CN115011998B - Method for rapidly preparing self-supporting catalytic layer based on zeolite imidazole organic framework membrane - Google Patents
Method for rapidly preparing self-supporting catalytic layer based on zeolite imidazole organic framework membrane Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 31
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000013384 organic framework Substances 0.000 title claims abstract description 7
- 239000010457 zeolite Substances 0.000 title claims abstract description 7
- 239000012528 membrane Substances 0.000 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- -1 transition metal salt Chemical class 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000004070 electrodeposition Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000002041 carbon nanotube Substances 0.000 claims description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 32
- 239000004744 fabric Substances 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004246 zinc acetate Substances 0.000 claims description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 2
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 97
- 239000000243 solution Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 239000002356 single layer Substances 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 11
- 229960000314 zinc acetate Drugs 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
Classifications
-
- 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
- C25B11/095—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 at least one of the compounds being organic
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
Abstract
The invention belongs to the technical field of inorganic nano materials, and discloses a method for rapidly preparing a self-supporting catalytic layer based on a zeolite imidazole organic framework film, which comprises the steps of respectively dissolving 2-methylimidazole and transition metal salt in the same solvent, and uniformly dispersing by ultrasonic waves; then mixing the two obtained solutions into electrolyte according to equal volume in an electrolytic cell, taking a flaky porous conductive substrate as a working electrode, taking a carbon rod electrode as a counter electrode and a reference electrode, and electrifying to perform electrodeposition; washing the flaky porous conductive substrate deposited with the catalyst precursor by using an alcohol solvent, and then flattening and drying; and finally, pyrolyzing the dried substrate in an inert atmosphere, and naturally cooling to room temperature to obtain the self-supporting catalytic layer. The porous catalytic layer prepared by the method has a self-supporting structure, so that the preparation process of the catalytic layer is greatly simplified, and the porous catalytic layer has the advantages of good conductivity, high mass transfer efficiency, high active site density and the like, and has practical application significance and economic benefit.
Description
Technical Field
The invention belongs to the technical field of inorganic nano materials, and particularly relates to a preparation method of a self-supporting catalytic layer.
Background
Hydrogen fuel cells and metal-air cells are emerging energy conversion devices with the advantages of high power density, environmental friendliness, and the like. Such devices all require an air electrode with good oxygen reduction activity as the cathode. At present, noble metal materials such as platinum (Pt) are commonly used catalysts for Oxygen Reduction Reaction (ORR), however, the expensive cost of noble metal catalysts greatly hinders large-scale industrial application. In order to reduce the manufacturing cost of the fuel cell and promote the commercial application of the fuel cell, the development of non-noble metal catalysts is an important point of attention of researchers.
Among the numerous catalytic materials, zeolite Imidazole Frameworks (ZIFs) have a rich nitrogen-metal structure and unique dodecahedral morphology, attracting researchers' attention. By carbonizing the ZIF precursor, highly dispersed catalyst particles with a good pore structure can be obtained. Based on this method, a large number of highly active catalysts were developed and showed good oxygen reduction activity in the RDE test. However, most catalysts exist in the form of powder, and thus, when used for forming a catalytic layer of an electrode, the addition of a binder is required to fix the catalyst powder on the surface of a gas diffusion layer or an ion exchange membrane. However, most binders do not have conductivity, so the addition of binders can reduce the conductivity of the catalyst; at the same time, too much binder can cover the active sites of the catalyst, reducing the activity of the catalyst. In addition, in the process from the catalyst powder to the catalytic layer, the prior art cannot accurately control the pore structure of the catalytic layer, which is unfavorable for preparing the catalytic layer with good pore structure.
Recently many researchers have begun to study self-supporting electrodes to achieve freedom from adhesive dependencies. Self-supporting electrodes have many advantages, such as high specific surface area, high active site density, fast electron transport paths, short ion diffusion lengths, good pore structure, etc., which can enhance the conductivity of the catalytic layer, reducing mass transfer losses in electrochemical reactions. However, the existing preparation method of the self-supporting catalytic layer still has the problems of long deposition time, low active site density, uncontrollable catalytic layer structure and the like.
