CN109174146A - One-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material and preparation method and application - Google Patents
One-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material and preparation method and application Download PDFInfo
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- CN109174146A CN109174146A CN201810816502.XA CN201810816502A CN109174146A CN 109174146 A CN109174146 A CN 109174146A CN 201810816502 A CN201810816502 A CN 201810816502A CN 109174146 A CN109174146 A CN 109174146A
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 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 title claims abstract description 24
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000011669 selenium Substances 0.000 claims abstract description 34
- 239000002070 nanowire Substances 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000006260 foam Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- NLZOGIZKBBJWPB-UHFFFAOYSA-N [Na].[SeH2] Chemical compound [Na].[SeH2] NLZOGIZKBBJWPB-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 230000036571 hydration Effects 0.000 claims description 9
- 238000006703 hydration reaction Methods 0.000 claims description 9
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 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 description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000010287 polarization Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- -1 Transition metal selenides Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000003346 selenoethers Chemical class 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of one-dimensional basic cobaltous carbonate dimensional Co Se/NF heterojunction structure composite material and preparation method and application, which includes: by basic carbonate cobalt nanowire Co (CO3)0.5(OH)·0.11H2O, selenium source, cobalt source carry out solvent thermal reaction in solvent one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material is made；Wherein, basic cobaltous carbonate is nanowire supported on nickel foam NF.The heterojunction structure composite material has excellent electro-catalysis and cycle performance and then can be applied in electro-catalysis hydrolysis, while the preparation method has simple process, cheap advantage.
Description
Technical field
The present invention relates to heterojunction structure composite materials, and in particular, to a kind of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF
Heterojunction structure composite material and preparation method and application.
Background technique
The selenides of transition metal due to its with unique physics and chemistry property, thus catalysis, electrochemistry and
The fields such as gas sensor have a wide range of applications, so as to cause the high interest of people.Transition metal selenides is due to it
Have the characteristics that the high and low cost of catalytic activity, be readily synthesized, good stability, has become a hot topic of research.Traditional transition gold
Category has cobaltous selenide, two cobaltous selenides etc., is mostly the selenides of single transition metal, for different morphologies heterojunction structure selenides
Research it is relatively fewer.
The performance of electro-catalysis hydrolysis is largely dependent on its electrode material, the direction that current electrode material is mainly studied
Have a precious metal materials such as transition metal-type material and platinum, iridium, for example, transition metal oxide, sulfide, selenides, phosphide and
Mix transition-metal oxide etc..That there are catalytic performances is poor for general single transition metal material, chemical kinetics performance is poor,
Recycling the defects of unstable, such as Hongxiu Zhang et al. reports list on the RSC Advance periodical of RSC database
One two cobaltous selenide electrode materials, but its catalytic activity for hydrogen evolution difference and cyclical stability are bad in the case of comparing.Tingting
Liu et al. people is on the ChemComm periodical of RSC database, it was recently reported that single cobaltous selenide is in 10mA/cm2Current density under analyse
Oxygen overpotential reaches 292mV, and liberation of hydrogen overpotential reaches 121mV.It can be seen that general single transition metal electrode material
Still have the defects that the needs such as electro catalytic activity is poor, circulation is unstable are promoted.
Summary of the invention
The object of the present invention is to provide a kind of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material and its
Preparation method and application, the heterojunction structure composite material have excellent electro-catalysis and cycle performance and then can be applied to
In electro-catalysis hydrolysis, while the preparation method has simple process, cheap advantage.
To achieve the goals above, it is multiple that the present invention provides a kind of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structures
The preparation method of condensation material, comprising: by basic carbonate cobalt nanowire Co (CO3)0.5(OH)·0.11H2O, selenium source, cobalt source are in solvent
Middle progress solvent thermal reaction is to be made one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material；Wherein, alkali formula carbon
Sour cobalt nanowire is carried on nickel foam NF.
