CN110479320A - A kind of efficiently difunctional decomposition water power catalyst and preparation method thereof - Google Patents
A kind of efficiently difunctional decomposition water power catalyst and preparation method thereof Download PDFInfo
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- CN110479320A CN110479320A CN201910777521.0A CN201910777521A CN110479320A CN 110479320 A CN110479320 A CN 110479320A CN 201910777521 A CN201910777521 A CN 201910777521A CN 110479320 A CN110479320 A CN 110479320A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 64
- 239000010941 cobalt Substances 0.000 claims abstract description 64
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000004744 fabric Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 239000002073 nanorod Substances 0.000 claims abstract description 25
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 24
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 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 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 13
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000001103 potassium chloride Substances 0.000 claims abstract description 12
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 12
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 230000005611 electricity Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000010411 electrocatalyst Substances 0.000 claims description 3
- 210000002700 urine Anatomy 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 50
- 239000001257 hydrogen Substances 0.000 abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 abstract description 39
- 239000001301 oxygen Substances 0.000 abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 38
- 230000000694 effects Effects 0.000 abstract description 35
- 239000000243 solution Substances 0.000 abstract description 30
- 238000004458 analytical method Methods 0.000 abstract description 26
- 238000006555 catalytic reaction Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 8
- -1 Cobaltous selenide Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- ZETYICZOEMMWEG-UHFFFAOYSA-N [C].[C].[Pt] Chemical compound [C].[C].[Pt] ZETYICZOEMMWEG-UHFFFAOYSA-N 0.000 description 5
- JEUJLYFOFHOMTM-UHFFFAOYSA-N [C].[Ru]=O Chemical compound [C].[Ru]=O JEUJLYFOFHOMTM-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000008055 phosphate buffer solution Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003869 coulometry Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J35/61—Surface area
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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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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- B82Y40/00—Manufacture or treatment of nanostructures
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The present invention provides a kind of efficiently difunctional decomposition water power catalyst and preparation method thereof, are related to electrocatalytic decomposition water technical field.The present invention mixes cobalt acetate, ammonium fluoride, urea and solvent, obtains mixed solution;Carbon cloth is immersed again and carries out hydro-thermal reaction in the mixed solution, obtains the carbon cloth that surface growth has cobalt nanorod presoma;Then there is the carbon cloth of cobalt nanorod presoma to be electrochemically transformed surface growth, obtain the efficiently difunctional decomposition water power catalyst;It is described be electrochemically transformed use three-electrode system, using surface growth have the carbon cloth of cobalt nanorod presoma as working electrode, using saturated calomel electrode as reference electrode, using the mixed solution of selenium dioxide, potassium chloride and water as electrolyte.Elctro-catalyst prepared by the present invention has liberation of hydrogen high activity and analysis oxygen high activity, has good stability, can efficiently realize complete solution water, the practical direction for having pushed electrocatalytic decomposition water towards the lower applying electrical potential of more high current density is developed.
Description
Technical field
The present invention relates to electrocatalytic decomposition water technical field, in particular to a kind of efficiently difunctional decomposition water power catalyst and
Preparation method.
Background technique
Electrocatalytic decomposition water technology can obtain the new energy transformation technology of the renewable hydrogen energy by people as one kind
More and more concerns.The electrolysis of water is made of two half-reactions: (1) Hydrogen evolving reaction of cathode;(2) oxygen of anode is precipitated
Reaction.But due to the influence of the poor proton hydrogen of electrode surface and the adsorption energy of molecular oxygen, during practical electrolysis water
A large amount of energy consumption, therefore all more difficult progress of single reaction that hydrogen is precipitated and oxygen is precipitated are brought, so needing high activity
Elctro-catalyst come reduce reaction needed for overpotential and accelerate kinetics process.
Currently, precious metal based catalysts have a good electrocatalytic decomposition water activity, for example, platinum alloy have it is good
Activity is precipitated in hydrogen, and there is iridium/ruthenium oxide etc. good oxygen activity is precipitated.But the scarcity of noble metal hinders such urge
Application of the agent in actual demand.In the recent period, the non-metallic catalyst of many high efficiency low costs is widely studied, wherein most analysis
There is hydrogen catalyst good hydrogen activity is precipitated in an acidic solution, and it is general very poor that activity is precipitated in the hydrogen in alkaline solution;Analysis
VPO catalysts in alkaline solution there is good oxygen activity is precipitated, and stability is poor in acid solution.Therefore, in identical electrolysis
Realize that complete solution water hydrogen and oxygen production still suffers from huge challenge in liquid.