Disclosure of Invention
The invention aims to solve the technical problems of complex preparation flow of a self-supporting catalytic layer, difficult regulation and control of a catalytic layer structure and the like, and provides a rapid preparation method of the self-supporting catalytic layer based on a zeolite imidazole organic framework membrane aiming at uncontrollability in the traditional catalytic layer spraying process. The method uses a flaky porous conductive substrate as a carrier, and prepares the self-supporting catalytic layer with a stepped pore structure by a current-driven rapid in-situ deposition and high-temperature carbonization method. The porous catalytic layer has a self-supporting structure, so that the preparation process of the catalytic layer is greatly simplified, and the porous catalytic layer has the advantages of good conductivity, high mass transfer efficiency, high active site density and the like, and can be applied to various energy storage and conversion devices such as zinc-air batteries, fuel cells and the like. In addition, the simple preparation process makes the invention easy to amplify, and has practical application significance and economic benefit.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention provides a self-supporting catalytic layer rapid preparation method based on a zeolite imidazole organic framework membrane, which comprises the following steps:
(1) Respectively dissolving 2-methylimidazole and transition metal salt in the same solvent, and uniformly dispersing by ultrasonic;
(2) Mixing the two solutions obtained in the step (1) into an electrolyte according to the equal volume in an electrolytic cell, wherein the molar ratio of 2-methylimidazole to transition metal salt in the electrolyte is 2:1, a step of; electrifying a flaky porous conductive substrate serving as a working electrode, a carbon rod electrode serving as a counter electrode and a reference electrode to perform electrodeposition, wherein a catalyst precursor is generated on the flaky porous conductive substrate;
(3) Washing the flaky porous conductive substrate deposited with the catalyst precursor by using an alcohol solvent, and then flattening and drying;
(4) Heating the dried substrate to 900-1000 ℃ in inert atmosphere, keeping the temperature for 1-3 hours, and naturally cooling to room temperature to obtain the self-supporting catalytic layer.
Further, the solvent in the step (1) is methanol or ethanol.
Further, the transition metal salt in the electrolyte in the step (2) is zinc acetate.
Further, the transition metal salt in the electrolyte in the step (2) is zinc acetate and cobalt nitrate, and the molar ratio of the zinc acetate to the cobalt nitrate is 17:3.
further, the transition metal salt in the electrolyte in the step (2) is zinc acetate, cobalt nitrate and ferrous sulfate, and the molar ratio of the zinc acetate, the cobalt nitrate and the ferrous sulfate is 50:9:1.
further, the sheet porous conductive substrate in the step (2) is carbon paper or carbon nanotube cloth.
Further, the energizing mode in the step (2) is a potentiostatic method or a galvanostatic method, the potentiostatic method has a potential of-4 to-6V, and the galvanostatic method has a current of-1 to-3 mA/cm 2 。
Further, the inert atmosphere in the step (4) is nitrogen or argon.
The beneficial effects of the invention are as follows:
the invention aims to develop a rapid preparation method of a self-supporting catalytic layer, which reduces the manufacturing cost of the catalytic layer and optimizes the pore structure of the catalytic layer. Compared with the traditional preparation methods of the catalytic layers such as a spray coating method, a transfer printing method, a brushing method and the like, the self-supporting catalytic layer is directly prepared on the conductive substrate through electrodeposition-pyrolysis two-step operation, so that the preparation flow of the traditional electrode is greatly simplified, and the time cost of the catalytic layer production is reduced. The invention also regulates and controls the pore structure of the catalytic layer, and prepares the self-supporting catalytic layer with a stepped pore structure. Research shows that the existence of the stepped hole structure greatly improves the diffusion efficiency of the gas in the catalytic layer, thereby improving the electrocatalytic effect of the catalytic layer. In zinc-air battery applications, such self-supporting, stepped pore catalytic layers exhibit performance approaching that of commercial Pt/C catalytic layers, yet are much less costly to produce than Pt-based noble metal catalytic layers. In conclusion, the invention can improve the current manufacturing process of the catalytic layer, reduce the manufacturing cost and has important practical significance and economic effect.
