CN115975213B - Nickel-based metal organic framework prepared based on solvothermal synthesis method, synthesis method and application thereof - Google Patents
Nickel-based metal organic framework prepared based on solvothermal synthesis method, synthesis method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000013099 nickel-based metal-organic framework Substances 0.000 title claims abstract description 37
- 238000004729 solvothermal method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000012265 solid product Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 55
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 17
- 239000007772 electrode material Substances 0.000 claims description 13
- 239000003990 capacitor Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
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- 239000002077 nanosphere Substances 0.000 abstract description 2
- 239000002127 nanobelt Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 30
- 239000000843 powder Substances 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000012621 metal-organic framework Substances 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 239000002033 PVDF binder Substances 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 239000006260 foam Substances 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000013118 MOF-74-type framework Substances 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 4
- 241000234314 Zingiber Species 0.000 description 3
- 235000006886 Zingiber officinale Nutrition 0.000 description 3
- 235000008397 ginger Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 230000001627 detrimental effect Effects 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nickel-based metal organic framework prepared based on a solvothermal synthesis method, a synthesis method and application thereof, and belongs to the technical field of resources and environment. The synthesis method comprises the following steps: dissolving metal salt in an organic solvent to obtain a solution A; (2) Dissolving an organic ligand in an organic solvent to obtain a solution B; (3) Adding the solution A and the solution B into a reaction kettle for solvothermal reaction; (4) Filtering, washing and drying a solid product obtained by the reaction to obtain a nickel-based metal organic framework; the metal salt comprises a nickel salt. The preparation method of the invention is simple, low in cost and easy for mass production. The prepared nickel metal organic framework has larger specific surface area, multiple morphologies such as nano rods, lamellar nano belts, nanospheres, nano sheets and the like, and good stability and electrochemical performance.
Description
Technical Field
The invention relates to the technical field of resources and environment, in particular to a nickel-based metal organic framework prepared based on a solvothermal synthesis method, a synthesis method and application thereof.
Background
Metal Organic Frameworks (MOFs) are porous nano-materials with periodic network structures, which are formed by taking metal ions or metal clusters as nodes and connecting the metal ions or the metal clusters with organic ligands through autonomous assembly. The material has the characteristics of large specific surface area, flexible pore structure, multiple active sites, high thermal stability, recoverability, adjustable structure and the like. The metal sites with homogeneously dispersed coordination unsaturation in the material make MOFs material have wide application prospect in the field of energy storage.
There have been studies showing that MOFs materials can be applied in electrode materials for batteries, capacitors, supercapacitors. The common electrode materials of the super capacitor are carbon-based materials, conductive polymers and metal oxides. Electrochemical performance of the supercapacitor is closely related to porosity, specific surface area, size and crystallinity of the electrode material. The porous structure and high specific surface area of MOFs material can be formulated so that the MOFs material has enough electroactive sites for supercapacitor charge storage, and is considered to have excellent electrode material potential. Although the ordered porous structure of MOFs materials has some benefit to the performance of supercapacitors, certain inherent properties of the materials are detrimental to electrochemical reactions, thereby limiting their application in supercapacitors. For example, MOFs are porous, but many MOFs have smaller pore sizes than ions in the electrolyte and are not suitable for ion transport; in addition, in MOFs materials, metal center ions and coordination ions are connected by covalent bonds and van der Waals forces, so that the structure is not very stable, and the charge and discharge processes of pseudocapacitors are processes of continuous intercalation and deintercalation of ions, so that the cycle life of the MOFs materials is limited. In addition, MOFs materials have the problem of insufficient water stability when applied to water pollutant treatment. Because of weak coordination between metal and organic ligands, MOFs skeleton is easy to be attacked by water molecules, and problems of ligand displacement, structural decomposition and the like are generated, so that the porosity is lost.
Disclosure of Invention
Aiming at the problems of water stability and insufficient conductivity of MOFs, the invention provides a nickel-based metal organic framework prepared based on a solvothermal synthesis method, a synthesis method and application thereof. By carrying out doped metal modification on the parent MOFs material, the structural stability and the electrochemical performance of the material are improved, and the original network topology structure is not changed.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows: provided is a synthesis method of a nickel-based metal organic framework prepared based on a solvothermal synthesis method, comprising the following steps:
(1) Dissolving metal salt in an organic solvent to obtain a solution A;
(2) Dissolving an organic ligand in an organic solvent to obtain a solution B;
(3) Adding the solution A and the solution B into a reaction kettle for solvothermal reaction;
(4) Filtering, washing and drying a solid product obtained by the reaction to obtain a nickel-based metal organic framework;
the metal salt comprises a nickel salt.
Preferably, the nickel salt is nickel nitrate and/or nickel chloride.
Preferably, the metal salt further comprises a cobalt salt and/or an iron salt.
Preferably, the organic ligand comprises terephthalic acid (H 2 BDC), trimesic acid (H) 3 BTC), 2, 5-dihydroxyterephthalic acid (H) 4 DOBDC)。
Preferably, the molar ratio of metal ions to the organic ligand in the metal salt is 2:1.
Preferably, the solvothermal reaction is carried out at a temperature of 120-200 ℃ for 12-24 hours.
Preferably, the solvothermal reaction is at 140 ℃ for 24 hours.
