CN109012683A - A kind of preparation method of cobalt molybdate tiny balloon elctro-catalyst - Google Patents
A kind of preparation method of cobalt molybdate tiny balloon elctro-catalyst Download PDFInfo
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- CN109012683A CN109012683A CN201810902066.8A CN201810902066A CN109012683A CN 109012683 A CN109012683 A CN 109012683A CN 201810902066 A CN201810902066 A CN 201810902066A CN 109012683 A CN109012683 A CN 109012683A
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- tiny balloon
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- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract 2
- 238000005245 sintering Methods 0.000 claims description 16
- 239000011684 sodium molybdate Substances 0.000 claims description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims 3
- 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 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- -1 molybdenum ion Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HNIASRFAODUYDL-UHFFFAOYSA-N acetyl acetate;sodium Chemical compound [Na].CC(=O)OC(C)=O HNIASRFAODUYDL-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910018864 CoMoO4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004616 Na2MoO4.2H2 O Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 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
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- FDEIWTXVNPKYDL-UHFFFAOYSA-N sodium molybdate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][Mo]([O-])(=O)=O FDEIWTXVNPKYDL-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
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- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- 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
It the invention discloses a kind of preparation method of cobalt molybdate tiny balloon elctro-catalyst, the steps include: to weigh cobalt nitrate, sodium molybdate, anhydrous sodium acetate respectively, deionized water be added, stirring is to being completely dissolved, gained mixed solution is subjected to hydro-thermal reaction, to after completion of the reaction, drying sample after cleaning；Sample after drying is carried out to high-temperature heat treatment in air atmosphere to get cobalt molybdate tiny balloon sample is arrived.This method improves electrolysis water separative efficiency, and reduces the use cost of elctro-catalyst.
Description
Technical field
The invention belongs to nano material synthesis technical fields, and in particular to a kind of low cost prepares cobalt molybdate tiny balloon
Method.
Background technique
In view of being on the rise for energy crisis and problem of environmental pollution, the clean energy resource of Sustainable Development is to compel to be essential
It wants.The exploitation of green energy resource hydrogen is conducive to alleviate current energy environment crisis, and elctro-catalyst water-splitting hydrogen production gas is recognized
For one of the effective way for being generation hydrogen.Main producing method of the electrolysis water as hydrogen energy source, generally includes two half-reactions,
It is to produce hydrogen and produce oxygen process, and the dynamics that the bottleneck of electrolysis water essentially consists in Oxygen anodic evolution reaction (OER) is slow, causes respectively
The transformation efficiency of water electrolysis hydrogen production is lower, and seeking high catalytic activity and the stable oxygen evolution reaction elctro-catalyst of performance becomes electrolysis water
The key of improved efficiency.The highest analysis oxygen elctro-catalyst of activity is metal oxide containing precious metals (such as IrO at present2And RuO2), but it is expensive
Metal material scarcity of resources, selling at exorbitant prices are unfavorable for being mass produced.Therefore, efficient, stable non-expensive there is an urgent need to develop
Metallic catalyst replaces noble metal catalyst.Due to transition metal relative low price and it is with good electrocatalysis
Can, therefore widely paid close attention to.Research shows that the elctro-catalyst of hollow micro-nano structure specific surface area with higher, more
Active site, lower density and thermal diffusion coefficient have more excellent electro-catalysis living compared to bulk or solid construction
Property.
Cobalt molybdate (CoMoO4) it is a kind of cheap transition metal oxide, there is good electrochemical stability and higher
Electro catalytic activity, so far, the preparation method report about cobalt molybdate hollow sphere are considerably less, for example, (1) utilizes silica
Bead prepares cobalt molybdate hollow sphere as template, and silicon oxide pellets effectively remove the complexity (RSC for increasing reaction
Adv., 2016,6,51710)；(2) using metal organic-molybdenum salt as reactant, organic solvent passes through as reaction dissolvent
Multistep reaction prepares cobalt molybdate hollow sphere, wherein the use of metal organic salt and organic solvent, improves preparation cost, and
The removal of organic matter makes reaction process become complicated, this will be unfavorable for the marketization (Chem. of cobalt molybdate hollow sphere preparation
Mater. 2016,28,2417).
Summary of the invention
In order to solve noble metal analysis oxygen elctro-catalyst there are scarcity of resources, selling at exorbitant prices the problems such as, the purpose of the present invention is
A kind of cobalt molybdate (CoMoO is provided4) tiny balloon elctro-catalyst preparation method, this method improves electrolysis water separative efficiency,
And reduce the use cost of elctro-catalyst.