Drawings
FIG. 1 is a scanning electron microscope image of the surface of the self-supporting catalytic layer prepared in example 1;
FIG. 2 is a scanning transmission electron microscope image of the self-supporting catalytic layer prepared in example 1;
FIG. 3 is a graph showing the oxygen reduction performance of the self-supporting catalytic layer prepared in example 1 in 0.1M KOH;
FIG. 4 is a graph showing oxygen reduction performance of the self-supporting catalytic layer prepared in example 1 in a zinc-air cell;
fig. 5 is a graph showing oxygen reduction performance of the self-supporting catalytic layer prepared in comparative example 1 in a zinc-air battery.
Detailed Description
In order to further understand the summary, features and effects of the present invention, a detailed description will be given below with reference to examples and drawings.
Example 1
(1) 0.49g of 2-methylimidazole was dissolved in 25ml of methanol and designated as solution 1; taking a reagent bottle, dissolving 0.47g of anhydrous zinc acetate and 0.13g of cobalt nitrate hexahydrate in 25ml of methanol, and recording as a solution 2 for later use;
(2) Cutting carbon nano tube cloth with the thickness of 3mm multiplied by 3mm as a substrate, vertically placing the carbon nano tube cloth in an electrolytic cell, mixing the solution 1 and the solution 2 in the electrolytic cell, and enabling the liquid level to be beyond the upper end of the carbon nano tube cloth; the molar ratio of the 2-methylimidazole to the transition metal salt (zinc acetate and cobalt nitrate) in the mixed solution is 2:1, a step of;
(3) Setting a double-electrode system, taking a carbon rod as a counter electrode and a reference electrode, taking carbon nano tube cloth as a working electrode, and applying a constant potential of-5V between the electrodes to carry out electrodeposition for 10min; the catalyst precursor is generated on the carbon nano tube cloth;
(4) Taking out the deposited sample, uniformly flushing the front and back surfaces with ethanol, repeating for 3 times, and naturally airing to obtain a self-supporting catalytic layer precursor;
(5) And (3) airing the carbon nano tube cloth treated in the previous step, then placing the dried carbon nano tube cloth into a tube furnace, heating the carbon nano tube cloth to 950 ℃ from room temperature at a speed of 5 ℃/min under the protection of argon, then keeping the carbon nano tube cloth at 950 ℃ for 1 hour, and taking out a sample after naturally cooling the carbon nano tube cloth to the room temperature to obtain the self-supporting catalytic layer.
Fig. 1 and 2 show the surface of the catalytic layer after deposition and high temperature carbonization treatment. In fig. 1, a thin film structure is formed on the carbon nanotube fabric, and the structure is a catalytic layer converted from ZIF. FIG. 2 is a scanning transmission electron microscope characterization of a portion of a catalytic layer, where it can be observed that a large number of nanoparticles are embedded on a carbon backbone.
To verify the oxygen reduction reaction effect of the catalytic layer, a rotating disk electrode test, a half cell test and a zinc-air cell test were performed on the catalytic layer, and specific steps are as follows.
1. Rotary Disk Electrode (RDE) test
(1) Cutting the sheet electrode into a wafer with the diameter of 5 mm;
(2) Deionized water and 5% Nafion film solution are mixed according to the volume ratio of 20:1 preparing a solution for later use;
(3) Soaking the cut electrode slice in the solution for 1 minute, then pasting the electrode slice on the surface of a working electrode, and airing;
(4) Using a three-electrode system, and performing oxygen reduction performance test on the working electrode in a five-mouth flask under a 0.1M KOH system, wherein in the test process, oxygen is ensured to be introduced into a solution system at a flow rate of 50 mL/min; the linear voltammetric scan method was used, with a scan rate in the range of 1.0 to 0.2V (vs. reversible hydrogen electrode) and a scan rate of 5mV/s.