Cobaltous selenide is a kind of typical Transition-metal dichalcogenide, is had simultaneously in alkalinity and neutral solution good
The characteristic of catalytic hydrogen evolution and analysis oxygen, therefore the huge concern by researcher.However active surface area and difference that cobaltous selenide is low
Electron-transporting affects its electrocatalytic decomposition water activity under high currents, especially traditional hydro-thermal, heat of solution and high temperature
The preparation method of selenizing hardly results in the cobaltous selenide electrode material of high activity surface product, is also difficult to improve cobaltous selenide electrode material
Electro catalytic activity.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of efficiently difunctional decomposition water power catalyst and its preparation sides
Method.Elctro-catalyst prepared by the present invention has good electrocatalytic decomposition elutriation hydrogen activity and oxygen evolution activity, in identical electrolyte
In can efficiently realize complete solution water, pushed electrocatalytic decomposition water towards the functionization side of the lower applying electrical potential of more high current density
To development.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of efficiently difunctional preparation methods for decomposing water power catalyst, comprising the following steps:
(1) cobalt acetate, ammonium fluoride, urea and solvent are mixed, obtains mixed solution;
(2) carbon cloth is immersed and carries out hydro-thermal reaction in the mixed solution, obtaining surface growth has cobalt nanorod presoma
Carbon cloth;
(3) there is the carbon cloth of cobalt nanorod presoma to be electrochemically transformed surface growth, obtain described efficiently double
Function Decomposition water power catalyst;
Described be electrochemically transformed uses three-electrode system, has the carbon cloth of cobalt nanorod presoma as work using surface growth
Electrode, using saturated calomel electrode as reference electrode, using the mixed solution of selenium dioxide, potassium chloride and water as electrolyte.
Preferably, the solvent in the step (1) is the mixed solvent of water and ethyl alcohol;The in the mixed solvent water and ethyl alcohol
Volume ratio be 2:1.
Preferably, the amount ratio of cobalt acetate in the step (1), ammonium fluoride, urea and solvent be 3~5mmol:7~
9mmol:15~25mmol:90~120mL.
Preferably, the temperature of hydro-thermal reaction is 80~120 DEG C in the step (2), and the time is 8~12h.
It preferably, further include the cooling successively carried out to gained carbon cloth, washing in the step (2) after hydro-thermal reaction
And drying;The washing is successively using deionized water and ethyl alcohol progress supersound washing;The temperature of the drying is 60 DEG C, the time
For 2h.
Preferably, the molar concentration of selenium dioxide is 5~15mmol/L in step (3) electrolyte, and potassium chloride rubs
Your concentration is 40~60mmol/L.
Preferably, the applied voltage being electrochemically transformed in the step (3) is -0.7~-0.8V, and the applied voltage is
Potential relative to reference electrode.
Preferably, the temperature being electrochemically transformed in the step (3) is 40~60 DEG C, and the time is 20~40min.
Preferably, after being electrochemically transformed in the step (3), further include to the working electrode after electrochemical conversion successively
It is washed and is dried;The washing is successively using benzene, deionized water and ethyl alcohol progress supersound washing;The temperature of the drying
It is 60 DEG C, time 2h.
It is described efficiently double the present invention provides the efficient difunctional decomposition water power catalyst of above scheme the method preparation
Function Decomposition water power catalyst is cobalt hydroxide-cobaltous selenide composite electrocatalyst.
The present invention provides a kind of efficiently difunctional preparation methods for decomposing water power catalyst, comprising the following steps: (1) will
Cobalt acetate, ammonium fluoride, urea and solvent mixing, obtain mixed solution;(2) carbon cloth is immersed and carries out hydro-thermal in the mixed solution
Reaction obtains the carbon cloth that surface growth has cobalt nanorod presoma;(3) there is the carbon of cobalt nanorod presoma to surface growth
Cloth is electrochemically transformed, and the efficiently difunctional decomposition water power catalyst is obtained.The present invention is by hydro-thermal method in carbon cloth surfaces
Then cobalt nanorod presoma is converted to cobalt hydroxide using the method for electrochemical conversion by in-situ preparation cobalt nanorod presoma
With the composite Nano bar material of cobaltous selenide.The present invention constructs cobalt hydroxide-cobaltous selenide compound electric using the method being electrochemically transformed
Pole material, the i.e. efficient difunctional decomposition water power catalyst realize high activity surface product and multicomponent catalysis material
It is effective compound, effectively increase the liberation of hydrogen and analysis oxygen performance of elctro-catalyst electrocatalytic decomposition water;Also, system provided by the invention
Preparation Method is simple, strong operability.
