the above-described preparation method.
According to another aspect of the present application, there is provided a flow cell electrolyzer comprising an anode, an anode chamber, a cathode chamber and a gas chamber;
Wherein the cathode contains the cathode catalyst.
The cathode is obtained by coating a dispersion liquid containing the cathode catalyst on carbon paper;
In the cathode, the coating amount of the cathode catalyst is 0.5-2 mg/cm 2.
The loading area of the cathode catalyst on the cathode electrode plate accounts for 5-100% of the carbon paper surface area.
Optionally, the coating size of the cathode catalyst in the cathode electrode slice is 1cm x 1cm;
optionally, the size of the anode catalyst in the anode electrode slice is 1cm x 2cm;
Optionally, the loading of the cathode catalyst in the cathode electrode sheet is 1mg.
The device is based on a GDE system, the cathode generates a reduction reaction of carbon dioxide, the anode generates an oxygen evolution reaction, high-selectivity reduction of carbon dioxide under high current density can be realized, and meanwhile, the device can meet the reduction of carbon dioxide of a three-electrode system and a two-electrode system, and further provides reference value for practical application of CO 2 RR.
Wherein the anode electrode sheet includes an anode catalyst.
A gas diffusion electrode system (GDE) is constructed between the gas chamber and the cathode chamber by using carbon paper; a proton exchange membrane is arranged between the anode chamber and the cathode chamber; the electrocatalytic carbon dioxide reduction reaction (CO 2 RR) takes place on the cathode and the Oxygen Evolution Reaction (OER) takes place on the anode.
A catholyte containing CO 2 is arranged in the cathode chamber, and an anolyte is arranged in the anode chamber;
The catholyte is a KCl solution saturated by CO 2, and the anolyte is an alkaline solution;
Optionally, the concentration of KCl in the KCl solution of the saturated CO 2 is 0.5M-3M;
Optionally, the anode alkaline solution is KOH solution, and the concentration is 0.5M-3M;
Optionally, the concentration of KCl in the KCl solution of saturated CO 2 is 3m and the ph is 4.
Optionally, the anode KOH solution has a concentration of 1m and a ph of 14.
The anode electrode plate is a commercial RuIrTi net.
Optionally, the area of the anode electrode plate is 1cm 2～3.75cm2;
Optionally, the size of the carbon paper in the cathode electrode slice is 3cm x 3cm;
according to another aspect of the application there is provided the use of a flow cell electrolyser as described above for an alcohol fuel cell, carbon monoxide reduction or nitrogen reduction.
The flow cell electrolysis device is assembled by the following steps and methods:
step one, preparation of CuNi-N-CNS catalyst Material
(1) 0.6G phenol and 2.1mL37wt% formaldehyde solution are mixed, 15mL0.1M sodium hydroxide solution is added, heated and stirred for 30min at 70 ℃, 65mL deionized water containing 0.96g F127 surfactant is added, and stirring is continued for more than 15h at 70 ℃;
(2) 0.8925g of zinc nitrate, 0.0363g of copper nitrate and 0.0436g of nickel nitrate are weighed, 25mL of deionized water is added, stirring is carried out to obtain a solution A, 1.2g of 2-methylimidazole is weighed, 25mL of deionized water is added, stirring is carried out to obtain a solution B, the solution B is poured into the solution A, and ultrasonic treatment is carried out for 2 hours to obtain CuNi-ZIF-8 suspension;
(3) Taking 8mL Resol-F127 solution and 24mL of CuNi-ZIF-8 suspension to react for 20h at 150 ℃ in a 50mL polytetrafluoroethylene-lined reaction kettle;
(4) Taking the precipitate after the reaction, washing, centrifuging, and freeze-drying for 24 hours;
(5) Placing the dried sample in a tube furnace, and performing a two-step pyrolysis method (the temperature is raised to 350 ℃ at the rate of 3 ℃/min at room temperature, then the temperature is kept at 350 ℃ for 1 hour, then the temperature is raised to 900 ℃ at the rate of 3 ℃/min, and then the temperature is kept at 900 ℃ for 2 hours, and then the temperature is naturally lowered) in an argon atmosphere to obtain a copper-nickel alloy modified nitrogen-doped carbon nano sheet material;
step two, preparing CuNi-N-CNS electrode liquid for electrochemical test
And 5mg of the CuNi-N-CNS catalyst prepared in the step one is dispersed in 500 mu L of mixed solution of water, ethanol, isopropanol and Nafion, uniformly dispersed by ultrasonic, 100 mu L of suspension liquid is dripped at the position of 1cm 2 of the center of 3 x 3cm 2 carbon paper, and the suspension liquid is used for electrochemical testing after natural drying.