Realizing the technical solution of the object of the invention is: a kind of preparation of the elctro-catalyst of cobalt molybdate hollow microsphere structure
Method mainly comprises the steps that
(1) preparation of the hollow oxide microsphere predecessor of cobalt ions and molybdenum ion: Co (NO is weighed respectively3)2.6H2O (nitric acid
Cobalt), Na2MoO4.2H2O(sodium molybdate), NaAC (anhydrous sodium acetate), be added deionized water, magnetic agitation is to being completely dissolved, by institute
It obtains in the reaction kettle of mixed solution addition polytetrafluoroethylene (PTFE) and carries out hydro-thermal reaction, to which after completion of the reaction, reaction kettle is taken out and certainly
It is so cooled to room temperature, collects the solid precipitation object in reaction kettle, and uses deionized water and washes of absolute alcohol for several times respectively, and do
Dry sample；
(2) preparation of cobalt molybdate hollow microsphere structure: the solid sample of drying is placed in pipe type sintering furnace, in air atmosphere
Under, in the reaction temperature of setting and high-temperature heat treatment is carried out to sample in the reaction time, is taken out after sample is cooled to room temperature, i.e.,
Obtain cobalt molybdate tiny balloon sample.
Further, in step (1), the molar ratio of cobalt nitrate, sodium molybdate and anhydrous sodium acetate is 1:1:10, and three is in institute
The molar concentration obtained in mixed solution is respectively 0.033 mol/L, 0.033 mol/L and 0.33 mol/L.
Further, in step (1), the magnetic agitation time is 0.5h-1h.
Further, in step (1), the hydro-thermal reaction time 12h-24h, preferably 20h, hydrothermal temperature is
160OC-180 OC, preferably 180OC, reactant solution volume are the 60% of reaction kettle total volume.
Further, in step (1), drying temperature 60OC, drying time are for 24 hours.
Further, in step (2), sintering temperature is 400 under air atmosphereOC -600 OC, preferably 500OC is protected
Warm sintering time is 2h, heating rate 10OC/min。
Compared with prior art, the invention has the following beneficial effects:
The present invention prepares the cobalt molybdate tiny balloon of efficient OER electro catalytic activity using simple effective method, is conducive to reality
The promotion of existing electro-catalysis splitting water efficiency, while advantageously reducing the use cost of elctro-catalyst.
Detailed description of the invention
Fig. 1 is the XRD diagram spectrum analysis (500 DEG C of sintering temperature, sintering time 2h) of cobalt molybdate tiny balloon sample.
Fig. 2 is that the TEM of cobalt molybdate tiny balloon sample schemes (500 DEG C of sintering temperature, sintering time 2h).
Fig. 3 is that the SEM of cobalt molybdate tiny balloon sample schemes (a: low range, b: high magnification；500 DEG C of sintering temperature, sintering
Time 2h).
Fig. 4 is LSV polarization curve (the circulation volt for the Current density-voltage relationship for reacting cobalt molybdate tiny balloon sample
The test of peace method, sample sintering temperature is respectively 400 DEG C, 500 DEG C, 600 DEG C).
Specific embodiment
Below with reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
The first step weighs 1mmol(290mg respectively) cobalt nitrate, 1mmol(240mg) sodium molybdate, 4mmol(820mg) acetic anhydride
Sodium is respectively completely dissolved in 10ml deionized water, sodium molybdate aqueous solution is slowly added into cobalt nitrate aqueous solution first, and
It is aided with magnetic agitation, is then slowly added into the aqueous solution of sodium acetate in the mixed solution of above-mentioned sodium molybdate and cobalt nitrate, and
By the mixed solution of these three reactants magnetic agitation 0.5h at room temperature, the solution of reactant is finally transferred to 50ml volume
Polytetrafluoroethylene (PTFE) reaction kettle in, the volume of reactant solution is the 60% of reactor volume, by reaction kettle in 180 OC is closed
Heat 20h, after reaction kettle cooled to room temperature, the solid precipitation object in reaction kettle taken out, and using deionized water and
Alcohol is cleaned, then by the sample after cleaning 60OC is dry for 24 hours, is collected into the predecessor of cobalt molybdate tiny balloon.
The predecessor of cobalt molybdate tiny balloon is placed in pipe type sintering furnace by second step, and heat is carried out in air atmosphere
Processing, heating rate 10 OC/min, heat treatment temperature 500 OC, soaking time 2h, obtains black after reaction
Cobalt molybdate hollow microsphere structure sample.
Embodiment 2
The first step weighs 1mmol(290mg respectively) cobalt nitrate, 1mmol(240mg) sodium molybdate, 4mmol(820mg) acetic anhydride
Sodium is respectively completely dissolved in 10ml deionized water, sodium molybdate aqueous solution is slowly added into cobalt nitrate aqueous solution first, and
It is aided with magnetic agitation, is then slowly added into the aqueous solution of sodium acetate in the mixed solution of above-mentioned sodium molybdate and cobalt nitrate, and
By the mixed solution of these three reactants magnetic agitation 0.5h at room temperature, the solution of reactant is finally transferred to 50ml volume
Polytetrafluoroethylene (PTFE) reaction kettle in, the volume of reactant solution is the 60% of reactor volume, by reaction kettle in 180 OC is closed
Heat 20h, after reaction kettle cooled to room temperature, the solid precipitation object in reaction kettle taken out, and using deionized water and
Alcohol is cleaned, then by the sample after cleaning 60OC is dry for 24 hours, is collected into the predecessor of cobalt molybdate tiny balloon.
