CN109174146B - One-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material and preparation method and application thereof - Google Patents
One-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002070 nanowire Substances 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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 11
- 239000006260 foam Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 239000011669 selenium Substances 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 17
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- 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
- RBRLCUAPGJEAOP-UHFFFAOYSA-M sodium selanide Chemical compound [Na+].[SeH-] RBRLCUAPGJEAOP-UHFFFAOYSA-M 0.000 claims description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 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 3
- 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 abstract description 3
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 10
- 230000010287 polarization Effects 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003346 selenoethers Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 Transition metal selenides Chemical class 0.000 description 2
- NLZOGIZKBBJWPB-UHFFFAOYSA-N [Na].[SeH2] Chemical compound [Na].[SeH2] NLZOGIZKBBJWPB-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004678 hydrides Chemical class 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
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- 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 one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: basic cobalt carbonate nanowire Co (CO)3)0.5(OH)·0.11H2Carrying out solvothermal reaction on O, a selenium source and a cobalt source in a solvent to prepare a one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material; wherein, basic cobaltous carbonate nanometer line is loaded on foam nickel NF. The heterostructure composite material has excellent electrocatalysis and cycle performance, so that the heterostructure composite material can be applied to electrocatalysis hydrolysis, and meanwhile, the preparation method has the advantages of simple process and low cost.
Description
Technical Field
The invention relates to a heterostructure composite material, in particular to a one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material and a preparation method and application thereof.
Background
Transition metal selenides have been widely used in the fields of catalysis, electrochemistry, gas sensors, etc. due to their unique physical and chemical properties, thus attracting great interest. The transition metal selenide has the characteristics of high catalytic activity, low cost, easy synthesis, good stability and the like, and becomes a hot point of research. The traditional transition metals include cobalt selenide, cobalt diselenide and the like, most of the transition metals are selenides of single transition metal, and research on heterostructured selenides with various shapes is relatively less.
The performance of electrocatalytic hydrolysis depends on the electrode material, and the main research directions of the current electrode materials are transition metal materials and noble metal materials such as platinum and iridium, such as transition metal oxides, sulfides, selenides, phosphides, mixed transition metal oxides and the like. The defects of poor catalytic performance, poor chemical and dynamic performance, unstable cycle and the like of common single transition metal materials, such as Hongxiu Zhang and the likeA single cobalt diselenide electrode material is reported in an RSC Advance journal of an RSC database, but the hydrogen evolution catalytic activity and the cycling stability of the cobalt diselenide electrode material are poor under the comparative conditions. In the Chemcomm journal of RSC database, Tingting Liu et al reported that single cobalt selenide was at 10mA/cm2The overpotential for oxygen evolution reaches 292mV and the overpotential for hydrogen evolution reaches 121mV under the current density of (1). Therefore, it can be seen that the single transition metal electrode material still has the defects of poor electrocatalytic activity, unstable cycle and the like which need to be improved.
Disclosure of Invention
The invention aims to provide a one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material, a preparation method and application thereof.
In order to achieve the purpose, the invention provides a preparation method of a one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material, which comprises the following steps: basic cobalt carbonate nanowire Co (CO)3)0.5(OH)·0.11H2Carrying out solvothermal reaction on O, a selenium source and a cobalt source in a solvent to prepare a one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material; wherein, basic cobaltous carbonate nanometer line is loaded on foam nickel NF.
The invention also provides a one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material which is prepared by the preparation method.
The invention further provides an application of the one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material in electrocatalytic hydrolysis.
In the technical scheme, the one-dimensional basic cobalt carbonate, the two-dimensional CoSe and the NF are compounded to obtain the heterostructure composite material, and the heterostructure composite material has the performances of good electrocatalytic activity and good cycling stability and can be used as an electrode material for electrocatalytic hydrolysis; wherein, the concentration is 10mA/cm2At current density, the heterostructure compositeThe overpotential of oxygen evolution of the material is 255mV, and the overpotential of hydrogen evolution is 128 mV; after 1000 cycles, the electrocatalytic activity of the heterostructure composite material can still keep relatively stable, which shows that the heterostructure composite material has good stability. Meanwhile, the preparation method has the advantages of simple operation, low cost, mild condition and environmental protection, and further can be popularized in a large area.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1a is a Scanning Electron Microscope (SEM) image at 40K magnification of a heterostructure composite prepared in example 1;
FIG. 1b is a Scanning Electron Microscope (SEM) image at 7K magnification of a heterostructure composite prepared in example 1;
FIG. 2 is a Transmission Electron Microscopy (TEM) image of the heterostructure composite prepared in example 1;
FIG. 3 is an X-ray diffraction (XRD) pattern of the heterostructure composite prepared in example 1;
FIG. 4 is a graph of oxygen evolution polarization for the heterostructure composite prepared in example 1;
FIG. 5 is a plot of linear voltammograms after 1000 cycles of oxygen evolution for the heterostructure composite prepared in example 1;
FIG. 6 is a hydrogen evolution polarization plot for the heterostructure composite prepared in example 1;
fig. 7 is a linear voltammogram after 1000 cycles of hydrogen evolution for the heterostructure composite prepared in example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material, which comprises the following steps: basic cobalt carbonate nanowire Co (CO)3)0.5(OH)·0.11H2Carrying out solvothermal reaction on O, a selenium source and a cobalt source in a solvent to prepare a one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material; wherein, basic cobaltous carbonate nanometer line is loaded on foam nickel NF.
