CN107321366A - A kind of elctro-catalyst of efficient-decomposition aquatic products hydrogen production oxygen and preparation method thereof - Google Patents
A kind of elctro-catalyst of efficient-decomposition aquatic products hydrogen production oxygen and preparation method thereof Download PDFInfo
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- CN107321366A CN107321366A CN201710452828.4A CN201710452828A CN107321366A CN 107321366 A CN107321366 A CN 107321366A CN 201710452828 A CN201710452828 A CN 201710452828A CN 107321366 A CN107321366 A CN 107321366A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000001301 oxygen Substances 0.000 title claims abstract description 28
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000006213 oxygenation reaction Methods 0.000 title abstract description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 12
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 229910003266 NiCo Inorganic materials 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 15
- 238000004073 vulcanization Methods 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 Co3O4 Chemical compound 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing 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
- 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
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C01G53/006—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses elctro-catalyst of a kind of efficient-decomposition aquatic products hydrogen production oxygen and preparation method thereof, the present invention utilizes two one-step hydrothermals, and the NiCo of different-thickness is constructed by regulating and controlling the concentration of growth-promoting media2S4Nanometer sheet.Thickness has a good electrochemical surface area for 70 80nm nanometer sheet, superior electron transport ability, more reactivity sites, and excellent performance is embodied in the production oxygen reaction of aquatic products hydrogen is decomposed using GaAs solar cells.The catalyst elements rich content, with low cost simultaneously, and preparation technology is simple, and catalytic performance is good, is that light is converted directly into the application study that the field of hydrogen provides the foundation.
Description
Technical field
The invention belongs to electrocatalytic decomposition aquatic products hydrogen production oxygen field, and in particular to a kind of efficient-decomposition aquatic products hydrogen produces the electricity of oxygen
Catalyst and preparation method thereof.
Background technology
With the rapid development of science and technology, a large amount of consumption of non-renewable energy resources, energy crisis is increasingly serious；Hydrogen is made
For a kind of reproducible clean energy resource, it is considered as the following reply maximally effective energy of energy scarcity problem；Decomposing aquatic products hydrogen entirely is
A kind of simple and environmentally-friendly, excellent chemical energy storage mode, and effective elctro-catalyst can be lifted and hydrogen and production oxygen are produced in full decomposition water
Performance.
Elctro-catalyst plays vital effect during full decomposition water, can accelerate two half-reactions：Liberation of hydrogen
（HER）With analysis oxygen（OER）Reaction rate.The main electrocatalyst materials with premium properties are Pt, Ru, your gold such as Ir at present
Category and its oxide, but the reason for be due to that these catalyst are expensive, content is rare, easily poisoned, it is limited in electricity
The further application in Xie Shui fields, therefore a kind of efficient non-noble metal elctro-catalyst of development has important Research Significance.
Transition group metallic oxide and sulfide, such as Co3O4, NiO,CoS2, NiS2With spinelle or pyrite knot
Structure, is common liberation of hydrogen catalyst, but due to its low electric conductivity and low electron transfer rate, limit it complete in OER and HER
Application in terms of decomposition water.Nowadays the catalyst on two-functional electrolytic reported mainly has NiFe-LDH, NiCo2S4Receive
Rice noodles, Co-P compounds etc., good catalytic performance is respectively provided with, but a kind of catalyst will meet low overpotential, Gao Wen simultaneously
Qualitatively require to be still a problem.
The content of the invention
First purpose of the present invention is to provide a kind of drive using gallium arsenide solar cell and efficient-decomposition aquatic products
Hydrogen produces the elctro-catalyst of oxygen.The catalyst has excellent liberation of hydrogen analysis oxygen performance, and overpotential and Tafel slopes are relatively low, surely
Qualitative good, under the driving of gallium arsenide solar cell, there is bipolar electrode substantial amounts of bubble to emerge, so that it is direct to improve light
Turn the efficiency of hydrogen, and preparation method is simple and convenient, it is with low cost, a large amount of productions can be easy to.
The present invention provides following technical scheme：A kind of efficient-decomposition aquatic products hydrogen produces the elctro-catalyst of oxygen, and the catalyst is
Thickness is 70-80nm NiCo2S4Nanometer sheet, the NiCo2S4Nanometer sheet has loose structure.
