CN106732649A - A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst - Google Patents
A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000001301 oxygen Substances 0.000 title claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 5
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000003708 ampul Substances 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 238000010586 diagram Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- B01J35/30—
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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 method of alkaline oxygen evolution reaction elctro-catalyst, first conductive substrates are cleaned by ultrasonic, the aqueous solution with soluble cobalt, soluble manganese salt, ammonium fluoride and urea is prepared again, in reactor, vertical-growth manganese cobalt subcarbonate nano-array multilevel hierarchy on the surface of the substrate；The aqueous solution with water soluble alkali, reducing agent is reconfigured at, after-treatment is carried out, structure and performance optimization are carried out to manganese cobalt subcarbonate multi-stage nano array；It is last, under nitrogen or argon gas atmosphere, to be calcined at a temperature of 200~1000 DEG C in tube furnace, the alkaline oxygen evolution reaction elctro-catalyst of the cobalt oxide nano-array multilevel hierarchy for mixing manganese is obtained.Present invention employs the method for simple Hydrothermal Synthesiss/calcination processing, process is simple, it is easy to regulate and control, resulting product excellent performance is a kind of elctro-catalyst with fine prospect in the application process of alkaline decomposition water.
Description
Technical field
The present invention be on elctro-catalyst, it is more particularly to a kind of transient metal doped with nano-array multilevel hierarchy
Alkaline oxygen evolution reaction elctro-catalyst preparation method.
Background technology
New energy simultaneously has no lack of, but really to realize the output of new energy, also there are many problems.Come from water decomposition
Hydrogen Energy has good development prospect, but it is critical only that the dynamic process of the oxygen evolution reaction (OER) of water splitting processes is slow, sternly
The whole efficiency for producing hydrogen process is hindered again, therefore, develop an urgent demand that efficient oxygen evolution reaction catalysts are human survivals.
There are a large amount of researchs on OER catalyst before this, mostly concentrated on metal-air battery, fuel cell etc., or even conduct
Bifunctional catalyst is applied in lithium battery and above-mentioned energy storage and production capacity device, and wherein cobalt and manganese oxide material is also studied for
Photochemical catalyzing field.The state of research object is also of all kinds, there is powder, nano particle, nanocrystal, nanoporous
Structure etc., is to prepare the novel material of high surface area, structure to expose more avtive spots, finding new reaction machine mostly
System is with more preferable guiding experiment.The noble metal based compound such as ruthenium, iridium is current most efficient oxygen-separating catalyst, yet with too high
Cost and scarcity of resources, limit their application and popularization.Another point need to arouse attention, the battery of business electrolysis water
Current potential (1.8-2.0V) is higher by 570-770mV than minimum overpotential (1.23V) in theory, and catalyst stability is poor.Cause
This, exploitation stability and high efficiency, aboundresources and cheap oxygen-separating catalyst are particularly important.
The content of the invention
The purpose of the present invention, primarily to solving existing oxygen evolution reaction catalysts during water is catalytically decomposed, is present
Catalysis overpotential it is higher, the problems such as stability difference, there is provided a kind of transient metal doped with nano-array multilevel hierarchy
Alkaline oxygen evolution reaction elctro-catalyst, significantly reduces the overpotential of oxygen evolution reaction and plays spike potential, and improve catalytic reaction
Stability, for decompose aqueous systems oxygen-separating catalyst functional direction design with performance optimization provide new thinking and plan
Slightly.
The present invention is achieved by following technical solution.