In the preparation method, the dosage of each material can be selected in a wide range, but in order to further improve the electrocatalytic performance and the cycle performance of the heterostructure composite material, the dosage ratio of the basic cobalt carbonate nanowire, the selenium source, the cobalt source and the NF is preferably 0.02-0.08 g: 0.5-2.5 mmol: 0.5-2.5 mmol: 2.4-4 mmol.
In the above preparation method, the amount of the solvent may be selected within a wide range, but in order to further improve the electrocatalytic performance and the cycle performance of the heterostructure composite, it is preferable that the ratio of the amount of the basic cobalt carbonate nanowire to the amount of the solvent is 0.02 to 0.08 g: 30-40 mL.
In the above-described production method, the conditions of the solvothermal reaction can be selected within a wide range, but in order to further improve the electrocatalytic performance and the cycle performance of the heterostructure-composite material, it is preferable that the solvothermal reaction satisfies the following conditions: the reaction temperature is 140 ℃ and 200 ℃, and the reaction time is 1-5 h.
In the above preparation method, the kinds of the selenium source, the cobalt source and the solvent may be selected within a wide range, but in order to further improve the electrocatalytic performance and the cycle performance of the heterostructure composite material, it is preferable that the selenium source is selected from at least one of sodium hydroselenide, selenium dioxide and selenium powder, the cobalt source is selected from at least one of cobalt acetate tetrahydrate, cobalt nitrate hexahydrate and cobalt chloride hexahydrate, and the solvent is selected from at least one of water and ethanol.
Among the above preparation methods, the preparation method of the basic cobalt carbonate nanowire can be selected in a wide range, but in order to further improve the electrocatalytic performance and the cycle performance of the heterostructure composite, preferably, the basic cobalt carbonate nanowire is prepared by the following method: and (2) performing hydrothermal reaction on a cobalt source, ammonium fluoride, urea and foamed nickel in water, and then cleaning and drying to obtain the basic cobalt carbonate nanowire.
In the above method for preparing basic cobalt carbonate nanowires, the amount of each material can be selected in a wide range, but in order to further improve the electrocatalytic performance and the cycle performance of the prepared heterostructure composite material, the ratio of the amount of cobalt source, ammonium fluoride, urea, nickel foam and water is preferably 1-5 mmol: 2-8 mmol: 5-20 mmol: 2.4-4 mmol: 30-40 mL;
in the above method for preparing basic cobalt carbonate nanowires, the conditions of the hydrothermal reaction can be selected within a wide range, but in order to further improve the electrocatalytic performance and the cycle performance of the prepared heterostructure composite material, preferably, the hydrothermal reaction satisfies the following conditions: the reaction temperature is 100-180 ℃, and the reaction time is 10-60 min;
in the above method for preparing basic cobalt carbonate nanowires, the kind of the cobalt source may be selected within a wide range, but in order to further improve the electrocatalytic performance and the cycle performance of the prepared heterostructure composite material, preferably, the cobalt source is selected from at least one of cobalt nitrate hexahydrate, cobalt acetate tetrahydrate and cobalt chloride hexahydrate.
The invention also provides a one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material which is prepared by the preparation method.
In the invention, the size of the one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material can be selected in a wide range, but in order to further improve the electrocatalytic performance and the cycle performance of the prepared heterostructure composite material, the length of the one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material is preferably 5-7 um, and the width is preferably 40-80 nm.
The invention further provides an application of the one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material in electrocatalytic hydrolysis.
The present invention will be described in detail below by way of examples.
