CN116497397A - Self-supporting catalyst for electrolyzed water and preparation method and application thereof - Google Patents
Self-supporting catalyst for electrolyzed water and preparation method and application thereof Download PDFInfo
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- CN116497397A CN116497397A CN202310537483.8A CN202310537483A CN116497397A CN 116497397 A CN116497397 A CN 116497397A CN 202310537483 A CN202310537483 A CN 202310537483A CN 116497397 A CN116497397 A CN 116497397A
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- electrolyzed water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002023 wood Substances 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 17
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000197 pyrolysis Methods 0.000 claims abstract description 17
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 16
- 238000004070 electrodeposition Methods 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 239000002659 electrodeposit Substances 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 241001070947 Fagus Species 0.000 description 3
- 235000010099 Fagus sylvatica Nutrition 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000670 limiting effect Effects 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
- 238000001000 micrograph Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 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
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000011144 upstream manufacturing 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The application discloses an electrolyzed water self-supporting catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: selecting carbonized wood as a substrate, putting the carbonized wood into a metal salt solution, and adopting an electrochemical deposition technology to electrodeposit transition metal on the carbonized wood in situ to obtain a precursor hybridized by metal and the carbonized wood; the precursor and melamine are subjected to co-pyrolysis, so that metal nano particles are coated in the nitrogen doped carbon nano tube and grow on carbonized wood in situ, and the electrolyzed water self-supporting catalyst is obtained.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to an electrolytic water self-supporting catalyst, and a preparation method and application thereof.
Background
With the rapid development of human society and global economy, the consumption of traditional fossil fuels creates serious global environmental problems and energy crisis. Under the drive of the 'double carbon' target, developing efficient, low-carbon and sustainable clean energy and energy storage conversion technology is an effective way to solve the problem. Preparation of high purity hydrogen (H) using renewable electrically driven electrochemical water splitting 2 ) Is a promising sustainable energy strategy. The slow kinetics of the Hydrogen Evolution Reaction (HER) greatly impedes the energy efficiency and large-scale application of water splitting, and therefore a highly efficient and durable electrocatalyst is needed.
The existing electrocatalyst has low current density (less than or equal to 100 mAcm) -2 ) The lower working is good, the stability is limited, and the method is not suitable for large-scale water-splitting hydrogen production. In addition, these catalysts are usually in powder form, but due to the cumbersome slurry electrode preparation process, current densities at industrial level ±>500mAcm -2 ) The lower requires a higher overpotential for HER. And the catalytic activity and durability are easy to be reduced under the extreme catalytic reaction environments such as industrial current density, strong acid and strong alkaline solution and the like.
Disclosure of Invention
The invention aims to solve the problems in the background technology and provides an electrolytic water self-supporting catalyst and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides a preparation method of an electrolytic water self-supporting catalyst, which comprises the following steps:
selecting carbonized wood as a substrate, putting the carbonized wood into a metal salt solution, and adopting an electrochemical deposition technology to electrodeposit transition metal on the carbonized wood in situ to obtain a precursor hybridized by metal and the carbonized wood;
and (3) carrying out co-pyrolysis on the precursor and melamine to coat the metal nano particles in the nitrogen doped carbon nano tube, and growing the metal nano particles on carbonized wood in situ to obtain the electrolyzed water self-supporting catalyst.
Preferably, the carbonized wood is obtained by carbonizing natural wood at high temperature, including but not limited to natural beech chips and bamboo.
Preferably, the carbonized wood is obtained by carbonizing natural wood at a carbonization temperature of 850-950 ℃ for 1-3 hours.
Preferably, the metal salt solution is at least one of nickel nitrate solution, cobalt nitrate solution and ferric nitrate solution, and the solubility of the metal salt solution is 0.03-0.08M.
Preferably, the metal is at least one of Fe, co, and Ni, and corresponds to the metal contained in the metal salt solution.
Preferably, the co-pyrolysis is performed under the conditions of a protective gas atmosphere, a pyrolysis temperature of 700-900 ℃ and a pyrolysis time of 1-3 h, wherein the protective gas comprises but is not limited to nitrogen and argon, the diameter of the carbon nano tube formed by the co-pyrolysis can be influenced by the pyrolysis temperature, and the length or uniformity of the carbon nano tube formed by the co-pyrolysis can be influenced by the pyrolysis time.
