CN109692710A - A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material - Google Patents
A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material Download PDFInfo
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- CN109692710A CN109692710A CN201910068367.XA CN201910068367A CN109692710A CN 109692710 A CN109692710 A CN 109692710A CN 201910068367 A CN201910068367 A CN 201910068367A CN 109692710 A CN109692710 A CN 109692710A
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- nickel foam
- solution
- supermolecule
- grid material
- metallic
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000006260 foam Substances 0.000 title claims abstract description 51
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003446 ligand Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 49
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 206010001497 Agitation Diseases 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 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 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims 2
- 150000004677 hydrates Chemical class 0.000 claims 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 235000003891 ferrous sulphate Nutrition 0.000 abstract description 2
- 239000011790 ferrous sulphate Substances 0.000 abstract description 2
- 238000013459 approach Methods 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 1
- 239000013076 target substance Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910002505 Co0.8Fe0.2 Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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—
-
- B01J35/33—
-
- B01J35/56—
-
- 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 present invention provides a kind of preparation methods of nickel foam original position supported bi-metallic supermolecule grid material, it first passes through solvent-thermal method and prepares containing sulfate radicals and 4, the precursor solution of 4'- bipyridine ligand, then cobalt nitrate/the ferrous sulfate of amount of substance such as addition and a 1 cm*2 cm nickel foam, 12 hours of low temperature crystallization obtain target substance.This method is simple and direct efficiently, has universality, can not provide a kind of new approaches and available strategy applied to electro-catalysis complete solution water all the time to solve oversubscription sub-grid because being limited to the factors such as supermolecule grid poor chemical stability, inactive site.Has the function of good electro-catalysis complete solution water using the material that this method is prepared.
Description
Technical field
The invention belongs to synthesize supermolecule grid material technical field, and in particular to a kind of foam with complete solution water function
The preparation method of nickel original position supported bi-metallic supermolecule grid material and its application of electro-catalysis complete solution water.
Background technique
Supermolecule grid material is constructed using intermolecular non-covalent interaction with multi-level, multichannel
Ordered Materials.Often with have large specific surface area, cellular structure high-sequential, porosity high, thermal stability and chemical stability compared with
Well, the advantages that synthetic method is various and is easy to functional modification is widely used in the fields such as gas storage, catalysis, sensing.
Increasingly deficient and environmental pollution with non-renewable fossil resource gets worse, development cleaning, green can
Continuous energy is imperative.Hydrogen Energy has high energy density and combustion product pollution-free, is very promising clean energy resource.
Water electrolysis hydrogen production method uses the earth to store water resource abundant as raw material, and the hydrogen purity of preparation is high, and nothing in electrolytic process
Any pollutant emission is more preferably hydrogen production process.Current most effective elctro-catalyst is still noble metal catalyst, but
Because supermolecule grid material large specific surface area, designability are strong, clear in structure, the pass of people is increasingly subject in electro-catalysis field
Note.
With the rapid development of human industry and the extensive application of supermolecule grid material, every profession and trade is to oversubscription sub-grid material
The functionalization of material requires more harsh and quantity demand growing, and the mankind increasingly pay close attention to clean energy resource, therefore, invention
One kind is simple and efficient, freely design, low-temperature operation, universality is strong, yield the is high method for preparing supermolecule grid material especially
It is important.
Summary of the invention
It is an object of the invention to provide a kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material,
This method is simple, strong operability, universality is strong, yield is high.
A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material of the invention is closed using substep
At as ligand stock, presoma is made in pyroreaction for selection 4,4'- bipyridyl, elemental sulfur, vulcanized sodium, deionized water first
Solution, the cabaltous nitrate hexahydrate of low temperature addition thereafter, green vitriol are uniformly mixed, sufficiently dissolution as metal ion source,
It refilters, nickel foam is then added, cools down at a slow speed and stands, is prepared into target product.
A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material of the invention, including following step
It is rapid:
It (1), is in molar ratio 2.23:2.53:2.53 by 4,4'- bipyridyl, elemental sulfur, vulcanized sodium in poly- four ethylene reactions kettle
After being stirred, deionized water is added and carries out secondary agitation mixing, then seals, later by temperature program with 1 DEG C/min
Heating rate be warming up to 150 DEG C, it is isothermal reaction 72 hours, cold with the rate of temperature fall of 0.1 DEG C/min finally by cooling process
But it to 70 DEG C and keeps the temperature, obtains containing sulfate radicals and 4, the precursor solution of 4'- bipyridine ligand；
(2), under 70 DEG C of heat preservations, cabaltous nitrate hexahydrate is added in the precursor solution of above-mentioned preparation, in green vitriol
Any one or two kinds be uniformly mixed, filtering obtains yellowish-brown clear solution, a nickel foam is immersed, with the cooling of 1 DEG C/min
Rate is cooled to 30 DEG C, stands 12 hours, obtains nickel foam original position supported bi-metallic supermolecule grid material, taking-up washes with water,
Naturally dry.