The present invention also provides a kind of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material, the one-dimensional alkali
Formula cobalt carbonate@dimensional Co Se/NF heterojunction structure composite material is prepared by above-mentioned preparation method.
Invention further provides a kind of one-dimensional basic cobaltous carbonate dimensional Co Se/NF heterojunction structure as above-mentioned is compound
Application of the material in electro-catalysis hydrolysis.
In the above-mentioned technical solutions, the present invention by one-dimensional basic cobaltous carbonate, dimensional Co Se and NF carry out it is compound obtain it is different
Matter structural composite material, the heterojunction structure composite material have that electro catalytic activity is good, performance of good cycling stability, can be used as electricity
The electrode material of catalyzing hydrolysis；Wherein, in 10mA/cm2Under current density, the analysis oxygen overpotential of the heterojunction structure composite material is
255mV, liberation of hydrogen overpotential are 128mV；After 1000 circulations, the electro catalytic activity of the heterojunction structure composite material remains to protect
It holds more stable, illustrates that its is with good stability.Meanwhile the preparation method has easy to operate, low in cost, condition temperature
With environmentally protective advantage, and then can be widely applied.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 a is the scanning electron microscope (SEM) of 40K times of the amplification of heterojunction structure composite material prepared by embodiment 1
Figure；
Fig. 1 b is scanning electron microscope (SEM) figure of 7K times of the amplification of heterojunction structure composite material prepared by embodiment 1；
Fig. 2 is transmission electron microscope (TEM) figure of heterojunction structure composite material prepared by embodiment 1；
Fig. 3 is x-ray diffraction pattern (XRD) figure of heterojunction structure composite material prepared by embodiment 1；
Fig. 4 is the analysis oxygen polarization curve of heterojunction structure composite material prepared by embodiment 1；
Fig. 5 is linear volt-ampere curve figure after the analysis oxygen 1000 of heterojunction structure composite material prepared by embodiment 1 encloses；
Fig. 6 is the liberation of hydrogen polarization curve of heterojunction structure composite material prepared by embodiment 1；
Fig. 7 is linear volt-ampere curve figure after the liberation of hydrogen 1000 of heterojunction structure composite material prepared by embodiment 1 encloses.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material,
It include: by basic carbonate cobalt nanowire Co (CO3)0.5(OH)·0.11H2O, selenium source, cobalt source carry out solvent thermal reaction in solvent
One-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material is made；Wherein, basic cobaltous carbonate it is nanowire supported in
On nickel foam NF.
In the above preparation method, the dosage of each material can select in a wide range, but in order to further increase
The electrocatalysis characteristic and cycle performance of heterojunction structure composite material, it is preferable that basic carbonate cobalt nanowire, selenium source, cobalt source, NF
Amount ratio is 0.02-0.08g:0.5-2.5mmol:0.5-2.5mmol:2.4-4mmol.
In the above preparation method, the dosage of solvent can select in a wide range, but different in order to further increase
The electrocatalysis characteristic and cycle performance of matter structural composite material, it is preferable that basic carbonate cobalt nanowire, solvent amount ratio be
0.02-0.08g:30-40mL.
In the above preparation method, the condition of solvent thermal reaction can select in a wide range, but in order to further
Improve the electrocatalysis characteristic and cycle performance of heterojunction structure composite material, it is preferable that solvent thermal reaction meets the following conditions: reaction
Temperature is 140-200 DEG C, reaction time 1-5h.
In the above preparation method, the type of selenium source, cobalt source and solvent can select in a wide range, but in order into
The electrocatalysis characteristic and cycle performance of one step raising heterojunction structure composite material, it is preferable that selenium source is selected from sodium hydrogen selenide, titanium dioxide
At least one of selenium and selenium powder, cobalt source is in four water four hydration cobalt acetate, cabaltous nitrate hexahydrate and cobalt chloride hexahydrate
At least one, solvent is selected from least one of water, ethyl alcohol.