The present invention provides the efficient difunctional decomposition water power catalyst of method made above preparation.Electricity provided by the invention
When cathode and anode of the catalyst as electrocatalytic decomposition water, good liberation of hydrogen and analysis are all had in alkalinity and neutral electrolyte
Oxygen activity, and have good stability, i.e., elctro-catalyst prepared by the present invention can efficiently realize complete solution water, push electrocatalytic decomposition
The practical direction of water towards the lower applying electrical potential of more high current density is developed.Embodiment the result shows that, height provided by the invention
Difunctional decomposition water power catalyst is imitated with liberation of hydrogen high activity and analysis oxygen high activity, and as the cathode of electrocatalytic decomposition water and
When anode, platinum carbon // ruthenium-oxide composition bipolar electrode that high current catalytic activity and stability will be substantially better than precious metal is complete
Solve aqueous systems.
Detailed description of the invention
Fig. 1 is cobalt hydroxide-cobaltous selenide combination electrode prepared by embodiment 1 and platinum carbon carbon cloth electrode prepared by comparative example 1
The linear scan curve of electrocatalytic hydrogen evolution (alkaline electrolyte) and corresponding Tafel slope comparison diagram, (a) is linear in Fig. 1
Scanning curve figure (b) is Tafel slope figure;
Ruthenium-oxide carbon cloth electrode prepared by cobalt hydroxide-cobaltous selenide combination electrode and comparative example 2 prepared by Fig. 2 embodiment 1
The linear scan curve and corresponding Tafel slope comparison diagram of oxygen (alkaline electrolyte) are analysed in electro-catalysis, and (a) is linear in Fig. 2
Scanning curve figure (b) is Tafel slope figure;
Fig. 3 be cobalt hydroxide-cobaltous selenide combination electrode to and platinum carbon // ruthenium-oxide electrode to electro-catalysis complete solution water (alkaline electro
Solve liquid) linear scan curve and stability comparison diagram, (a) is linear scan curve graph in Fig. 3, (b) is stability
Figure;
Fig. 4 is that cobalt hydroxide-cobaltous selenide combination electrode liberation of hydrogen (neutral electrolyte) linear scan prepared by embodiment 1 is bent
Line and corresponding Tafel slope figure, (a) is linear scan curve graph in Fig. 4, (b) is Tafel slope figure;
Fig. 5 is the linear scan song that cobalt hydroxide-cobaltous selenide combination electrode prepared by embodiment 1 analyses oxygen (neutral electrolyte)
Line and corresponding Tafel slope figure, (a) is linear scan curve graph in Fig. 5, (b) is Tafel slope figure;
Fig. 6 is that cobalt hydroxide-cobaltous selenide combination electrode is bent to the linear scan to electro-catalysis complete solution water (neutral electrolyte)
Line and stability figure, (a) is linear scan curve graph in Fig. 6, (b) is stability figure.
Specific embodiment
The present invention provides a kind of efficiently difunctional preparation methods for decomposing water power catalyst, comprising the following steps:
(1) cobalt acetate, ammonium fluoride, urea and solvent are mixed, obtains mixed solution;
(2) carbon cloth is immersed and carries out hydro-thermal reaction in the mixed solution, obtaining surface growth has cobalt nanorod presoma
Carbon cloth;
(3) there is the carbon cloth of cobalt nanorod presoma to be electrochemically transformed surface growth, obtain described efficiently double
Function Decomposition water power catalyst;
Described be electrochemically transformed uses three-electrode system, has the carbon cloth of cobalt nanorod presoma as work using surface growth
Electrode, using saturated calomel electrode as reference electrode, using the mixed solution of selenium dioxide, potassium chloride and water as electrolyte.
The present invention mixes cobalt acetate, ammonium fluoride, urea and solvent, obtains mixed solution.In the present invention, the solvent
The preferably mixed solvent of water and ethyl alcohol;The volume ratio of the in the mixed solvent water and ethyl alcohol is preferably 2:1.In the present invention,
The cobalt acetate, ammonium fluoride, urea and solvent amount ratio be preferably 3~5mmol:7~9mmol:15~25mmol:90~
120mL, more preferably 4mmol:8mmol:20mmol:105mL.The present invention is to the cobalt acetate, ammonium fluoride, urea and solvent
Source does not require particularly, using commercial product well known in the art.The present invention is preferably by the cobalt acetate, ammonium fluoride
It is added in the solvent and is mixed with urea;The mixing preferably carries out under stirring conditions.In the present invention, described
The time of stirring is preferably 30min;The present invention does not require the speed of the stirring particularly, can guarantee in the time
It is interior to be uniformly mixed each component.After mixing, the mixed solution of pink colour is obtained.