Target product prepared by the present invention consists of two parts, first is that bimetallic supermolecule grid material, it, which has, changes
Formula Co0.5Fe0.5(H2O)3(4,4'-bpy) (SO4)·(H2O)1.5, wherein 4,4'-bpy 4,4'- bipyridyl, the other is
Nickel foam.
A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material of the invention, method is simple, can
Strong operability, universality are strong, yield is high, the nickel foam original position supported bi-metallic oversubscription subnet with complete solution water function of preparation
Grid material, electro-catalysis complete solution water function, in the KOH solution of 1 mol/L, current density is 10 mA/cm2When oxygen evolution
Reaction overpotential is 278 mV, and hydrogen evolution reaction overpotential is 170 mV, and complete solution water potential is 1.63 V.
Detailed description of the invention
Fig. 1 is the present invention with the powder diffraction of the nickel foam original position supported bi-metallic supermolecule grid material of method of fractional steps preparation
Figure (a, load in situ, b, unsupported)；
Fig. 2 is the present invention with the scanning electron microscope (SEM) photograph of the nickel foam original position supported bi-metallic supermolecule grid material of method of fractional steps preparation；
Fig. 3 is the linear sweep voltammetry figure of target product electro-catalysis oxygen evolution reaction；
Fig. 4 is the linear sweep voltammetry figure of target product electro-catalysis hydrogen evolution reaction；
Fig. 5 is the linear surface sweeping voltammogram of target product complete solution water reaction.
Specific embodiment
Embodiment 1:
A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material, comprising the following steps:
(1), by 4, the 4- bipyridyl of 2.23mmol, 0.347g, 2.53 mmol, 0.081g in the poly- four ethylene reactions kettle of 20 mL
Elemental sulfur, the vulcanized sodium of 2.53mmol, 0.197g is stirred, and after 16.7 mL deionized waters are added, it is mixed to carry out secondary agitation
It closes, then seals, be warming up to 150 DEG C later with the heating rate of 1 DEG C/min, isothermal reaction 72 hours, then pass through cooling process
70 DEG C of heat preservations are cooled to the rate of temperature fall of 0.1 DEG C/min, obtain containing sulfate radicals and 4, the precursor solution of 4'- bipyridine ligand.
(2), thereafter in the environment of 70 DEG C, 0.327g, 1.125 mmol are added in precursor solution reaction kettle obtained
Cabaltous nitrate hexahydrate, 0.313g, 1.125 mmol green vitriol be uniformly mixed, so that it is sufficiently dissolved dispersion, mistake
Filter, obtains yellowish-brown clear solution；Clear solution is transferred in clean reaction kettle and by the nickel foam having a size of 1 cm *, 2 cm
It immerses in solution, is cooled to 30 DEG C with the rate of temperature fall of 1 DEG C/min, stands 12 hours, acquisition structural unit is Co0.5Fe0.5
Water is used in the nickel foam original position supported bi-metallic supermolecule grid material of (μ-H2O) 3 (4,4'-bpy) (SO4) (H2O) 1.5, taking-up
Cleaning, naturally dry.Its electro-catalysis complete solution is aqueous can are as follows: in the KOH solution of 1mol/L, current density is 10 mA/
Oxygen evolution reaction overpotential is 278 mV when cm2, and hydrogen evolution reaction overpotential is 170 mV, and complete solution water potential is 1.63V.
Embodiment 2:
A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material, comprising the following steps:
(1), same as Example 1.