A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst, comprises the following steps that：
(1) conductive substrates are cleaned by ultrasonic 5~20 minutes in the hydrochloric acid of 1~5 mol/L, are then transferred to acetone molten
It is cleaned by ultrasonic 5~20 minutes in liquid, transfers in ethanol solution and be cleaned by ultrasonic 5~20 minutes, it is finally abundant with deionized water
Conductive substrates are rinsed, then is put into 50~80 DEG C of baking oven and is dried；
(2) prepare precursor solution, the precursor solution comprising concentration for 0.01-0.04 mol/Ls soluble cobalt,
Concentration is the soluble manganese salt of 0.001-0.04 mol/Ls, concentration for the ammonium fluoride and concentration of 0.01-1 mol/Ls are 0.01-1
The total ion concentration of the aqueous solution of the urea of mol/L, manganese ion and cobalt ions maintains 0.047 mol/L；
Above-mentioned precursor solution magnetic agitation is transferred in reactor after 5~40 minutes, then by after step (1) treatment
Conductive substrates are inclined and are put into reactor, are then covered reactor and are tightened, and are placed in drying box and are warming up to 80 DEG C~200 DEG C,
Set of time is 5~20 hours, brings it about hydro-thermal reaction, and whole course of reaction causes that vertical-growth goes out on conductive substrates surface
Manganese cobalt subcarbonate nano-array；
(3) conductive substrates after hydro-thermal reaction in step (2) terminates are taken out, by sufficient deionized water rinsing it
Afterwards, it is placed in 30~80 DEG C of drying box and is dried, drying time is 60~180 minutes；
(4) configuration has water soluble alkali, concentration of the concentration for 0-5 mol/Ls for the reducing agent of 0-5 mol/Ls is water-soluble
Liquid, and water soluble alkali is not simultaneously 0, magnetic agitation 5~30 minutes with the concentration of reducing agent；
And magnetic agitation 5~30 minutes；
The conductive substrates that step (3) is obtained incline the small burning for being put into and filling above-mentioned water soluble alkali, reducing agent aqueous solution
In cup, and 0.1-10 hours in solution is not stood under normal temperature, bring it about reaction so that above-mentioned manganese cobalt basic carbonate
There is alkaline etching and reduction reaction on salt nano-array surface, so as to change product structure and increase its Lacking oxygen, formative
The excellent manganese cobalt subcarbonate nano-array multilevel hierarchy of energy；
(5) conductive substrates after the middle immersion of step (4) are taken out again and a large amount of deionized water rinsings are used, after fully rinsing
It is placed in 30~80 DEG C of vacuum drying chamber and dries 60~180 minutes；
(6) step (5) dried conductive substrates are horizontally placed on magnetic boat, then this magnetic boat is placed in the quartz ampoule of tube furnace
Center section, calcines 0.5~10 hour in atmosphere stable in properties, at a temperature of 100~1000 DEG C, is cooled to room
Temperature, manganese cobalt subcarbonate nano-array multilevel hierarchy is changed into the alkalescence analysis of the cobalt/cobalt oxide nano-array multilevel hierarchy for mixing manganese
Oxygen reacts elctro-catalyst.
The conductive substrates of the step (1) are any one of nickel foam or carbon cloth.
The soluble cobalt and manganese salt of the step (2) are any one of nitrate, sulfate or acetate.
The water soluble alkali of the step (4) is the highly basic of alkali metal containing, and reducing agent is sodium borohydride.
The atmosphere stable in properties of the step (6) is nitrogen or argon gas atmosphere.
Beneficial effects of the present invention are as follows：
The preparation method is made up of simple hydro-thermal reaction and low temperature calcination treatment, and step is simple, the reaction time is short, operation
Convenient, repeatability extremely friendly to environment is strong；Material of the invention is fabulous elctro-catalyst in alkaline oxygen evolution reaction,
When current density is 10mA/cm2When, reaction overpotential is 0.31V, considerably beyond the 0.44V of business Ir/C catalyst, and stabilization
Property is fabulous.By will introduce other transition metals in material, doping effect brings a series of benefits to the present invention, not only favorably
In OH-Absorption, and the potential barrier of oxygen evolution reaction can be reduced, and super thin vapor interface is formed between solid-liquid two-phase so that
Oxygen is easily desorbed, so as to promote the generation of oxygen evolution reaction.In addition, nano-array multilevel hierarchy significantly increases electrode activity material
The specific surface area of material, can provide more avtive spots for reaction, and the collaboration of this series of factors enhances the material in alkalescence
Electro-catalysis ability in oxygen evolution reaction.