The test results are shown in fig. 3, and it can be seen from fig. 3 that the catalytic layer has better oxygen reduction catalytic activity for the initial potential of oxygen reduction reaction > 0.9V.
2. Half cell testing
(1) Immersing the flaky catalytic layer in deionized water for 1 minute;
(2) Attaching the soaked catalytic layer on 2mm multiplied by 2mm hydrophobic carbon paper with a microporous layer, and hot-pressing for 2 minutes at 130 ℃ and 0.2MPa to obtain a gas diffusion electrode;
(3) Filling a gas diffusion electrode into a self-made half-cell testing device, taking 0.1M KOH solution as electrolyte, using a three-electrode system, taking a prepared sample as a working electrode, a silver chloride electrode as a reference electrode, and a carbon rod electrode as a counter electrode for testing;
(4) The linear voltammetric scan method was used with a scan rate in the range of 1 to-0.2V (relative to the reversible hydrogen electrode) of 100mV/s.
3. Zinc-air battery test
(1) Immersing the thermally treated flaky catalytic layer in deionized water for 1 minute;
(2) Pasting the soaked catalytic layer on 2mm multiplied by 2mm hydrophobic carbon paper with a microporous layer, and hot-pressing for 2 minutes at 130 ℃ and 0.1MPa to obtain a gas diffusion electrode;
(3) The gas diffusion electrode was incorporated into a self-made zinc-air cell with 6M KOH and 0.2M Zn added between the catalytic layer and the zinc plate 2+ The solution, one end of the working electrode is introduced with oxygen (flow 20 ml/min) or directly contacted with the atmosphere;
(4) The linear voltammetric scan was used, ranging from an open circuit voltage of the cell to 0.5V (compared to the reversible hydrogen electrode), at a scan rate of 200mV/s.
The zinc-air cell can be used for characterizing the catalytic activity of the catalyst and the performance of the catalytic layer under the actual working condition, as shown in fig. 4, in the self-made zinc-air cell, the open circuit voltage is 1.47V, and the maximum power density is 220mW cm -2 Very close to the commercial Pt/C catalytic layer, this suggests that the catalytic layer has good catalytic activity and good mass transfer properties.
Example 2
(1) 0.49g of 2-methylimidazole was dissolved in 25ml of methanol and designated as solution 1; taking a reagent bottle, dissolving 0.47g of anhydrous zinc acetate and 0.13g of cobalt nitrate hexahydrate in 25ml of methanol, and recording as a solution 2 for later use;
(2) Cutting hydrophilic carbon paper with the thickness of 3mm multiplied by 3mm as a substrate, vertically placing the hydrophilic carbon paper in an electrolytic cell, mixing the solution 1 and the solution 2 in the electrolytic cell, and enabling the liquid level to be beyond the upper end of the carbon paper; the molar ratio of the 2-methylimidazole to the transition metal salt (zinc acetate and cobalt nitrate) in the mixed solution is 2:1, a step of;
(3) Setting a double-electrode system, taking a carbon rod as a counter electrode and a reference electrode, taking carbon paper as a working electrode, and applying-3 mA/cm between the electrodes 2 Performing electrodeposition under constant current for 15min; generating a catalyst precursor on carbon paper;
(4) Taking out the deposited sample, uniformly flushing the front and back surfaces with ethanol, repeating for 3 times, and naturally airing to obtain a self-supporting catalytic layer precursor;
(5) And (3) airing the carbon paper treated in the previous step, then placing the carbon paper into a tubular furnace, heating the carbon paper to 950 ℃ from room temperature at a speed of 5 ℃/min under the protection of argon, then keeping the carbon paper at 950 ℃ for 1 hour, and taking out the sample after naturally cooling the carbon paper to room temperature to obtain the self-supporting catalytic layer.
To verify the oxygen reduction effect of the above catalytic layer, a rotating disk electrode test, a half cell test and a zinc-air cell test were performed on the catalytic layer, and the specific procedure was as in example 1.