(2), in the environment of 70 DEG C, six hydrations of 0.655g, 2.25mmol are added in ligand solution reaction kettle obtained
Cobalt nitrate is uniformly mixed, it is made sufficiently to dissolve dispersion, filters, obtains pink clear solution.Solution is transferred to clean reaction kettle
In and the nickel foam having a size of 1cm*2cm immersed in solution, be cooled to 30 DEG C with the rate of temperature fall of 1 DEG C/min, it is small to stand 12
When after obtain structural unit be Co (μ-H2O) 3 (4,4'-bpy) (SO4) (H2O) 1.5 nickel foam in situ load oversubscription subnet
Grid material, taking-up wash with water, naturally dry.Its electro-catalysis complete solution is aqueous can are as follows: in the KOH solution of 1 mol/L, electricity
Oxygen evolution reaction overpotential is 334 mV when current density is 10 mA/cm2, and hydrogen evolution reaction overpotential is 224 mV, complete solution
Water potential is 1.82 V.
Embodiment 3:
A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material, comprising the following steps:
(1), same as Example 1.
(2), in the environment of 70 DEG C, 0.524g, 1.8mmol six is added in ligand solution reaction kettle obtained and is hydrated nitre
Sour cobalt, the green vitriol of 0.125g, 0.45mmo are uniformly mixed, so that it is sufficiently dissolved dispersion, filter, obtain orange-yellow clear
Clear solution.Solution is transferred in clean reaction kettle and will be immersed in solution having a size of 1cm*2cm nickel foam, with 1 DEG C/min's
Rate of temperature fall is cooled to 30 DEG C, and it is Co0.8Fe0.2 (μ-H2O) 3 (4,4'-bpy) that structural unit is obtained after standing 12 hours
(SO4) the nickel foam original position supported bi-metallic supermolecule grid material of (H2O) 1.5, taking-up wash with water, naturally dry.
Its electro-catalysis complete solution is aqueous can are as follows: in the KOH solution of 1 mol/L, oxygen evolution reacted when current density is 10 mA/cm2
Current potential is 305 mV, and hydrogen evolution reaction overpotential is 198 mV, and complete solution water potential is 1.72 V.
Embodiment 4:
A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material, comprising the following steps:
(1), same as Example 1.
(2), in the environment of 70 DEG C, six hydrations of 0.131g, 0.45 mmol are added in ligand solution reaction kettle obtained
Cobalt nitrate, 0.500g, the green vitriol of 1.8 mmol are uniformly mixed, so that it is sufficiently dissolved dispersion, filter, obtain yellowish-brown
Clear solution.By solution be transferred in clean reaction kettle and will having a size of the nickel foam of 2 cm of 1cm * immerse solution in, with 1 DEG C/
The rate of temperature fall of min is cooled to 30 DEG C, and it is Co that structural unit is obtained after standing 12 hours0.2Fe0.8(μ-H2O)3(4,4'-bpy)
(SO4)·(H2O)1.5Nickel foam original position supported bi-metallic supermolecule grid material, taking-up wash with water, naturally dry.
Its electro-catalysis complete solution is aqueous can are as follows: in the KOH solution of 1 mol/L, current density is 10 mA/cm2When oxygen evolution reacted
Current potential is 312 mV, and hydrogen evolution reaction overpotential is 192 mV, and complete solution water potential is 1.76 V.
Embodiment 5:
A kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material, comprising the following steps:
(1), same as Example 1.
(2), in the environment of 70 DEG C, seven hydrations of 0.626g, 2.25 mmol are added in ligand solution reaction kettle obtained
Ferrous sulfate is uniformly mixed, it is made sufficiently to dissolve dispersion.Filtering, obtains yellow clear solution, and be transferred in clean reaction kettle simultaneously
Nickel foam having a size of 1cm*2cm is immersed in solution, 30 DEG C are cooled to the rate of temperature fall of 1 DEG C/min, after standing 12 hours
Acquisition structural unit is Fe (μ-H2O)3(4,4'-bpy)(SO4)·(H2O)1.5Nickel foam in situ load oversubscription sub-grid material
Material, taking-up wash with water, naturally dry.Its electro-catalysis complete solution is aqueous can are as follows: in the KOH solution of 1 mol/L, electric current is close
Degree is 10 mA/cm2When oxygen evolution reaction overpotential be 340 mV, hydrogen evolution reaction overpotential be 237 mV, complete solution water power
Position is 1.86 V.
The structural unit of nickel foam original position supported bi-metallic supermolecule grid material prepared by above-described embodiment is
CoxFe1-x(μ-H2O)3(4,4'-bpy)(SO4)·(H2O)1.5 (X=0,0.2,0.5,0.8,1.0).By adjust bimetallic it
Between ratio, contrast different metal ratio nickel foam in situ load supermolecule grid material the aqueous energy of electro-catalysis complete solution.