Example 1
1) Dissolving 1mmol of cobalt nitrate hexahydrate, 3mmol of ammonium fluoride and 10mmol of urea in 35ml of deionized water, magnetically stirring for 30min, transferring the mixed solution into a 50ml reaction kettle, and adding cleaned 6cm2Nickel foam (0.141g, 2.4 mmol); placing the reaction kettle in a constant temperature box at 120 ℃ for reaction for 10 hours; after the reaction is finished, cleaning and drying are carried out to obtain one-dimensional Co (CO)3)0.5(OH)·0.11H2O/NF nanowire 0.2626g (containing 0.0446g Co (CO)3)0.5(OH)·0.11H2O)；
2) Adding mixed solution of cobalt acetate tetrahydrate and sodium hydroselenide (30ml, containing cobalt acetate tetrahydrate and sodium hydroselenide each 1.2mmol) into 50ml reaction kettle, adding 0.2626g of one-dimensional Co (CO)3)0.5(OH)·0.11H2Sealing the O/NF nanowire, putting the reaction kettle into a constant-temperature drying oven at 180 ℃ for reaction for 3 hours, cleaning after the reaction is finished, and drying at 70 ℃ to obtain one-dimensional and two-dimensional Co (CO)3)0.5(OH)·0.11H2O @ CoSe/NF heterostructure composites.
Example 2
1) Dissolving 2mmol of cobalt nitrate hexahydrate, 5mmol of ammonium fluoride and 5mmol of urea in 35ml of deionized water, magnetically stirring for 30min, transferring the mixed solution into a 50ml reaction kettle, and adding cleaned 6cm2Nickel foam (0.141 g); placing the reaction kettle in a thermostat at 140 ℃ for reaction for 10 hours; after the reaction is finished, cleaning and drying are carried out to obtain one-dimensional Co (CO)3)0.5(OH)·0.11H20.2894g of O/NF nanowire (containing 0.0714g of Co (CO)3)0.5(OH)·0.11H2O)；
2) Mixing cobalt acetate tetrahydrate and seleniumSodium hydride mixed solution (30ml, containing cobalt acetate tetrahydrate and sodium hydroselenide each 1mmol) was charged into a 50ml reaction vessel, and 0.2894g of the above one-dimensional Co (CO) was further charged into the vessel3)0.5(OH)·0.11H2Sealing the O/NF nanowire, putting the reaction kettle into a constant-temperature drying oven at 160 ℃ for 5 hours, cleaning after the reaction is finished, and drying at 70 ℃ to obtain one-dimensional and two-dimensional Co (CO)3)0.5(OH)·0.11H2O @ CoSe/NF heterostructure composites.
Example 3
1) Dissolving 3mmol of cobalt nitrate hexahydrate, 5mmol of ammonium fluoride and 15mmol of urea in 35ml of deionized water, magnetically stirring for 30min, transferring the mixed solution into a 50ml reaction kettle, and adding cleaned 9cm2Nickel foam (0.2328g, 4 mmol); placing the reaction kettle in a constant temperature box at 160 ℃ for reaction for 5 hours; after the reaction is finished, cleaning and drying are carried out to obtain one-dimensional Co (CO)3)0.5(OH)·0.11H20.3125g of O/NF nanowire (containing 0.0723g of Co (CO)3)0.5(OH)·0.11H2O)；
2) Adding mixed solution of cobalt acetate tetrahydrate and sodium hydrogen selenide (30ml, containing cobalt acetate tetrahydrate and sodium hydrogen selenide 1.5mmol respectively) into a 50ml reaction kettle, and adding 0.3125g of one-dimensional Co (CO) into the kettle3)0.5(OH)·0.11H2Sealing the O/NF nanowire, putting the reaction kettle into a constant-temperature drying oven at 180 ℃ for reaction for 1h, cleaning after the reaction is finished, and drying at 70 ℃ to obtain one-dimensional and two-dimensional Co (CO)3)0.5(OH)·0.11H2O @ CoSe/NF heterostructure composites.
Example 4
1) Dissolving 2mmol of cobalt nitrate hexahydrate, 6mmol of ammonium fluoride and 5mmol of urea in 35ml of deionized water, magnetically stirring for 30min, transferring the mixed solution into a 50ml reaction kettle, and adding cleaned 9cm2Nickel foam (0.2328 g); placing the reaction kettle in a thermostat at 140 ℃ for reaction for 15 hours; after the reaction is finished, cleaning and drying are carried out to obtain one-dimensional Co (CO)3)0.5(OH)·0.11H2O/NF nanowire 0.3067g (containing 0.0727g Co (CO)3)0.5(OH)·0.11H2O)；
2) Adding mixed solution of cobalt acetate tetrahydrate and sodium hydroselenide (30ml, containing cobalt acetate tetrahydrate and sodium hydroselenide 2mmol each) into a 50ml reaction kettle, adding 0.3067g of one-dimensional Co (CO)3)0.5(OH)·0.11H2Sealing the O/NF nanowire, putting the reaction kettle into a constant-temperature drying oven at 160 ℃ for 5 hours, cleaning after the reaction is finished, and drying at 70 ℃ to obtain one-dimensional and two-dimensional Co (CO)3)0.5(OH)·0.11H2O @ CoSe/NF heterostructure composites.
