CN107999079B - Preparation method and application of Cu (II) -MOF/Ni-based composite material - Google Patents
Preparation method and application of Cu (II) -MOF/Ni-based composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000010949 copper Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 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
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005516 engineering process 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 9
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LDOMKUVUXZRECL-UHFFFAOYSA-N 2-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=C(C(O)=O)C=CC=C1C(O)=O LDOMKUVUXZRECL-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-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
- 230000008859 change Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 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
- 239000008204 material by function Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 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
- 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
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- 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)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a preparation method based on a Cu (II) -MOF/Ni composite material and application of the material in electrolysis of water and oxygen evolution, and belongs to the technical field of catalysis technology and composite materials. The main steps are copper nitrate aqueous solution and H6Preparing melamine @ Cu (II) -MOF gel from the L solution and melamine; uniformly coating the gel on an activated nickel screen, and heating and pyrolyzing the gel; preparing the Cu (II) -MOF/Ni composite material. The composite material has the advantages of low cost of raw materials, simple preparation process, low reaction energy consumption and industrial application prospect. The catalyst is used for efficiently catalyzing electrolysis water to generate oxygen, and has good oxygen generation electrocatalytic activity and electrochemical stability.
Description
Technical Field
The invention relates to a preparation method based on a Cu (II) -MOF/Ni composite material and application of the catalyst in water electrolysis and oxygen evolution, belonging to the technical field of catalysis technology and composite materials.
Background
With the rapid development of social economy and the increasing world population, the consumption of fossil fuels, such as coal and petroleum, by human beings brings unprecedented pressure and challenges to the existing energy storage and natural environment. In order to meet the requirements of new energy consumption and improvement of the quality of life of the existing population, sustainable clean energy carriers are urgently sought in all countries in the world. Electrocatalytic direct decomposition of water to produce hydrogen is considered an effective way to achieve this process. The electrocatalytic water decomposition reaction comprises two half reactions of Hydrogen Evolution (HER) and Oxygen Evolution (OER), and the factors from the aspects of resistance, reaction and transmission, namely the intrinsic energy loss of the system and the price, activity and stability of the existing catalyst greatly limit the popularization and wide application of the electrocatalytic water decomposition reaction. Although oxygen evolution is only a half reaction, the power loss of the system operation for driving the oxygen evolution reaction is the largest, and the bottleneck of improving the overall efficiency is formed. The method finds a novel oxygen evolution electrocatalyst which is cheap and easy to obtain and has stable performance, and has wide and important practical significance for long-term development of hydrogen energy, reduction of environmental pollution and even alleviation of energy problems in the world.
Among many of the systems explored, iridium dioxide (IrO)2) And ruthenium dioxide (RuO)2) Is considered most effective. However, their scarce and expensive prices limit their wide practical application, and for this reason, it is an opportunity and challenge to develop efficient, inexpensive, and earth-rich non-noble metal oxygen evolution catalysts to reduce the consumption of oxygen evolution electricity.
As a new class of porous crystalline materials, Metal Organic Frameworks (MOFs) have recently gained wide application in the fields of gas storage, separation, catalysis, identification, drug delivery, and the like. On 8.6.2017, Nanjing aerospace university professor Stadium, Zhang school just professor, and XuGuiyin doctor, published the article "expanding metallic organic frameworks for energy storage in batteries and supercapacitors". The paper introduces the use of MOFs in lithium ion batteries, sodium ion batteries, lithium sulfur batteries, lithium selenium batteries, lithium oxygen batteries and supercapacitors. The periodic porous structure, high specific surface area and structural diversity of MOFs offer unique advantages for the construction of carbon or (and) metal-based nanomaterials with them as precursors. Currently, there is an increasing research on functional materials derived from MOFs precursors or templates, for example, porous carbon, metal oxide, metal/carbon and metal oxide/carbon nanomaterials have been reported, and the constructed 3D metal oxides, used for high-efficiency supercapacitors, lithium ion batteries and oxygen reduction, have exhibited excellent properties. One innovative strategy that is currently being adopted is to load MOFs with nanocarbon materials such as graphene and multi-walled Carbon Nanotubes (CNTs), and then prepare carbon-based composite electrocatalysts through high-temperature pyrolysis to prevent product agglomeration and increase the specific surface area thereof. Although the MOFs are very diverse, the number of electrocatalysts MOFs precursors that are easy to prepare and convert to controlled morphology is limited, and the addition of carbon dots improves the electrocatalytic performance of MOF materials. Professor university of middle and south, and his team, in 2016, first used Carbon Dots (CDs) as a multilayer graphene petal-like rutile TiO2"designer additive" of (1). This study utilized CDs to induce rutile TiO2The nano particles grow into nano needles which are further self-assembled into a three-dimensional petal-shaped structure, good ultrathin graphite carbon can be generated through thermal annealing, and the integral electric conductivity can be obviously improvedThereby producing rapid electron migration. The development adopts a one-step room temperature process, the MOF containing carbon points is prepared by utilizing melamine, the material loaded on a nickel net is used as a precursor, and the material is pyrolyzed in the air to prepare the CDs/Cu (II) -MOF/Ni high-efficiency catalyst.