Claims (6)
1. a kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material, it is characterised in that: it includes following
Step:
(1), after 4,4'- bipyridyl, elemental sulfur, vulcanized sodium being stirred in poly- four ethylene reactions kettle, be added deionized water
And secondary agitation mixing is carried out, it then seals, is warming up to 150 DEG C by temperature program later with the heating rate of 1 DEG C/min, perseverance
Temperature reaction 72 hours, is cooled to 70 DEG C finally by cooling process with the rate of temperature fall of 0.1 DEG C/min and keeps the temperature, obtain containing sulfate radicals
With the precursor solution of 4,4'- bipyridine ligand；
(2), under 70 DEG C of heat preservations, cabaltous nitrate hexahydrate is added in the precursor solution of above-mentioned preparation, in green vitriol
Any one or two kinds be uniformly mixed, filtering obtains yellowish-brown clear solution, a nickel foam is immersed, with the cooling of 1 DEG C/min
Rate is cooled to 30 DEG C, stands 12 hours, obtains nickel foam original position supported bi-metallic supermolecule grid material, taking-up washes with water,
Naturally dry.
2. a kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material according to claim 1,
It is characterized in that: the step are as follows:
(1), by 4, the 4- bipyridyl of 2.23mmol, 0.347g, 2.53 mmol, 0.081g in the poly- four ethylene reactions kettle of 20 mL
Elemental sulfur, the vulcanized sodium of 2.53mmol, 0.197g is stirred, and after 16.7 mL deionized waters are added, it is mixed to carry out secondary agitation
It closes, then seals, be warming up to 150 DEG C later with the heating rate of 1 DEG C/min, isothermal reaction 72 hours, then pass through cooling process
70 DEG C of heat preservations are cooled to the rate of temperature fall of 0.1 DEG C/min, obtain containing sulfate radicals and 4, the precursor solution of 4'- bipyridine ligand；
(2), thereafter in the environment of 70 DEG C, be added in precursor solution reaction kettle obtained 0.327g, 1.125 mmol six
Nitric hydrate cobalt, 0.313g, the green vitriol of 1.125 mmol are uniformly mixed, so that it is sufficiently dissolved dispersion, filter, obtain
Yellowish-brown clear solution；Clear solution is transferred in clean reaction kettle and will be immersed having a size of the nickel foam of 1 cm *, 2 cm
In solution, 30 DEG C are cooled to the rate of temperature fall of 1 DEG C/min, stands 12 hours, acquisition structural unit is Co0.5Fe0.5(μ-H2O)3
(4,4'-bpy)(SO4)·(H2O)1.5Nickel foam original position supported bi-metallic supermolecule grid material, taking-up washes with water, is natural
It dries.
3. a kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material according to claim 1,
It is characterized in that: the step are as follows:
(1), by 4, the 4- bipyridyl of 2.23mmol, 0.347g, 2.53 mmol, 0.081g in the poly- four ethylene reactions kettle of 20 mL
Elemental sulfur, the vulcanized sodium of 2.53mmol, 0.197g is stirred, and after 16.7 mL deionized waters are added, it is mixed to carry out secondary agitation
It closes, then seals, be warming up to 150 DEG C later with the heating rate of 1 DEG C/min, isothermal reaction 72 hours, then pass through cooling process
70 DEG C of heat preservations are cooled to the rate of temperature fall of 0.1 DEG C/min, obtain containing sulfate radicals and 4, the precursor solution of 4'- bipyridine ligand；
(2), in the environment of 70 DEG C, six nitric hydrates of 0.655g, 2.25mmol are added in ligand solution reaction kettle obtained
Cobalt is uniformly mixed, it is made sufficiently to dissolve dispersion, filters, obtains pink clear solution, solution is transferred in clean reaction kettle simultaneously
It will be immersed in solution having a size of the nickel foam of 1 cm *, 2 cm, be cooled to 30 DEG C with the rate of temperature fall of 1 DEG C/min, it is small to stand 12
When after obtain structural unit be Co (μ-H2O)3(4,4'-bpy)(SO4)·(H2O)1.5Nickel foam in situ load oversubscription sub-grid
Material, taking-up wash with water, naturally dry.