After obtaining mixed solution, the present invention, which immerses carbon cloth, carries out hydro-thermal reaction in the mixed solution, and it is raw to obtain surface
Carbon cloth with cobalt nanorod presoma.In the present invention, the reaction kettle of the hydro-thermal reaction is preferably tetrafluoroethene liner
Stainless steel hydrothermal reaction kettle.The present invention does not require the source of the carbon cloth and type particularly, and use is well known in the art
Carbon cloth.The mixed solution is preferably first placed in the reaction kettle of hydro-thermal reaction by the present invention, and loading is preferably 70%;Again
Carbon cloth is immersed in the mixed solution and carries out hydro-thermal reaction.In the present invention, the temperature of the hydro-thermal reaction is preferably 80
~120 DEG C, more preferably 100 DEG C, the time is preferably 8~12h, more preferably 10h;The temperature of the hydro-thermal reaction preferably passes through
High temperature oven is realized, i.e., the reaction kettle equipped with mixed solution and carbon cloth is placed in high temperature oven and carries out water at said temperatures
Thermal response.In the present invention, the cobalt acetate, ammonium fluoride and urea are in hydrothermal reaction process in carbon cloth surfaces in-situ preparation cobalt
Nanometer rods presoma;Wherein, the ingredient of the cobalt nanorod presoma is basic cobaltous carbonate, and ammonium fluoride is generated as cobalt nanorod
Template.
After hydro-thermal reaction, the present invention further preferably includes cooling, washing and the drying successively carried out to gained carbon cloth.The present invention
The method of the cooling is not required particularly, using method well known in the art, specifically such as naturally cools to room
Temperature.In the present invention, the washing preferably successively carries out supersound washing using deionized water and ethyl alcohol;The deionized water and
The time of EtOH Sonicate washing is both preferably 5min;The present invention does not want the concrete operation method of the supersound washing particularly
It asks, using method well known in the art.In the present invention, the temperature of the drying is preferably 60 DEG C, and the time is preferably 2h;
The drying is preferably dried in vacuo.After drying, the carbon cloth that surface growth has cobalt nanorod presoma is obtained.
Obtain surface growth have the carbon cloth of cobalt nanorod presoma after, the present invention to the surface growth have cobalt nanorod before
The carbon cloth for driving body is electrochemically transformed, and the efficiently difunctional decomposition water power catalyst is obtained.In the present invention, the electrification
Learn conversion use three-electrode system, using surface growth have the carbon cloth of cobalt nanorod presoma as working electrode, to be saturated calomel
Electrode is as reference electrode, using the mixed solution of selenium dioxide, potassium chloride and water as electrolyte.The present invention is to three electrode
Electrode is not required particularly in system, using well known in the art to electrode, specifically such as carbon-point, platinized platinum, iron
The conductive electrodes such as piece.In the present invention, the molar concentration of selenium dioxide is preferably 5~15mmol/L in the electrolyte, more excellent
It is selected as 10mmol/L, the molar concentration of potassium chloride is preferably 40~60mmol/L, more preferably 50mmol/L;The present invention will be described
Working electrode is immersed in the electrolyte electrode and reference electrode and constitutes three-electrode system.In the present invention, the electrification
The applied voltage for learning conversion is preferably -0.7~-0.8V, more preferably -0.7V;The applied voltage is relative to reference electrode
Potential (in the specific embodiment of the invention, the applied voltage is expressed as -0.7Vvs saturated calomel electrode).In the present invention
In, the temperature of the electrochemical conversion is preferably 40~60 DEG C, and more preferably 60 DEG C;The temperature of the electrochemical conversion is preferably logical
Cross water-bath realization.In the present invention, the time of the electrochemical conversion is preferably 20~40min, more preferably 40min;It is described
The time of electrochemical conversion is controlled by the retention time of applied voltage, and the retention time of the applied voltage is electrification
Learn the time of conversion.Cobalt nanorod presoma is converted to cobalt hydroxide-cobaltous selenide by the method being electrochemically transformed by the present invention
Composite Nano bar material, specific reaction process are as follows: Co2++2OH-→Co(OH)2, Co2++Se4++6e-→ CoSe, wherein OH-
Water in electrolyte.
After electrochemical conversion, the present invention further preferably include the working electrode after electrochemical conversion is successively carried out washing and
It is dry.In the present invention, the washing preferably successively carries out supersound washing using benzene, deionized water and ethyl alcohol;The benzene is gone
The time of ionized water and EtOH Sonicate washing is both preferably 2min, and the present invention does not have the concrete operation method of the supersound washing
It is special to require, using method well known in the art.During electrochemical conversion, the generation of the adjoint side reaction of meeting,
That is Se4++4e-→ Se, to be adsorbed on cobalt hydroxide-cobaltous selenide compound for potassium chloride in the elemental selenium and electrolyte that side reaction generates
Nano-bar material surface, the present invention wash away elemental selenium by benzene, wash away potassium chloride by deionized water.In the present invention, described
Dry temperature is preferably 60 DEG C, and the time is preferably 2h;The drying is preferably dried in vacuo.After drying, obtain described efficient
Difunctional decomposition water power catalyst.