Disclosure of Invention
One of the technical tasks of the invention is to make up the defects of the prior art, and provide a preparation method based on a Cu (II) -MOF/Ni composite material, wherein the method has the advantages of low cost of raw materials, simple preparation process, low reaction energy consumption and industrial application prospect.
The second technical task of the invention is to provide the application of the composite material, namely the composite material is used for efficiently catalyzing water electrolysis for oxygen evolution and has good electrocatalytic activity and electrochemical stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1. preparation method of Cu (II) -MOF/Ni-based composite material
0.47-0.57g of copper nitrate is mixed with 1.0-2.0mL of water to prepare copper nitrate aqueous solution, 0.05-0.07g of H6Mixing the L powder with 0.20-0.30mL of dimethyl sulfoxide to prepare a ligand solution, adding 0.02-0.04g of melamine powder, and shaking to form melamine @ Cu (II) -MOF gel;
uniformly coating 0.012-0.013g of melamine @ Cu (II) -MOF gel on an activated nickel screen with the area of 0.5cm multiplied by 1cm, placing the activated nickel screen in a tube furnace, heating to 300 ℃ at the heating rate of 2 ℃/min under the air atmosphere, preserving heat for 3h, and then cooling to room temperature at the cooling rate of 2 ℃/min; preparing the Cu (II) -MOF/Ni composite material.
The preparation method of the Cu (II) -MOF/Ni-based composite material is characterized in that the H is6An L ligand having the structural formula:
H6the preparation steps of L are as follows:
0.084mol of amino isophthalic acid, 0.134mol of NaOH and 0.1 mol of NaOH are mixed04mol NaHCO3Adding into 140ml distilled water, mixing, and stirring at 0 deg.C for 30 min; simultaneously dropwise adding 1, 4-dioxane solution of cyanuric chloride; heating the mixture at 100 deg.C for 24H, adjusting pH of the mixture solution to 2 with HCl, filtering, washing with distilled water several times, and drying at room temperature to obtain H6L ligand in 95% yield.
A1, 4-dioxane solution of cyanuric chloride was prepared by dissolving 0.02mol of cyanuric chloride in 70mL of 1, 4-dioxane.
The activated nickel screen is prepared by sequentially performing ultrasonic treatment on the nickel screen in acetone, absolute ethyl alcohol and distilled water for 2-4min, washing to remove surface impurities, and then soaking the nickel screen in nitric acid with the mass fraction of 40% for ultrasonic treatment for 1 min.
The nickel mesh was purchased from electrochemistry corporation and had an areal density of 280-420g/m2The aperture is 0.2-0.6mm, and the longitudinal tensile strength is 106N/cm2Transverse tensile strength of 76N/cm2And the porosity is 97.2%.
The Cu (II) -MOF has a chemical formula of [ Cu3L(H2O)3]·10H2O.5 DMA; one structural unit of the compound is composed of 3 Cu (II) positive ions, three water molecules and 5DMA molecules, wherein the DMA is N, N-dimethylacetamide; the Cu (II) -MOF/Ni-based composite material is a hybrid material formed by carbon dots, nano copper oxide and porous carbon, and the hybrid material is loaded on a nickel net to form the composite material.
2. Use of a Cu (II) -MOF/Ni-based composite material as described above for catalysis of oxygen evolution from electrolysis of water
A Cu (II) -MOF/Ni-based composite material with an area of 0.5cm multiplied by 1cm is used as a working electrode; a three-electrode electrochemical workstation was used, a Pt sheet (5 mm. times.5 mm. times.0.1 mm) was used as a counter electrode, an Ag/AgCl electrode was used as a reference electrode, and the oxygen evolution performance of electrocatalytic decomposition water was tested in an electrolyte solution of 0.5M KOH.