It is a further object of the present invention to provide the preparation method of the elctro-catalyst of above-mentioned efficient-decomposition aquatic products hydrogen production oxygen, the party
Method comprises the following steps：
Step 1）Divalent nickel salt and divalent cobalt are mixed according to a certain percentage with hexamethylenetetramine, the methanol solution added
In stir, obtain mixed solution；
Step 2）By the Ni foams and step 1 of certain size）In the solution that is completely dissolved be placed in reactor, carry out hydro-thermal anti-
Should, obtain other product；
Step 3）By step 2）In after obtained other product takes out, wash drying；
Step 4）Other product and a certain amount of sulfidising solution are placed in reactor, secondary hydro-thermal reaction is carried out, you can obtain
Product catalyst.
Further, the step 2）In hydrothermal growth condition be 170-190 DEG C, growth time is 8-12h.
Further, the step 4）In secondary hydrothermal growth condition be 140-160 DEG C, growth time is 5-7h.
Further, in the step 1 the ratio between divalent nickel salt, divalent cobalt and hexamethylenetetramine three is 1:
2:4。
Further, the sulfidising solution in the step 4 is the thioacetyl amine aqueous solution that concentration is 200-300mg/l.
Further, the catalyst has excellent liberation of hydrogen analysis oxygen performance, and overpotential and Tafel slopes are relatively low, surely
Qualitative good, under the driving of gallium arsenide solar cell, there is bipolar electrode substantial amounts of bubble to emerge, so that it is direct to improve light
Turn the efficiency of hydrogen.
It is preferred that, step 1）Middle divalent nickel salt and divalent cobalt are respectively Co (NO3)2·6H2O and Ni (NO3)2·6H2O,
And both contents are different, Ni (NO3)2·6H2O content is respectively 14.5mg, 29mg, 145mg, 290mg, 362.5mg,
Co(NO3)2·6H2O content is 29mg, 58mg, 290mg, 580mg, 725mg, and the content of hexamethylenetetramine is respectively
60mg、120mg、600mg、1200mg、1500mg。
It is preferred that, step 2）The condition of middle hydro-thermal reaction is 180 DEG C, reacts 10h.
It is preferred that, step 3）In obtained other product be NiCo-LDH, with hydrotalcite structure, with different-thickness
Laminated structure.
It is preferred that, step 4）In secondary hydro-thermal reaction condition be 150 DEG C, react 6h.
The application passes through to NiCo2S4Nanometer sheet catalyst carries out appearance structure regulation and control, is prepared for receiving with different-thickness
Rice piece catalyst, the catalyst of optimum thickness is applied during two-functional electrolytic, urged with high performance HER and OER
Change activity, optimize appearance structure, more preferable prospect is provided for the research of full decomposition water.
The gain effect of the present invention is：NiCo is prepared for using two one-step hydrothermals2S4Nanometer sheet catalyst, preparation method
Technique is simple, easy to implement and reproducible；The catalyst of preparation has larger specific surface area, good electronics conduction
Power, exposed electro-chemical activity site is more, and has in the reaction of electro-catalysis full decomposition water a superior performance, overpotential and
Tafel slopes are low, have good stability, more excellent compared to other similar catalyst performances in electro-catalysis production hydrogen production oxygen reaction,
Connected with gallium arsenide solar cell, realize that light directly changes the function of hydrogen.
Brief description of the drawings
Fig. 1 shows the XRD of the nanometer sheet catalyst of the different-thickness prepared in 1-5 of the embodiment of the present invention, wherein
A-e corresponds to the XRD of embodiment 1-5 products respectively.
Fig. 2 shows the scanning electron microscope sem photo of vulcanization nickel-cobalt catalyst prepared by the embodiment of the present invention 1.
Fig. 3 shows the scanning electron microscope sem photo of vulcanization nickel-cobalt catalyst prepared by the embodiment of the present invention 2.
Fig. 4 shows the scanning electron microscope sem photo of vulcanization nickel-cobalt catalyst prepared by the embodiment of the present invention 3.
Fig. 5 shows the scanning electron microscope sem photo of vulcanization nickel-cobalt catalyst prepared by the embodiment of the present invention 4.
Fig. 6 shows the scanning electron microscope sem photo of vulcanization nickel-cobalt catalyst prepared by the embodiment of the present invention 5.