The self-supporting catalytic layer is successfully prepared on the carbon paper, and after pyrolysis at 950 ℃, the inactive metal (Zn) volatilizes in a large amount, so that a rich pore structure is formed. Meanwhile, the relatively low pyrolysis temperature also enables the volatilization of active components in the catalytic layer to be less, which is beneficial to the improvement of catalytic activity.
Example 3
(1) 0.49g of 2-methylimidazole was dissolved in 25ml of methanol and designated as solution 1; taking a reagent bottle, dissolving 0.47g of anhydrous zinc acetate, 0.13g of cobalt nitrate hexahydrate and 0.01g of ferrous sulfate heptahydrate in 25ml of methanol, and recording as a solution 2 for later use;
(2) Cutting carbon nano tube cloth with a filling layer of 3mm multiplied by 3mm as a substrate, vertically placing the carbon nano tube cloth in an electrolytic cell, mixing the solution 1 and the solution 2 in the electrolytic cell, and enabling the liquid level to at least exceed the upper end of the carbon nano tube cloth; the molar ratio of the 2-methylimidazole to the transition metal salt (zinc acetate, cobalt nitrate and ferrous sulfate) in the mixed solution is 2:1, a step of;
(3) Setting a double-electrode system, taking a carbon rod as a counter electrode and a reference electrode, taking carbon nano tube cloth with a filling layer as a working electrode, and applying-1 mA/cm between the electrodes 2 Performing electrodeposition under constant current for 15min; generating a catalyst precursor on carbon paper;
(4) Taking out the deposited sample, uniformly flushing the front and back surfaces with ethanol, repeating for 3 times, and naturally airing to obtain a self-supporting catalytic layer precursor;
(5) And (3) airing the carbon paper treated in the previous step, then placing the carbon paper into a tubular furnace, heating the carbon paper to 1000 ℃ from room temperature at a speed of 5 ℃/min under the protection of argon, then keeping the carbon paper at the temperature of 1000 ℃ for 3 hours, and taking out the sample after naturally cooling the carbon paper to the room temperature to obtain the self-supporting catalytic layer.
To verify the oxygen reduction effect of the above catalytic layer, a rotating disk electrode test, a half cell test and a zinc-air cell test were performed on the catalytic layer, and the specific procedure was as in example 1.
Three metal elements of zinc, cobalt and iron are introduced into the self-supporting catalytic layer, and the introduction of the iron element is beneficial to forming a bimetal synergistic catalytic effect, so that the electrocatalytic activity of the catalytic layer is further improved. Meanwhile, the carbonization temperature is increased, the carbonization time is prolonged, zn element is fully volatilized, and the improvement of the quality activity of the catalytic layer is facilitated.
Example 4
(1) 0.49g of 2-methylimidazole was dissolved in 25ml of methanol and designated as solution 1; taking a reagent bottle, dissolving 0.47g of anhydrous zinc acetate and 0.13g of cobalt nitrate hexahydrate in 25ml of methanol, and recording as a solution 2 for later use;
(2) Cutting a single-layer carbon nano tube cloth with the thickness of 3mm multiplied by 3mm as a substrate, vertically placing the single-layer carbon nano tube cloth in an electrolytic cell, mixing the solution 1 and the solution 2 in the electrolytic cell, and enabling the liquid level to exceed the upper end of the single-layer carbon nano tube cloth; the molar ratio of the 2-methylimidazole to the transition metal salt (zinc acetate and cobalt nitrate) in the mixed solution is 2:1, a step of;
(3) Setting a double-electrode system, taking a carbon rod as a counter electrode and a reference electrode, taking single-layer carbon nanotube cloth as a working electrode, applying-4V between the electrodes, and carrying out constant voltage deposition for 15min; the catalyst precursor is generated on the single-layer carbon nano tube cloth;
(4) Taking out the deposited sample, uniformly flushing the front and back surfaces with ethanol, repeating for 3 times, and naturally airing to obtain a self-supporting catalytic layer precursor;
(5) And (3) airing the carbon paper treated in the previous step, then placing the carbon paper into a tubular furnace, heating the carbon paper to 900 ℃ from room temperature at a speed of 5 ℃/min under the protection of argon, then keeping the carbon paper at 900 ℃ for 2 hours, and taking out the sample after naturally cooling the carbon paper to room temperature to obtain the self-supporting catalytic layer.
