CN110205636A - A kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode - Google Patents
A kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 197
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 95
- 238000004070 electrodeposition Methods 0.000 claims abstract description 34
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004020 conductor Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000004458 analytical method Methods 0.000 claims abstract description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 6
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KTYKZQRFFNXTQA-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].O.[Ta+5].[Ir+3] Chemical compound [O-2].[O-2].[O-2].[O-2].O.[Ta+5].[Ir+3] KTYKZQRFFNXTQA-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004376 petroleum reforming Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 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
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- 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
Abstract
The invention discloses a kind of preparation methods for the self-cradling type three-dimensional porous structure double-function catalyzing electrode for belonging to electrolysis water hydrogen making and oxygen technical field.The preparation of the double-function catalyzing electrode is using nickel screen as cathode, and inertia electric conductor is anode, nickel chloride, ammonium chloride aqueous solution in, carry out electro-deposition under room temperature, condition of normal pressure, prepare the porous nickel of three-dimensional level；Hereafter using obtained nickel screen as the cathode of electro-deposition, it the use of inertia electric conductor is anode, immerse containing nickel nitrate, ferrous sulfate, ethylene glycol aqueous solution in, carry out electrodeposition process again under room temperature, condition of normal pressure, obtain the ferronickel/nickel/nickel catalysis electrode with porous hierarchical structure；The present invention realizes to obtain big effective active area, Bubble channel and excellent electric conductivity by two step electro-deposition, shows the electrode of excellent electrochemistry liberation of hydrogen and analysis oxygen performance under alkaline condition.Preparation process is simple, quick, pollution-free and be easy to amplify, and is convenient for industrialized production manufacture.
Description
Technical field
The invention belongs to electrolysis water hydrogen makings and oxygen technical field.In particular to a kind of three-dimensional porous knot of self-cradling type
The preparation method of structure double-function catalyzing electrode,
Background technique
With the rapid growth of energy demand and the exhaustion of fossil fuel, need to develop a kind of clean energy of green to replace
For fossil fuel.Hydrogen is because having many advantages, such as that combustion heat value is high, source is wide and reaction product is pollution-free, it is considered to be following energy
Source carrier.But most hydrogen source is in natural gas or coal, petroleum reforming process at present, along with a large amount of titanium dioxides
The discharge of the environmental contaminants such as carbon, sulfur dioxide.Therefore, it is following most potential for developing the water electrolysis hydrogen production technology of zero carbon emission
One of hydrogen producing technology.Current water electrolysis hydrogen production process energy consumption is high, at high cost, seriously hinders extensive electrolysis water industrial development,
Liberation of hydrogen catalyst, the oxygen-separating catalyst with high catalytic activity are researched and developed, is the effective ways for reducing electrolysis water process energy consumption.Platinum group
Noble metal is considered as the liberation of hydrogen catalyst of optimum performance, meanwhile, iridium dioxide or ruthenic oxide are optimal oxygen-separating catalysts.
Since content is small in these metallic element earth's crust, the market price is expensive, can not promote and apply in business electrolysis water field.Therefore,
Research and develop cheap, preparation process is simple, and the electrolysis water catalyst of high activity is most important.In addition, preparing liberation of hydrogen, analysis
When oxygen catalysis electrode, if anode, cathode are different materials, it will lead to the increase of manufacturing equipment quantity, improve manufacturing cost.Cause
This, research and development preparation process is simple, and cheap, the self-supporting double-function catalyzing electrode of high catalytic activity has important valence
Value.
Currently, the elctro-catalyst majority industrially used is powder catalyst, need active material using binder etc.
Material is fixed on a current collector, and there are obvious shortcomings for such technique.On the one hand, active site is easy to be covered by binder, drops
Low catalytic activity；On the other hand, preparation cost is undesirably increased using binder, preparation process is cumbersome.In order to solve
This problem, the present invention propose a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode.By electro-catalysis
Agent is combined into one with collector, can not only reduce electrode preparation cost, while can also significantly improve catalysis electrode stability.