Preferably, the addition amount of the melamine is 1-2.5 g, and the addition amount of the melamine can influence the quantity, the shape and the tubular quantity of the carbon nano tubes formed by the co-pyrolysis.
Preferably, the electrochemical deposition technology adopts a three-electrode system, the voltage range is-0.6 to-1.2V, and the metal load in carbonized wood is regulated and controlled by regulating the electrochemical deposition parameters such as deposition voltage, deposition time and the like, so that the controllable preparation of the catalyst is realized.
The preparation method of the invention has the technical principle that: and depositing metal in the metal salt solution on pore channels and surfaces of carbonized wood to serve as a precursor by an electrochemical deposition technology, then polymerizing the precursor and melamine to generate g-C3N4 in the co-pyrolysis process, reducing metal ions into metal seeds, decomposing the g-C3N4 to provide a carbon source and a nitrogen source along with the rise of temperature, and catalyzing decomposition products of the g-C3N4 by the metal seeds to grow nitrogen-doped carbon nano tubes to finally form metal nano particles coated in the nitrogen-doped carbon nano tubes.
The Ni metal nano particles are coated in the carbon nano tube, and the carbon layer on the periphery can prevent the Ni metal nano particles from directly contacting with electrolyte, so that the corrosion resistance is improved, the electrochemical leaching of Ni metal in the catalytic reaction process is slowed down, and the stability is improved; on the other hand, the carbon layer and the internal Ni metal can form a synergistic interface effect to induce charge redistribution and improve the catalytic activity.
The invention also provides an electrolytic water self-supporting catalyst prepared by the preparation method, and the electrolytic water self-supporting catalyst has a three-dimensional hierarchical porous structure.
The invention also provides application of the self-supported catalyst in industrial-grade current density water electrolysis hydrogen production.
The invention has the beneficial effects that:
1. according to the invention, carbonized wood is used as a carbon source of a precursor and a self-supporting substrate, and is converted into the electrolyzed water self-supporting catalyst with high conductivity and three-dimensional hierarchical porous structure through an electrochemical deposition technology and co-pyrolysis, so that the preparation process of the catalyst is simple and easy to regulate and control.
2. In the preparation process, the nitrogen-doped carbon nano tube packaging metal nano particles formed by co-pyrolysis of the precursor and the melamine realize the highly uniform dispersion of metal nano ions, avoid agglomeration, on one hand, are beneficial to the full exposure of catalytic active sites, and form a synergistic interface effect between the metal and the carbon nano tube, induce charge redistribution and improve the catalytic activity; on the other hand, the metal nano particles are prevented from being directly contacted with the electrolyte, so that the corrosion resistance and the stability of the metal nano particles are improved.
3. The self-supporting catalyst for electrolyzed water has a three-dimensional hierarchical porous structure of carbonized wood, so that the self-supporting catalyst can be used as a gas diffusion electrode to directly prepare hydrogen by electrolyzed water, meanwhile, the binder required by the traditional electrode preparation method is avoided, the mass transmission and gas diffusion in the electrocatalytic water decomposition are enhanced, and the hydrogen preparation energy consumption is reduced.
4. The self-supported catalyst for electrolyzed water realizes the concentration of more than or equal to 500mA/cm under the low overvoltage of less than 0.5V 2 The industrial-grade current density hydrogen production, and the water electrolysis hydrogen production efficiency is high.
The features and advantages of the present invention will be described in detail by way of example with reference to the accompanying drawings.
Drawings
FIG. 1 is an SEM image of an electrolyzed water self-supporting catalyst prepared according to an embodiment of the present invention.
FIG. 2 is a TEM image of an electrolyzed water self-supporting catalyst prepared according to an embodiment of the present invention.
FIG. 3 is an X-ray diffraction pattern of an electrolyzed water self supporting catalyst and carbonized wood prepared in accordance with an embodiment of the present invention.
FIG. 4 is a comparison of acid catalyzed hydrogen evolution activity of electrolyzed water self-supporting catalysts prepared in accordance with an embodiment of the present invention and Pt/c catalysts.