Example 5
1) Dissolving 4mmol of cobalt nitrate hexahydrate, 6mmol of ammonium fluoride and 20mmol of urea in 35ml of deionized water, magnetically stirring for 30min, transferring the mixed solution into a 50ml reaction kettle, and adding cleaned 9cm2Nickel foam (0.2328 g); placing the reaction kettle in a constant temperature box at 160 ℃ for reaction for 15 h; after the reaction is finished, cleaning and drying are carried out to obtain one-dimensional Co (CO)3)0.5(OH)·0.11H20.2894g of O/NF nanowire (containing 0.0566g of Co (CO)3)0.5(OH)·0.11H2O)；
2) Adding mixed solution of cobalt acetate tetrahydrate and sodium hydroselenide (30ml, containing cobalt acetate tetrahydrate and sodium hydroselenide 0.7mmol respectively) into 50ml reaction kettle, adding 0.2894g of one-dimensional Co (CO) into the kettle3)0.5(OH)·0.11H2Sealing the O/NF nanowire, putting the reaction kettle into a constant-temperature drying oven at 180 ℃ for reaction for 1h, cleaning after the reaction is finished, and drying at 70 ℃ to obtain one-dimensional and two-dimensional Co (CO)3)0.5(OH)·0.11H2O @ CoSe/NF heterostructure composites.
Detection example 1
1) The product obtained in example 1 was subjected to morphology analysis by a Scanning Electron Microscope (SEM), and the results are shown in fig. 1a and 1b, indicating that the prepared sample was a nanowire structure, having a length of 5um to 7um and a width of 40nm to 80 nm.
2) The analysis of the composition of the product obtained in example 1 by a Transmission Electron Microscope (TEM) showed that the sample was a one-dimensional and two-dimensional heterostructure, in which the one-dimensional structure was basic cobalt carbonate nanowires and the two-dimensional structure was CoSe flakes, as shown in fig. 2.
3) The product obtained in the step 1 is detected by X-ray diffraction (XRD), the result is shown in figure 3, and the obtained spectrum corresponds to Co (CO) of JCPDS standard card NO.48-00833)0.5(OH)·0.11H2The diffraction peak of O and the diffraction peak of CoSe corresponding to JCPDS standard card No.89-2004 are completely coincided. The XRD pattern can well prove that the substance is Co (CO)3)0.5(OH)·0.11H2O @ CoSe/NF composite material.
Detection example 2
The following tests were performed using the electrochemical workstation CHI660E, manufactured by Shanghai Chenghua instruments, Inc.
The following tests all used a three electrode system in which the one and two dimensional Co (CO) prepared in example 1 was used3)0.5(OH)·0.11H2The O @ CoSe/NF heterostructure composite material is used as a working electrode (cut into a sheet of 1cm multiplied by 1cm, and the loading capacity is 6mg/cm2) (ii) a A carbon rod electrode and a silver-silver chloride electrode are respectively used as a counter electrode and a reference electrode; a KOH solution of 1mol/L was used as an electrolyte.
1) Electrochemical Linear Sweep Voltammetry (LSV) testing
One-dimensional and two-dimensional Co (CO) is obtained by electrochemical linear sweep voltammetry3)0.5(OH)·0.11H2Polarization curve of catalytic performance of O @ CoSe/NF heterostructure composite material for oxygen evolution and hydrogen evolution in alkaline solution. In the oxygen evolution performance test, the scanning speed adopted in the interval of potential 1.1-1.8V vs. RHE is 2mV-1With 90% iR compensation, it can be seen from the polarization curve obtained from the test (see FIG. 4) that at a current density of 10mA cm-2The potential for oxygen evolution was 1.485V vs. rhe. Compared with the theoretical hydrolysis potential, the oxygen evolution potential of the composite material has very low over potential of 255mV, and the oxygen evolution performance of the material is superior. In a hydrogen evolution performance test, the scanning speed adopted in the interval of-0.6-0V vs. RHE is 5mV-1With 90% of iR compensation, the polarization curve obtained from the test (see FIG. 6) can be obtained at a current density of 10mA cm-2When the hydrogen evolution is carried out, the potential of hydrogen evolution is 0.128V vs. RHE, and the hydrogen evolution performance is excellent.
