CN109576730A - A kind of preparation method and application of the cobaltosic oxide nano chip arrays electrode of iron modification - Google Patents
A kind of preparation method and application of the cobaltosic oxide nano chip arrays electrode of iron modification Download PDFInfo
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- CN109576730A CN109576730A CN201811386271.XA CN201811386271A CN109576730A CN 109576730 A CN109576730 A CN 109576730A CN 201811386271 A CN201811386271 A CN 201811386271A CN 109576730 A CN109576730 A CN 109576730A
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- Prior art keywords
- carbon cloth
- chip arrays
- electrode
- cobaltosic oxide
- iron
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 192
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 238000003491 array Methods 0.000 title claims abstract description 126
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 96
- 238000012986 modification Methods 0.000 title claims abstract description 71
- 230000004048 modification Effects 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 158
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 150
- 239000004744 fabric Substances 0.000 claims abstract description 149
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 50
- 239000010941 cobalt Substances 0.000 claims description 50
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002184 metal Substances 0.000 claims description 49
- -1 obtain 1 Chemical compound 0.000 claims description 45
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 27
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 27
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 229910017604 nitric acid Inorganic materials 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 26
- 238000011010 flushing procedure Methods 0.000 claims description 25
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 18
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 16
- 238000004502 linear sweep voltammetry Methods 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229940101209 mercuric oxide Drugs 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- 238000000970 chrono-amperometry Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YKHQSWIVNHQJSW-UHFFFAOYSA-N iron;oxalonitrile Chemical compound [Fe].N#CC#N YKHQSWIVNHQJSW-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
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- 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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- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
A kind of preparation method and application of the cobaltosic oxide nano chip arrays electrode of iron modification, it belongs to electrochemical catalysis and energy field, and in particular to a kind of preparation method and application of electrode.The invention aims to solve the problems, such as that existing nano material oxygen evolution reaction catalytic performance under harsh alkaline condition is low.Method: the one, processing of carbon cloth；Two, solution is prepared；Three, it impregnates；Four, anion etches；Five, it makes annealing treatment, obtains the cobaltosic oxide nano chip arrays electrode of cobaltosic oxide nano chip arrays electrode and iron modification.A kind of electrolysis water oxygen evolution reaction that the cobaltosic oxide nano chip arrays electrode of iron modification is used to be catalyzed in alkaline environment.The present invention can get a kind of cobaltosic oxide nano chip arrays electrode of iron modification.
Description
Technical field
The invention belongs to electrochemical catalysis and energy fields, and in particular to a kind of preparation method and application of electrode.
Background technique
The environmental pollution as caused by fossil fuel and increased energy demand, seek environmentally friendly renewable energy
It is particularly important.In numerous alternative energy sources, due to high-energy density and carbon-free characteristic, hydrogen is considered being hopeful into future
For the substitute of carbon-based fossil energy.Electrolysis water is the extensive effective means for producing hydrogen, and in the process, water is both unique original
Material is unique by-product again, and production method is environmentally friendly, institute's hydrogen producing purity is high.Electrolysis water process includes two half-shadows
Reaction, is the evolving hydrogen reaction of cathode and the oxygen evolution reaction of anode respectively.However, slowly to be analysed oxygen by dynamics anti-for hydrolytic process
It should limit.Oxygen evolution reaction is four electron transfer process, is related to the fracture of oxygen hydrogen bond and the generation of oxygen-oxygen bond, theory limitation
It is 1.23 volts.Therefore, high efficiency oxygen evolution reaction elctro-catalyst is explored and designs to the energy for reducing overpotential and promotion overall process
Amount efficiency is of great significance.Noble metal base (ruthenium base or iridium base) is still the efficient oxygen evolution reaction catalysts of current mainstream.So
And natural low memory, stability are poor, cost height limits the large-scale application of noble metal sill.Therefore, development is without your gold
Belong to and the analysis oxygen catalysis material of efficient stable is of great significance.Wherein, transition metal oxide/hydroxide is shown efficiently
Oxygen evolution reaction electro catalytic activity.In addition to chemical composition, the structure of elctro-catalyst is also to influence a key factor of catalytic performance.
Although two-dimentional transition metal oxide/hydroxide illustrates good analysis oxygen performance, but most of shortages are advantageous more
Pore property.In order to make two-dimensional material that there is porosity characteristic, it is particularly significant to develop a kind of surface chemistry adjusting method.
There is the nano material more and more synthesized using metal organic frame as stencil design in recent years.Metal organic frame
It is a kind of fast-developing porous material, is reacted by organic linker and metal ion or ion cluster, due to chemistry and knot
Structure diversity is illustrated in fields such as heterogeneous catalysis, energy storage and conversions and is widely applied.Structurally ordered, ligand is adjustable,
The feature that surface area is big and metallic site makes the active position density of metal-organic framework material high more.Metal organic frame
It is unstable under especially acid and alkaline condition in water, but an ideal template is provided to design a variety of electrode materials.
General conversion regime is to be made annealing treatment to material in different gaseous environments to mix nonmetallic heteroatoms, such as more
Mesoporous metal oxide, carbide, nitride or their composite material.This process is along with as caused by organic material evaporation
Porous generation.Desirably, the basic structure and pattern of the material obtained all maintain well.But it is organic with metal
Frame be stencil design synthesis nano material under harsh alkaline condition oxygen evolution reaction catalytic performance it is low, reached in current density
To 10mA/cm2When, the overpotential for the most of oxygen evolution reaction elctro-catalysts reported at present is all larger than 295mV.
Summary of the invention
It is low the invention aims to solve existing nano material oxygen evolution reaction catalytic performance under harsh alkaline condition
The problem of, and a kind of preparation method and application of the cobaltosic oxide nano chip arrays electrode of iron modification is provided.
A kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification, is completed by the following steps:
One, the processing of carbon cloth:
Concentrated nitric acid is added in the liner of hydrothermal reaction kettle, then carbon cloth is immersed in concentrated nitric acid, then by hydro-thermal reaction
It is 2h~4h in 95 DEG C~105 DEG C of baking oven that kettle, which is put into temperature, the carbon cloth that obtains that treated；After dehydrated alcohol flushing processing
Carbon cloth 2 times~4 times, reusing distilled water flushing, treated carbon cloth 2 times~4 times, obtain removal surface oxide layer carbon cloth；
The carbon cloth for removing surface oxide layer is stored in dehydrated alcohol；
Two, solution is prepared:
1., cabaltous nitrate hexahydrate is dissolved into deionized water, obtain cobalt nitrate solution；
Step 2 1. described in cobalt nitrate solution concentration be 30mmol/L~50mmol/L；
2., 1,2- methylimidazole is dissolved into deionized water, obtain 1,2- methylimidazole solution；
Step 2 2. described in DMIZ 1,2 dimethylimidazole solution concentration be 30mmol/L~50mmol/L；
3., 1,2- methylimidazole solution is added in cobalt nitrate solution, obtain bluish violet suspension；
Step 2 3. described in DMIZ 1,2 dimethylimidazole solution and cobalt nitrate solution volume ratio be 1:1；
Three, it impregnates:
It is immersed in bluish violet suspension after the carbon cloth for the removal surface oxide layer being stored in dehydrated alcohol is taken out, then
3h~5h is reacted at room temperature, then carbon cloth is taken out, and is finally 50 DEG C~70 DEG C in temperature using distilled water flushing 3 times~5 times
Lower dry 8h~10h obtains the carbon cloth that growth has cobalt-based metal organic frame nano-chip arrays；
Four, anion etches:
1., the potassium ferricyanide is dissolved into deionized water, obtain potassium ferricyanide solution；
Step 4 1. described in potassium ferricyanide solution concentration be 1g/L~5g/L；
2., will growth there is the carbon cloth of cobalt-based metal organic frame nano-chip arrays to be immersed in potassium ferricyanide solution, then
Mixing speed is that magnetic agitation reacts 1h~3h under 50r/min~70r/min, then carbon cloth is taken out, and rinses 3 using deionized water
It is secondary~5 times, then 8h~10h is dried at being 50 DEG C~70 DEG C in temperature, obtain the cobalt-based metal organic frame that growth has iron to modify
The carbon cloth of nano-chip arrays；
Five, it makes annealing treatment:
The carbon cloth of cobalt-based metal organic frame nano-chip arrays that growth has iron to modify is put into tube furnace, then by tubular type
Furnace is warming up to 300 DEG C~400 DEG C with 1.5 DEG C/min~2.5 DEG C/min heating rate, then in the case where temperature is 300 DEG C~400 DEG C
Anneal 1.5h~2.5h, then cooled to room temperature, obtains the cobaltosic oxide nano chip arrays electrode of iron modification.
The mass fraction of concentrated nitric acid described in further step one is 67%~69%.
Further step two 1. described in cobalt nitrate solution concentration be 35mmol/L~40mmol/L.
Further step two 2. described in DMIZ 1,2 dimethylimidazole solution concentration be 35mmol/L~40mmol/L.
Further step four 1. described in potassium ferricyanide solution concentration be 2g/L~2.5g/L.
Concentrated nitric acid is added in the liner of hydrothermal reaction kettle in further step one, then carbon cloth is immersed in concentrated nitric acid
In, then it is 2h~3h in 95 DEG C~100 DEG C of baking oven that hydrothermal reaction kettle, which is put into temperature, the carbon cloth that obtains that treated；Use nothing
Treated carbon cloth 2 times~3 times for water-ethanol flushing, and reusing distilled water flushing, treated carbon cloth 2 times~3 times, is removed
The carbon cloth of surface oxide layer；The carbon cloth for removing surface oxide layer is stored in dehydrated alcohol.
It is immersed in after taking out the carbon cloth for the removal surface oxide layer being stored in dehydrated alcohol in further step three
In bluish violet suspension, then 3h~4h is reacted at room temperature, then carbon cloth is taken out, using distilled water flushing 3 times~4 times, finally
Dry 8h~9h at being 50 DEG C~60 DEG C in temperature, obtains the carbon cloth that growth has cobalt-based metal organic frame nano-chip arrays.
Further step four 2. in will growth there is the carbon cloth of cobalt-based metal organic frame nano-chip arrays to be immersed in iron cyanogen
Change in potassium solution, then low whipping speed is that magnetic agitation reacts 1h~2h under 50r/min~70r/min, then carbon cloth is taken out, and is made
It is rinsed 3 times~4 times with deionized water, then dry 8h~9h at being 50 DEG C~60 DEG C in temperature, obtains the cobalt that growth has iron to modify
The carbon cloth of Base Metal organic frame nano-chip arrays.
The carbon cloth for the cobalt-based metal organic frame nano-chip arrays that growth has iron to modify is put into further step five
In tube furnace, then tube furnace is warming up to 300 DEG C~350 DEG C with 1.5 DEG C/min~2 DEG C/min heating rate, then in temperature
It is annealing 1.5h~2h at 300 DEG C~350 DEG C, then cooled to room temperature, obtains the cobaltosic oxide nano piece battle array of iron modification
Column electrode.
A kind of electrolysis elutriation oxygen that the cobaltosic oxide nano chip arrays electrode of iron modification is used to be catalyzed in alkaline environment is anti-
It answers.