The electrolytic water based on the Cu (II) -MOF/Ni composite material catalyzes oxygen evolution when the current density J is 10mA/cm2When the potential is 1.35Vvs RHE; the high-efficiency oxygen evolution catalytic activity of the material is demonstrated; before and after 1000 times of circulation, no obvious change is found in the polarization curve of the material, which indicates that the catalyst hasHas good stability.
The beneficial technical effects of the invention are as follows:
(1) simple process and easy industrialization
The preparation method is based on the preparation of the Cu (II) -MOF/Ni composite material, the room temperature one-step method is adopted, the Cu (II) -MOF gel doped with melamine, namely the melamine @ Cu (II) -MOF gel, then, the melamine is subjected to in-situ thermal decomposition to form carbon dots through one-step heating in air atmosphere, the Cu (II) -MOF is subjected to in-situ thermal decomposition to form nano copper oxide and porous carbon to form a ternary nano hybrid material, and the hybrid material is loaded on a nickel net to form the Cu (II) -MOF/Ni composite material.
(2) High catalytic oxygen evolution efficiency and good stability
The invention provides an electrocatalytic oxygen evolution catalyst based on a Cu (II) -MOF/Ni composite material, which is directly used as a working electrode to catalyze water to decompose and evolve oxygen, so that the traditional working electrode is prevented from adopting perfluorinated resin or other adhesives to bond catalyst powder, more active sites are exposed, and the composite material-based electrocatalytic oxygen evolution catalyst is high in catalytic efficiency and good in stability.
Detailed Description
The present invention is further described with reference to the following examples, but the scope of the present invention is not limited to the examples, and modifications made by those skilled in the art to the technical solutions of the present invention should fall within the scope of the present invention.
Example 1 preparation method of Cu (II) -MOF/Ni-based composite material
0.470g of copper nitrate was mixed with 1.0mL of water to prepare an aqueous copper nitrate solution, and 0.05g of H was added6Mixing the L powder with 0.20mL of dimethyl sulfoxide to prepare a ligand solution, adding 0.02g of melamine powder, and shaking to form melamine @ Cu (II) -MOF gel; uniformly coating 0.012g of melamine @ Cu (II) -MOF gel on an activated nickel screen with the area of 0.5cm multiplied by 1cm, placing the activated nickel screen in a tube furnace, heating to 300 ℃ at the temperature rise rate of 2 ℃/min under the air atmosphere, preserving heat for 3h, and then cooling to a room at the temperature fall rate of 2 ℃/minWarming; preparing the Cu (II) -MOF/Ni composite material.
Example 2 preparation method of Cu (II) -MOF/Ni-based composite material
0.57g of copper nitrate was mixed with 2.0mL of water to prepare an aqueous copper nitrate solution, and 0.07g of H was added6Mixing the L powder with 0.30mL of dimethyl sulfoxide to prepare a ligand solution, adding 0.04g of melamine powder, and shaking to form melamine @ Cu (II) -MOF gel;
uniformly coating 0.013g of melamine @ Cu (II) -MOF gel on an activated nickel screen with the area of 0.5cm multiplied by 1cm, placing the activated nickel screen in a tube furnace, heating to 300 ℃ at the heating rate of 2 ℃/min under the air atmosphere, preserving heat for 3h, and then cooling to room temperature at the cooling rate of 2 ℃/min; preparing the Cu (II) -MOF/Ni composite material.
Example 3
1. Preparation method of Cu (II) -MOF/Ni-based composite material
0.52g of copper nitrate was mixed with 1.5mL of water to prepare an aqueous copper nitrate solution, and 0.06g of H was added6Mixing the L powder with 0.25mL of dimethyl sulfoxide to prepare a ligand solution, adding 0.03g of melamine powder, and shaking to form melamine @ Cu (II) -MOF gel;
uniformly coating 0.013g of melamine @ Cu (II) -MOF gel on an activated nickel screen with the area of 0.5cm multiplied by 1cm, placing the activated nickel screen in a tube furnace, heating to 300 ℃ at the heating rate of 2 ℃/min under the air atmosphere, preserving heat for 3h, and then cooling to room temperature at the cooling rate of 2 ℃/min; preparing the Cu (II) -MOF/Ni composite material.