In the above preparation method, the preparation method of basic carbonate cobalt nanowire can select in a wide range, still
In order to further increase the electrocatalysis characteristic and cycle performance of heterojunction structure composite material, it is preferable that basic carbonate cobalt nanowire
It is prepared by the following method and obtains: cobalt source, ammonium fluoride, urea, nickel foam are subjected to hydro-thermal reaction in water, then clean, dry
Basic carbonate cobalt nanowire is made.
In the preparation method of above-mentioned basic carbonate cobalt nanowire, the dosage of each material can select in a wide range,
But in order to further increase the electrocatalysis characteristic and cycle performance of heterojunction structure composite material obtained, it is preferable that cobalt source, fluorine
Change ammonium, urea, nickel foam, water amount ratio be 1-5mmol:2-8mmol:5-20mmol:2.4-4mmol:30-40mL；
In the preparation method of above-mentioned basic carbonate cobalt nanowire, the condition of hydro-thermal reaction can be selected in a wide range
It selects, but in order to further increase the electrocatalysis characteristic and cycle performance of heterojunction structure composite material obtained, it is preferable that hydro-thermal
Reaction meets the following conditions: reaction temperature is 100-180 DEG C, reaction time 10-60min；
In the preparation method of above-mentioned basic carbonate cobalt nanowire, the type of cobalt source can select in a wide range, but
It is the electrocatalysis characteristic and cycle performance in order to further increase heterojunction structure composite material obtained, it is preferable that cobalt source is selected from
Cabaltous nitrate hexahydrate, four hydration at least one of cobalt acetates and cobalt chloride hexahydrate.
The present invention also provides a kind of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material, the one-dimensional alkali
Formula cobalt carbonate@dimensional Co Se/NF heterojunction structure composite material is prepared by above-mentioned preparation method.
In the present invention, the size of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material can be wide
Selection in range, but in order to further increase the electrocatalysis characteristic and cycle performance of heterojunction structure composite material obtained, it is excellent
Selection of land, the length of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material are 5um-7um, width 40nm-
80nm。
Invention further provides a kind of one-dimensional basic cobaltous carbonate dimensional Co Se/NF heterojunction structure as above-mentioned is compound
Application of the material in electro-catalysis hydrolysis.
The present invention will be described in detail by way of examples below.
Embodiment 1
1) by 1mmol cabaltous nitrate hexahydrate, 3mmol ammonium fluoride, 10mmol urea is dissolved in 35ml deionized water, and magnetic force stirs
After mixing 30min, mixed solution is transferred in 50ml reaction kettle, then cleaned 6cm is added thereto2Nickel foam (0.141g,
2.4mmol)；Reaction kettle is placed in 120 DEG C of insulating boxs, 10h is reacted；After reaction, it cleans, drying obtains one-dimensional Co
(CO3)0.5(OH)·0.11H2O/NF nano wire the 0.2626g ((CO of Co containing 0.0446g3)0.5(OH)·0.11H2O)；
2) by four hydration cobalt acetates and sodium hydrogen selenide mixed solution, (30ml is hydrated cobalt acetates containing four and sodium hydrogen selenide is each
It 1.2mmol) is added in the reaction kettle of 50ml, then the one-dimensional Co (CO of above-mentioned 0.2626g is added into kettle3)0.5(OH)·0.11H2O/
NF nano wire, sealing, it is 3h that reaction kettle is put into the reaction time in 180 DEG C of thermostatic drying chamber, is cleaned after the reaction was completed, 70 DEG C
It is dry, obtain one-dimensional and dimensional Co (CO3)0.5(OH)·0.11H2O@CoSe/NF heterojunction structure composite material.