The principle of the present invention and advantage:
The carbon cloth that the present invention uses is the commercialization carbon cloth of purchase, has corrosion resistance, electric conductivity, flexibility and integral type three
Tie up structure；First using the inoxidzable coating of concentrated nitric acid processing carbon cloth surfaces, then make cobalt ions and 1,2- methylimidazole occurs
Complexation reaction is deposited in carbon cloth substrate based on room temperature liquid deposition reaction principle, then, the cobalt-based metal organic frame of synthesis
Nano-chip arrays are reacted with fewrricyanic acid radical ion, and the cobalt-based metal organic frame nanometer of iron modification has been obtained after over etching
Chip arrays；Finally, annealed processing has obtained the cobaltosic oxide nano chip arrays electrode of iron modification, the modification of iron is greatly mentioned
High electron transfer efficiency, improves the utilization of active site, catalytic performance increases substantially；Iron modification prepared by the present invention
The directly life of cobaltosic oxide nano chip arrays electrode is carbon cloth substrate, is conducive to the stability of catalyst, and porous structure and
The synergistic effect of nano-chip arrays is conducive to the efficient utilization of the infiltration of electrolyte, ion-transfer and active site；By this hair
Bright method can be realized the cobaltosic oxide nano chip arrays electrode of the modification of the iron based on carbon cloth, be conducive to have machine frame with metal
Frame is that template is designed building Heteroatom doping or the nano-array material of modification is widely used in the relevant field of the energy.
Advantages of the present invention:
(1), cost is controllable: material required for the present invention is cheap and easily-available, it is only necessary to a piece of commercialized carbon cloth and one
Quantitative concentrated nitric acid, cabaltous nitrate hexahydrate, the potassium ferricyanide and DMIZ 1,2 dimethylimidazole；
(2), easy to operate: although the processing of carbon cloth and high annealing need to provide certain temperature environment, but entire
Synthesis process does not need high pressure, electric field, stringent gaseous environment etc.；
(3), catalytic activity is high: it is not high in cost, under conditions of easy to operate, iron modification prepared by the present invention obtained
Cobaltosic oxide nano chip arrays electrode still has good catalytic performance, significantly provides and analyses oxygen under harsh alkaline condition
Reacting catalytic performance, when oxygen evolution reaction current density reaches 10mA/cm2And 20mA/cm2When, overpotential only be respectively 290mV~
295mV and 310mV~315mV, and Tafel slope, down to 74.7mV/dev, oxygen evolution reaction performance good in this way can give the credit to
In the efficient utilization of good electric conductivity and active site that the modification of iron generates, and generated in nanometer sheet abundant
The synergistic effect of open space, nano-chip arrays and conductive substrates between nano-pore, nanometer sheet is conducive to the infiltration of electrolyte
With the diffusion of oxygen, while be conducive to improve catalyst stability.
The present invention can get a kind of cobaltosic oxide nano chip arrays electrode of iron modification.
Detailed description of the invention
Fig. 1 is the SEM figure of the cobaltosic oxide nano chip arrays electrode of iron modification prepared by embodiment two；
Fig. 2 is the cobaltosic oxide nano chip arrays electrode of the iron modification prepared under different fewrricyanic acid ion concentrations
Linear sweep voltammetry figure, 1 is four oxidations three of the iron modification prepared under 1.25g/L potassium ferricyanide solution in embodiment one in figure
The linear sweep voltammetry curve of cobalt nano-chip arrays electrode, 2 be to prepare under 2.5g/L potassium ferricyanide solution in embodiment two
The linear sweep voltammetry curve of the cobaltosic oxide nano chip arrays electrode of iron modification, 3 be in embodiment three in 5g/L iron cyaniding
The linear sweep voltammetry curve of the cobaltosic oxide nano chip arrays electrode of the iron modification prepared under potassium solution；
Fig. 3 is linear sweep voltammetry figure, 1 carbon cloth to remove surface oxide layer obtained in two step 1 of embodiment in figure
Linear sweep voltammetry curve, the linear scan of the 2 cobaltosic oxide nano chip arrays electrodes obtained for one step 5 of embodiment
Volt-ampere curve, 3 be the linear scan volt of the cobaltosic oxide nano chip arrays electrode for the iron modification that two step 5 of embodiment obtains
Pacify curve；
The voltage of the cobaltosic oxide nano chip arrays electrode for the iron modification that Fig. 4 obtains for two step 5 of embodiment is at any time
Change curve, the current density of curve 1 is 10mA/cm in figure2, the current density of curve 2 is 20mA/cm2。
Specific embodiment
Specific embodiment 1: present embodiment is a kind of preparation of the cobaltosic oxide nano chip arrays electrode of iron modification
Method is completed by the following steps:
One, the processing of carbon cloth:
Concentrated nitric acid is added in the liner of hydrothermal reaction kettle, then carbon cloth is immersed in concentrated nitric acid, then by hydro-thermal reaction
It is 2h~4h in 95 DEG C~105 DEG C of baking oven that kettle, which is put into temperature, the carbon cloth that obtains that treated；After dehydrated alcohol flushing processing
Carbon cloth 2 times~4 times, reusing distilled water flushing, treated carbon cloth 2 times~4 times, obtain removal surface oxide layer carbon cloth；
The carbon cloth for removing surface oxide layer is stored in dehydrated alcohol；
Two, solution is prepared:
1., cabaltous nitrate hexahydrate is dissolved into deionized water, obtain cobalt nitrate solution；
Step 2 1. described in cobalt nitrate solution concentration be 30mmol/L~50mmol/L；
2., 1,2- methylimidazole is dissolved into deionized water, obtain 1,2- methylimidazole solution；
Step 2 2. described in DMIZ 1,2 dimethylimidazole solution concentration be 30mmol/L~50mmol/L；
3., 1,2- methylimidazole solution is added in cobalt nitrate solution, obtain bluish violet suspension；
Step 2 3. described in DMIZ 1,2 dimethylimidazole solution and cobalt nitrate solution volume ratio be 1:1；
Three, it impregnates:
It is immersed in bluish violet suspension after the carbon cloth for the removal surface oxide layer being stored in dehydrated alcohol is taken out, then
3h~5h is reacted at room temperature, then carbon cloth is taken out, and is finally 50 DEG C~70 DEG C in temperature using distilled water flushing 3 times~5 times
Lower dry 8h~10h obtains the carbon cloth that growth has cobalt-based metal organic frame nano-chip arrays；
Four, anion etches:
1., the potassium ferricyanide is dissolved into deionized water, obtain potassium ferricyanide solution；
Step 4 1. described in potassium ferricyanide solution concentration be 1g/L~5g/L；
2., will growth there is the carbon cloth of cobalt-based metal organic frame nano-chip arrays to be immersed in potassium ferricyanide solution, then
Mixing speed is that magnetic agitation reacts 1h~3h under 50r/min~70r/min, then carbon cloth is taken out, and rinses 3 using deionized water
It is secondary~5 times, then 8h~10h is dried at being 50 DEG C~70 DEG C in temperature, obtain the cobalt-based metal organic frame that growth has iron to modify
The carbon cloth of nano-chip arrays；
Five, it makes annealing treatment:
The carbon cloth of cobalt-based metal organic frame nano-chip arrays that growth has iron to modify is put into tube furnace, then by tubular type
Furnace is warming up to 300 DEG C~400 DEG C with 1.5 DEG C/min~2.5 DEG C/min heating rate, then in the case where temperature is 300 DEG C~400 DEG C
Anneal 1.5h~2.5h, then cooled to room temperature, obtains the cobaltosic oxide nano chip arrays electrode of iron modification.
