CN108187751A - A kind of preparation method and applications of isomorphism metal-organic framework material - Google Patents
A kind of preparation method and applications of isomorphism metal-organic framework material Download PDFInfo
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- CN108187751A CN108187751A CN201810027272.9A CN201810027272A CN108187751A CN 108187751 A CN108187751 A CN 108187751A CN 201810027272 A CN201810027272 A CN 201810027272A CN 108187751 A CN108187751 A CN 108187751A
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910004039 HBF4 Inorganic materials 0.000 claims abstract description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims abstract description 3
- 239000013384 organic framework Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 abstract 1
- 239000010953 base metal Substances 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000000446 fuel Substances 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- -1 salt cobalt chloride Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000002178 crystalline material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000010583 slow cooling Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to a kind of isomorphism metal-organic framework materials, disclose a kind of base metal electro-catalysis water oxidation catalyst.This method is respectively with metal salt cobalt chloride, nickel chloride and two kinds of salt mixing, ligand 5'（3,5 dicarboxyphenyis）‑[1,1'：3', 1 " terphenyl] 3,3 ", 5,5 " tetrabasic carboxylic acid (H6L), solvent DMA, HBF4And pink colour, dark green, pale pink shape crystal cobalt metal-organic framework material 1, nickel metal-organic framework material 2, cobalt/nickel metal-organic framework material 3 is made in water under hydrothermal synthesizing condition, i.e., three kinds of crystal grinding refinements are obtained the electrocatalysis material.The preparation method of electrocatalysis material is relatively easy in the present invention, acquired elctro-catalyst has preferable electrolysis elutriation oxygen ability, the Tafel slopes of material 1,2,3 are respectively 89 mV/decade, 124 mV/decade, 78 mV/decade, are 10 mA/cm in current density2When hydrogen-evolution overpotential be 420 mV, 510 mV, 380 mV are a kind of ideal high performance catalyst materials, can be used for the new energy fields such as electrocatalytic decomposition water oxygen, fuel cell.
Description
Technical field
Synthesis and applied technical field the invention belongs to catalyst, and in particular to a kind of copper-based with electrocatalysis characteristic
The preparation method of metal-organic framework material and its application in terms of electro-catalysis water oxygen.
Background technology
Increasingly serious with energy and environment problem, the clean energy resource of development low cost environment close friend has attracted people wide
General concern.Wherein, it is considered most promising using efficient and low-cost elctro-catalyst catalytic decomposition water hydrogen making
One of the approach for preparing clean energy resource.However, the high energy barrier for the water oxidation process for being related to 4 electronics and proton translocation is limited by,
Develop key of the catalyst of high activity, low overpotential for water oxidation process as electro-catalysis water decomposition.Transiting metal oxidation
Object is very potential water oxidation catalyst, this mainly has benefited from the essence of metal oxide water oxygen in alkaline electrolyte
Characteristic.On sustainable development source is solved the problems, such as, electrochemistry will play a critically important effect, especially in primary battery
Chemical energy is stored and be converted into electric energy and electrolytic cell in electric energy stored and be converted into chemical energy.During electrolysis water,
Due to Oxygen anodic evolution（OER）Kinetics process it is slow, limit the rate of entire electrolysis water reaction, therefore there is an urgent need to open
Send out OER elctro-catalysts efficient, especially exploitation is distributed wider non-precious metal catalyst.The metal of rising in recent years has
Machine frame frame material (Metal-Organic Frameworks, MOFs) is exactly to have one of such catalyst material in this way, it is
By inorganic metal center（Metal ion or metal cluster）It is connected with each other with the organic ligand of bridging by self assembly, one kind of formation
Crystalline state porous material with periodic network structure.
Invention content
Based on this, the present invention provides a kind of method for preparing cobalt nickel isomorphism and its heterometallocenes organic framework materials, and
Composite material is applied to electro-catalysis and analyses oxygen, preparation method is rationally simple, has excellent performance.It is novel the purpose of the present invention is being directed to
MOFs analyses the application in oxygen field in electro-catalysis, provides a kind of by six sour ligand H6The cobalt that L is assembled with Co, Ni metal ion-
The system of metal-organic framework material 1, ni-au category organic framework materials 2, cobalt/3 electrocatalysis material of ni-au category organic framework materials
Preparation Method and application.