FIG. 5 is a graph showing the stability test of the electrolytic water self-supporting catalyst prepared in the example of the present invention in an acidic solution.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It will be apparent that the embodiments described are some, but not all, of the embodiments of the present application. The components of the embodiments of the present application, which are generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations. In the description of the present application, it should be noted that, the azimuth or positional relationship indicated by the terms "inner", "outer", etc. are based on the azimuth or positional relationship shown in the drawings, or the azimuth or positional relationship that is commonly put when the product of the application is used, are merely for convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element to be referred to must have a specific azimuth, be configured and operated in a specific azimuth, and therefore should not be construed as limiting the present application. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In the description of the present application, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the terms in this application will be understood by those of ordinary skill in the art in a specific context.
The present invention will be described in detail with reference to the accompanying drawings.
Example 1
The embodiment provides a preparation method of an electrolyzed water self-supporting catalyst, which comprises the following steps:
the size of the sample is 4 multiplied by 0.2cm 3 Washing natural beech wood chips with deionized water and ethanol, naturally drying for 12 hours, placing the dried natural beech wood chips into a tube furnace, carbonizing at high temperature in an argon atmosphere, heating the furnace body temperature to 300 ℃ from room temperature at a heating rate of 2 ℃/min, preserving heat for 1 hour, then heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, after the reaction is finished, placing the prepared carbonized wood into deionized water and ethanol solution for cleaning for several times, and drying at 60 ℃ for 12 hours to obtain carbonized wood which is recorded as CW;
electrochemical deposition of Ni (OH) on carbonized wood using a three electrode system 2 Nano particles, wherein mercury/oxidized mercury is used as a reference electrode, a platinum sheet is used as a counter electrode, the prepared carbonized wood is used as a working electrode, and the electrolyte is Ni (NO) with the concentration of 0.05M 3 ) 2 ·6H 2 O solution. Cutting carbonized wood into pieces of 1×2×0.1cm 3 The cut carbon sheet is soaked in ethanol for 10s, and then the carbon sheet is clamped into the platinum sheetThe electrode is clamped and partially immersed into Ni (NO) 3 ) 2 ·6H 2 In O electrolyte, cyclic Voltammetry (CV) scanning is carried out on a CHI660E electrochemical workstation at room temperature, the voltage range is-0.6V to-1.2V, the scanning speed is 20mV/s, the cycle is 50 times, deionized water and ethanol are used for cleaning for a plurality of times after the electrodeposition is finished, and the precursor is obtained and is marked as Ni (OH) 2 /CW；
The precursor Ni (OH) prepared above is mixed 2 And (2) placing melamine with the mass of 2.0g in two independent porcelain boats respectively, placing the melamine in the center and the upstream of a tube furnace, heating the melamine from room temperature to 500 ℃ at a heating rate of 5 ℃/min under the condition of Ar atmosphere in the tube furnace, preserving heat for 1h, heating the melamine to 800 ℃ at the same heating rate, preserving heat for 2h, cooling the melamine to room temperature after the co-pyrolysis reaction of the melamine and the melamine is finished, washing the obtained sample with deionized water and ethanol for a plurality of times, drying the sample at room temperature, and finally obtaining the electrolyzed water self-supporting catalyst which is denoted as Ni@NCNT/CW-2.0.
The embodiment provides an electrolyzed water self-supporting catalyst Ni@NCNT/CW-2.0 prepared by the preparation method of the embodiment, which has a three-dimensional hierarchical porous structure, so that the electrolyzed water self-supporting catalyst can be used as a gas diffusion electrode and can be directly used as an electrode for hydrogen production by water electrolysis, meanwhile, the binder such as Nafion solution required by the traditional electrode preparation method is avoided, the resistance can be reduced, the electron transmission rate and the gas diffusion can be improved, and the like.
The embodiment provides application of the electrolyzed water self-supporting catalyst Ni@NCNT/CW-2.0 in industrial-grade current density electrolyzed water hydrogen production.
Example 2
This example provides a method for preparing an electrolytic water self-supporting catalyst, and the rest of the steps are the same as in example 1, except that the addition amount of melamine is changed to 1.5g, and the prepared electrolytic water self-supporting catalyst is denoted as Ni@NCNT/CW-1.5.
Example 3
This example provides a method for preparing an electrolytic water self-supporting catalyst, and the rest of the steps are the same as in example 1, except that the addition amount of melamine is changed to 1.0g, and the prepared electrolytic water self-supporting catalyst is denoted as Ni@NCNT/CW-1.0.