Step three, preparing a flow cell device for electrocatalytic carbon dioxide reduction assembled by CuNi-N-CNS/CP and RuIrTi mesh electrodes
Taking RuIrTi meshes of 1 x 2cm as anodes and Ti sheets as conductive current collectors; the dried carbon paper coated with the catalyst is used as a cathode, a hydrophobic layer on the back of the carbon paper can be used for carbon dioxide in a gas chamber to pass through, a hydrophilic layer of the carbon paper contacts with catholyte, and a catalytic process occurs on the three-phase interface; controlling the gas flow rate to be 20mL/min, and controlling the flow rate of the electrolyte by a peristaltic pump; an Ag|AgCl electrode is used as a reference electrode and is inserted into the catholyte; the gas product was analyzed by injecting it into a gas chromatograph using a 1mL injection needle, and the faraday efficiency was calculated.
In the application, the carbon dioxide reduction reaction (CO 2 Reduction Reaction) is called CO 2 RR for short; the oxygen evolution reaction (Oxygen Evolution Reaction) is abbreviated as OER;
in the application, the carbon paper is called CP for short;
in the present application, the carbon nanoplatelets (Carbon nanosheets) are abbreviated as CNS.
The application has the beneficial effects that at least comprises:
(1) The material preparation scheme provided by the application has universality and can be used for synthesizing other similar bimetal alloy nitrogen-doped carbon nano sheet materials. As an electrocatalyst for CO 2 RR, it can exhibit excellent catalytic activity, selectivity and stability. The copper-nickel alloy modified nitrogen-doped carbon nano-sheet material is used as an electrocatalyst for electrocatalytic carbon dioxide reduction reaction, has excellent catalytic activity, and has high catalytic selectivity and good stability. The preparation method of the material is simple, the condition is easy to realize, and the material can be produced in a large scale.
(2) The CuNi-N-CNS material provided by the application is used as a cathode catalyst for carbon dioxide reduction in a 3MKCl electrolyte with saturated CO 2, and is assembled into a flow cell device for electrocatalytic carbon dioxide reduction by using a stable commercial RuIrTi mesh as an anode catalyst for oxygen evolution reaction in an alkaline electrolyte, under a three-electrode system, the electrolysis of carbon dioxide can be driven under a lower overpotential, and carbon monoxide products can be simultaneously generated at the cathode with high efficiency (the Faraday efficiency of carbon monoxide generation can reach 95 percent at the highest). In addition, the device can realize the ultra-large current density under the acidic condition, the current density of 500mA cm -2 can be achieved under the potential of-1.0V (vs RHE), and the Faraday efficiency of carbon monoxide is still close to 90%. And the device has good long-term stability, can operate for 24 hours under the high current density of 150mA cm -2, and the selectivity is not basically attenuated. Under a two-electrode system, an ultra-high current density exceeding 1A cm -2 can be achieved.
(3) The flow cell device provided by the application is innovative in structural design and electrolyte selection, and the use of the acidic electrolyte effectively avoids carbonation side reaction, improves the utilization of carbon dioxide raw materials, and simultaneously can effectively inhibit hydrogen evolution reaction and improve the selectivity of carbon-oxygen products by high concentration K + and Cl -.