The advantages of present embodiment:
(1), cost is controllable: material required for present embodiment is cheap and easily-available, it is only necessary to a piece of commercialized carbon cloth
With a certain amount of concentrated nitric acid, cabaltous nitrate hexahydrate, the potassium ferricyanide and DMIZ 1,2 dimethylimidazole；
(2), easy to operate: although the processing of carbon cloth and high annealing need to provide certain temperature environment, but entire
Synthesis process does not need high pressure, electric field, stringent gaseous environment etc.；
(3), catalytic activity is high: not high in cost, under conditions of easy to operate, the iron of present embodiment preparation obtained is repaired
The cobaltosic oxide nano chip arrays electrode of decorations still has good catalytic performance, significantly provides under harsh alkaline condition
Oxygen evolution reaction catalytic performance, when oxygen evolution reaction current density reaches 10mA/cm2And 20mA/cm2When, overpotential is only respectively
290mV~295mV and 310mV~315mV, and Tafel slope is down to 74.7mV/dev, oxygen evolution reaction performance good in this way
It can be attributed to the fact that the efficient utilization for the good electric conductivity and active site that the modification of iron generates, and be generated in nanometer sheet
Nano-pore abundant, the open space between nanometer sheet, nano-chip arrays and conductive substrates synergistic effect be conducive to be electrolysed
The infiltration of liquid and the diffusion of oxygen, while being conducive to improve the stability of catalyst.
Present embodiment can get a kind of cobaltosic oxide nano chip arrays electrode of iron modification.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: dense nitre described in step 1
The mass fraction of acid is 67%~69%.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: institute in step 1
The mass fraction for the concentrated nitric acid stated is 68%.Other steps are the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: step 2 1. in
The concentration of the cobalt nitrate solution is 35mmol/L~40mmol/L.Other steps are identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: step 2 2. in
The concentration of the DMIZ 1,2 dimethylimidazole solution is 35mmol/L~40mmol/L.Other steps and specific embodiment one to
Four is identical.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: step 4 1. in
The concentration of the potassium ferricyanide solution is 2g/L~2.5g/L.Other steps are identical as specific embodiment one to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: step 4 1. in
The concentration of the potassium ferricyanide solution is 1.25g/L.Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: will in step 1
Concentrated nitric acid is added in the liner of hydrothermal reaction kettle, then carbon cloth is immersed in concentrated nitric acid, then hydrothermal reaction kettle is put into temperature
For 2h~3h in 95 DEG C~100 DEG C of baking ovens, the carbon cloth that obtains that treated；Using dehydrated alcohol flushing, treated carbon cloth 2 times
~3 times, reusing distilled water flushing, treated carbon cloth 2 times~3 times, obtains the carbon cloth of removal surface oxide layer；Table will be removed
The carbon cloth of face oxide layer is stored in dehydrated alcohol.Other steps are identical as specific embodiment one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: will in step 3
The carbon cloth for the removal surface oxide layer being stored in dehydrated alcohol is immersed in bluish violet suspension after taking out, then anti-at room temperature
3h~4h is answered, then carbon cloth is taken out, using distilled water flushing 3 times~4 times, dry 8h at being finally 50 DEG C~60 DEG C in temperature~
9h obtains the carbon cloth that growth has cobalt-based metal organic frame nano-chip arrays.Other steps and one to eight phase of specific embodiment
Together.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: step 4 2. in
There is the carbon cloth of cobalt-based metal organic frame nano-chip arrays to be immersed in potassium ferricyanide solution growth, then low whipping speed is
Magnetic agitation reacts 1h~2h under 50r/min~70r/min, then carbon cloth is taken out, and is rinsed 3 times~4 times using deionized water, then
Dry 8h~9h at being 50 DEG C~60 DEG C in temperature, obtains the cobalt-based metal organic frame nano-chip arrays that growth has iron to modify
Carbon cloth.Other steps are identical as specific embodiment one to nine.
Specific embodiment 11: one of present embodiment and specific embodiment one to ten difference are: in step 5
The carbon cloth for the cobalt-based metal organic frame nano-chip arrays that growth has iron to modify is put into tube furnace, then by tube furnace with 1.5
DEG C/min~2 DEG C/min heating rate is warming up to 300 DEG C~350 DEG C, then the 1.5h that anneals at being 300 DEG C~350 DEG C in temperature
~2h, then cooled to room temperature obtain the cobaltosic oxide nano chip arrays electrode of iron modification.Other steps and specific implementation
Mode one to ten is identical.