4. a kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material according to claim 1,
It is characterized in that: the step are as follows:
(1), by 4, the 4- bipyridyl of 2.23mmol, 0.347g, 2.53 mmol, 0.081g in the poly- four ethylene reactions kettle of 20 mL
Elemental sulfur, the vulcanized sodium of 2.53mmol, 0.197g is stirred, and after 16.7 mL deionized waters are added, it is mixed to carry out secondary agitation
It closes, then seals, be warming up to 150 DEG C later with the heating rate of 1 DEG C/min, isothermal reaction 72 hours, then pass through cooling process
70 DEG C of heat preservations are cooled to the rate of temperature fall of 0.1 DEG C/min, obtain containing sulfate radicals and 4, the precursor solution of 4'- bipyridine ligand；
(2), in the environment of 70 DEG C, six nitric hydrate of 0.524g, 1.8mmol is added in ligand solution reaction kettle obtained
Cobalt, the green vitriol of 0.125g, 0.45mmo are uniformly mixed, so that it is sufficiently dissolved dispersion, filter, obtain orange-yellow clarification
Solution is transferred in clean reaction kettle and will be immersed in solution having a size of 1 cm *, 2 cm nickel foam, with 1 DEG C/min's by solution
Rate of temperature fall is cooled to 30 DEG C, and it is Co that structural unit is obtained after standing 12 hours0.8Fe0.2(μ-H2O)3(4,4'-bpy)(SO4)·
(H2O)1.5Nickel foam original position supported bi-metallic supermolecule grid material, taking-up wash with water, naturally dry.
5. a kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material according to claim 1,
It is characterized in that: the step are as follows:
(1), by 4, the 4- bipyridyl of 2.23mmol, 0.347g, 2.53 mmol, 0.081g in the poly- four ethylene reactions kettle of 20 mL
Elemental sulfur, the vulcanized sodium of 2.53mmol, 0.197g is stirred, and after 16.7 mL deionized waters are added, it is mixed to carry out secondary agitation
It closes, then seals, be warming up to 150 DEG C later with the heating rate of 1 DEG C/min, isothermal reaction 72 hours, then pass through cooling process
70 DEG C of heat preservations are cooled to the rate of temperature fall of 0.1 DEG C/min, obtain containing sulfate radicals and 4, the precursor solution of 4'- bipyridine ligand；
(2), in the environment of 70 DEG C, six nitric hydrates of 0.131g, 0.45 mmol are added in ligand solution reaction kettle obtained
Cobalt, 0.500g, the green vitriol of 1.8 mmol are uniformly mixed, so that it is sufficiently dissolved dispersion, filter, and obtain yellowish-brown clarification
Solution, by solution be transferred in clean reaction kettle and will having a size of the nickel foam of 1 cm *, 2 cm immerse solution in, with 1 DEG C/
The rate of temperature fall of min is cooled to 30 DEG C, and it is Co that structural unit is obtained after standing 12 hours0.2Fe0.8(μ-H2O)3(4,4'-bpy)
(SO4)·(H2O)1.5Nickel foam original position supported bi-metallic supermolecule grid material, taking-up wash with water, naturally dry.
6. a kind of preparation method of nickel foam original position supported bi-metallic supermolecule grid material according to claim 1,
It is characterized in that: the step are as follows:
(1), by 4, the 4- bipyridyl of 2.23mmol, 0.347g, 2.53 mmol, 0.081g in the poly- four ethylene reactions kettle of 20 mL
Elemental sulfur, the vulcanized sodium of 2.53mmol, 0.197g is stirred, and after 16.7 mL deionized waters are added, it is mixed to carry out secondary agitation
It closes, then seals, be warming up to 150 DEG C later with the heating rate of 1 DEG C/min, isothermal reaction 72 hours, then pass through cooling process
70 DEG C of heat preservations are cooled to the rate of temperature fall of 0.1 DEG C/min, obtain containing sulfate radicals and 4, the precursor solution of 4'- bipyridine ligand；
(2), in the environment of 70 DEG C, seven hydrated sulfuric acids of 0.626g, 2.25 mmol are added in ligand solution reaction kettle obtained
Ferrous iron is uniformly mixed, it is made sufficiently dissolve dispersion, and filtering obtains yellow clear solution, and is transferred in clean reaction kettle and by ruler
The very little nickel foam for being 1 cm *, 2 cm immerses in solution, 30 DEG C is cooled to the rate of temperature fall of 1 DEG C/min, after standing 12 hours
Acquisition structural unit is Fe (μ-H2O)3(4,4'-bpy)(SO4)·(H2O)1.5Nickel foam in situ load oversubscription sub-grid material
Material, taking-up wash with water, naturally dry.
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