CN107999079A - One kind is based on the preparation method and application of Cu (II)-MOF/Ni composite materials - Google Patents
One kind is based on the preparation method and application of Cu (II)-MOF/Ni composite materials Download PDFInfo
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- CN107999079A CN107999079A CN201711472640.2A CN201711472640A CN107999079A CN 107999079 A CN107999079 A CN 107999079A CN 201711472640 A CN201711472640 A CN 201711472640A CN 107999079 A CN107999079 A CN 107999079A
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- mof
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- melamine
- nickel screen
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000499 gel Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 61
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LDOMKUVUXZRECL-UHFFFAOYSA-N 2-aminobenzene-1,3-dicarboxylic acid Chemical class NC1=C(C(O)=O)C=CC=C1C(O)=O LDOMKUVUXZRECL-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000012360 testing method 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The application of elutriation oxygen is electrolysed the invention discloses a kind of preparation method based on Cu (II) MOF/Ni composite materials and based on the material, belongs to catalysis technique, technical field of composite materials.It is had main steps that copper nitrate aqueous solution, H6Melamine@Cu (II) MOF gels are made in L solution and melamine；It is online that the gel is evenly applied to activated ni, heating pyrolysis；It is made and is based on Cu (II) MOF/Ni composite materials.The composite material prepares that raw materials used cost is low, and preparation process is simple, and energy consumption of reaction is low, has prospects for commercial application.The catalyst is used for efficient catalytic electrolysis elutriation oxygen, has good analysis oxygen electro catalytic activity and electrochemical stability.
Description
Technical field
It is electrolysed the present invention relates to a kind of preparation method based on Cu (II)-MOF/Ni composite materials and based on the catalyst
The application of elutriation oxygen, belongs to catalysis technique, technical field of composite materials.
Background technology
As the high speed development of social economy and the continuous of world population increase, the mankind are to fossil fuel, such as coal and oil
Deng consumption, bring unprecedented pressure and challenge to existing energy reserves and natural environment.For the energy that reply is newborn
The requirement that source is consumed and existing population quality of life improves, countries in the world urgently search out the sustainable clean energy resource used
Carrier.Electro-catalysis, which directly decomposes water and prepares hydrogen, to be considered realizing the process effective manner.The reaction of electrocatalytic decomposition water includes
Liberation of hydrogen (hydrogen evolution reaction, HER) and analysis oxygen (oxygen evolution reaction, OER) two
A half-reaction, come self-resistance, three intrinsic energy losses of aspect systems of reaction and transmission and existing catalyst price,
Factor in terms of activity and stability, all significantly limit its popularization and extensive use.Although it is only a half-reaction to analyse oxygen,
But in order to drive the power consumption penalty that oxygen evolution reaction is brought to system operation maximum, become the bottleneck for improving whole efficiency.Seek
The new analysis oxygen elctro-catalyst for looking for cheap and easy to get and performance to stablize, to long term growth Hydrogen Energy, reduces environmental pollution or even alleviation generation
Energy problem in the range of boundary, has extensive and important realistic meaning.
In the system much explored, iridium dioxide (IrO2) and ruthenic oxide (RuO2) it is considered most effective.However,
Their rare and expensive prices, limit its actual application extensively, for this reason, developing efficient, inexpensive and earth rich content
Base metal oxygen-separating catalyst, reduce analysis oxygen electric consumption become an opportunities and challenges.
As a kind of novel porous crystalline material, in recent years, Metal-organic frame (MOFs) is stored in gas, separation,
The fields such as catalysis, identification and drug delivery have been widely used.On June 8th, 2017, Nanjing Aero-Space University Dou Hui religions
Award, Zhang Jiaogang professors and doctor Xu Guiyin etc. have delivered paper " Exploring metal organic frameworks for
energy storage in batteries and supercapacitors”.Paper MOFs lithium ion battery,
The application of sodium-ion battery, lithium-sulfur cell, lithium selenium cell, lithium-oxygen battery and ultracapacitor.The periodically porous knots of MOFs
The diversity of structure, high specific surface area and structure, there is provided using its as precursor build carbon or (and) metal-based nano material
Unique advantage.At present, it is increasing to come from the research of MOFs precursors or the functional material of template, for example, porous carbon, metal aoxidize
Thing, metal/carbon and metal oxide/carbon nanomaterial have been reported, constructed 3D metal oxides, for efficient super electricity
Container, lithium ion battery and hydrogen reduction, have shown excellent property.At present frequently with an innovative strategy be to utilize example
Nano carbon material such as graphene, multi-walled carbon nanotube (multiwalled carbon nanotubes, CNTs) loads MOFs, then
C-base composte material elctro-catalyst is prepared by high temperature pyrolysis, to prevent product from reuniting and improve its specific surface area.Although MOFs
Species is various, but elctro-catalyst MOFs precursor limited amounts that are easily prepared and being changed into controlled morphologies, and the addition meeting of carbon dots
Improve performance of the MOF materials in terms of electro-catalysis.2016, Central South University Ji Xiaobo professors and its team were first carbon dots
(CDs) it is used as multi-layer graphene petal-shaped rutile TiO2" designer's additive ".Research and utilization CDs induces golden red
Stone-type TiO2Nanoparticle growth is nanoneedle, and nanoneedle is further self-assembled into the petal-like structures of three-dimensional, passes through thermal annealing
Good ultra-thin graphitic carbon can be produced, overall electrical conductivity can be significantly improved, so as to produce quick electron transfer.This exploitation
Using a step room temperature process, it is prepared for using melamine containing carbon dots MOF, using the material being supported on nickel screen as precursor,
It is pyrolyzed in atmosphere, is prepared for CDs/Cu (II)-MOF/Ni effective catalysts.