Fig. 7 a and Fig. 7 b show transmission electron microscope of the vulcanization nickel-cobalt catalyst of the preparation of the embodiment of the present invention 4 under different multiples
TEM photos.
Fig. 8 a show that the electro-catalysis production hydrogen linear sweep voltammetry of vulcanization nickel-cobalt catalyst prepared by 1-5 of the embodiment of the present invention is bent
Line chart.
Fig. 8 b show the electro-catalysis production hydrogen Tafel slope figures of vulcanization nickel-cobalt catalyst prepared by 1-5 of the embodiment of the present invention.
Fig. 9 a show that the electro-catalysis production oxygen linear sweep voltammetry of vulcanization nickel-cobalt catalyst prepared by 1-5 of the embodiment of the present invention is bent
Line chart.
Fig. 9 b show the electro-catalysis production oxygen Tafel slope figures of vulcanization nickel-cobalt catalyst prepared by 1-5 of the embodiment of the present invention.
Figure 10 a show the vulcanization nickel-cobalt catalyst of the preparation of the embodiment of the present invention 4 as bipolar electrode and the line of gallium arsenide cells
Property scanning volt-ampere curve figure.
It is steady that Figure 10 b show that vulcanization nickel-cobalt catalyst prepared by the embodiment of the present invention 4 is connected with gallium arsenide solar cell
Qualitative figure.
Embodiment
Technical scheme is described in detail with reference to example.Obviously, described example is only to show
Meaning property, the full content of the present invention can not be included.Those skilled in the art are changed what is obtained under the inspiration of the present invention
Every other example, belongs to the scope of protection of the invention.
A kind of efficient-decomposition aquatic products hydrogen of the present invention produces the elctro-catalyst of oxygen, and the catalyst is that thickness is 70-80nm's
NiCo2S4Nanometer sheet, the NiCo2S4Nanometer sheet has loose structure.
The preparation method of the elctro-catalyst of above-mentioned efficient-decomposition aquatic products hydrogen production oxygen, this method comprises the following steps：
Step 1）Divalent nickel salt and divalent cobalt are mixed according to a certain percentage with hexamethylenetetramine, the methanol solution added
In stir, obtain mixed solution；
Step 2）By the Ni foams and step 1 of certain size）In the solution that is completely dissolved be placed in reactor, carry out hydro-thermal anti-
Should, obtain other product；
Step 3）By step 2）In after obtained other product takes out, wash drying；
Step 4）Other product and a certain amount of sulfidising solution are placed in reactor, secondary hydro-thermal reaction is carried out, you can obtain
Product catalyst.
Further, the step 2）In hydrothermal growth condition be 170-190 DEG C, growth time is 8-12h.
Further, the step 4）In secondary hydrothermal growth condition be 140-160 DEG C, growth time is 5-7h.
Further, in the step 1 the ratio between divalent nickel salt, divalent cobalt and hexamethylenetetramine three is 1:
2:4。
Further, the sulfidising solution in the step 4 is the thioacetyl amine aqueous solution that concentration is 200-300mg/l.
Further, the catalyst has excellent liberation of hydrogen analysis oxygen performance, and overpotential and Tafel slopes are relatively low, surely
Qualitative good, under the driving of gallium arsenide solar cell, there is bipolar electrode substantial amounts of bubble to emerge, so that it is direct to improve light
Turn the efficiency of hydrogen.
Embodiment 1：
NiCo2S4The preparation method of nanometer sheet electrocatalyst materials, comprises the following steps：
（1）1cm × 1.5cm nickel foam is placed in 1M hydrochloric acid progress ultrasonic cleaning 10min, with largely going after taking-up
Ionized water is rinsed well, is then dried in 40 DEG C of vacuum drying chamber.
（2）Configure NiCo-LDH growth solutions：14.5mg Ni (NO are weighed respectively3)2·6H2O, 29mg Co
(NO3)2·6H2It is dissolved in 30mL methanol, then magnetic agitation 30min, makes after O and 60mg hexamethylenetetramine, mixing
It is well mixed, and the element proportioning for obtaining Ni and Co is 1:2 clarification growth solution.
（3）Dried Ni foams are put into 50 mL reactor, growth solution is slowly toppled over, make loading about
For 80%.Reactor is placed in stainless steel sleeve and sealed, is then placed into air dry oven and is heated, reaction temperature
180 DEG C are maintained at, the reaction time is 10h, afterwards takes out reactor, and room temperature is cooled in atmosphere.After sample is taken out, use
Substantial amounts of deionized water is washed, and the residual solution on surface is removed.