The purpose of the present invention is what is be achieved through the following technical solutions, which had in the NaOH solution of 1M
Cobalt-metal-organic framework material 1 of stability, ni-au category organic framework materials 2, cobalt/ni-au category organic framework materials 3（Cobalt-
Metal-organic framework material 1, ni-au category organic framework materials 2, cobalt/3 three kinds of material preparation sides of ni-au category organic framework materials
Method is similar, and structure is identical, as isomorphism material）, they are prepared by hydro-thermal method, are included the following steps:
（1）By metal salt, H6L, n,N-dimethylacetamide, HBF4Ultrasound, obtains mixed solution after being mixed with water；
（2）By above-mentioned steps（1）Obtained mixed solution is transferred in ptfe autoclave, is carried out at 100-150 DEG C
Hydro-thermal reaction（Further preferably hydrothermal temperature is 120 DEG C, and the hydro-thermal reaction time is 2-3 days, obtains bulk crystals；
（3）By above-mentioned steps（2）Obtained bulk crystals are impregnated with ethyl alcohol, to remove the residual solvent molecule in duct.
（4）By above-mentioned steps（3）Obtained bulk crystals are cleaned up with ethyl alcohol, it is dry to get to the electro-catalysis
Material cobalt-metal-organic framework material 1, ni-au category organic framework materials 2, cobalt/ni-au category organic framework materials 3.
The metal salt is cobalt chloride or nickel chloride.
The n,N-dimethylacetamide, HBF4Volume ratio with deionized water is 1.5-3：0.5-1.5：0.5-1.5,
N,N-dimethylacetamide, HBF4Metal salt and H are immersed in the amount of deionized water6L.Cobalt chloride and/or nickel chloride are with matching
Body H6The mass ratio of L is 3-3.5: 1-1.5 .
Electricity is carried out in the NaOH of 1M as electro-catalysis oxygen-separating catalyst using 3 kinds of crystalline materials prepared by above step
Catalytic water oxidation test.It is as follows：
1）Obtained MOF is weighed into 5mg, adds in 0.2ml naphthols, 0.8ml deionized waters, ultrasonic 30min, which is uniformly mixed, to be prepared into
Solution electrode is spare.
2）By step 1）Obtained solution electrode painting takes 5 microlitres of electrodes of working in glass electrode, using platinum filament as to electricity
Pole, formed by reference electrode of Ag/AgCl electrodes three-electrode system be inserted into the NaOH solution of pH=14 carry out oxygen evolution it is anti-
It should.
The present invention has the following advantages：
1）Method prepared by the present invention is relatively easy, and controllability is strong；
2）Catalyst material prepared by the present invention is bulk crystals, and good crystallinity can parse to obtain by mono-crystalline structures
Accurate three-dimensional structure information, and can be easily separated and washes clean；
3）Catalyst material prepared by the present invention has the ability of excellent electrocatalytic decomposition elutriation oxygen；
4）The transition metal M OF electro-catalysis analysis oxygen performance of investigation and comparison of the present invention different metal node；
5）The preparation of the present invention is laboratory commonly used equipment, does not need to special equipment, technological process is simple.
Description of the drawings
Fig. 1 is the coordination of metal ion in crystalline material cobalt -1 elctro-catalyst of metal-organic framework material prepared by the present invention
Environment map.
Fig. 2 is the three-layer laminated figure of crystalline material cobalt -1 catalyst material of metal-organic framework material prepared by the present invention.
Fig. 3 is the coordination of metal ion in 2 elctro-catalyst of crystalline material ni-au category organic framework materials prepared by the present invention
Environment map.
Fig. 4 is the three-layer laminated of 2 electrocatalyst materials of crystalline material ni-au category organic framework materials prepared by the present invention
Figure.