(4) The electrolytic carbon dioxide flow cell device provided by the application has the advantages of low price, simplicity in operation and excellent performance, has a wide application prospect in the aspects of energy conversion and storage, and provides a reference for practical application of converting carbon dioxide into value-added chemicals.
Drawings
FIG. 1 is a scanning electron microscope image of the CuNi-N-CNS;
FIG. 2 is a transmission electron microscope image of the CuNi-N-CNS;
FIG. 3 is a high power transmission electron microscope image of a CuNi alloy in the CuNi-N-CNS;
FIG. 4 is an XRD pattern for CuNi-N-CNS;
FIG. 5 is a schematic diagram of an electrocatalytic reduction carbon dioxide flow cell apparatus according to example 4 of the present application;
FIG. 6 is a graph of a linear scan of a CuNi-N-CNS electrode material applied to a flow cell device tested in example 4 of the present application;
FIG. 7 is a graph showing the relationship between Faraday selection efficiency and electrode potential of the product of CuNi-N-CNS electrode material tested in a flow cell apparatus in example 4 of the present application;
FIG. 8 is a graph of potential versus current density for a CuNi-N-CNS electrode material employing different catholyte in a flow cell apparatus in accordance with example 5 of the present application.
FIG. 9 shows the adsorption and desorption curves and pore size distribution of CuNi-N-CNS.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials and reagents in the examples of the application were purchased commercially, with the proton membrane being purchased from dupont, usa; the carbon paper was purchased from ori corporation.
The analysis method in the embodiment of the application is as follows:
A Scanning Electron Microscope (SEM) of the sample is characterized by adopting a JSM6700-F model field emission scanning electron microscope;
XRD of the sample is characterized by using a Miniflex600 powder diffractometer;
The cyclic voltammetry of the electrodes was measured on a CHI760E electrochemical workstation from the company shiwa in the open sea;
an Shimadzu GC2014C instrument is adopted for gas chromatography analysis;
The liquid phase nuclear magnetic analysis adopts a JNM-ECZ600R instrument.
Example 1 preparation of copper-nickel alloy modified Nitrogen doped carbon nanoplatelet (CuNi-N-CNS) samples
(1) 0.6G phenol and 2.1mL37wt% formaldehyde solution are mixed, 15mL0.1M sodium hydroxide solution is added, heated and stirred for 30min at 70 ℃, 65mL deionized water containing 0.96g F127 surfactant is added, and stirring is continued for more than 15h at 70 ℃;
(2) 0.8925g of zinc nitrate, 0.0363g of copper nitrate and 0.0436g of nickel nitrate are weighed, 25mL of deionized water is added, stirring is carried out to obtain a solution A, 1.2g of 2-methylimidazole is weighed, 25mL of deionized water is added, stirring is carried out to obtain a solution B, the solution B is poured into the solution A, and ultrasonic treatment is carried out for 2 hours to obtain CuNi-ZIF-8 suspension;
(3) Taking 8mL Resol-F127 solution and 24mL of CuNi-ZIF-8 suspension to react for 20h at 150 ℃ in a 50mL polytetrafluoroethylene-lined reaction kettle;
(4) Taking the precipitate after the reaction, washing, centrifuging, and freeze-drying for 24 hours;
(5) And (3) placing the dried sample in a tube furnace, and performing a two-step pyrolysis method (the temperature is raised to 350 ℃ at the rate of 3 ℃/min at room temperature, then the temperature is kept at 350 ℃ for 1 hour, then the temperature is raised to 900 ℃ at the rate of 3 ℃/min, and then the temperature is kept at 900 ℃ for 2 hours, and finally the temperature is naturally lowered) in an argon atmosphere, so as to obtain the copper-nickel alloy modified nitrogen-doped carbon nano sheet material.