The content of the invention
One of technical assignment of the present invention is in order to make up for the deficiencies of the prior art, there is provided one kind is based on Cu (II)-MOF/
The preparation method of Ni composite materials, the raw materials used cost of this method is low, and preparation process is simple, and energy consumption of reaction is low, has industry should
Use prospect.
The purposes that the two of the technical assignment of the present invention are to provide the composite material, will the composite material be used to efficiently urge
Change electrolysis elutriation oxygen, there is good electro catalytic activity and electrochemical stability.
To achieve the above object, the technical solution adopted by the present invention is as follows：
1. one kind is based on the preparation method of Cu (II)-MOF/Ni composite materials
0.47-0.57g copper nitrates and 1.0-2.0mL water are blended, copper nitrate aqueous solution is made, by 0.05-0.07gH6L powder
Ligand solution is mixed to prepare with 0.20-0.30mL dimethyl sulfoxide (DMSO)s, adds 0.02-0.04g melamine powders, shaking is formed
Melamine@Cu (II)-MOF gels；
Melamine@Cu (II)-MOF gels of 0.012-0.013g are taken to be evenly applied to the activated ni that area is 0.5cm × 1cm
On the net, it is placed in tube furnace, under air atmosphere, with the heating rate of 2 DEG C/min, is heated to 300 DEG C, 3h is kept the temperature, then, with 2 DEG C
/ min rate of temperature fall is cooled to room temperature；It is made and is based on Cu (II)-MOF/Ni composite materials.
A kind of preparation method for being based on Cu (II)-MOF/Ni composite materials, it is characterised in that the H6L ligands, structure
It is as follows to make formula：
H6L preparation processes are as follows：
By 0.084mol amino isophthalic acids, 0.134mol NaOH and 0.104mol NaHCO3It is added to 140ml distilled water
In, after mixing 30min is stirred at 0 DEG C；The 1,4- dioxane solutions of cyanuric trichloride are added dropwise dropwise at the same time；The mixed liquor exists
24h is heated at 100 DEG C, the pH=2 of mixture solution is adjusted with HCl, filtering, is washed with distilled water several times, after drying at room temperature
Obtain H6L ligands, its yield are 95%.
The 1,4- dioxane solutions of cyanuric trichloride are that the cyanuric trichloride of 0.02mol is dissolved in six alkane of 1,4- dioxies of 70mL
It is made.
The activation nickel screen, is to remove nickel screen in acetone, absolute ethyl alcohol and distillation underwater ultrasound 2-4min, washing successively
Surface irregularities, then nickel screen is immersed in the nitric acid ultrasound 1min that mass fraction is 40% and is made.
The nickel screen, buys in ElectroChem, surface density 280-420g/m2, aperture 0.2-0.6mm, longitudinal stretching
Intensity is 106N/cm2, transverse tensile strength 76N/cm2, porosity 97.2%.
Cu (the II)-MOF, chemical formula are [Cu3L(H2O)3]·10H2O·5DMA；One construction unit is 3
Cu (II) cation, three hydrones and 5 DMA molecules are formed, and DMA is n,N-dimethylacetamide；It is described based on Cu (II)-
MOF/Ni composite materials, are to form hybrid material by carbon dots, nano cupric oxide and porous carbon, which is supported on nickel screen
Form composite material.