Specific embodiment 12: present embodiment is with one to one of 11 difference of specific embodiment: step 5
The carbon cloth of the middle cobalt-based metal organic frame nano-chip arrays for having iron to modify growth is put into tube furnace, then by tube furnace with 2
DEG C/heating rate of min is warming up to 350 DEG C, then anneal at being 350 DEG C in temperature 2h, then cooled to room temperature, it obtains iron and repairs
The cobaltosic oxide nano chip arrays electrode of decorations.Other steps are identical as specific embodiment one to 11.
Specific embodiment 13: present embodiment is that a kind of cobaltosic oxide nano chip arrays electrode of iron modification is used for
The electrolysis water oxygen evolution reaction being catalyzed in alkaline environment.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification, is according to the following steps
It completes:
One, the processing of carbon cloth:
Concentrated nitric acid is added in the liner of hydrothermal reaction kettle, then carbon cloth is immersed in concentrated nitric acid, then by hydro-thermal reaction
It is 3h in 100 DEG C of baking oven that kettle, which is put into temperature, the carbon cloth that obtains that treated；Using dehydrated alcohol flushing, treated carbon cloth 3 times,
Reusing distilled water flushing, treated carbon cloth 3 times, obtains the carbon cloth of removal surface oxide layer；The carbon of surface oxide layer will be removed
Cloth is stored in dehydrated alcohol；
The mass fraction of concentrated nitric acid described in step 1 is 68%；
Two, solution is prepared:
1., cabaltous nitrate hexahydrate is dissolved into deionized water, obtain cobalt nitrate solution；
Step 2 1. described in cobalt nitrate solution concentration be 40mmol/L；
2., 1,2- methylimidazole is dissolved into deionized water, obtain 1,2- methylimidazole solution；
Step 2 2. described in DMIZ 1,2 dimethylimidazole solution concentration be 40mmol/L；
3., 1,2- methylimidazole solution is added in cobalt nitrate solution, obtain bluish violet suspension；
Step 2 3. described in DMIZ 1,2 dimethylimidazole solution and cobalt nitrate solution volume ratio be 1:1；
Three, it impregnates:
It is immersed in bluish violet suspension after the carbon cloth for the removal surface oxide layer being stored in dehydrated alcohol is taken out, then
4h is reacted at room temperature, then carbon cloth is taken out, and using distilled water flushing 4 times, dry 8h at being finally 60 DEG C in temperature is given birth to
Carbon cloth with cobalt-based metal organic frame nano-chip arrays；
Four, anion etches:
1., the potassium ferricyanide is dissolved into deionized water, obtain potassium ferricyanide solution；
Step 4 1. described in potassium ferricyanide solution concentration be 1.25g/L；
2., will growth there is the carbon cloth of cobalt-based metal organic frame nano-chip arrays to be immersed in potassium ferricyanide solution, then
Mixing speed is that magnetic agitation reacts 2h under 60r/min, then carbon cloth is taken out, and is rinsed 4 times using deionized water, then be in temperature
Dry 8h, obtains the carbon cloth for the cobalt-based metal organic frame nano-chip arrays that growth has iron to modify at 60 DEG C；
Five, it makes annealing treatment:
The cobalt-based metal for having the carbon cloth of cobalt-based metal organic frame nano-chip arrays and growth to have iron to modify growth is organic
The carbon cloth of frame nano-chip arrays is put into tube furnace, then tube furnace is warming up to 350 DEG C with the heating rate of 2 DEG C/min, then
It anneals 2h, then cooled to room temperature at being 350 DEG C in temperature, obtains cobaltosic oxide nano chip arrays electrode and iron modification
Cobaltosic oxide nano chip arrays electrode.
A length of 0.5cm × 0.5cm of the carbon cloth described in step 1 of embodiment one.
Embodiment two: a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification, is according to the following steps
It completes:
One, the processing of carbon cloth:
Concentrated nitric acid is added in the liner of hydrothermal reaction kettle, then carbon cloth is immersed in concentrated nitric acid, then by hydro-thermal reaction
It is 3h in 100 DEG C of baking oven that kettle, which is put into temperature, the carbon cloth that obtains that treated；Using dehydrated alcohol flushing, treated carbon cloth 3 times,
Reusing distilled water flushing, treated carbon cloth 3 times, obtains the carbon cloth of removal surface oxide layer；The carbon of surface oxide layer will be removed
Cloth is stored in dehydrated alcohol；
The mass fraction of concentrated nitric acid described in step 1 is 68%；
Two, solution is prepared:
1., cabaltous nitrate hexahydrate is dissolved into deionized water, obtain cobalt nitrate solution；
Step 2 1. described in cobalt nitrate solution concentration be 40mmol/L；
2., 1,2- methylimidazole is dissolved into deionized water, obtain 1,2- methylimidazole solution；
Step 2 2. described in DMIZ 1,2 dimethylimidazole solution concentration be 40mmol/L；
3., 1,2- methylimidazole solution is added in cobalt nitrate solution, obtain bluish violet suspension；
Step 2 3. described in DMIZ 1,2 dimethylimidazole solution and cobalt nitrate solution volume ratio be 1:1；
Three, it impregnates:
It is immersed in bluish violet suspension after the carbon cloth for the removal surface oxide layer being stored in dehydrated alcohol is taken out, then
4h is reacted at room temperature, then carbon cloth is taken out, and using distilled water flushing 4 times, dry 8h at being finally 60 DEG C in temperature is given birth to
Carbon cloth with cobalt-based metal organic frame nano-chip arrays；
Four, anion etches:
1., the potassium ferricyanide is dissolved into deionized water, obtain potassium ferricyanide solution；
Step 4 1. described in potassium ferricyanide solution concentration be 2.5g/L；
2., will growth there is the carbon cloth of cobalt-based metal organic frame nano-chip arrays to be immersed in potassium ferricyanide solution, then
Mixing speed is that magnetic agitation reacts 2h under 60r/min, then carbon cloth is taken out, and is rinsed 4 times using deionized water, then be in temperature
Dry 8h, obtains the carbon cloth for the cobalt-based metal organic frame nano-chip arrays that growth has iron to modify at 60 DEG C；
Five, it makes annealing treatment:
The cobalt-based metal for having the carbon cloth of cobalt-based metal organic frame nano-chip arrays and growth to have iron to modify growth is organic
The carbon cloth of frame nano-chip arrays is put into tube furnace, then tube furnace is warming up to 350 DEG C with the heating rate of 2 DEG C/min, then
It anneals 2h, then cooled to room temperature at being 350 DEG C in temperature, obtains cobaltosic oxide nano chip arrays electrode and iron modification
Cobaltosic oxide nano chip arrays electrode.