（4）Configure sulfide precursor solution：The thioacetamide for weighing 200mg is dissolved in 30 mL deionized water
In, the precursor solution clarified after magnetic agitation 30min；
（5）The NiCo-LDH/Ni foam of homoepitaxial are placed in reactor, carried out after addition precursor solution at sealing
Reason, then heats 6h by reactor in air dry oven, and reaction temperature is 150 DEG C.Reactor, which is cooled to after room temperature, steeps Ni
Foam is taken out, and is respectively cleaned three times with ethanol and deionized water, dispels the sediment on sample, and sample then is placed in into 40 DEG C true
Dried in empty drying box.
Embodiment 2：
Other steps such as embodiment 1, only by step（2）It is changed to：Weigh 29mg Ni (NO3)2·6H2O, 58mg Co
(NO3)2·6H2In 30mL methanol is dissolved in after O and 120mg hexamethylenetetramine, mixing
Embodiment 3：
Other steps such as embodiment 1, only by step（2）It is changed to：Weigh 145mg Ni (NO3)2·6H2O, 290mg Co
(NO3)2·6H2It is dissolved in after O and 600mg hexamethylenetetramine, mixing in 30mL methanol.
Embodiment 4：
Other steps such as embodiment 1, only by step（2）It is changed to：Weigh 290mg Ni (NO3)2·6H2O, 580mg Co
(NO3)2·6H2It is dissolved in after O and 1200mg hexamethylenetetramine, mixing in 30mL methanol.
Embodiment 5：
Other steps such as embodiment 1, only by step（2）It is changed to：Weigh 362.5mg Ni (NO3)2·6H2O, 725mg Co
(NO3)2·6H2It is dissolved in after O and 1500mg hexamethylenetetramine, mixing in 30mL methanol.
The nanometer sheet catalyst of the different-thickness prepared in 1-5 of the embodiment of the present invention is respectively designated as NiCo2S4- 1,
NiCo2S4- 2, NiCo2S4- 3, NiCo2S4- 4, NiCo2S4-5；
Fig. 1 represents the XRD photos of the nanometer sheet catalyst of different-thickness, as seen from Figure 1, the nanometer sheet catalyst of very thin thickness
XRD peak intensity be not it is obvious that with the increase of thickness, the peak intensity of catalyst strengthens, and spinel structure is more obvious.
Fig. 2 is scanned photograph of the embodiment 1 under different multiples, and thickness is 5nm or so,
Fig. 3 is scanned photograph of the embodiment 2 under different multiples, and thickness is 10nm or so,
Fig. 4 is scanned photograph of the embodiment 3 under different multiples, and thickness is 20nm or so,
Fig. 5 be scanned photograph of the embodiment 4 under different multiples, thickness be 70 ~ 80 nm between,
Fig. 6 is scanned photograph of the embodiment 5 under different multiples, and thickness is 100nm or so.
Fig. 7 represents the TEM photos of nanometer sheet catalyst prepared by embodiment 4, and NiCo is found out by Fig. 72S4Nanometer sheet has good
Good crystal structure, interplanar distance is that 0.234nm and 0.283nm corresponds to crystal face respectively（400）With（311）.
Fig. 8 represents the electro-catalysis H2-producing capacity curve of vulcanization nickel-cobalt catalyst prepared by embodiment 1-5, has Fig. 8 a to see
Go out, with the increase of thickness, Hydrogen Evolution Performance has been lifted, but the Hydrogen Evolution Performance of the catalyst of the preparation of embodiment 5 has declined, it is real
The properties of sample for applying the preparation of example 4 is optimal, is 10mA/cm in current density2The overpotential at place is 80mv, and Tafel slopes are
58.5mv/dec。
Fig. 9 represents the electro-catalysis production oxygen performance curve of vulcanization nickel-cobalt catalyst prepared by embodiment 1-5, can be seen by Fig. 9 a
Go out, with the increase of thickness, analysis oxygen performance has been lifted, but the analysis oxygen performance of the catalyst of the preparation of embodiment 5 has declined, it is real
The properties of sample for applying the preparation of example 4 is optimal, is 10mA/cm in current density2The overpotential at place is 243mv, and Tafel slopes are
54.9mv/dec。
Figure 10 represents that the performance that vulcanization nickel-cobalt catalyst prepared by embodiment 4 is connected as bipolar electrode with gallium arsenide cells is bent
Line.It can be seen that by Figure 10 a and turn the efficiency of hydrogen by light can to reach that 16.55%, Figure 10 b can be seen that catalyst has good
Stability.