2. it is used for the application for being electrolysed the catalysis of elutriation oxygen based on Cu (II)-MOF/Ni composite materials as described above
Using area be 0.5cm × 1cm based on Cu (II)-MOF/Ni composite materials as working electrode；Use three electrode electrochemicals
Work station is learned, Pt pieces (5mm × 5mm × 0.1mm) are that Ag/AgCl electrodes are reference electrode, are 0.5M in electrolyte to electrode
Electrocatalytic decomposition elutriation oxygen performance is tested in KOH aqueous solutions.
It is above-mentioned that oxygen is analysed based on the catalysis of Cu (II)-MOF/Ni composite materials electrolysis water, as current density, J=10mA/cm2When,
Current potential is 1.35Vvs RHE；Illustrate that the material efficiently analyses oxygen catalytic activity；Before and after circulation 1000 times, the polarization of such material is bent
Line does not find obvious change, shows that catalyst is with good stability.
The beneficial technique effect of the present invention：
(1) simple process, is easy to industrialize
The present invention is based on the preparation of Cu (II)-MOF/Ni composite materials, One-step Reaction At Room Temperature, the convenient Cu that doping melamine is made
(II)-MOF gels, i.e. melamine@Cu (II)-MOF gels, then, are heated, melamine is in situ by a step air atmosphere
Thermally decompose and thermally decompose nano cupric oxide and porous carbon for carbon dots, Cu (II)-MOF original positions, form ternary nano hybrid material, this is miscellaneous
Change material load on nickel screen, composition is based on Cu (II)-MOF/Ni composite materials, and the preparation process technique is simple, simple and easy to control,
Product preparation efficiency is high, is easy to industrialize.
(2) catalysis analysis oxygen efficiency is high and stability is good
The present invention provides a kind of electro-catalysis oxygen-separating catalyst for being based on Cu (II)-MOF/Ni composite materials, due to the catalyst
Directly as working electrode catalysis water decomposition analysis oxygen, eliminate conventional operation electrode and sticked using perfluorinated resin or other adhesives
Catalyst fines is tied, thus exposes more avtive spots so that the catalysis analysis oxygen based on the composite material, high catalytic efficiency
And stability is good.
Embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not only limited to implement
Example, the change that professionals in the field makees technical solution of the present invention, is within the scope of protection of the invention interior.
A kind of preparation method for being based on Cu (II)-MOF/Ni composite materials of embodiment 1
0.470g copper nitrates and 1.0mL water are blended, copper nitrate aqueous solution is made, by 0.05gH6L powder and 0.20mL dimethyl
Sulfoxide is mixed to prepare ligand solution, adds 0.02g melamine powders, and shaking forms melamine@Cu (II)-MOF gels；Take
Melamine@Cu (II)-MOF gels of 0.012g be evenly applied to area be 0.5cm × 1cm activated ni it is online, be placed in pipe
In formula stove, under air atmosphere, with the heating rate of 2 DEG C/min, 300 DEG C are heated to, keeps the temperature 3h, then, cooled down with 2 DEG C/min fast
Rate is cooled to room temperature；It is made and is based on Cu (II)-MOF/Ni composite materials.
A kind of preparation method for being based on Cu (II)-MOF/Ni composite materials of embodiment 2
0.57g copper nitrates and 2.0mL water are blended, copper nitrate aqueous solution is made, by 0.07gH6L powder and 0.30mL dimethyl
Sulfoxide is mixed to prepare ligand solution, adds 0.04g melamine powders, and shaking forms melamine@Cu (II)-MOF gels；
Take 0.013g melamine@Cu (II)-MOF gels be evenly applied to area be 0.5cm × 1cm activated ni it is online,
It is placed in tube furnace, under air atmosphere, with the heating rate of 2 DEG C/min, is heated to 300 DEG C, 3h is kept the temperature, then, with 2 DEG C/min
Rate of temperature fall is cooled to room temperature；It is made and is based on Cu (II)-MOF/Ni composite materials.
Embodiment 3
1. one kind is based on the preparation method of Cu (II)-MOF/Ni composite materials
0.52g copper nitrates and 1.5mL water are blended, copper nitrate aqueous solution is made, by 0.06gH6L powder and 0.25mL dimethyl
Sulfoxide is mixed to prepare ligand solution, adds 0.03g melamine powders, and shaking forms melamine@Cu (II)-MOF gels；
Take 0.013g melamine@Cu (II)-MOF gels be evenly applied to area be 0.5cm × 1cm activated ni it is online,
It is placed in tube furnace, under air atmosphere, with the heating rate of 2 DEG C/min, is heated to 300 DEG C, 3h is kept the temperature, then, with 2 DEG C/min
Rate of temperature fall is cooled to room temperature；It is made and is based on Cu (II)-MOF/Ni composite materials.