The present invention provides the efficiently difunctional preparation methods for decomposing water power catalyst described above, and the present invention is using electrification
The method for learning conversion constructs cobalt hydroxide-cobaltous selenide combination electrode material, the i.e. efficient difunctional decomposition water power catalyst,
It is long-pending effective compound with multicomponent catalysis material to realize high activity surface, effectively increases elctro-catalyst electrocatalytic decomposition water
Liberation of hydrogen and analysis oxygen performance;Also, preparation method provided by the invention is simple, strong operability.
It is described efficiently double the present invention provides the efficient difunctional decomposition water power catalyst of above scheme the method preparation
Function Decomposition water power catalyst is cobalt hydroxide-cobaltous selenide composite electrocatalyst.Elctro-catalyst provided by the invention is urged as electricity
When changing the cathode and anode that decompose water, good liberation of hydrogen and oxygen evolution activity are all had in alkalinity and neutral electrolyte, and stablize
Property is good, i.e., elctro-catalyst prepared by the present invention can efficiently realize complete solution water, push electrocatalytic decomposition water towards bigger electricity
The practical direction of the lower applying electrical potential of current density is developed.
Efficiently difunctional decomposition water power catalyst and preparation method thereof provided by the invention is carried out below with reference to embodiment
Detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The efficiently difunctional preparation for decomposing water power catalyst (cobalt hydroxide-cobaltous selenide combination electrode):
(1) carbon cloth surfaces grow cobalt nanorod presoma: 4mmol cobalt acetate, 8mmol ammonium fluoride and 20mmol urea is molten
It solves in the mixed solvent (water: the volume ratio of ethyl alcohol is 2:1) of 105mL, forms uniform pink colour solution within magnetic agitation 30 minutes.
The solution is added in the stainless steel hydrothermal reaction kettle of the tetrafluoroethene liner of 50mL, loading 70%.Then by one piece
Carbon cloth is added in solution, and reaction kettle is placed in high temperature oven and is heated 10 hours for 100 DEG C.Cooled to room temperature is taken out
Carbon cloth is washed 5 minutes with deionized water and EtOH Sonicate respectively, and it is 2 hours dry to be put into 60 DEG C of vacuum ovens.
(2) electrochemical conversion prepares cobalt hydroxide-cobaltous selenide combination electrode: being electrochemically transformed using three-electrode system
Preparation, by the material prepared in (1) as working electrode, platinum plate electrode is used as to electrode, and saturated calomel electrode is as reference electricity
Pole, the mixed solution of selenium dioxide, potassium chloride and water is as electrolyte (selenium dioxide 10mmol/L, potassium chloride 50mmol/L).
Above three electrode is immersed in electrolyte, electrotransformation reaction is carried out in 60 DEG C of water-bath, applied voltage is full for -0.7Vvs
It is kept for 40 minutes with calomel electrode.Then respectively with benzene, deionized water and EtOH Sonicate 2 minutes remove absorption elemental selenium and
Salt is put into 60 DEG C of vacuum ovens dryings 2 hours, obtains cobalt hydroxide-cobaltous selenide combination electrode, i.e., efficient difunctional decomposition water
Elctro-catalyst.
Comparative example 1
The preparation of platinum carbon carbon cloth electrode:
Take 4 milligram of 20% platinum carbon solid that solution (700 μ L deionized waters, 270 μ L dehydrated alcohols and the 30 μ L naphthalenes of 1mL are added
Phenol mixed solution) in, ultrasonic disperse 1 hour.It takes 100 μ L suspensions to drip on clean carbon cloth, is put into 60 DEG C of vacuum ovens
It is 2 hours dry.
Comparative example 2
The preparation of ruthenium-oxide carbon cloth electrode:
Take 4 milligrams of ruthenium-oxide solids that solution (700 μ L deionized waters, 270 μ L dehydrated alcohols and the 30 μ L naphthols of 1mL are added
Mixed solution) in, ultrasonic disperse 1 hour.It takes 100 μ L suspensions to drip on clean carbon cloth, it is dry to be put into 60 DEG C of vacuum ovens
Dry 2 hours.