Brief description of the drawings
Fig. 1 is the CONSTRUCTED SPECIFICATION figure (SEM) of the material shown in comparative example；
Fig. 2 a are the scanning electron microscope (SEM) photographs (SEM) of the low power of the material shown in comparative example；Fig. 2 b, c are comparative examples 2
Shown in material high power scanning electron microscope (SEM) photograph (SEM)；Fig. 2 d are the Energy disperaive quantitative analysis of the material shown in comparative example 2
Figure (EDS)；
Fig. 3 is the low power scanning electron microscope (SEM) photograph (SEM) of the material shown in embodiment 1；
Fig. 4 is times scanning electron microscope (SEM) photograph (SEM) in material shown in embodiment 1；
Fig. 5 is the high power scanning electron microscope (SEM) photograph (SEM) of the material shown in embodiment 1
Fig. 6 is the Energy disperaive quantitative analysis figure (EDS) of the material shown in embodiment 1；
Fig. 7 is the x-ray photoelectron energy spectrum diagram (XPS) of the cobalt element of the material shown in embodiment 1；
Fig. 8 is the x-ray photoelectron energy spectrum diagram (XPS) of the manganese element of the material shown in embodiment 1；
Fig. 9 is the x-ray photoelectron energy spectrum diagram (XPS) of the oxygen element of the material shown in embodiment 1；
Figure 10 is that the material and embodiment 4 shown in embodiment 1, the material shown in embodiment 5 are analysed in the basic conditions
Polarization curve (LSV) comparison diagram of oxygen reaction, reference electrode is saturated calomel electrode；
Figure 11 is the material and embodiment 2 shown in embodiment 1, the material shown in embodiment 3, comparative example in alkali
Polarization curve (LSV) comparison diagram of oxygen evolution reaction under the conditions of property, reference electrode is saturated calomel electrode；
Figure 12 is the constant-pressure stable test chart that material shown in embodiment 1 carries out oxygen evolution reaction in the basic conditions.
Specific embodiment
Below by specific embodiment, the invention will be further described, what embodiment was merely exemplary, and unrestricted
Property.
Embodiment 1
Conductive substrates are nickel foam, and cobalt source is cobalt nitrate, and reducing agent is sodium borohydride.
(1) it is cleaned by ultrasonic nickel foam as conductive substrates 10 minutes in the hydrochloric acid of 5 mol/Ls, is then transferred to third
It is cleaned by ultrasonic 10 minutes in ketone solution, transfers in ethanol solution and be cleaned by ultrasonic 10 minutes, is finally fully rushed with deionized water
Conductive substrates are washed, is then put into 60 DEG C of baking oven and is dried.
(2) preparation precursor solution, the cobalt nitrate comprising 0.03516 mol/L, the manganese nitrate of 0.01172 mol/L,
The ammonium fluoride of 0.2 mol/L, the urea of 0.25 mol/L.The solution magnetic agitation is transferred in reactor after 10 minutes,
The nickel foam after step (1) treatment is inclined again is put into reactor, then reactor covered and is tightened, be placed in drying box and rise
To 100 DEG C, set of time is 10 hours to temperature, brings it about hydro-thermal reaction, and whole course of reaction causes to be hung down on conductive substrates surface
Growing straight grows manganese cobalt subcarbonate nano-array；
(3) conductive substrates after hydro-thermal reaction in step (2) terminates are taken out, by sufficient deionized water rinsing it
Afterwards, it is placed in 60 DEG C of drying box and dries 180 minutes；
(4) sodium borohydride solution of NaOH of the configuration containing 3 mol/Ls and 1 mol/L, in 10 points of magnetic agitation
After clock, nickel foam that step (3) is obtained is tilting to be put into the small beaker for filling configuration solution and will not in solution, normal temperature
It is lower to stand 1 hour, bring it about reaction so that alkaline etching occurs on above-mentioned manganese cobalt subcarbonate nano-array surface and goes back
Original reaction, so as to change product structure and increase its Lacking oxygen, the excellent manganese cobalt subcarbonate nano-array of forming properties is more
Level structure；
(5) nickel foam after the middle immersion of step (4) is taken out again and uses a large amount of deionized water rinsings, will after fully rinsing
It is placed in 60 DEG C of vacuum drying chamber and dries 180 minutes；
(6) being placed in the nickel foam obtained in step (5) carries out low-temperature treatment in tube furnace.It is horizontally placed on magnetic boat,
This magnetic boat is placed in quartz ampoule center section again, is calcined 3 hours in argon gas, at a temperature of 250 DEG C, be cooled to room temperature,
Manganese cobalt subcarbonate nano-array multilevel hierarchy is changed into the alkalescence analysis oxygen of the cobalt/cobalt oxide nano-array multilevel hierarchy for mixing manganese
Reaction elctro-catalyst, is named as NaOH＆NaBH4@MnxCo3-xO4-1:3。
Using three-electrode system, the performance to the material in the electrolyte of the potassium hydroxide solution of 0.1 mol/L is entered
Row analysis oxygen performance test.Wherein, to electrode it is platinized platinum, reference electrode is saturated calomel electrode, and sweep speed is 5mV/s.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the low power of the material shown in embodiment 1, it can be seen that NaOH＆NaBH4@
MnxCo3-xO4-1:3 are uniformly adhered to substrate surface；
Fig. 4 is times scanning electron microscope (SEM) photograph (SEM) in material shown in embodiment 1, it can be seen that the material is long on piece
The nano-array multilevel hierarchy of line.