Fig. 5 is 3 SEM elemental analysis figures of crystalline material cobalt/ni-au category organic framework materials prepared by the present invention.
Fig. 6 is X-ray powder diffraction (XRD) figure of three kinds of crystalline material elctro-catalysts prepared by the present invention.
Fig. 7 is polarization curve of three kinds of crystalline material electrocatalyst materials in the NaOH of 1M prepared by the present invention.
Fig. 8 is Tafel curve figure of three kinds of crystalline material electrocatalyst materials in the NaOH of 1M prepared by the present invention.
Fig. 9 is impedance diagram of three kinds of crystalline material electrocatalyst materials in the NaOH of 1M prepared by the present invention.
Figure 10 is cobalt/3 crystalline material electrocatalyst materials of ni-au category organic framework materials prepared by the present invention 1M's
IT schemes in NaOH.
Specific embodiment
It is further illustrated the present invention with reference to embodiment, but the scope of protection of present invention is not limited to implement
The range of example statement.
Embodiment 1
Take 0.15mmol cobalt chlorides, 0.05mmolH6L、3mlDMA、0.5mlHBF4It is put into beaker with 0.5ml water, carries out ultrasound
Its reactant is made to uniformly disperse in the solution；Obtained homogeneous mixture solotion is transferred in 25ml ptfe autoclaves；
It will put into 120 DEG C of constant temperature ovens and react equipped with mixed solution reaction kettle, then slow cooling to room temperature, it is blocky brilliant that pink colour can be obtained
Body；Obtained pink colour bulk crystals ethyl alcohol is impregnated 3 days, is then cleaned up, and is dried at 60 DEG C to get to the electricity
Catalysis material cobalt-metal-organic framework material 1, the coordination context diagram of the metal ion of the crystalline material are shown in figure with three-dimensional accumulation graph
1st, Fig. 2, its XRD data such as Fig. 6, it can be seen that coincide with simulation drawing into this.
Embodiment 2
Take 0.15mmol nickel chlorides, 0.05mmolH6L、3mlDMA、0.5mlHBF4It is put into beaker with 0.5ml water, carries out ultrasound
Its reactant is made to uniformly disperse in the solution；Obtained homogeneous mixture solotion is transferred in 25ml ptfe autoclaves；
It will put into 120 DEG C of constant temperature ovens and react equipped with mixed solution reaction kettle, then slow cooling to room temperature, can obtain dark green color strip-shaped
Crystal；It cleans up after obtained dark green web crystal is impregnated 3 days with ethyl alcohol, and is dried at 60 DEG C to get to described
Electrocatalysis material ni-au category organic framework materials 2, the coordination context diagram of the metal ion of the crystalline material are shown in three-dimensional accumulation graph
Fig. 3, Fig. 4, its XRD data such as Fig. 6, it can be seen that coincide with simulation drawing into this.
Embodiment 3
Take 0.3mmol nickel chlorides, 0.15mmol nickel chlorides, 0.05mmolH6L、3mlDMA、0.5mlHBF4It is put into 0.5ml water
In beaker, carrying out ultrasound makes its reactant uniformly disperse in the solution；Obtained homogeneous mixture solotion is transferred to 25ml poly- four
In vinyl fluoride reaction kettle；It will put into 120 DEG C of constant temperature ovens and react equipped with mixed solution reaction kettle, then slow cooling to room
Temperature can obtain pale pink crystal；Wash clean after obtained pale pink crystal is impregnated clearly 3 days with ethyl alcohol, and it is dry at 60 DEG C, i.e.,
The electrocatalysis material cobalt/ni-au category organic framework materials 3 are obtained, Fig. 5 is shown in the SEM elemental analyses of the crystalline material, it
XRD data such as Fig. 6, it can be seen that coincide with simulation drawing into this.