2) Cyclic Voltammetry (CV) test
Obtaining one-dimensional and two-dimensional Co (CO) in alkaline solution by electrochemical cyclic voltammetry3)0.5(OH)·0.11H2And the O @ CoSe/NF heterostructure composite material has electrocatalytic stability. At 50mV. s without iR compensation-1The polarization reaction of oxygen evolution and hydrogen evolution is carried out on the material for 1000 circles at the scanning speed, and a polarization curve is measured by linear scanning voltammetry after 1000 circles. As can be seen from fig. 5, the oxygen evolution polarization curve after 1000 cycles was almost the same as the initial oxygen evolution polarization curve, and the material was obtained to have excellent stability in terms of oxygen evolution. From fig. 7, it can be seen that the polarization curve of hydrogen evolution after 1000 cycles is well overlapped with the original polarization curve, showing that the material is excellent in stability in hydrogen evolution.
The products of examples 2 to 5 were tested according to the methods of test examples 1 to 2, and the results were substantially consistent with those of example 1.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material for electrocatalytic hydrolysis is characterized by comprising the following steps: basic cobalt carbonate nanowire Co (CO)3)0.5(OH)·0.11H2Carrying out solvothermal reaction on O, a selenium source and a cobalt source in a solvent to prepare the one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material; wherein the basic cobalt carbonate nano-wires are loaded on the foam nickel NF;
the basic cobalt carbonate nanowire is prepared by the following method: and (2) performing hydrothermal reaction on a cobalt source, ammonium fluoride, urea and foamed nickel in water, and then cleaning and drying to obtain the basic cobalt carbonate nanowire.
2. The preparation method according to claim 1, wherein the dosage ratio of the basic cobalt carbonate nanowire to the selenium source to the cobalt source to the NF is 0.02-0.08 g: 0.5-2.5 mmol: 0.5-2.5 mmol: 2.4-4 mmol.
3. The preparation method according to claim 1, wherein the dosage ratio of the basic cobalt carbonate nanowires to the solvent is 0.02-0.08 g: 30-40 mL.
4. The production method according to claim 1, wherein the solvothermal reaction satisfies the following condition: the reaction temperature is 140 ℃ and 200 ℃, and the reaction time is 1-5 h.
5. The production method according to claim 1, wherein the selenium source is selected from at least one of sodium hydroselenide, selenium dioxide and selenium powder, the cobalt source is selected from at least one of cobalt acetate tetrahydrate, cobalt nitrate hexahydrate and cobalt chloride hexahydrate, and the solvent is ethanol.
6. The preparation method according to claim 1, wherein the cobalt source, ammonium fluoride, urea, nickel foam and water are used in a ratio of 1-5 mmol: 2-8 mmol: 5-20 mmol: 2.4-4 mmol: 30-40 mL.
7. The production method according to claim 1, wherein the hydrothermal reaction satisfies the following condition: the reaction temperature is 100-180 ℃, and the reaction time is 10-60 min.
8. A one-dimensional basic cobalt carbonate @ two-dimensional CoSe/NF heterostructure composite material, characterized in that it is prepared by the preparation method of any one of claims 1 to 7.
9. The composite of claim 8, wherein the one-dimensional cobalt hydroxycarbonate @ two-dimensional CoSe/NF heterostructure composite is dimensioned as: the length is 5-7 μm, and the width is 40-80 nm.
10. Use of the one-dimensional cobalt hydroxycarbonate @ two-dimensional CoSe/NF heterostructure composite of claim 8 or 9 in electrocatalytic hydrolysis.
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| CN110975907B (en) * | 2019-12-02 | 2021-09-10 | 大连理工大学 | Preparation method of foam nickel electrode loaded with iron and basic cobalt carbonate for catalyzing oxidation of water or organic matters |
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| CN111495413B (en) * | 2020-05-29 | 2021-04-02 | 中南大学 | Oxygen evolution cobalt diselenide/tin dioxide @ nitrogen-doped ketjen black composite catalyst and preparation method and application thereof |
| CN113380553B (en) * | 2021-05-25 | 2022-10-04 | 三峡大学 | Co 3 S 4 /Co(CO 3 ) 0.5 (OH)·0.11H 2 O-grade nanowire array electrode material |
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