The predecessor of cobalt molybdate tiny balloon is placed in pipe type sintering furnace by second step, and heat is carried out in air atmosphere
Processing, heating rate 10 OC/min, heat treatment temperature 400 OC, soaking time 2h, obtains black after reaction
Cobalt molybdate hollow microsphere structure sample.
Embodiment 3
The first step weighs 1mmol(290mg respectively) cobalt nitrate, 1mmol(240mg) sodium molybdate, 4mmol(820mg) acetic anhydride
Sodium is respectively completely dissolved in 10ml deionized water, sodium molybdate aqueous solution is slowly added into cobalt nitrate aqueous solution first, and
It is aided with magnetic agitation, is then slowly added into the aqueous solution of sodium acetate in the mixed solution of above-mentioned sodium molybdate and cobalt nitrate, and
By the mixed solution of these three reactants magnetic agitation 0.5h at room temperature, the solution of reactant is finally transferred to 50ml volume
Polytetrafluoroethylene (PTFE) reaction kettle in, the volume of reactant solution is the 60% of reactor volume, by reaction kettle in 180OC is closed
Heat 20h, after reaction kettle cooled to room temperature, the solid precipitation object in reaction kettle taken out, and using deionized water and
Alcohol is cleaned, then by the sample after cleaning 60OC is dry for 24 hours, is collected into the predecessor of cobalt molybdate tiny balloon.
The predecessor of cobalt molybdate tiny balloon is placed in pipe type sintering furnace by second step, and heat is carried out in air atmosphere
Processing, heating rate 10 OC/min, heat treatment temperature 600 OC, soaking time 2h, obtains black after reaction
Cobalt molybdate hollow microsphere structure sample.
Fig. 1 is the X ray diffracting spectrum (XRD) of cobalt molybdate tiny balloon sample, analysis shows products therefrom is pure molybdenum
Sour cobalt (JCPDS card number: 21-0868), Fig. 2 and Fig. 3 are the transmission electron microscope picture (TEM) of cobalt molybdate tiny balloon sample and sweep
Electron microscope (SEM) is retouched, as can be seen from the figure the pattern of cobalt molybdate sample is hollow microsphere structure, the diameter dimension of tiny balloon
About 0.5 μm -3.0 μm of distribution, Fig. 4 is different heat treatment temperature (400 OC, 500 OC, 600 OC the cobalt molybdate obtained under) is empty
The OER electro catalytic activity test chart of heart microsphere sample, electrolyte used is potassium hydroxide solution (concentration 1M/L), using linear
It is 10mA/cm that voltammetry (LSV) three groups of samples of test, which are scanned, in current density2Corresponding overpotential, 500 OC is heat-treated cobalt molybdate
The overpotential of tiny balloon is 343mV, less than 400 OC and 600 OC is heat-treated the overpotential of cobalt molybdate tiny balloon, therefore,
500 OThe cobalt molybdate tiny balloon that C is heat-treated shows best OER electro catalytic activity.
Claims (9)
1. a kind of preparation method of cobalt molybdate tiny balloon elctro-catalyst, which comprises the following steps:
(1) cobalt nitrate, sodium molybdate, anhydrous sodium acetate are weighed respectively, deionized water is added, and stir to being completely dissolved, gained is mixed
It closes solution and carries out hydro-thermal reaction, to after completion of the reaction, drying sample after cleaning；
(2) sample after drying is carried out to high-temperature heat treatment in air atmosphere to get cobalt molybdate tiny balloon sample is arrived.
2. preparation method as described in claim 1, which is characterized in that in step (1), cobalt nitrate, sodium molybdate and acetic anhydride
The molar ratio of sodium is 1:1:10, and molar concentration of the three in gained mixed solution is respectively 0.033 mol/L, 0.033 rubs
You/liter and 0.33 mol/L.
3. preparation method as described in claim 1, which is characterized in that in step (1), mixing time 0.5h-1h.
4. preparation method as described in claim 1, which is characterized in that in step (1), the hydro-thermal reaction time 12h-24h, water
Thermal response temperature is 160OC-180 OC。
5. preparation method as described in claim 1, which is characterized in that in step (1), the hydro-thermal reaction time 20h, hydro-thermal is anti-
Answering temperature is 180OC。
6. preparation method as described in claim 1, which is characterized in that in step (1), drying temperature 60OC, drying time
For for 24 hours.
7. preparation method as described in claim 1, which is characterized in that in step (2), sintering temperature is 400 under air atmosphereOC -600 OC, heat preservation sintering time are 2h.
8. preparation method as described in claim 1, which is characterized in that in step (2), sintering temperature is 500 under air atmosphereOC。
9. preparation method as described in claim 1, which is characterized in that in step (2), heating rate 10OC/min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810902066.8A CN109012683B (en) | 2018-08-09 | 2018-08-09 | Preparation method of cobalt molybdate hollow microsphere electrocatalyst |
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