Example 2 characterization of copper-nickel alloy modified nitrogen doped carbon nanoplatelet (CuNi-N-CNS) samples
The morphology of the copper-nickel alloy modified nitrogen-doped carbon nano sheet material obtained in the embodiment 1 is characterized in detail by adopting a scanning electron microscope, a scanning picture is shown as a figure 1, and the prepared sample can be obviously observed to have the shape of a salix leaf-shaped ultrathin nano sheet;
the material is characterized by adopting a transmission electron microscope under high magnification, as shown in fig. 2 and 3, the existence of a porous structure of the nano sheet can be observed, and the existence of alloy nano particles on the ultrathin nano sheet substrate can be obviously observed and is coated by a carbon layer.
The material was characterized by XRD, as shown in fig. 4, with the corresponding peak at 22 ° being a carbon peak, and the peaks at the 43.6 °, 50.8 ° and 74.7 ° positions corresponding to the (225) crystal plane of the Cu 0.81Ni0.19 alloy.
FIG. 9 shows the adsorption and desorption curves and pore size distribution of CuNi-N-CNS. The specific surface area is 984.21m 2/g according to the BET method and BJH model analysis data respectively; the total pore volume of the single-point adsorption is 0.79cm 3/g.
Example 3 copper nickel alloy modified Nitrogen doped carbon nanoplatelet (CuNi-N-CNS) samples were tested for performance in conventional H-cells
(1) Dispersing 5mg of the CuNi-N-CNS catalyst prepared in the first step in 500 mu L of mixed solution of water, ethanol, isopropanol and Nafion, uniformly dispersing by ultrasonic, dripping 100 mu L of suspension on 1 x 2cm 2 carbon paper, coating the carbon paper with the area of 1cm 2, and naturally drying to obtain a cathode electrode;
(2) The cathode and the anode electrolyte in the traditional H-type electrolytic cell use 0.5M potassium bicarbonate solution of saturated carbon dioxide;
(3) Performing CV test in the potential range of-1.8V to-0.8V by using an Ag|AgCl electrode as a reference electrode to activate the electrode;
(4) After activation of the electrodes, a linear scan curve (LSV) test was performed at a scan rate of 5 mV/s;
(5) And (3) performing constant potential test to obtain i-t curves under different potentials, taking out the gas phase products at the electrolysis time t of about 600s, analyzing the gas phase products by using gas chromatography, calculating Faraday efficiencies of the different products according to a standard gas sample and electrolysis electric quantity, and plotting.
Example 4 performance test of copper nickel alloy modified nitrogen doped carbon nanoplatelets (CuNi-N-CNS) samples in self-made flow cell
(1) Dispersing 5mg of the CuNi-N-CNS catalyst prepared in the first step in 500 mu L of mixed solution of water, ethanol, isopropanol and Nafion, uniformly dispersing by ultrasonic, taking 100 mu L of suspension liquid drop at the center of carbon paper of 3 x 3cm 2, coating the surface area of the suspension liquid drop at 2 of 1cm, and naturally drying to obtain a cathode electrode;
(2) In the flow cell, a cathode adopts a 3M potassium chloride solution of saturated carbon dioxide, and an anode adopts a 1M potassium hydroxide solution;
(3) Under a three-electrode system, an Ag|AgCl electrode is used as a reference electrode, and in the test, the electrode potential is converted into a reversible hydrogen electrode potential (vs RHE), and the activation potential is set to be-1.2V to-0.2V;
(4) After activation of the electrodes, a linear scan curve (LSV) test was performed at a scan rate of 5 mV/s;
(5) And (3) performing constant potential test to obtain i-t curves under different potentials, taking out the gas phase products at the electrolysis time t of about 600s, analyzing the gas phase products by using gas chromatography, calculating Faraday efficiencies of the different products according to a standard gas sample and electrolysis electric quantity, and plotting.