Fig. 5 is the high power scanning electron microscope (SEM) photograph (SEM) of the material shown in embodiment 1, can be seen compared with comparative example
Go out, by after alkali and sodium borohydride treatment, it is coarse that the nanowire surface of array multilevel hierarchy becomes；
Fig. 6 is the Energy disperaive quantitative analysis figure (EDS) of the material shown in embodiment 1, and power spectrum shows the peak of manganese, cobalt, oxygen,
Can be concluded that synthesized material is NaOH＆NaBH4@MnxCo3-xO4-1:3, and ratio approximate 1：2：4, the energy with comparative example
Spectrum is consistent substantially；
Fig. 7 is the x-ray photoelectron energy spectrum diagram (XPS) of the cobalt element of the material shown in embodiment 1, it is known that the valence state of cobalt
Have+3 and+2；
Fig. 8 is the x-ray photoelectron energy spectrum diagram (XPS) of the manganese element of the material shown in embodiment 1, it is known that manganese valence
Have+3 and+2；
Fig. 9 is the x-ray photoelectron energy spectrum diagram (XPS) of the oxygen element of the material shown in embodiment 1, it is known that embodiment 1
Shown in material contain oxygen element；
Figure 10 is that the material and embodiment 4 shown in embodiment 1, the material shown in embodiment 5 are analysed in the basic conditions
Oxygen reaction polarization curve (LSV) comparison diagram, by performance comparison it can be seen that in embodiment step (4) NaOH and boron hydrogen
The consumption for changing sodium can be such that the analysis oxygen performance of the material reaches most preferably, and reference electrode is saturated calomel electrode；
Figure 11 is the material and embodiment 2 shown in embodiment 1, the material shown in embodiment 3, comparative example in alkali
Polarization curve (LSV) comparison diagram of oxygen evolution reaction under the conditions of property, reference electrode is saturated calomel electrode, institute in embodiment 1,2,3
The analysis oxygen performance of the material for showing is superior to material and business Ir/C catalyst shown in comparative example, and in embodiment 1
Shown material is NaOH＆NaBH4@MnxCo3-xO4-1:3 performance is the most excellent, is much better than business Ir/C, and it is drawn through conversion
The overpotential of oxygen evolution reaction process, contrast situation refers to table 1.
Table 1
Figure 12 is the constant-pressure stable test chart that material shown in embodiment 1 carries out oxygen evolution reaction in the basic conditions,
Understand under the voltage of 0.66V (relative to saturation calomel), tested by the constant pressures of 15 hours, the electric current that the material is produced keeps
In 92.2% higher level.
Embodiment 2
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：Hydroxide in step (4)
Sodium is different with the consumption of sodium borohydride, respectively 3M and 0M, is NaOH@Mn by the material designationxCo3-xO4-1:3.The energy of embodiment 2
Enough reach goal of the invention.
Embodiment 3
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：Hydroxide in step (4)
Sodium is different with the consumption of sodium borohydride, and the material designation is NaBH by respectively 0M and 1M4@MnxCo3-xO4-1:3.The energy of embodiment 3
Enough reach goal of the invention.
Embodiment 4
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：Hydroxide in step (4)
Sodium is different with the consumption of sodium borohydride, respectively 1M and 1M.Embodiment 4 can reach goal of the invention.
Embodiment 5
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：Hydroxide in step (4)
Sodium is different with the consumption of sodium borohydride, respectively 5M and 1M.Embodiment 5 can reach goal of the invention.
Embodiment 6
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By leading in step (1)
Electric substrate is changed to carbon cloth, and acquired results equally can reach invention effect.Embodiment 6 can reach goal of the invention.
Embodiment 7
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By argon gas in step (6)
Atmosphere is changed to nitrogen atmosphere, and acquired results equally can reach invention effect.Embodiment 7 can reach goal of the invention.
Comparative example
The comparative example is prior art, and preparation method is with the difference of embodiment 1：By step (3) water
Step (6) low-temperature treatment is directly carried out after thermally grown, lacks step of the invention (4) and (5), according to manganese cobalt charge ratio 1:3,
It is Mn by the material designationxCo3-xO4-1:3。
Fig. 1 is the CONSTRUCTED SPECIFICATION figure (SEM) of the material shown in comparative example, it can be clearly seen that the material is on piece
The nanometer hierarchical structure of line long.