Embodiment 2
1) by 2mmol cabaltous nitrate hexahydrate, 5mmol ammonium fluoride, 5mmol urea is dissolved in 35ml deionized water, and magnetic force stirs
After mixing 30min, mixed solution is transferred in 50ml reaction kettle, then cleaned 6cm is added thereto2Nickel foam (0.141g)；
Reaction kettle is placed in 140 DEG C of insulating boxs, 10h is reacted；After reaction, it cleans, drying obtains one-dimensional Co (CO3)0.5
(OH)·0.11H2O/NF nano wire the 0.2894g ((CO of Co containing 0.0714g3)0.5(OH)·0.11H2O)；
2) by four hydration cobalt acetates and sodium hydrogen selenide mixed solution, (30ml is hydrated cobalt acetates containing four and sodium hydrogen selenide is each
It 1mmol) is added in the reaction kettle of 50ml, then the one-dimensional Co (CO of above-mentioned 0.2894g is added into kettle3)0.5(OH)·0.11H2O/NF
Nano wire, sealing, it is 5h that reaction kettle is put into the reaction time in 160 DEG C of thermostatic drying chamber, is cleaned after the reaction was completed, and 70 DEG C dry
It is dry, obtain one-dimensional and dimensional Co (CO3)0.5(OH)·0.11H2O@CoSe/NF heterojunction structure composite material.
Embodiment 3
1) by 3mmol cabaltous nitrate hexahydrate, 5mmol ammonium fluoride, 15mmol urea is dissolved in 35ml deionized water, and magnetic force stirs
After mixing 30min, mixed solution is transferred in 50ml reaction kettle, then cleaned 9cm is added thereto2Nickel foam (0.2328g,
4mmol)；Reaction kettle is placed in 160 DEG C of insulating boxs, 5h is reacted；After reaction, it cleans, drying obtains one-dimensional Co
(CO3)0.5(OH)·0.11H2O/NF nano wire the 0.3125g ((CO of Co containing 0.0723g3)0.5(OH)·0.11H2O)；
2) by four hydration cobalt acetates and sodium hydrogen selenide mixed solution, (30ml is hydrated cobalt acetates containing four and sodium hydrogen selenide is each
It 1.5mmol) is added in the reaction kettle of 50ml, then the one-dimensional Co (CO of above-mentioned 0.3125g is added into kettle3)0.5(OH)·0.11H2O/
NF nano wire, sealing, it is 1h that reaction kettle is put into the reaction time in 180 DEG C of thermostatic drying chamber, is cleaned after the reaction was completed, 70 DEG C
It is dry, obtain one-dimensional and dimensional Co (CO3)0.5(OH)·0.11H2O@CoSe/NF heterojunction structure composite material.
Embodiment 4
1) by 2mmol cabaltous nitrate hexahydrate, 6mmol ammonium fluoride, 5mmol urea is dissolved in 35ml deionized water, and magnetic force stirs
After mixing 30min, mixed solution is transferred in 50ml reaction kettle, then cleaned 9cm is added thereto2Nickel foam (0.2328g)；
Reaction kettle is placed in 140 DEG C of insulating boxs, 15h is reacted；After reaction, it cleans, drying obtains one-dimensional Co (CO3)0.5
(OH)·0.11H2O/NF nano wire the 0.3067g ((CO of Co containing 0.0727g3)0.5(OH)·0.11H2O)；
2) by four hydration cobalt acetates and sodium hydrogen selenide mixed solution, (30ml is hydrated cobalt acetates containing four and sodium hydrogen selenide is each
It 2mmol) is added in the reaction kettle of 50ml, then the one-dimensional Co (CO of above-mentioned 0.3067g is added into kettle3)0.5(OH)·0.11H2O/NF
Nano wire, sealing, it is 5h that reaction kettle is put into the reaction time in 160 DEG C of thermostatic drying chamber, is cleaned after the reaction was completed, and 70 DEG C dry
It is dry, obtain one-dimensional and dimensional Co (CO3)0.5(OH)·0.11H2O@CoSe/NF heterojunction structure composite material.