To verify the oxygen reduction effect of the above catalytic layer, a rotating disk electrode test, a half cell test and a zinc-air cell test were performed on the catalytic layer, and the specific procedure was as in example 1.
In this embodiment, a single-layer carbon nanotube cloth is selected as the deposition substrate of the self-supporting catalytic layer. The substrate has ultra-thin thickness, ultra-thin carbon nanotube diameter and abundant pore structure. These conditions provide a basis for the growth of the catalytic layer precursor. Meanwhile, after high-temperature conversion, the obtained ultrathin catalytic layer has the advantages of high quality activity, good mass transfer performance and the like.
Example 5
(1) 0.49g of 2-methylimidazole was dissolved in 25ml of methanol and designated as solution 1; taking a reagent bottle, dissolving 0.47g of anhydrous zinc acetate and 0.13g of cobalt nitrate hexahydrate in 25ml of methanol, and recording as a solution 2 for later use;
(2) Cutting a single-layer carbon nano tube cloth with the thickness of 3mm multiplied by 3mm as a substrate, vertically placing the single-layer carbon nano tube cloth in an electrolytic cell, mixing the solution 1 and the solution 2 in the electrolytic cell, and enabling the liquid level to exceed the upper end of the single-layer carbon nano tube cloth; the molar ratio of the 2-methylimidazole to the transition metal salt (zinc acetate and cobalt nitrate) in the mixed solution is 2:1, a step of;
(3) Setting a double-electrode system, taking a carbon rod as a counter electrode and a reference electrode, taking single-layer carbon nanotube cloth as a working electrode, applying-6V between the electrodes, and carrying out constant voltage deposition for 15min; the catalyst precursor is generated on the single-layer carbon nano tube cloth;
(4) Taking out the deposited sample, uniformly flushing the front and back surfaces with ethanol, repeating for 3 times, and naturally airing to obtain a self-supporting catalytic layer precursor;
(5) And (3) airing the carbon paper treated in the previous step, then placing the carbon paper into a tubular furnace, heating the carbon paper to 900 ℃ from room temperature at a speed of 5 ℃/min under the protection of argon, then keeping the carbon paper at 900 ℃ for 2 hours, and taking out the sample after naturally cooling the carbon paper to room temperature to obtain the self-supporting catalytic layer.
To verify the oxygen reduction effect of the above catalytic layer, a rotating disk electrode test, a half cell test and a zinc-air cell test were performed on the catalytic layer, and the specific procedure was as in example 1.
In this embodiment, the deposition voltage is set to-6V, and a higher voltage may generate a larger deposition current, with more ZIF precursor deposited on the substrate during the same deposition time. After carbonization treatment, the quality of the self-supporting catalytic layer in unit area is also improved, so that the area activity of the catalytic layer is improved to a certain extent.
Comparative example 1
(1) 0.49g of 2-methylimidazole was dissolved in 25ml of methanol and designated as solution 1; taking a reagent bottle, dissolving 0.47g of anhydrous zinc acetate, 0.13g of cobalt nitrate hexahydrate and 0.01g of ferrous sulfate heptahydrate in 25ml of methanol, and recording as a solution 2 for later use;
(2) Cutting out 3mm multiplied by 3mm foam nickel as a substrate, vertically placing the substrate in an electrolytic cell, mixing the solution 1 and the solution 2 in the electrolytic cell, and enabling the liquid level to at least exceed the upper end of the substrate; the molar ratio of the 2-methylimidazole to the transition metal salt (zinc acetate, cobalt nitrate and ferrous sulfate) in the mixed solution is 2:1, a step of;
(3) Setting a double-electrode system, using a carbon rod as a counter electrode and a reference electrode, using foam nickel as a working electrode, and applying-3 mA/cm between the electrodes 2 Performing electrodeposition under constant current for 15min; generating a catalyst precursor on the foam nickel;
(4) Taking out the deposited sample, uniformly flushing the front and back surfaces with ethanol, repeating for 3 times, and naturally airing to obtain a self-supporting catalytic layer precursor;
(5) And (3) airing the carbon paper treated in the previous step, then placing the carbon paper into a tubular furnace, heating the carbon paper to 950 ℃ from room temperature at a speed of 5 ℃/min under the protection of argon, then keeping the carbon paper at 950 ℃ for 1 hour, and taking out the sample after naturally cooling the carbon paper to room temperature to obtain the self-supporting catalytic layer.