Fig. 2 a are the scanning electron microscope (SEM) photographs (SEM) of the low power of the material shown in comparative example, it can be seen that generation material is equal
Even is attached to substrate surface；Fig. 2 b, c are the high power scanning electron microscope (SEM) photographs (SEM) of the material shown in comparative example 2, are schemed by b
With c figures it can be seen that the material that base surface is uniformly adhered to is the nano-array multilevel hierarchy of line long on piece, and nano wire
Surface smoother；Fig. 2 d are the Energy disperaive quantitative analysis figures (EDS) of the material shown in comparative example 2, wherein containing manganese,
Cobalt, oxygen element, and its ratio approximate 1：2：4, it is known that generation material is MnxCo3-xO4-1:3.Its performance far away from embodiment 1,
Reference can be made to shown in Fig. 8 and Biao 1.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (5)
1. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst, comprises the following steps that：
(1) conductive substrates are cleaned by ultrasonic 5~20 minutes in the hydrochloric acid of 1~5 mol/L, are then transferred in acetone soln
It is cleaned by ultrasonic 5~20 minutes, transfers in ethanol solution and be cleaned by ultrasonic 5~20 minutes, is finally fully rinsed with deionized water
Conductive substrates, then be put into 50~80 DEG C of baking oven and be dried；
(2) precursor solution is prepared, the precursor solution is soluble cobalt, the concentration of 0.01-0.04 mol/Ls comprising concentration
For the soluble manganese salt of 0.001-0.04 mol/Ls, concentration for the ammonium fluoride and concentration of 0.01-1 mol/Ls rub for 0.01-1
You/liter urea the aqueous solution, the total ion concentration of manganese ion and cobalt ions maintains 0.047 mol/L；
Above-mentioned precursor solution magnetic agitation is transferred in reactor after 5~40 minutes, then by the conduction after step (1) treatment
Substrate tilt is put into reactor, is then covered reactor and is tightened, be placed in drying box be warming up to 80 DEG C~200 DEG C, time
It is set to 5~20 hours, brings it about hydro-thermal reaction, whole course of reaction causes that vertical-growth goes out manganese cobalt on conductive substrates surface
Subcarbonate nano-array；
(3) conductive substrates after hydro-thermal reaction terminates in taking-up step (2), after by sufficient deionized water rinsing, will
It is placed in 30~80 DEG C of drying box and is dried, and drying time is 60~180 minutes；
(4) configuration is the aqueous solution of the reducing agent of 0-5 mol/Ls with the water soluble alkali, concentration that concentration is 0-5 mol/Ls, and
Water soluble alkali is not simultaneously 0, magnetic agitation 5~30 minutes with the concentration of reducing agent；
The conductive substrates that step (3) is obtained are inclined and are put into the small beaker for filling above-mentioned water soluble alkali, reducing agent aqueous solution,
And not in solution, 0.1-10 hours is stood under normal temperature, bring it about reaction so that above-mentioned manganese cobalt subcarbonate nanometer
There is alkaline etching and reduction reaction in array surface, so as to change product structure and increase its Lacking oxygen, forming properties are excellent
Manganese cobalt subcarbonate nano-array multilevel hierarchy；
(5) conductive substrates after the middle immersion of step (4) are taken out again and a large amount of deionized water rinsings are used, by it after fully rinsing
It is placed in 30~80 DEG C of vacuum drying chamber and dries 60~180 minutes；
(6) step (5) dried conductive substrates are horizontally placed on magnetic boat, then this magnetic boat is placed in the middle of the quartz ampoule of tube furnace
Part, calcines 0.5~10 hour in atmosphere stable in properties, at a temperature of 100~1000 DEG C, is cooled to room temperature, manganese
The alkalescence analysis oxygen that cobalt subcarbonate nano-array multilevel hierarchy is changed into the cobalt/cobalt oxide nano-array multilevel hierarchy for mixing manganese is anti-
Answer elctro-catalyst.
2. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst according to claim 1, it is characterised in that the step
Suddenly the conductive substrates of (1) are any one of nickel foam or carbon cloth.
3. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst according to claim 1, it is characterised in that the step
Suddenly the soluble cobalt and manganese salt of (2) are any one of nitrate, sulfate or acetate.
4. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst according to claim 1, it is characterised in that the step
Suddenly the water soluble alkali of (4) is the highly basic of alkali metal containing, and reducing agent is sodium borohydride.
5. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst according to claim 1, it is characterised in that the step
Suddenly the atmosphere stable in properties of (6) is nitrogen or argon gas atmosphere.
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