Example 4
This example provides a method for preparing an electrolyzed water self-supporting catalyst, except that the metal salt solution used for electrochemical deposition is changed to Co (NO) with a concentration of 0.05M 3 ) 2 ·6H 2 O solution, the prepared electrolyzed water self-supporting catalyst is denoted as Co@NCNT/CW, and the rest of the steps are the same as in example 1.
Example 5
This example provides a method for preparing an electrolyzed water self-supporting catalyst, except that the metal salt solution used for electrochemical deposition is changed to Fe (NO) with a concentration of 0.05M 3 ) 2 ·6H 2 O, the prepared electrolyzed water self-supporting catalyst is marked as Fe@NCNT/CW, and the rest steps are the same as in example 1.
Example 6
This example provides a method for preparing an electrolyzed water self-supporting catalyst, except that the metal salt solution used for electrochemical deposition is changed to Co (NO) with concentration of 0.05M 3 ) 2 ·6H 2 O solution and Ni (NO) at a concentration of 0.05M 3 ) 2 ·6H 2 The solution of O was mixed in a molar ratio of 1:1, and the prepared electrolyzed water self-supporting catalyst was designated NiCo@NCNT/CW, and the rest of the steps were the same as in example 1.
Example 7
This example provides a method for preparing an electrolyzed water self-supporting catalyst, except that the metal salt solution used for electrochemical deposition is changed to Ni (NO) with concentration of 0.05M 3 ) 2 ·6H 2 O solution, co (NO) at a concentration of 0.05M 3 ) 2 ·6H 2 O solution, fe (NO) with concentration of 0.05M 3 ) 2 ·6H 2 The solution of O was mixed in a molar ratio of 3:1:1, and the prepared electrolytic water self-supporting catalyst was designated as NiCoFe@NCNT/CW, and the rest of the steps were the same as in example 1.
1. Electrolyzed water performance test on electrolyzed water self-supporting catalyst
The self-supporting catalyst Ni@NCNT/CW-2.0 prepared by the preparation method of the embodiment 1 is respectively prepared into a scanning electron microscope sample and a transmission electron microscope sample, and the scanning electron microscope sample and the transmission electron microscope sample are respectively placed under a scanning electron microscope and a transmission electron microscope for observation to obtain a scanning electron microscope image (SEN image) and a transmission electron microscope image (TEN image), wherein the SEN image is shown in figure 1, and the TEN image is shown in figure 2.
As can be seen from fig. 1, ni metal nano ions are encapsulated in carbon nanotubes and grown in situ in pores and surfaces of carbonized wood, each carbon nanotube is coated with Ni nano particles, which are located at the tips of the carbon nanotubes and are highly dispersed, which is advantageous for sufficient exposure of catalytically active sites and improvement of catalytic activity, and the electrolytic water self-supported catalyst is shown to have a three-dimensional hierarchical porous structure.
As can be seen from fig. 2, the Ni metal nano-ions are coated in the carbon nanotubes to form a core-shell structure.
2. Static structural analysis on carbonized wood and electrolyzed water self-supporting catalysts
The carbonized wood and the electrolyzed water self-supporting catalyst prepared according to the preparation method of the example 1 are respectively subjected to X-ray diffraction analysis to obtain corresponding X-ray diffraction patterns, as shown in figure 3.
XRD diffraction peaks at 44.5 °, 51.8 °, and 76.4 ° in fig. 3 correspond to characteristic peaks of metallic Ni, respectively, and XRD diffraction peaks at 24.8 ° and 43.6 ° correspond to characteristic peaks of graphitic carbon, respectively, indicating that the nitrogen-doped carbon nanotube-coated Ni metal nanoparticles have a crystalline phase structure of metallic Ni instead of forming nitride or carbide of Ni.