(6) Performing stability test, setting constant current electrolysis under different current densities, and detecting Faraday efficiency change of the product under different reaction times;
(7) Under the two-electrode system, after the electrodes are activated, testing LSV, setting the voltage to be 0-3.5V, respectively carrying out constant voltage electrolysis at 2.0V, 2.2V, 2.4V, 2.8V and 3.0V, and testing the current and Faraday efficiency.
FIG. 5 is a schematic diagram of an electrocatalytic reduction carbon dioxide flow cell apparatus according to example 4 of the present application.
FIG. 6 is a graph showing a linear scan of a CuNi-N-CNS electrode material tested in a flow cell apparatus using example 4 of the present application, from which it can be seen that an ultra-high current density of approximately 700mA cm -2 can be achieved at a potential of-1.2V. The current density of 100mA cm -2 is generally considered as industrial current density; the partial current density of CO (jCO = jtotal × FECO) can be calculated by combining fig. 6 and fig. 7, and it is obvious that the partial current density of carbon monoxide (several hundred) is far higher than the industrial current density in the potential interval of about-0.8 to 1V, so that the practical application is possible.
FIG. 7 is a graph showing the relationship between Faraday selection efficiency and electrode potential of the product of CuNi-N-CNS electrode material tested in a flow cell device in example 4 of the present application, wherein the Faraday efficiency of the carbon monoxide product is higher than 90% in the potential interval of-0.8V to-1.0V, and good selectivity is shown.
Example 5 performance comparison test of copper nickel alloy modified nitrogen doped carbon nanoplate (CuNi-N-CNS) samples for different catholyte solutions in self-made flow cell
(1) Dispersing 5mg of the CuNi-N-CNS catalyst prepared in the first step in 500 mu L of mixed solution of water, ethanol, isopropanol and Nafion, uniformly dispersing by ultrasonic, taking 100 mu L of suspension liquid drop at the center of carbon paper of 3 x 3cm 2, coating the surface area of the suspension liquid drop at 2 of 1cm, and naturally drying to obtain a cathode electrode;
(2) Different catholyte solutions were prepared and pH values were measured with a pH meter, and the same range of E (vs RHE) was set according to the nernst equation E (vs RHE) =e (vs ag|agcl) +0.059 pH.
Comprising the following steps:
(a) A 0.5M potassium bicarbonate solution of unsaturated carbon dioxide, the pH of the solution measured to be 8.2;
(b) A 0.5M potassium bicarbonate solution of saturated carbon dioxide, pH of the solution measured 7.2;
(c) 3M potassium chloride solution of unsaturated carbon dioxide, pH of the solution measured 5.5;
(d) A 3M potassium chloride solution of saturated carbon dioxide, pH of the solution measured to be 4;
(e) 1M potassium chloride solution of unsaturated carbon dioxide;
(f) A 0.5M potassium chloride solution of unsaturated carbon dioxide.
FIG. 8 is a graph showing the potential versus current density comparison of CuNi-N-CNS electrode materials using different catholyte solutions in a flow cell apparatus, according to example 5 of the present application, where it can be seen that the use of 3M potassium chloride solution with saturated carbon dioxide can effectively increase the current density.
Example 6 anode RuIrTi mesh for electrochemical testing of OER
The reaction performance of oxygen evolution is tested by using a mercury oxidized mercury electrode as a reference electrode, a platinum mesh counter electrode and a commercial RuIrTi mesh working electrode and a 1M potassium hydroxide solution as an electrolyte, and the corresponding overpotential is detected at 10mA cm -2.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (10)
1. A bimetal alloy modified carbon nano sheet material is characterized in that,
The method comprises the steps of including nitrogen-doped carbon nano-sheets and copper-nickel alloy particles grown on the surfaces of the nitrogen-doped carbon nano-sheets in situ;
the copper-nickel alloy particles are coated by a carbon layer, and the thickness of the carbon layer is 4-6 nm;
The content of the copper-nickel alloy particles in the bimetal alloy modified carbon nano sheet material is 2.0 to 8.0 weight percent; wherein the content of copper element is 1.0-4.0 wt% and the content of nickel element is 1.0-4.0 wt%;
The particle size of the copper-nickel alloy particles is 30-60 nm;
The specific surface area of the bimetal alloy modified carbon nano sheet material is 984.21-1466.95 m 2/g;
the single-point adsorption total pore volume of the bimetal alloy modified carbon nano-sheet material is 0.60-0.90 cm 3/g;
the micropore aperture of the nitrogen-doped carbon nano sheet is 0.5 nm-2.0 nm.