Example 4
Examples 1 to 3 of a method for preparing a composite material based on Cu (II) -MOF/Ni, characterized in that the H is6An L ligand having the structural formula:
H6the preparation steps of L are as follows:
0.084mol of amino isophthalic acid, 0.134mol of NaOH and 0.104mol of NaHCO are added3Adding into 140ml distilled water, mixing, and stirring at 0 deg.CStirring for 30 min; simultaneously dropwise adding 1, 4-dioxane solution of cyanuric chloride; heating the mixture at 100 deg.C for 24H, adjusting pH of the mixture solution to 2 with HCl, filtering, washing with distilled water several times, and drying at room temperature to obtain H6L ligand in 95% yield;
a1, 4-dioxane solution of cyanuric chloride was prepared by dissolving 0.02mol of cyanuric chloride in 70mL of 1, 4-dioxane.
Example 5
The activated nickel screen of the embodiment 1-3 is prepared by sequentially performing ultrasonic treatment on the nickel screen in acetone, absolute ethyl alcohol and distilled water for 2-4min, washing to remove surface impurities, and then soaking the nickel screen in nitric acid with the mass fraction of 40% for ultrasonic treatment for 1 min; the nickel mesh was purchased from electrochemistry corporation and had an areal density of 280-420g/m2The aperture is 0.2-0.6mm, and the longitudinal tensile strength is 106N/cm2Transverse tensile strength of 76N/cm2And the porosity is 97.2%.
Example 6 use of a Cu (II) -MOF/Ni-based composite for catalysis of oxygen evolution from electrolyzed water
Using the Cu (II) -MOF/Ni-based composite material with the area of 0.5cm multiplied by 1cm in example 1, example 2 or example 3 as a working electrode; using a three-electrode electrochemical workstation, taking a Pt sheet (5mm multiplied by 0.1mm) as a counter electrode and an Ag/AgCl electrode as a reference electrode, testing the oxygen evolution performance of the electrocatalytic decomposition water in 0.5M KOH aqueous solution, and when the current density J is 10mA/cm2When the potential is 1.35Vvs RHE; the high-efficiency oxygen evolution catalytic activity of the material is demonstrated; before and after 1000 times of circulation, no obvious change is found in the polarization curve of the material, which indicates that the catalyst has good stability.
Claims (5)
1. A preparation method based on a Cu (II) -MOF/Ni composite material is characterized by comprising the following steps:
0.47-0.57g of copper nitrate is mixed with 1.0-2.0mL of water to prepare copper nitrate aqueous solution, 0.05-0.07g of H6Mixing the L powder with 0.20-0.30mL of dimethyl sulfoxide to prepare a ligand solution, adding 0.02-0.04g of melamine powder, and shaking to form melamine @ Cu (II) -MOF gel;
uniformly coating 0.012-0.013g of melamine @ Cu (II) -MOF gel on an activated nickel screen with the area of 0.5cm multiplied by 1cm, placing the activated nickel screen in a tube furnace, heating to 300 ℃ at the heating rate of 2 ℃/min under the air atmosphere, preserving heat for 3h, and then cooling to room temperature at the cooling rate of 2 ℃/min; preparing CDs/CuO-C/Ni composite materials, namely catalysts based on Cu (II) -MOF/Ni composite materials.
2. The method of claim 1, wherein the H comprises a Cu (II) -MOF/Ni composite material6An L ligand having the structural formula:
3. the preparation method of the Cu (II) -MOF/Ni-based composite material according to claim 1, wherein the activated nickel screen is prepared by sequentially performing ultrasonic treatment on the nickel screen in acetone, absolute ethyl alcohol and distilled water for 2-4min, washing to remove surface impurities, and then immersing the nickel screen in 40 mass percent nitric acid for ultrasonic treatment for 1 min.
4. The method for preparing the Cu (II) -MOF/Ni-based composite material according to claim 1, wherein the Cu (II) -MOF/Ni-based composite material is a hybrid material composed of carbon dots, nano-copper oxide and porous carbon, and the hybrid material is loaded on a nickel net.
5. Use of a cu (ii) -MOF/Ni-based composite material prepared by the preparation method of claim 1 for the catalytic oxygen evolution by electrolysis of water.
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