At the same time, prepared electrode is used not only for anode hydrogen-precipitating electrode, additionally it is possible to be used as cathode and analyse oxygen electrode, significantly drop
Low electrolysis water electrode special preparation cost.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode,
It is characterized in that, this method prepares a kind of ferronickel/nickel/nickel catalysis electrode with porous hierarchical structure；
The preparation of the self-cradling type three-dimensional porous structure double-function catalyzing electrode comprises the steps of:
Step 1: using nickel screen as cathode, inertia electric conductor be anode, nickel chloride, ammonium chloride aqueous solution in, room temperature,
Normal pressure, 1~5A/cm of current density2Under the conditions of carry out electrodeposition process；
Step 2: the cathodic metal nickel screen obtained with deionized water rinsing step one, the metal nickel screen are used as second step
The cathode of electro-deposition, using inertia electric conductor be anode, immerse containing nickel nitrate, ferrous sulfate, ethylene glycol aqueous solution in,
Room temperature, normal pressure, current density are 2~50mA/cm2Under the conditions of carry out electrodeposition process, obtain the nickel with porous hierarchical structure
Iron/nickel/nickel catalysis electrode, i.e. self-cradling type three-dimensional porous structure double-function catalyzing electrode；
Step 3, after the two step electrodeposition process by sequence given herein above, by the ferronickel of the porous hierarchical structure/
Nickel/nickel electrode nickel screen takes out, and using deionized water clean the surface, obtains the self-cradling type three-dimensional porous structure of finished product after dry
Double-function catalyzing electrode.
The volume ratio of water and ethylene glycol is 1:0~1:4 in water liquid used in the step 2.
The molar ratio of nickel nitrate and ferrous sulfate is 1:5~5:1 in the water liquid of the step 2
The inertia electric conductor is that platinum or titanium plate ruthenium.
The metal nickel screen of the step 1 can use nickel foam, nickel wire, foam copper, copper mesh, carbon cloth, graphene film generation
It replaces.
Ferronickel/nickel/nickel electrode of the porous hierarchical structure of the preparation manufactures hydrogen for electrolysis hydrogen oxidation aqueous solutions of potassium
And oxygen, the ferronickel/nickel/nickel electrode are both used as hydrogen-precipitating electrode, also serve as analysis oxygen electrode.
The electrolysis hydrogen oxidation aqueous solutions of potassium concentration is 1~6 molar concentration.
The beneficial effects of the invention are as follows compared with prior art, preparation process of the invention is simple, and technical method is easy to put
Greatly, low in raw material price, the electrode being prepared have high catalytic activity and excellent stability, both can be used as Oxygen anodic evolution
Electrode, and cathode hydrogen evolution electrode can be used as.The electrode is used for extensive water electrolysis hydrogen production, and water electrolysis hydrogen production energy consumption is effectively reduced
With production hydrogen cost.Therefore it has the advantage that
1. synthesis technology is simple and quick, catalyst is realized only by two step short time electro-deposition；
2. using self-cradling type three-dimensional porous structure double-function catalyzing electrode as anode and cathode, to electrolysis water,
Current density is 10mA/cm2When, overpotential is only 33 millivolts, better than noble metal platinum and commercialization iridium tantalum pentoxide as yin
The performance of the electrolytic cell of pole and anode.
3. even if the double-function catalyzing electrode under high current density, is still able to maintain lower overpotential and makes for a long time
With stability, technical performance is better than noble metal catalyst.
Detailed description of the invention
The scanning electron microscope (SEM) photograph of Fig. 1 catalysis electrode wherein a, b be different amplification porous level nickel sweeping on nickel screen
Retouch electron microscope；C, d is ferronickel/nickel/nickel catalysis electrode scanning electron microscope (SEM) photograph of different amplification.
Fig. 2 is self-cradling type three-dimensional porous structure ferronickel/nickel/nickel catalysis electrode oxygen Precipitation Characteristics；
Fig. 3 is the influence that current density ferronickel/nickel/nickel catalysis electrode oxygen is precipitated catalytic activity in step 1；
Fig. 4 is the influence that catalytic activity is precipitated in the pairs of ferronickel/nickel of aqueous solution group/nickel catalysis electrode oxygen in step 2；
Fig. 5 is ferronickel/nickel/nickel catalysis electrode Hydrogen Evolution Performance.