A length of 0.5cm × 0.5cm of the carbon cloth described in step 1 of embodiment two.
Embodiment three: a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification, is according to the following steps
It completes:
One, the processing of carbon cloth:
Concentrated nitric acid is added in the liner of hydrothermal reaction kettle, then carbon cloth is immersed in concentrated nitric acid, then by hydro-thermal reaction
It is 3h in 100 DEG C of baking oven that kettle, which is put into temperature, the carbon cloth that obtains that treated；Using dehydrated alcohol flushing, treated carbon cloth 3 times,
Reusing distilled water flushing, treated carbon cloth 3 times, obtains the carbon cloth of removal surface oxide layer；The carbon of surface oxide layer will be removed
Cloth is stored in dehydrated alcohol；
The mass fraction of concentrated nitric acid described in step 1 is 68%；
Two, solution is prepared:
1., cabaltous nitrate hexahydrate is dissolved into deionized water, obtain cobalt nitrate solution；
Step 2 1. described in cobalt nitrate solution concentration be 40mmol/L；
2., 1,2- methylimidazole is dissolved into deionized water, obtain 1,2- methylimidazole solution；
Step 2 2. described in DMIZ 1,2 dimethylimidazole solution concentration be 40mmol/L；
3., 1,2- methylimidazole solution is added in cobalt nitrate solution, obtain bluish violet suspension；
Step 2 3. described in DMIZ 1,2 dimethylimidazole solution and cobalt nitrate solution volume ratio be 1:1；
Three, it impregnates:
It is immersed in bluish violet suspension after the carbon cloth for the removal surface oxide layer being stored in dehydrated alcohol is taken out, then
4h is reacted at room temperature, then carbon cloth is taken out, and using distilled water flushing 4 times, dry 8h at being finally 60 DEG C in temperature is given birth to
Carbon cloth with cobalt-based metal organic frame nano-chip arrays；
Four, anion etches:
1., the potassium ferricyanide is dissolved into deionized water, obtain potassium ferricyanide solution；
Step 4 1. described in potassium ferricyanide solution concentration be 5g/L；
2., will growth there is the carbon cloth of cobalt-based metal organic frame nano-chip arrays to be immersed in potassium ferricyanide solution, then
Mixing speed is that magnetic agitation reacts 2h under 60r/min, then carbon cloth is taken out, and is rinsed 4 times using deionized water, then be in temperature
Dry 8h, obtains the carbon cloth for the cobalt-based metal organic frame nano-chip arrays that growth has iron to modify at 60 DEG C；
Five, it makes annealing treatment:
The cobalt-based metal for having the carbon cloth of cobalt-based metal organic frame nano-chip arrays and growth to have iron to modify growth is organic
The carbon cloth of frame nano-chip arrays is put into tube furnace, then tube furnace is warming up to 350 DEG C with the heating rate of 2 DEG C/min, then
It anneals 2h, then cooled to room temperature at being 350 DEG C in temperature, obtains cobaltosic oxide nano chip arrays electrode and iron modification
Cobaltosic oxide nano chip arrays electrode.
A length of 0.5cm × 0.5cm of the carbon cloth described in step 1 of embodiment three.
Fig. 1 is the SEM figure of the cobaltosic oxide nano chip arrays electrode of iron modification prepared by embodiment two；
From fig. 1, it can be seen that the microstructure of the cobaltosic oxide nano chip arrays electrode of iron modification prepared by embodiment two is
The uniformly nano-chip arrays of rule.
X-ray photoelectron spectroscopy is shown two in the cobaltosic oxide nano chip arrays electrode of iron modification prepared by embodiment two
Valence cobalt, trivalent cobalt and ferric iron coexist.
The carbon cloth for the cobalt-based metal organic frame nano-chip arrays that fewrricyanic acid ion concentration has iron to modify growth
The test that catalytic performance influences:
In a standard three electrode electrolytic cell, as reference electrode, coated graphite rod electrrode is used as to electrode mercuric oxide electrode,
For the cobaltosic oxide nano chip arrays electrode of iron modification prepared by embodiment one as working electrode, electrolyte is concentration
Three electrodes are connected by the potassium hydroxide solution of 1.0mol/L respectively at electrochemical workstation, electrochemical data are tested, as 1 in Fig. 2
It is shown；
In a standard three electrode electrolytic cell, as reference electrode, coated graphite rod electrrode is used as to electrode mercuric oxide electrode,
For the cobaltosic oxide nano chip arrays electrode of iron modification prepared by embodiment two as working electrode, electrolyte is concentration
Three electrodes are connected by the potassium hydroxide solution of 1.0mol/L respectively at electrochemical workstation, electrochemical data are tested, as 2 in Fig. 2
It is shown；
In a standard three electrode electrolytic cell, as reference electrode, coated graphite rod electrrode is used as to electrode mercuric oxide electrode,
For the cobaltosic oxide nano chip arrays electrode of iron modification prepared by embodiment three as working electrode, electrolyte is concentration
Three electrodes are connected by the potassium hydroxide solution of 1.0mol/L respectively at electrochemical workstation, electrochemical data are tested, as 3 in Fig. 2
It is shown；
Fig. 2 is the cobaltosic oxide nano chip arrays electrode of the iron modification prepared under different fewrricyanic acid ion concentrations
Linear sweep voltammetry figure, 1 is four oxidations three of the iron modification prepared under 1.25g/L potassium ferricyanide solution in embodiment one in figure
The linear sweep voltammetry curve of cobalt nano-chip arrays electrode, 2 be to prepare under 2.5g/L potassium ferricyanide solution in embodiment two
The linear sweep voltammetry curve of the cobaltosic oxide nano chip arrays electrode of iron modification, 3 be in embodiment three in 5g/L iron cyaniding
The linear sweep voltammetry curve of the cobaltosic oxide nano chip arrays electrode of the iron modification prepared under potassium solution；
As can be seen from Figure 2, the concentration of potassium ferricyanide solution is different, carves to cobalt-based metal organic frame nano-chip arrays
Erosion, the catalytic performance of final product is essentially the same, illustrates the cobalt-based metal that fewrricyanic acid ion concentration has iron to modify growth
The catalytic performance of the carbon cloth of organic frame nano-chip arrays influences little.