2. A method for preparing a bimetal alloy modified carbon nano sheet material as set forth in claim 1, which is characterized in that,
The method comprises the following steps:
a) Mixing a solution containing phenolic resin with an F127 surfactant aqueous solution, and reacting to obtain Resol-F127 solution;
b) Mixing raw materials containing zinc nitrate, nickel nitrate, copper nitrate, 2-methylimidazole and water to obtain a metal ZIF-8 suspension;
c) Mixing the Resol-F127 solution obtained in a) with the metal ZIF-8 suspension obtained in b), performing hydrothermal reaction, and performing pyrolysis to obtain the bimetal alloy modified carbon nano sheet material.
3. The method according to claim 2, wherein,
The solution containing phenolic resin is obtained by mixing phenol, 37 weight percent formaldehyde solution and 0.1M sodium hydroxide solution;
Wherein the content of the phenol is 0.01-0.08 g/ml;
the volume ratio of the 37wt% formaldehyde solution to the 0.1M sodium hydroxide solution is 0.07-0.28;
In the F127 surfactant aqueous solution, the content of the F127 surfactant is 0.009-0.22 g/ml;
The temperature of the reaction is 60-80 ℃;
the reaction time is 12-20 h.
4. The method according to claim 2, wherein,
The ratio of the total molar amount of nickel element in the nickel nitrate to copper element in the copper nitrate to the molar amount of zinc element in the zinc nitrate is 1: 20-1: 10;
the molar ratio of zinc element in the zinc nitrate to the 2-methylimidazole is 1:6-1:4;
The ratio of the molar quantity of zinc element in the zinc nitrate to the volume of water is 3mmol/60 mL-3 mmol/40mL.
5. The method according to claim 2, wherein,
A) The volume ratio of the Resol-F127 solution obtained in the step (a) to the metal ZIF-8 suspension obtained in the step (b) is 1:6-1:1;
the temperature of the hydrothermal reaction is 120-160 ℃;
The hydrothermal reaction time is 12-24 hours;
The pyrolysis comprises the following processes:
Raising the temperature to 300-400 ℃ at the speed of 2-4 ℃/min, keeping the temperature for 1-2 hours, raising the temperature to 900-950 ℃ at the speed of 2-4 ℃/min, and keeping the temperature for 1-2 hours.
6. The method according to claim 2, wherein,
C) Drying before pyrolysis;
The drying is freeze drying;
The temperature of freeze drying is-40 to-10 ℃;
The freeze drying time is 12-24 h.
7. A cathode catalyst, characterized in that,
The cathode catalyst contains the bimetal alloy modified carbon nano sheet material of claim 1 or the bimetal alloy modified carbon nano sheet material prepared by the preparation method of any one of claims 2 to 6.
8. A flow cell electrolysis device is characterized in that,
Comprises an anode, an anode chamber, a cathode chamber and a gas chamber;
Wherein the cathode contains the cathode catalyst of claim 7.
9. The flow cell electrolyzer of claim 8 characterized in that,
The cathode is obtained by coating a dispersion liquid containing the cathode catalyst on carbon paper;
In the cathode, the coating amount of the cathode catalyst is 0.5-2 mg/cm 2.
10. Use of the flow cell electrolyser of any of claims 8 or 9 in alcohol fuel cells, carbon monoxide reduction or nitrogen reduction.
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