Embodiment 5
1) by 4mmol cabaltous nitrate hexahydrate, 6mmol ammonium fluoride, 20mmol urea is dissolved in 35ml deionized water, and magnetic force stirs
After mixing 30min, mixed solution is transferred in 50ml reaction kettle, then cleaned 9cm is added thereto2Nickel foam (0.2328g)；
Reaction kettle is placed in 160 DEG C of insulating boxs, 15h is reacted；After reaction, it cleans, drying obtains one-dimensional Co (CO3)0.5
(OH)·0.11H2O/NF nano wire the 0.2894g ((CO of Co containing 0.0566g3)0.5(OH)·0.11H2O)；
2) by four hydration cobalt acetates and sodium hydrogen selenide mixed solution, (30ml is hydrated cobalt acetates containing four and sodium hydrogen selenide is each
It 0.7mmol) is added in the reaction kettle of 50ml, then the one-dimensional Co (CO of above-mentioned 0.2894g is added into kettle3)0.5(OH)·0.11H2O/
NF nano wire, sealing, it is 1h that reaction kettle is put into the reaction time in 180 DEG C of thermostatic drying chamber, is cleaned after the reaction was completed, 70 DEG C
It is dry, obtain one-dimensional and dimensional Co (CO3)0.5(OH)·0.11H2O@CoSe/NF heterojunction structure composite material.
Detect example 1
1) morphology analysis is carried out to 1 products therefrom of embodiment by scanning electron microscope (SEM), as a result such as Fig. 1 a and figure
Shown in 1b, show that prepared sample is nanowire structure, length 5um-7um, width 40nm-80nm.
2) 1 products therefrom ingredient of embodiment is analyzed by transmission electron microscope (TEM), as a result such as Fig. 2 institute
Show, showing the sample is one-dimensional and two dimensional heterostructures, and wherein one-dimentional structure is basic carbonate cobalt nanowire, and two-dimensional structure is
CoSe thin slice.
3) 1 products therefrom is implemented by X-ray diffraction (XRD) detection, as a result as shown in figure 3, obtaining map and JCPDS mark
Co (CO corresponding to quasi- card NO.48-00833)0.5(OH)·0.11H2O diffraction maximum, JCPDS standard card NO.89-2004 institute are right
The diffraction maximum of the CoSe answered fits like a glove.This XRD diagram can be very good to prove that the substance is Co (CO3)0.5(OH)·0.11H2O@
CoSe/NF composite material.
Detect example 2
Test instrument is CHI660E electrochemical workstation, the manufacture of Shanghai Chen Hua Instrument Ltd. below.
Test is all made of three-electrode system below, wherein the one-dimensional and dimensional Co (CO for preparing embodiment 13)0.5
(OH)·0.11H2O@CoSe/NF heterojunction structure composite material (is cut into the piece of 1cm × 1cm, loading capacity is as working electrode
6mg/cm2)；Using carbon electrode and silver silver chloride electrode as to electrode and reference electrode；Made with the KOH solution of 1mol/L
For electrolyte.
1) electrochemistry linear scanning voltammetry (LSV) test
Voltammetry, which is scanned, by electrochemistry linear obtains one-dimensional and dimensional Co (CO3)0.5(OH)·0.11H2O@CoSe/NF is different
Matter structural composite material analyses the catalytic performance polarization curve of oxygen and liberation of hydrogen in alkaline solution.In analysis oxygen performance test, in electricity
Gesture is the sweep speed that uses in the section 1.1-1.8V vs.RHE for 2mVs-1And there is 90% iR to compensate, it is obtained from test
Polarization curve (such as Fig. 4), it can be seen that current density be 10mA cm-2When, the potential for analysing oxygen is 1.485V vs.RHE.This is multiple
It is 255mV that condensation material, which analyses oxygen voltage to have very low overpotential compared with theoretical water electrolytic potential, it can be seen that the analysis oxygen of the material
It can be superior.It is the sweep speed that is used in the section -0.6~0V vs.RHE for 5mVs in potential in Hydrogen Evolution Performance test-1
And have 90% iR compensation, available from the obtained polarization curve (see Fig. 6) of test in current density is 10mAcm-2
When, the potential of liberation of hydrogen is 0.128V vs.RHE, and Hydrogen Evolution Performance is excellent.