Linear voltammetric scan curve of Fig. 6-1. ferronickel/nickel/nickel catalysis electrode as anode of electrolytic water and cathode.
Fig. 6-2. ferronickel/nickel/nickel catalysis electrode is used for electrolysis water process technology performance
Specific embodiment
The present invention provides a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode, this prepares one
Kind has ferronickel/nickel/nickel catalysis electrode of porous hierarchical structure.
The preparation of the self-cradling type three-dimensional porous structure double-function catalyzing electrode comprises the steps of:
Step 1: using nickel screen as cathode, inertia electric conductor (platinum or titanium plate ruthenium) is anode, in nickel chloride, the water of ammonium chloride
In solution, room temperature, normal pressure, 1~5A/cm of current density2Under the conditions of carry out electrodeposition process；
Step 2: the cathodic metal nickel screen obtained with deionized water rinsing step one, the metal nickel screen are used as second step
The cathode of electro-deposition is anode using inertia electric conductor, immerse containing nickel nitrate and ferrous sulfate (molar ratio is 1:5~5:1),
It is 2~50mA/cm in room temperature, normal pressure, current density in the aqueous solution of ethylene glycol2Under the conditions of carry out electrodeposition process, had
There are ferronickel/nickel/nickel electrode of porous hierarchical structure, i.e. self-cradling type three-dimensional porous structure double-function catalyzing electrode；
Step 3, after the two step electrodeposition process by sequence given herein above, by the ferronickel of the porous hierarchical structure/
Nickel/nickel electrode nickel screen takes out, and using deionized water clean the surface, obtains the self-cradling type three-dimensional porous structure of finished product after dry
Double-function catalyzing electrode.Below in conjunction with specific implementation case, the present invention will be further described.
Embodiment 1
Step 1: as cathode after nickel screen dilute hydrochloric acid, ethyl alcohol, ultrapure water are cleaned up, platinized platinum is as anode, configuration
0.1M Ni(Cl)2With 2M NH4Cl solution is placed in beaker as electrolyte, by the anode of DC power supply, cathode respectively with platinum
Piece, nickel screen are connected, and are mounted in the beaker, and solution is made to submerge electrode；At room temperature, setting current density is
3A/cm2, electrodeposition process 90 seconds.
Step 2: using the porous nickel after step 1 electro-deposition as cathode, it is immersed in the Fe (NO for filling 1.5M3)2With
Ni (the NO of 1.5M3)2In (volume ratio 1:1) electrolyte solution, and by the anode connection platinized platinum of DC power supply, cathode connects nickel screen,
At room temperature, setting electric current density is 5mA/cm2, electrodeposition process 450 seconds, obtain the three-dimensional porous level nickel of self-supporting
Iron/nickel/nickel electrode.
In Fig. 1, a, b are scanning electron microscope (SEM) figure for the porous nickel that step 1 electro-deposition obtains in embodiment 1, can be seen
Level cavernous structure is formd on nickel screen fiber out.In Fig. 1 c, d be ferronickel/nickel after step 2 electro-deposition in case study on implementation 1/
The SEM of nickel schemes, it can be seen that ferronickel layered hydroxide is uniformly grown in level porous nickel.
Analysis oxygen electrode will be prepared as working electrode, platinized platinum as to electrode, mercury oxidation mercury as reference electrode into
Row test, carries out electrochemistry linear voltammetric scan, as shown in Figure 2 in 1M KOH solution, it can be seen that ferronickel/nickel/nickel performance
Excellent oxygen evolution activity is 10mA/cm in current density2When, required overpotential is only 190mV.