The aqueous test of electrocatalytic decomposition:
(1) test of electrocatalytic decomposition water is carried out in the potassium hydroxide aqueous solution of 1mol/L (i.e. alkaline electrolyte):
(1) Hydrogen Evolution Performance is tested:
The platinum carbon carbon cloth electrode prepared respectively with cobalt hydroxide-cobaltous selenide combination electrode of the preparation of embodiment 1, comparative example 1
As working electrode, platinum plate electrode is used as to electrode, and silver silver chloride electrode is made as reference electrode, 1mol/L potassium hydroxide solution
For electrolyte.Electrocatalytic hydrogen evolution reaction, the first electricity in 0V~-0.4V (corresponding standard hydrogen electrode) are carried out under three-electrode system
10 circle cyclic voltammetries are carried out with the speed of sweeping of 100mV in gesture section, to guarantee that catalyst is stablized during liberation of hydrogen.Then into
Line sweep test, scanning speed 5mV, sweep interval is 0~-0.4V, with the pass between current density and applying electrical potential
System carries out hydrogen evolution activity analysis, and the absolute value of current density is bigger, and applying electrical potential is lower, then it is better to represent catalyst activity,
Liberation of hydrogen speed is faster.The Tafel slope figure of electrode liberation of hydrogen is then calculated by linear scan curve.
Platinum carbon carbon cloth electrode electro-catalysis prepared by cobalt hydroxide-cobaltous selenide combination electrode and comparative example 1 prepared by embodiment 1
The linear scan curve of liberation of hydrogen and corresponding Tafel slope comparison diagram are as shown in Figure 1, (a) is linear scan curve in Fig. 1
Figure (b) is Tafel slope figure.From figure 1 it appears that in evolving hydrogen reaction, cobalt hydroxide-selenizing of the preparation of embodiment 1
Cobalt combination electrode realizes 20mAcm with the overpotential of 208mV-2Liberation of hydrogen electric current, its liberation of hydrogen electric current can under the overpotential of 314mV
Reach 100mAcm-2, the Tafel slope of liberation of hydrogen is 152mVdec-1。
(2) oxygen performance test is analysed:
Cobalt hydroxide-cobaltous selenide combination electrode, the ruthenium-oxide carbon cloth of the preparation of comparative example 2 prepared respectively with embodiment 1 is electric
Pole is used as working electrode, platinum plate electrode to electrode, and silver silver chloride electrode is as reference electrode, 1mol/L potassium hydroxide solution
As electrolyte.Electro-catalysis oxygen evolution reaction is carried out under three-electrode system, first 1.2~1.7V's (corresponding standard hydrogen electrode)
10 circle cyclic voltammetries are carried out with the speed of sweeping of 100mV in potential section, to guarantee that catalyst is stablized during analysing oxygen.Then
Linear scan test is carried out, scanning speed 5mV, sweep interval is 1.23~1.7V, between current density and applied voltage
Relationship carry out oxygen evolution activity analysis, the absolute value of current density is bigger, and applying electrical potential is lower, then represents catalyst activity and get over
Good, analysis oxygen speed is faster.The Tafel slope figure that electrode analyses oxygen is then calculated by linear scan curve.
Ruthenium-oxide carbon cloth electrode electricity prepared by cobalt hydroxide-cobaltous selenide combination electrode and comparative example 2 prepared by embodiment 1 is urged
The linear scan curve and corresponding Tafel slope comparison diagram for changing analysis oxygen are as shown in Fig. 2, (a) is that linear scan is bent in Fig. 2
Line chart (b) is Tafel slope figure.From figure 2 it can be seen that in oxygen evolution reaction, cobalt hydroxide-selenium of the preparation of embodiment 1
Change cobalt combination electrode and 20mAcm is realized with the overpotential of 268mV-2Analysis oxygen electric current, it is analysed under the overpotential of 297mV and 303mV
Oxygen electric current can reach 100mAcm-2And 200mAcm-2, analysis oxygen Tafel slope is 65mVdec-1。
(3) complete solution water is tested:
Cobalt hydroxide-cobaltous selenide the combination electrode prepared using embodiment 1 is simultaneously as the cathode and anode (i.e. hydrogen of electrolysis water
Cobalt oxide-cobaltous selenide combination electrode to);As a comparison: using platinum carbon carbon cloth electrode prepared by comparative example 1 as cathode, with comparison
Ruthenium-oxide carbon cloth electrode prepared by example 2 is as anode (i.e. platinum carbon // ruthenium-oxide electrode to).
Electrolyte is 1mol/L potassium hydroxide solution.The reaction of electro-catalysis complete solution water is carried out under two electrode systems, first 0
10 circle cyclic voltammetries are carried out with the speed of sweeping of 100mV in the potential section of~2.0V (corresponding standard hydrogen electrode), to guarantee to urge
Agent is stablized during electrolysis water.Then linear scan test, scanning speed 5mV are carried out, sweep interval is 0~2.0V,
Electrolysis water activity analysis is carried out with the relationship between current density and applied voltage, the absolute value of current density is bigger, and additional
Potential is lower, then it is better to represent catalyst activity, and electrolysis water speed is faster.Then tested using timing coulometry in 10mA
cm-2Variation of the applying electrical potential in 50 hours catalytic process under current density.