The test of electrolysis water oxygen evolution reaction:
In a standard three electrode electrolytic cell, as reference electrode, coated graphite rod electrrode is used as to electrode mercuric oxide electrode,
The carbon cloth of surface oxide layer is removed obtained in two step 1 of embodiment as working electrode, electrolyte is concentration 1.0mol/L's
Potassium hydroxide solution；Three electrodes are connected with electrochemical workstation respectively, electrochemical measurement is carried out using linear voltammetry, such as schemes
In 3 shown in 1；
In a standard three electrode electrolytic cell, as reference electrode, coated graphite rod electrrode is used as to electrode mercuric oxide electrode,
For the cobaltosic oxide nano chip arrays electrode that one step 5 of embodiment obtains as working electrode, electrolyte is concentration 1.0mol/L
Potassium hydroxide solution；Three electrodes are connected with electrochemical workstation respectively, carry out electrochemical measurement using linear voltammetry, such as
In Fig. 3 shown in 2；
In a standard three electrode electrolytic cell, as reference electrode, coated graphite rod electrrode is used as to electrode mercuric oxide electrode,
For the cobaltosic oxide nano chip arrays electrode for the iron modification that two step 5 of embodiment obtains as working electrode, electrolyte is concentration
The potassium hydroxide solution of 1.0mol/L；Three electrodes are connected with electrochemical workstation respectively, carry out electrification using linear voltammetry
Measurement is learned, as shown in 3 in Fig. 3；
Fig. 3 is linear sweep voltammetry figure, 1 carbon cloth to remove surface oxide layer obtained in two step 1 of embodiment in figure
Linear sweep voltammetry curve, the linear scan of the 2 cobaltosic oxide nano chip arrays electrodes obtained for one step 5 of embodiment
Volt-ampere curve, 3 be the linear scan volt of the cobaltosic oxide nano chip arrays electrode for the iron modification that two step 5 of embodiment obtains
Pacify curve；
As can be seen from Figure 3, the analysis oxygen catalytic activity of the cobaltosic oxide nano chip arrays electrode of iron modification is compared to four oxidations
Three cobalt nano-chip arrays electrodes and the carbon cloth by removing surface oxide layer (remove Surface Oxygen obtained in two step 1 of embodiment
Change the carbon cloth of layer) it is significantly improved, current density reaches 10mA/cm2When, the cobaltosic oxide nano chip arrays of iron modification
The overpotential of electrode is 290mV, and the overpotential of cobaltosic oxide nano chip arrays electrode is 360mV, and the overpotential of carbon cloth is
435mV.It is 20mA/cm when current density reaches2When, the overpotential of the cobaltosic oxide nano chip arrays electrode of iron modification is
310mV。
In a standard three electrode electrolytic cell, as reference electrode, coated graphite rod electrrode is used as to electrode mercuric oxide electrode,
For the cobaltosic oxide nano chip arrays electrode for the iron modification that two step 5 of embodiment obtains as working electrode, electrolyte is concentration
The potassium hydroxide solution of 1.0mol/L；Three electrodes are connected with electrochemical workstation respectively, carry out electrification using chronoamperometry
Learn measurement, current density 10mA/cm2, as shown in 1 in Fig. 4；
In a standard three electrode electrolytic cell, as reference electrode, coated graphite rod electrrode is used as to electrode mercuric oxide electrode,
For the cobaltosic oxide nano chip arrays electrode for the iron modification that two step 5 of embodiment obtains as working electrode, electrolyte is concentration
The potassium hydroxide solution of 1.0mol/L；Three electrodes are connected with electrochemical workstation respectively, carry out electrification using chronoamperometry
Learn measurement, current density 20mA/cm2, as shown in 2 in Fig. 4；
The voltage of the cobaltosic oxide nano chip arrays electrode for the iron modification that Fig. 4 obtains for two step 5 of embodiment is at any time
Change curve, the current density of curve 1 is 10mA/cm in figure2, the current density of curve 2 is 20mA/cm2。
As can be seen from Figure 4, when current density is 10mA/cm2When, overpotential only increases 5mV in 25 hours.Work as electric current
Density is 20mA/cm2When, overpotential increases 17mV within about 14 hours.Illustrate the iron that two step 5 of embodiment obtains
The cobaltosic oxide nano chip arrays electrode of modification is with good stability in catalysis oxygen evolution reaction.