Embodiment 4
Three kinds of isomorphism crystalline state electrocatalysis materials of gained are weighed 5mg to be put into 2mL sample cells, and the naphthols of 0.2ml thereto,
The water of 0.8ml, ultrasound uniformly, then take the sample drop of 5 μ L to be placed on the electrode on the glass-carbon electrode of a diameter of 3mm
The test of electro-catalysis water oxygenization is carried out in the NaOH of 1mol/L.The polarization curve of three kinds of crystalline materials is with Ta Feier datagrams as schemed
7（From left to right it is followed successively by Commercial RuO2、Co-MOF、Ni-MOF、Co-Ni-MOF）, Fig. 8（It is followed successively by from top to bottom
Ni-MOF、Co-MOF、Co-Ni-MOF、Commercial RuO2）, the Tafel slopes of material 1,2,3 are respectively 89 mV/
Decade, 124 mV/decade, 78 mV/decade are 10 mA/cm in current density2When hydrogen-evolution overpotential for 420 mV, 510
MV, 380 mV.Three kinds of crystalline materials obtain impedance diagram such as Fig. 9, it will be seen that cobalt/3 impedance of ni-au category organic framework materials<Cobalt-metal has
1 impedance of machine frame frame material<2 impedance of ni-au category organic framework materials, and to cobalt/ni-au category organic framework materials 3 1M's
It has done in NaOH solution and has been tested up to the IT of 40h, such as Figure 10, it can be seen that our material is more stable.
The above embodiments are only the preferred technical solution of the present invention, and are not construed as the limitation for the present invention, this Shen
Please in embodiment and embodiment in feature in the absence of conflict, mutually can arbitrarily combine.It is any to be familiar with this technology
The variation that the technical staff in field can readily occur within the ideas and principles of the present invention, replacing and improving should all cover at this
In the protection domain of invention.
Claims (8)
1. a kind of isomorphism metal-organic framework material, which is characterized in that the material include cobalt-metal-organic framework material,
Ni-au category organic framework materials, cobalt/ni-au category organic framework materials.
2. the preparation method of isomorphism metal-organic framework material described in claim 1, which is characterized in that include the following steps：
（1）By metal salt, H6L, n,N-dimethylacetamide, HBF4Ultrasound, obtains mixed solution after being mixed with water；
（2）By above-mentioned steps（1）Obtained mixed solution is transferred in ptfe autoclave, is carried out at 100-150 DEG C
Hydro-thermal reaction obtains bulk crystals；
（3）By above-mentioned steps（2）Obtained bulk crystals ethyl alcohol eight days soaking period, to remove the residual solvent molecule in duct.
3.（4）By above-mentioned steps（3）Obtained bulk crystals are cleaned up with ethyl alcohol, dry to get to the electrocatalysis material
Cobalt-metal-organic framework material, ni-au category organic framework materials, cobalt/ni-au category organic framework materials.
4. the preparation method of the isomorphism metal-organic framework material described in claim 2, which is characterized in that the metal salt is
Cobalt chloride and/or nickel chloride, the isomorphism metal-organic framework material being prepared include isomorphism cobalt-metal-organic framework material,
Ni-au category organic framework materials or cobalt/ni-au category organic framework materials
The preparation method of isomorphism metal-organic framework material described in claim 3, which is characterized in that N, N- dimethylacetamide
Amine, HBF4Volume ratio with deionized water is 1.5-3：0.5-1.5：0.5-1.5, n,N-dimethylacetamide, HBF4And deionization
The amount of water is immersed in metal salt and H6L.
5. the preparation method of the isomorphism metal-organic framework material described in claim 3, which is characterized in that cobalt chloride and/or chlorine
Change nickel and ligand H6The mass ratio of L is 3-3.5：1-1.5.
6. the preparation method of the isomorphism metal-organic framework material described in claim 2, which is characterized in that step (2) water
Thermal response temperature is 120 DEG C, and the hydro-thermal reaction time is 2-3 days.
7. the preparation method of the isomorphism metal-organic framework material described in claim 3, which is characterized in that the step 3）Washing
Product soaked in absolute ethyl alcohol afterwards, it is 2.5 ~ 4 days to impregnate total time.
8. the isomorphism metal-organic framework material being prepared described in claim any one of 1-7 is catalyzed in electrolysis water on analysis oxygen
Using.
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