3. Performance test for electrolyzed water decomposition with respect to electrolyzed water self-supporting catalyst as electrode material
The electrolyzed water self-supporting catalysts prepared in examples 1 to 3 were used as experimental groups and the existing Pt/c catalyst was used as control group at 0.5MH 2 SO 4 The solution was an electrolyte, ag/AgCl was a reference electrode, and the Pt plate was a counter electrode, and the electrolyzed water performance test of Ni@NCNT/CW catalyst and Pt/c catalyst was performed on an electrochemical workstation. Wherein the test voltage range of the Linear Sweep Voltammetry (LSV) is 0V to-1.2V (relative to the Ag/AgCl reference electrode)) The method comprises the steps of carrying out a first treatment on the surface of the The constant current stability test has a current density of 500mA/cm 2 . The hydrogen evolution test overpotential in the invention is opposite to the reversible hydrogen electrode. The results of the electrocatalytic activity test of the electrolyzed water self-supporting catalyst and the Pt/c catalyst are shown in FIG. 4, and the results of the stability test of the electrolyzed water self-supporting catalyst are shown in FIG. 5.
As can be seen from FIG. 4, the electrolyzed water self-supporting catalyst NiCo@NCNT/CW-2.0 has a commercial grade current density of 500mA/cm 2 And 1000mA/cm 2 The overpotential required by hydrogen production is 341mV and 382mV respectively, and the electrolyzed water self-supporting catalyst Ni@NCNT/CW-1.5 realizes 1000mA/cm under the low overvoltage of less than 0.5V 2 Hydrogen production by industrial current density, while Pt/c catalyst has current density higher than 500mA/cm 2 The overpotential required for hydrogen production is smaller, which indicates that the electrolytic water self-supporting catalyst has more excellent catalytic activity under the industrial current density.
As can be seen from FIG. 5, the constant current density was 500mA/cm 2 The stability test of the lower electrolyzed water self-supporting catalyst Ni@NCNT/CW for 100 hours shows that the voltage of the lower electrolyzed water self-supporting catalyst is not obviously attenuated, thus indicating that the Ni@NCNT/CW catalyst has excellent long-term durability.
The above embodiments are illustrative of the present invention, and not limiting, and any simple modifications of the present invention fall within the scope of the present invention.
Claims (10)
1. The preparation method of the self-supporting catalyst for electrolyzed water is characterized by comprising the following steps:
selecting carbonized wood as a substrate, putting the carbonized wood into a metal salt solution, and adopting an electrochemical deposition technology to electrodeposit transition metal on the carbonized wood in situ to obtain a precursor hybridized by metal and the carbonized wood;
and (3) carrying out co-pyrolysis on the precursor and melamine to coat the metal nano particles in the nitrogen doped carbon nano tube, and growing the metal nano particles on carbonized wood in situ to obtain the electrolyzed water self-supporting catalyst.
2. The method for preparing the electrolyzed water self-supporting catalyst according to claim 1, wherein: the carbonized wood is obtained by carbonizing natural wood at a high temperature.
3. The method for preparing the electrolyzed water self-supporting catalyst according to claim 2, wherein: the carbonized wood is obtained by carbonizing natural wood at the carbonization temperature of 850-950 ℃ for 1-3 hours.
4. The method for preparing the electrolyzed water self-supporting catalyst according to claim 1, wherein: the metal salt solution is at least one of nickel nitrate solution, cobalt nitrate solution and ferric nitrate solution, and the solubility of the metal salt solution is 0.03-0.08M.
5. The method for preparing the electrolyzed water self-supporting catalyst according to claim 1, wherein: the metal is at least one of Fe, co and Ni.
6. The method for preparing the electrolyzed water self-supporting catalyst according to claim 1, wherein: the co-pyrolysis is carried out in the presence of a protective gas atmosphere at a pyrolysis temperature of 700-900 ℃ for 1-3 hours.
7. The method for preparing the electrolyzed water self-supporting catalyst according to claim 1, wherein: the addition amount of the melamine is 1-2.5 g.
8. The method for preparing the electrolyzed water self-supporting catalyst according to claim 1, wherein: the electrochemical deposition technology adopts a three-electrode system, and the voltage range is-0.6 to-1.2V.
9. An electrolyzed water self-supporting catalyst prepared according to the method for preparing an electrolyzed water self-supporting catalyst according to any one of claims 1 to 8, characterized in that: the electrolyzed water self-supporting catalyst has a three-dimensional hierarchical porous structure.
10. Use of an electrolyzed water self-supporting catalyst as defined in claim 9 in the production of hydrogen from industrial grade current density electrolyzed water.
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