Embodiment 4
One kind described in embodiment 1-3 is based on the preparation method of Cu (II)-MOF/Ni composite materials, it is characterised in that the H6L
Ligand, structural formula are as follows：
H6L preparation processes are as follows：
By 0.084mol amino isophthalic acids, 0.134mol NaOH and 0.104mol NaHCO3It is added to 140ml distilled water
In, after mixing 30min is stirred at 0 DEG C；The 1,4- dioxane solutions of cyanuric trichloride are added dropwise dropwise at the same time；The mixed liquor exists
24h is heated at 100 DEG C, the pH=2 of mixture solution is adjusted with HCl, filtering, is washed with distilled water several times, after drying at room temperature
Obtain H6L ligands, its yield are 95%；
The 1,4- dioxane solutions of cyanuric trichloride are that the cyanuric trichloride of 0.02mol is dissolved in the six alkane system of 1,4- dioxies of 70mL
.
Embodiment 5
Nickel screen is activated described in embodiment 1-3, is to wash nickel screen successively in acetone, absolute ethyl alcohol and distillation underwater ultrasound 2-4min
Surface irregularities are washed away, then nickel screen is immersed in the nitric acid ultrasound 1min that mass fraction is 40% and is made；The nickel screen, in electrification
Company buys, surface density 280-420g/m2, aperture 0.2-0.6mm, longitudinal tensile strength 106N/cm2, cross directional stretch is strong
Spend for 76N/cm2, porosity 97.2%.
Embodiment 6 is based on the application that Cu (II)-MOF/Ni composite materials are used to be electrolysed the catalysis of elutriation oxygen
It is that 0.5cm × 1cm based on Cu (II)-MOF/Ni composite materials is work by embodiment 1, embodiment 2 or 3 area of embodiment
Make electrode；Using three-electrode electro Chemical work station, Pt pieces (5mm × 5mm × 0.1mm) are that Ag/AgCl electrodes are reference to electrode
Electrode, tests electrocatalytic decomposition elutriation oxygen performance, as current density, J=10mA/ in electrolyte is 0.5M KOH aqueous solutions
cm2When, current potential is 1.35Vvs RHE；Illustrate that the material efficiently analyses oxygen catalytic activity；Before and after circulation 1000 times, such material
Polarization curve does not find obvious change, shows that catalyst is with good stability.
Claims (5)
1. one kind is based on the preparation method of Cu (II)-MOF/Ni composite materials, it is characterised in that step is as follows：
0.47-0.57g copper nitrates and 1.0-2.0mL water are blended, copper nitrate aqueous solution is made, by 0.05-0.07gH6L powder with
0.20-0.30mL dimethyl sulfoxide (DMSO)s are mixed to prepare ligand solution, add 0.02-0.04g melamine powders, and shaking forms trimerization
Cyanamide@Cu (II)-MOF gels；
Melamine@Cu (II)-MOF gels of 0.012-0.013g are taken to be evenly applied to the activated ni that area is 0.5cm × 1cm
On the net, it is placed in tube furnace, under air atmosphere, with the heating rate of 2 DEG C/min, is heated to 300 DEG C, 3 h is kept the temperature, then, with 2
DEG C/min rate of temperature fall is cooled to room temperature；CDs/CuO-C/Ni composite materials are made, i.e., based on Cu (II)-MOF/Ni composite woods
The catalyst of material.
A kind of 2. preparation method for being based on Cu (II)-MOF/Ni composite materials as claimed in claim 1, it is characterised in that institute
State H6L ligands, structural formula are as follows：
。
A kind of 3. preparation method for being based on Cu (II)-MOF/Ni composite materials as claimed in claim 1, it is characterised in that institute
Activation nickel screen is stated, is that nickel screen is removed into surface irregularities in acetone, absolute ethyl alcohol and distillation underwater ultrasound 2-4min, washing successively,
Nickel screen is immersed in the nitric acid ultrasound 1min that mass fraction is 40% again to be made.
4. the preparation method of Cu (II)-MOF/Ni composite materials is based on as claimed in claim 1, it is characterised in that the Cu
(II)-MOF, chemical formula are [Cu3L(H2O)3]·10H2O·5DMA；One construction unit is 3 Cu（II）Cation, three
A hydrone and 5 DMA molecules are formed, and DMA is n,N-dimethylacetamide；It is described to be based on Cu (II)-MOF/Ni composite materials,
It is that hybrid material is formed by carbon dots, nano cupric oxide and porous carbon, which is supported on nickel screen and forms.
5. prepared by preparation method as claimed in claim 1 is catalyzed based on Cu (II)-MOF/Ni composite materials for electrolysis water
Analyse the application of oxygen.
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