To verify the oxygen reduction effect of the above catalytic layer, a rotating disk electrode test, a half cell test and a zinc-air cell test were performed on the catalytic layer, and the specific procedure was as in example 1.
In the comparative example, foamed nickel with higher porosity, larger pore diameter and smaller specific surface area is selected as the electrodeposited substrate. Due to the characteristics of the foam nickel, the catalytic layer structure is loose, and the density of active sites of the catalytic layer is extremely low. In the zinc-air battery test process, the current density and the power density are far lower than those of the self-supporting catalytic layer prepared by taking carbon nano tube cloth as a substrate, as shown in fig. 5.
The invention uses carbon paper, single-layer carbon nanotube cloth and carbon nanotube cloth with microporous layer as substrates, and prepares the non-noble metal self-supporting catalytic layer with a step pore structure by combining a rapid electrodeposition method and a one-step pyrolysis method. The pore structure and the active site density of the catalytic layer are optimized by regulating and controlling parameters such as metal types, pyrolysis temperature and time, deposition current, deposition voltage and the like. Compared with the traditional preparation method of the catalytic layer, the self-supporting catalytic layer has the advantages of simple preparation flow, low production cost, good mass transfer performance, strong conductivity and the like. Excellent performance was exhibited during the zinc-air battery test.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative, not restrictive, and many changes may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the appended claims, which are to be construed as falling within the scope of the present invention.
Claims (3)
1. A method for rapidly preparing a self-supporting catalytic layer based on a zeolite imidazole organic framework membrane is characterized by comprising the following steps:
(1) Respectively dissolving 2-methylimidazole and transition metal salt in the same solvent, and uniformly dispersing by ultrasonic;
the transition metal salt is zinc acetate and cobalt nitrate, and the molar ratio of the zinc acetate to the cobalt nitrate is 17:3, a step of; alternatively, the transition metal salt is zinc acetate, cobalt nitrate and ferrous sulfate, and the molar ratio of the zinc acetate, the cobalt nitrate and the ferrous sulfate is 50:9:1, a step of;
(2) Mixing the two solutions obtained in the step (1) into an electrolyte according to the equal volume in an electrolytic cell, wherein the molar ratio of 2-methylimidazole to transition metal salt in the electrolyte is 2:1, a step of; electrifying a flaky porous conductive substrate serving as a working electrode, a carbon rod electrode serving as a counter electrode and a reference electrode to perform electrodeposition, wherein a catalyst precursor is generated on the flaky porous conductive substrate;
wherein the flaky porous conductive substrate is carbon paper or carbon nanotube cloth;
wherein the electrifying mode is constantThe potential of the constant potential method is-4 to-6V, and the current of the constant current method is-1 to-3 mA/cm 2 ；
(3) Washing the flaky porous conductive substrate deposited with the catalyst precursor by using an alcohol solvent, and then flattening and drying;
(4) And heating the dried substrate to 900-1000 ℃ in an inert atmosphere, keeping the temperature for 1-3 hours, and naturally cooling to room temperature to obtain the self-supporting catalytic layer.
2. The method for rapid preparation of a self-supporting catalytic layer based on a zeolitic imidazolate framework membrane as claimed in claim 1, wherein the solvent in step (1) is methanol or ethanol.
3. The method for rapid preparation of a self-supporting catalytic layer based on zeolitic imidazoles organic framework membranes according to claim 1, characterized in that the inert atmosphere in step (4) is nitrogen or argon.
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