Claims (7)
1. a kind of efficient-decomposition water catalyst driven with gallium arsenide solar cell, it is characterised in that：The catalyst is thickness
For 70-80nm NiCo2S4Nanometer sheet, the NiCo2S4Nanometer sheet has loose structure.
2. a kind of side for preparing the efficient-decomposition water catalyst as claimed in claim 1 driven with gallium arsenide solar cell
Method, it is characterised in that：This method comprises the following steps：
Step 1）Divalent nickel salt and divalent cobalt are mixed according to a certain percentage with hexamethylenetetramine, the methanol solution added
In stir, obtain mixed solution；
Step 2）By the Ni foams and step 1 of certain size）In the solution that is completely dissolved be placed in reactor, carry out hydro-thermal anti-
Should, obtain other product；
Step 3）By step 2）In after obtained other product takes out, wash drying；
Step 4）Other product and a certain amount of sulfidising solution are placed in reactor, secondary hydro-thermal reaction is carried out, you can obtain
Product catalyst.
3. a kind of utilization gallium arsenide solar cell driving according to claim 2 and the electricity of efficient-decomposition aquatic products hydrogen production oxygen
The preparation method of catalyst, it is characterised in that：The step 2）In hydrothermal growth condition be 170-190 DEG C, growth time is
8-12h。
4. a kind of utilization gallium arsenide solar cell driving according to claim 2 and the electricity of efficient-decomposition aquatic products hydrogen production oxygen
The preparation method of catalyst, it is characterised in that：The step 4）In secondary hydrothermal growth condition be 140-160 DEG C, during growth
Between be 5-7h.
5. a kind of utilization gallium arsenide solar cell driving according to claim 2 and the electricity of efficient-decomposition aquatic products hydrogen production oxygen
The preparation method of catalyst, it is characterised in that：Divalent nickel salt, divalent cobalt and hexamethylenetetramine three in the step 1
Between ratio be 1:2:4.
6. a kind of utilization gallium arsenide solar cell driving according to claim 2 and the electricity of efficient-decomposition aquatic products hydrogen production oxygen
The preparation method of catalyst, it is characterised in that：Sulfidising solution in the step 4 is the thio second that concentration is 200-300mg/l
Amide solution.
7. a kind of electricity as claimed in claim 2 planted using gallium arsenide solar cell driving and efficient-decomposition aquatic products hydrogen production oxygen
The preparation method of catalyst, it is characterised in that：The catalyst has excellent liberation of hydrogen analysis oxygen performance, and overpotential and Tafel are oblique
Rate is relatively low, has good stability, under the driving of gallium arsenide solar cell, and there is bipolar electrode substantial amounts of bubble to emerge, from
And improve the efficiency that light directly turns hydrogen.
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| CN108940328A (en) * | 2018-06-28 | 2018-12-07 | 大连理工大学 | Nanometer sheet-modified molybdenum carbide electro-catalysis catalyst for preparing hydrogen of nanometer rods coupling three-dimensional composite material Ni-Co and preparation method thereof |
| CN109126797A (en) * | 2018-08-13 | 2019-01-04 | 广东工业大学 | A kind of electrocatalyst materials of water electrolysis hydrogen production and its preparation method and application |
| CN110026208A (en) * | 2019-05-10 | 2019-07-19 | 安徽师范大学 | Ni-based three nickel composite array elctro-catalyst of layered double-hydroxide@curing of the iron of heterojunction structure and its preparation method and application |
| CN110270351A (en) * | 2018-03-13 | 2019-09-24 | 吉林师范大学 | A kind of alkaline water electrolytic of high nickel content pentlandite phase nickel cobalt sulphide electrocatalyst and preparation method thereof |
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| WO2021184563A1 (en) * | 2020-03-19 | 2021-09-23 | 苏州楚捷新材料科技有限公司 | Preparation method for foamed nickel-based catalyst for hydrogen production by water electrolysis |
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