2) cyclic voltammetry (CV) is tested
One-dimensional in alkaline solution and dimensional Co (CO is obtained by electrochemical cyclic voltammetry3)0.5(OH)·0.11H2O@
CoSe/NF heterojunction structure composite material electro-catalysis stability.With 50mV.s in the case where no iR compensation-1Sweep speed pair
The polarization reactions of the analysis oxygen and liberation of hydrogen of 1000 circle of material progress, and polarization song is measured by linear sweep voltammetry after 1000 circles
Line.Analysis oxygen polarization curve is almost the same with initial analysis oxygen polarization curve after 1000 circles as seen from Figure 5, available to be somebody's turn to do
Stabilization sex expression of the material in terms of analysing oxygen is outstanding.And from Fig. 7 it is available 1000 circle after liberation of hydrogen polarization curve with
Original polarization curve is overlapped well, presents excellent in stability of the material in liberation of hydrogen.
The product of embodiment 2-5 is detected according to the method for above-mentioned detection example 1-2, testing result and embodiment 1
The testing result of product is consistent substantially.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material, which is characterized in that packet
It includes: by basic carbonate cobalt nanowire Co (CO3)0.5(OH)·0.11H2O, selenium source, cobalt source carried out in solvent solvent thermal reaction with
The one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material is made；Wherein, the basic carbonate cobalt nanowire
It is carried on nickel foam NF.
2. preparation method according to claim 1, wherein the basic carbonate cobalt nanowire, selenium source, cobalt source, the use of NF
Amount is than being 0.02-0.08g:0.5-2.5mmol:0.5-2.5mmol:2.4-4mmol.
3. preparation method according to claim 1, wherein the basic carbonate cobalt nanowire, solvent amount ratio be
0.02-0.08g:30-40mL.
4. preparation method according to claim 1, wherein the solvent thermal reaction meets the following conditions: reaction temperature is
140-200 DEG C, reaction time 1-5h.
5. preparation method according to claim 1, wherein the selenium source is in sodium hydrogen selenide, selenium dioxide and selenium powder
At least one, the cobalt source is selected from least one of four hydration cobalt acetates, cabaltous nitrate hexahydrate and cobalt chloride hexahydrate, institute
It states solvent and is selected from least one of water, ethyl alcohol.
6. preparation method according to claim 1, wherein the basic carbonate cobalt nanowire be prepared by the following method and
: cobalt source, ammonium fluoride, urea, nickel foam are subjected to hydro-thermal reaction in water, then cleans, dry so that the basic carbonate is made
Cobalt nanowire.
7. preparation method according to claim 6, wherein the cobalt source, ammonium fluoride, urea, nickel foam, water amount ratio be
1-5mmol:2-8mmol:5-20mmol:2.4-4mmol:30-40mL；
Preferably, the hydro-thermal reaction meets the following conditions: reaction temperature is 100-180 DEG C, reaction time 10-60min；
It is highly preferred that the cobalt source is selected from cabaltous nitrate hexahydrate, four hydration at least one of cobalt acetates and cobalt chloride hexahydrate.
8. a kind of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material, which is characterized in that the one-dimensional alkali formula
Cobalt carbonate@dimensional Co Se/NF heterojunction structure composite material passes through preparation method preparation described in any one of claim 1-7
And it obtains.
9. preparation method according to claim 8, wherein the one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure
Composite gauge are as follows: length 5um-7um, width 40nm-80nm.
10. a kind of one-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material as claimed in claim 8 or 9 is in electricity
Application in catalyzing hydrolysis.
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