Claims (10)
1. a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification, it is characterised in that the four of a kind of iron modification
The preparation method of Co 3 O nano-chip arrays electrode is completed by the following steps:
One, the processing of carbon cloth:
Concentrated nitric acid is added in the liner of hydrothermal reaction kettle, then carbon cloth is immersed in concentrated nitric acid, then hydrothermal reaction kettle is put
Entering temperature is 2h~4h in 95 DEG C~105 DEG C of baking oven, the carbon cloth that obtains that treated；Treated carbon is rinsed using dehydrated alcohol
Cloth 2 times~4 times, reusing distilled water flushing, treated carbon cloth 2 times~4 times, obtains the carbon cloth of removal surface oxide layer；It will go
Except the carbon cloth of surface oxide layer is stored in dehydrated alcohol；
Two, solution is prepared:
1., cabaltous nitrate hexahydrate is dissolved into deionized water, obtain cobalt nitrate solution；
Step 2 1. described in cobalt nitrate solution concentration be 30mmol/L~50mmol/L；
2., 1,2- methylimidazole is dissolved into deionized water, obtain 1,2- methylimidazole solution；
Step 2 2. described in DMIZ 1,2 dimethylimidazole solution concentration be 30mmol/L~50mmol/L；
3., 1,2- methylimidazole solution is added in cobalt nitrate solution, obtain bluish violet suspension；
Step 2 3. described in DMIZ 1,2 dimethylimidazole solution and cobalt nitrate solution volume ratio be 1:1；
Three, it impregnates:
It is immersed in bluish violet suspension after the carbon cloth for the removal surface oxide layer being stored in dehydrated alcohol is taken out, then in room
Temperature is lower to react 3h~5h, then carbon cloth is taken out, and using distilled water flushing 3 times~5 times, does at being finally 50 DEG C~70 DEG C in temperature
Dry 8h~10h obtains the carbon cloth that growth has cobalt-based metal organic frame nano-chip arrays；
Four, anion etches:
1., the potassium ferricyanide is dissolved into deionized water, obtain potassium ferricyanide solution；
Step 4 1. described in potassium ferricyanide solution concentration be 1g/L~5g/L；
2., there is the carbon cloth of cobalt-based metal organic frame nano-chip arrays to be immersed in potassium ferricyanide solution the growth, then stirring
Speed is that magnetic agitation reacts 1h~3h under 50r/min~70r/min, then carbon cloth is taken out, using deionized water rinse 3 times~
5 times, then 8h~10h is dried at being 50 DEG C~70 DEG C in temperature, obtain the cobalt-based metal organic frame nanometer that growth has iron to modify
The carbon cloth of chip arrays；
Five, it makes annealing treatment:
The carbon cloth of cobalt-based metal organic frame nano-chip arrays that growth has iron to modify is put into tube furnace, then by tube furnace with
The heating rate of 1.5 DEG C/min~2.5 DEG C/min is warming up to 300 DEG C~400 DEG C, then anneals at being 300 DEG C~400 DEG C in temperature
1.5h~2.5h, then cooled to room temperature obtain the cobaltosic oxide nano chip arrays electrode of iron modification.
2. a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification according to claim 1, special
Sign is that the mass fraction of concentrated nitric acid described in step 1 is 67%~69%.
3. a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification according to claim 1, special
The concentration for levying the cobalt nitrate solution described in being step 2 1. is 35mmol/L~40mmol/L.
4. a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification according to claim 1, special
The concentration for levying the DMIZ 1,2 dimethylimidazole solution described in being step 2 2. is 35mmol/L~40mmol/L.
5. a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification according to claim 1, special
The concentration for levying the potassium ferricyanide solution described in being step 4 1. is 2g/L~2.5g/L.
6. a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification according to claim 1, special
Sign is that concentrated nitric acid is added in the liner of hydrothermal reaction kettle in step 1, then carbon cloth is immersed in concentrated nitric acid, then by water
It is 2h~3h in 95 DEG C~100 DEG C of baking oven that thermal response kettle, which is put into temperature, the carbon cloth that obtains that treated；It is rinsed using dehydrated alcohol
Treated carbon cloth 2 times~3 times, and reusing distilled water flushing, treated carbon cloth 2 times~3 times, obtains removal surface oxide layer
Carbon cloth；The carbon cloth for removing surface oxide layer is stored in dehydrated alcohol.
7. a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification according to claim 1, special
Sign is in step 3 that bluish violet will be immersed in after the carbon cloth taking-up for the removal surface oxide layer being stored in dehydrated alcohol suspended
In liquid, then 3h~4h is reacted at room temperature, then carbon cloth is taken out, be finally 50 in temperature using distilled water flushing 3 times~4 times
DEG C~60 DEG C at dry 8h~9h, obtain the carbon cloth that growth has cobalt-based metal organic frame nano-chip arrays.
8. a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification according to claim 1, special
Levying in being step 4 2. has the carbon cloth of cobalt-based metal organic frame nano-chip arrays to be immersed in potassium ferricyanide solution growth,
Low whipping speed is that magnetic agitation reacts 1h~2h under 50r/min~70r/min, then carbon cloth is taken out again, uses deionized water
It rinses 3 times~4 times, then dry 8h~9h at being 50 DEG C~60 DEG C in temperature, it is organic to obtain the cobalt-based metal that growth has iron to modify
The carbon cloth of frame nano-chip arrays.
9. a kind of preparation method of the cobaltosic oxide nano chip arrays electrode of iron modification according to claim 1, special
Sign is that the carbon cloth for the cobalt-based metal organic frame nano-chip arrays that growth has iron to modify is put into tube furnace in step 5, then
Tube furnace is warming up to 300 DEG C~350 DEG C with 1.5 DEG C/min~2 DEG C/min heating rate, then in temperature is 300 DEG C~350
Anneal 1.5h~2h at DEG C, then cooled to room temperature, obtains the cobaltosic oxide nano chip arrays electrode of iron modification.
10. a kind of application of the cobaltosic oxide nano chip arrays electrode of iron modification as described in claim 1, it is characterised in that
A kind of electrolysis water oxygen evolution reaction that the cobaltosic oxide nano chip arrays electrode of iron modification is used to be catalyzed in alkaline environment.
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