Cobalt hydroxide-cobaltous selenide combination electrode to and platinum carbon // ruthenium-oxide electrode it is bent to the linear scan of electro-catalysis complete solution water
Line and stability comparison diagram as shown in figure 3, in Fig. 3 (a) be linear scan curve graph, (b) be stability figure.From Fig. 3
In as can be seen that complete solution water reaction in, complete solution water power stream of the cobalt hydroxide-cobaltous selenide combination electrode under the potential of 1.71V
For 10mAcm-2, the complete solution water power stream under the potential of 1.94V is 100mAcm-2;In 10mAcm-2Current density under, warp
The complete solution water experiment for spending 50 hours, applied voltage only increase 67mV;The catalysis of cobalt hydroxide-cobaltous selenide combination electrode high current
Activity and stability will be substantially better than platinum carbon // ruthenium-oxide composition bipolar electrode complete solution aqueous systems of precious metal.
(2) test of electrocatalytic decomposition water is carried out in the phosphate-buffered aqueous solution (i.e. neutral electrolyte) of 1mol/L potassium:
(1) Hydrogen Evolution Performance is tested:
Using cobalt hydroxide-cobaltous selenide combination electrode prepared by embodiment 1 as working electrode, platinum plate electrode is used as to electricity
Pole, silver silver chloride electrode is as reference electrode, and the phosphate buffer solution of 1mol/L potassium is as electrolyte.Under three-electrode system
Carry out electrocatalytic hydrogen evolution reaction, first in the potential section of 0~-0.4V (corresponding standard hydrogen electrode) with 100mV sweep it is fast into
Row 10 encloses cyclic voltammetry, to guarantee that catalyst is stablized during liberation of hydrogen.Then linear scan test, scanning speed are carried out
For 5mV, sweep interval is 0~-0.4V, carries out hydrogen evolution activity analysis, electricity using the relationship between current density and applied voltage
The absolute value of current density is bigger, and applying electrical potential is lower, then represents that catalyst activity is better, and liberation of hydrogen speed is faster.Then pass through
The Tafel slope figure of linear scan curve calculating electrode liberation of hydrogen.
Cobalt hydroxide-cobaltous selenide combination electrode liberation of hydrogen linear scan curve and corresponding tower prepared by embodiment 1 is luxuriant and rich with fragrance
Your slope figure (b) is Tafel slope figure as shown in figure 4, (a) is linear scan curve graph in Fig. 4.Figure 4, it is seen that
In evolving hydrogen reaction, cobalt hydroxide-cobaltous selenide combination electrode prepared by embodiment 1 realizes 20mAcm with the overpotential of 313mV-2
Liberation of hydrogen electric current, its liberation of hydrogen electric current can reach 50mAcm under the overpotential of 511mV-2, the Tafel slope of liberation of hydrogen is
181mV·dec-1。
(2) oxygen performance test is analysed:
Using cobalt hydroxide-cobaltous selenide combination electrode prepared by embodiment 1 as working electrode, platinum plate electrode is used as to electricity
Pole, silver silver chloride electrode are electrolyte as reference electrode, the phosphate buffer solution of 1mol/L potassium.Under three-electrode system into
Row electro-catalysis oxygen evolution reaction sweeps fast progress in the potential section of 1.2~1.7V (corresponding standard hydrogen electrode) first with 100mV
10 circle cyclic voltammetries, to guarantee that catalyst is stablized during analysing oxygen.Then linear scan test is carried out, scanning speed is
5mV, sweep interval are 1.2~1.7V, carry out oxygen evolution activity analysis with the relationship between current density and applied voltage, electric current is close
The absolute value of degree is bigger, and applying electrical potential is lower, then it is better to represent catalyst activity, and analysis oxygen speed is faster.Then by linear
Scanning curve calculates the Tafel slope figure of electrode analysis oxygen.