Embodiment 2
As cathode after nickel screen dilute hydrochloric acid, ethyl alcohol, ultrapure water are cleaned up, platinized platinum is as anode, 0.1MNi (Cl)2
With 2M NH4Cl solution is as electrolyte, and at room temperature, it is 1A/cm that current density, which is set separately,2、3A/cm2、5A/cm2,
Electro-deposition 90 seconds.Using the porous nickel after electro-deposition as cathode, 1.5MFe (NO3)2With 1.5M Ni (NO3)2(volume ratio 1:1) makees
It is at room temperature 5mA/cm in current density for electrolyte2, electro-deposition 450 seconds, obtain the three-dimensional porous level of self-supporting
Ferronickel/nickel/nickel electrode.This method is 2-50mA/cm in second step electro-deposition current density2It also can be implemented in range
Fig. 3 is that current density influences in step 1 in case study on implementation 2, it can be seen that when guarantee step 2 electro-deposition is identical
In the case of, step 1 electro-deposition current density increases, and the catalytic activity as analysis oxygen catalysis electrode also dramatically increases, but works as
Step 1 current density is greater than 3mA/cm2Afterwards, catalytic activity is close.
Embodiment 3
As cathode after nickel screen dilute hydrochloric acid, ethyl alcohol, ultrapure water are cleaned up, platinized platinum is as anode, 0.1MNi (Cl)2
With 2M NH4Cl solution is as electrolyte, is 3A/cm in current density at room temperature2, electro-deposition 90 seconds.After electro-deposition
Porous nickel as cathode, by the Fe (NO of 1.5M3)2With the Ni (NO of 1.5M3)2(volume ratio 1:1) is used as electrolyte, is dissolved in water
It is respectively in the electrolyte aqueous solution of 1:0,1:1,1:4 with ethylene glycol ratio, at room temperature, holding current density is 5mA/
cm2, electrodeposition process 450 seconds, obtain the three-dimensional porous level ferronickel/nickel/nickel electrode of self-supporting.This method is in second step electro-deposition
Current density is 2-50mA/cm2It also can be implemented in range
Fig. 4 is that different electrolytes match the comparison active influence of catalysis electrode in case study on implementation 3, it can be seen that with second two
Alcohol ratio increases, and catalytic activity has small-scale rising.
Embodiment 4
As cathode after nickel screen dilute hydrochloric acid, ethyl alcohol, ultrapure water are cleaned up, platinized platinum is as anode, 0.1MNi (Cl)2
With 2M NH4Cl solution is as electrolyte, is 3A/cm in current density at room temperature2, electro-deposition 90 seconds.After electro-deposition
Porous nickel as cathode, the Fe (NO of 1.5M3)2With the Ni (NO of 1.5M3)2(volume ratio 1:1) is used as electrolyte, in room temperature item
It is 5mA/cm in current density under part2, electro-deposition 200 seconds, obtain the three-dimensional porous level ferronickel/nickel/nickel electrode of self-supporting.
Fig. 5 is ferronickel/nickel/nickel electrode in case study on implementation 3 as hydrogen-precipitating electrode, by ferronickel bimetallic growth in situ more
On the level nickel of hole, the hydrogen evolution activity for the ferronickel that can be significantly improved is in current density for ferronickel/nickel/nickel electrode
10mA/cm2When, required overpotential is only 132mV.
Embodiment 5
Using the electrode prepared in example 2 as anode, using the electrode prepared in example 4 as cathode, in 1M KOH solution
Middle progress electrochemistry linear voltammetric scan (Fig. 6-1), shows excellent chemical property, is 10mA/ in current density
cm2When, required decomposition voltage is only that the bifunctional catalyst shows excellent stability to 1.56V. simultaneously,
500mA/cm2Current density under, constant-current electrolysis water running 200 hours (Fig. 6-2), there is no significant changes for decomposition voltage.
Claims (7)
1. a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode, which is characterized in that this method preparation
A kind of ferronickel/nickel/nickel catalysis electrode with porous hierarchical structure out；
The preparation of the self-cradling type three-dimensional porous structure double-function catalyzing electrode comprises the steps of:
Step 1: using nickel screen as cathode, inertia electric conductor be anode, nickel chloride, ammonium chloride aqueous solution in, room temperature, normal pressure,
1~5A/cm of current density2Under the conditions of carry out electrodeposition process；
Step 2: the cathodic metal nickel screen obtained with deionized water rinsing step one, the metal nickel screen are heavy as second step electricity
Long-pending cathode, using inertia electric conductor be anode, immerse containing nickel nitrate, ferrous sulfate, ethylene glycol aqueous solution in, normal
Temperature, normal pressure, current density are 2~50mA/cm2Under the conditions of carry out electrodeposition process, obtain the ferronickel with porous hierarchical structure/
Nickel/nickel catalysis electrode, i.e. self-cradling type three-dimensional porous structure double-function catalyzing electrode；
Step 3, after the two step electrodeposition process by sequence given herein above, by ferronickel/nickel/nickel of the porous hierarchical structure
The nickel screen of electrode takes out, and using deionized water clean the surface, the double function of self-cradling type three-dimensional porous structure of finished product are obtained after dry
It can catalysis electrode.
2. a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode according to claim 1, special
Sign is that the inertia electric conductor is that platinum or titanium plate ruthenium.
3. a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode according to claim 1, special
Sign is that the volume ratio of water and ethylene glycol is 1:0~1:4 in water liquid used in the step 2.
4. a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode according to claim 1, special
Sign is that the molar ratio of nickel nitrate and ferrous sulfate is 1:5~5:1 in the water liquid of the ethylene glycol of the step 2.
5. a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode according to claim 1, special
Sign is that the metal nickel screen of the step 1 can be replaced with nickel foam, nickel wire, foam copper, copper mesh, carbon cloth, graphene film.
6. a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode according to claim 1, special
Sign is, ferronickel/nickel/nickel electrode of the porous hierarchical structure of the preparation for electrolysis hydrogen oxidation aqueous solutions of potassium manufacture hydrogen and
Oxygen, the ferronickel/nickel/nickel electrode are both used as hydrogen-precipitating electrode, also serve as analysis oxygen electrode.
7. a kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode according to claim 6, special
Sign is that the electrolysis hydrogen oxidation aqueous solutions of potassium concentration is 1~6 molar concentration.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112044458A (en) * | 2020-08-21 | 2020-12-08 | 广东工业大学 | Multi-level metal phosphide and preparation method and application thereof |
| CN112695340A (en) * | 2021-01-03 | 2021-04-23 | 杜先明 | Preparation method of cathode for alkalescent beautifying water |
| CN112921351A (en) * | 2021-01-22 | 2021-06-08 | 清华大学 | Preparation method and application of self-supporting catalytic electrode |
| CN113913846A (en) * | 2021-11-09 | 2022-01-11 | 西南石油大学 | Water electrolysis hydrogen production oxygen generation reaction device |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106660013A (en) * | 2014-08-11 | 2017-05-10 | 新南创新私人有限公司 | Catalytic assembly |
| CN107385489A (en) * | 2016-05-15 | 2017-11-24 | 北京化工大学 | A kind of three-dimensional manometer flower-shape Ni-Fe complex hydroxides for carbonate electrolyte analyse oxygen anodes |
| US20180073153A1 (en) * | 2016-09-14 | 2018-03-15 | Kabushiki Kaisha Toshiba | Optically transparent oxygen generation catalyst, production method thereof, and chemical reactor utilizing the same |
| CN108193227A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Oxygen electrode and its preparation and application are analysed in the electro-catalysis of nickel-ferric spinel base |
-
2019
- 2019-04-22 CN CN201910324963.XA patent/CN110205636B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106660013A (en) * | 2014-08-11 | 2017-05-10 | 新南创新私人有限公司 | Catalytic assembly |
| CN107385489A (en) * | 2016-05-15 | 2017-11-24 | 北京化工大学 | A kind of three-dimensional manometer flower-shape Ni-Fe complex hydroxides for carbonate electrolyte analyse oxygen anodes |
| US20180073153A1 (en) * | 2016-09-14 | 2018-03-15 | Kabushiki Kaisha Toshiba | Optically transparent oxygen generation catalyst, production method thereof, and chemical reactor utilizing the same |
| CN108193227A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Oxygen electrode and its preparation and application are analysed in the electro-catalysis of nickel-ferric spinel base |
Non-Patent Citations (2)
| Title |
|---|
| I. HERRAIZ-CARDONA ET AL: "Double-template fabrication of three-dimensional porous nickel electrodes for hydrogen evolution reaction", 《SCIVERSE SCIENCEDIRECT》 * |
| XUNYU LU ET AL: "Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities", 《NATURE COMMUNICATIONS》 * |
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