Cobalt hydroxide-cobaltous selenide combination electrode analysis oxygen linear scan curve and corresponding tower prepared by embodiment 1 is luxuriant and rich with fragrance
Your slope figure (b) is Tafel slope figure as shown in figure 5, (a) is linear scan curve graph in Fig. 5.From figure 5 it can be seen that
In oxygen evolution reaction, cobalt hydroxide-cobaltous selenide combination electrode prepared by embodiment 1 realizes 10mAcm with the overpotential of 633mV-2
Analysis oxygen electric current, analysis oxygen Tafel slope be 226mVdec-1。
(3) complete solution water is tested:
Cobalt hydroxide-cobaltous selenide the combination electrode prepared using embodiment 1 is simultaneously as the cathode and anode (hydrogen-oxygen of electrolysis water
Change cobalt-cobaltous selenide combination electrode to), the phosphate buffer solution of 1mol/L potassium is electrolyte.Electricity is carried out under two electrode systems
It is catalyzed the reaction of complete solution water, 10 circles are carried out with the speed of sweeping of 100mV first in the potential section of 0~2.0V (corresponding standard hydrogen electrode)
Cyclic voltammetry, to guarantee that catalyst is stablized during electrolysis water.Then linear scan test is carried out, scanning speed is
5mV, sweep interval are 0~2.0V, carry out electrolysis water activity analysis, electric current using the relationship between current density and applied voltage
The absolute value of density is bigger, and applying electrical potential is lower, then it is better to represent catalyst activity, and electrolysis water speed is faster.Then use
Timing coulometry is tested in 10mAcm-2Variation of the applying electrical potential in 50 hours catalytic process under current density.
Cobalt hydroxide-cobaltous selenide combination electrode to electro-catalysis complete solution water linear scan curve and stability figure such as
Shown in Fig. 6, (a) is linear scan curve graph in Fig. 6, (b) is stability figure.From fig. 6 it can be seen that being reacted in complete solution water
In, complete solution water power stream of the cobalt hydroxide-cobaltous selenide combination electrode under the potential of 2.23V is 10mAcm-2;In 10mAcm-2
Current density under, tested by 50 hours complete solution water, applied voltage only increases 0.5V.
It can be seen from the above embodiments that, efficiently difunctional decomposition water power catalyst (cobalt hydroxide-prepared by the present invention
Cobaltous selenide combination electrode) there is liberation of hydrogen high activity and analysis oxygen high activity, and when cathode and anode as electrocatalytic decomposition water,
Good liberation of hydrogen and oxygen evolution activity are all had in alkalinity and neutral electrolyte, and is had good stability, can efficiently realize complete solution
Water.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of efficiently difunctional preparation method for decomposing water power catalyst, which comprises the following steps:
(1) cobalt acetate, ammonium fluoride, urea and solvent are mixed, obtains mixed solution;
(2) carbon cloth is immersed and carries out hydro-thermal reaction in the mixed solution, obtain the carbon that surface growth has cobalt nanorod presoma
Cloth;
(3) there is the carbon cloth of cobalt nanorod presoma to be electrochemically transformed surface growth, obtain described efficiently difunctional
Decompose water power catalyst;
Described be electrochemically transformed uses three-electrode system, has the carbon cloth of cobalt nanorod presoma as work electricity using surface growth
Pole, using saturated calomel electrode as reference electrode, using the mixed solution of selenium dioxide, potassium chloride and water as electrolyte.
2. preparation method according to claim 1, which is characterized in that the solvent in the step (1) is water and ethyl alcohol
Mixed solvent;The volume ratio of the in the mixed solvent water and ethyl alcohol is 2:1.
3. preparation method according to claim 1 or 2, which is characterized in that cobalt acetate, ammonium fluoride, urine in the step (1)
The amount ratio of element and solvent is 3~5mmol:7~9mmol:15~25mmol:90~120mL.
4. preparation method according to claim 1, which is characterized in that the temperature of hydro-thermal reaction is 80 in the step (2)
~120 DEG C, the time is 8~12h.
5. preparation method according to claim 1 or 4, which is characterized in that in the step (2) after hydro-thermal reaction, also
Including the cooling, washing and drying successively carried out to gained carbon cloth;The washing is successively using deionized water and ethyl alcohol progress
Supersound washing;The temperature of the drying is 60 DEG C, time 2h.
6. preparation method according to claim 1, which is characterized in that selenium dioxide rubs in step (3) electrolyte
Your concentration is 5~15mmol/L, and the molar concentration of potassium chloride is 40~60mmol/L.
7. preparation method according to claim 1, which is characterized in that the outer power-up being electrochemically transformed in the step (3)
Pressure is -0.7~-0.8V, and the applied voltage is the potential relative to reference electrode.
8. preparation method according to claim 1 or claim 7, which is characterized in that the temperature being electrochemically transformed in the step (3)
It is 40~60 DEG C, the time is 20~40min.
9. preparation method according to claim 1, which is characterized in that after being electrochemically transformed in the step (3), also wrap
It includes and the working electrode after electrochemical conversion is successively washed and dried;It is described washing for successively using benzene, deionized water and
Ethyl alcohol carries out supersound washing;The temperature of the drying is 60 DEG C, time 2h.
10. the efficient difunctional decomposition water power catalyst of claim 1~9 any one the method preparation, which is characterized in that
The efficiently difunctional decomposition water power catalyst is cobalt hydroxide-cobaltous selenide composite electrocatalyst.
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