Preferably, the organic solvent in step (1) and step (2) is N, N-Dimethylformamide (DMF).
The second technical scheme of the invention is as follows: a nickel-based metal organic framework synthesized according to the above synthesis method is provided.
The third technical scheme of the invention: the application of the nickel-based metal organic framework in the electrode material of a battery, a capacitor or a supercapacitor is provided.
The beneficial technical effects of the invention are as follows:
(1) The preparation method of the invention is simple, low in cost and easy for mass production.
(2) The nickel metal organic framework prepared by the invention has larger specific surface area (the specific surface area of the prepared product is 408.20-577.62 m) 2 In the range of/g), has various morphologies such as nanorods, lamellar nanoribbons, nanospheres, nanosheets and the like.
(3) According to the invention, the problem of insufficient structural stability of the nickel-based metal organic framework material caused by a hard and soft acid-base principle is relieved by introducing the bimetal, so that the improvement of the water stability of the nickel-based metal organic framework is realized, and the cycle performance of the material when being used as a pseudo-capacitor electrode material is greatly improved.
(4) The preparation method provided by the invention successfully grows the nickel-based metal organic framework material with the two-dimensional nano lamellar structure, reduces the size of the blocky MOFs material to the size of the nano sheet, exposes more surface metal positions, thereby generating more electrochemical active surface area, improving the specific capacitance of the material when the material is used as a pseudocapacitance electrode material for charge and discharge, and improving the electrochemical performance of the material.
Drawings
FIG. 1 is an SEM image of a nickel-based MOF prepared according to examples 1-6 of the present invention, where a is the nickel-based MOF prepared according to example 1, b is the nickel-based MOF prepared according to example 2, c is the nickel-based MOF prepared according to example 3, d is the nickel-based MOF prepared according to example 4, e is the nickel-based MOF prepared according to example 5, and f is the nickel-based MOF prepared according to example 6.
FIG. 2 is an XRD pattern of nickel-based MOFs prepared in examples 1-6 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
Weighing 4mmol of nickel nitrate hexahydrate Ni (NO) 3 ) 2 ·6H 2 O, dissolving in 15mLN, N-Dimethylformamide (DMF), and carrying out ultrasonic dissolution for 20min to obtain a green solution A; weigh 2mmol terephthalic acid (H) 2 BDC) is dissolved in 15mLN, N-Dimethylformamide (DMF) and is subjected to ultrasonic dissolution for 20min to obtain colorless transparent solution B; mixing A, B solution, pouring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, putting the reaction kettle into a baking oven, reacting for 24 hours at 140 ℃, taking out the reaction kettle after the reaction is finished, and cooling the reaction kettle to room temperature; respectively centrifugally washing the obtained green solution with N, N-Dimethylformamide (DMF), deionized water, absolute methanol and dichloromethane once to leave lower green powder; and (3) placing the cleaned green powder into a vacuum drying oven, and drying at 60 ℃ for 12 hours to obtain the green powder, namely the nickel-based metal organic framework, namely the Ni-BDC.
Ni-BDC powder, acetylene black and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 7:2:1, adding a proper amount of absolute ethyl alcohol dropwise into a mortar, and fully grinding to obtain uniform black paste. And uniformly smearing the black electrode slurry on the foam nickel after washing and drying, and putting the foam nickel into a vacuum drying oven for drying at 50 ℃ for 24 hours to obtain the electrode slice. The prepared electrode slice is used as a working electrode, and is placed in a three-electrode system together with a platinum wire counter electrode and an Ag/AgCl reference electrode, and an electrochemical workstation is used for carrying out electrochemical performance test.
The SEM of Ni-BDC obtained in example 1 is shown in FIG. 1 a, and the material structure is a block structure composed of lamellar structures. The XRD pattern of the prepared Ni-BDC is shown in figure 2, and characteristic peaks mainly appear near 8.50 degrees, 14.99 degrees, 15.88 degrees and 17.03 degrees, and accord with the XRD pattern characteristics of Ni-MOF (PCPDFNo. 35-1676).
Example 2
Weighing 4mmol of nickel nitrate hexahydrate Ni (NO) 3 ) 2 ·6H 2 O, dissolving in 15mLN, N-Dimethylformamide (DMF), and carrying out ultrasonic dissolution for 20min to obtain a green solution A; 2mmol of trimesic acid (H) was weighed out 3 BTC) is dissolved in 15mLN, N-Dimethylformamide (DMF) and is subjected to ultrasonic dissolution for 20min to obtain colorless transparent solution B; mixing A, B solution, pouring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, putting the reaction kettle into a baking oven, reacting for 24 hours at 140 ℃, taking out the reaction kettle after the reaction is finished, and cooling the reaction kettle to room temperature; respectively centrifugally washing the obtained green solution with N, N-Dimethylformamide (DMF), deionized water, absolute methanol and dichloromethane once to leave lower green powder; and (3) placing the cleaned green powder into a vacuum drying oven, and drying at 60 ℃ for 12 hours to obtain the green powder, namely the nickel-based metal organic framework, namely the Ni-BTC.
Ni-BTC powder, acetylene black and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 7:2:1, adding a proper amount of absolute ethyl alcohol dropwise into a mortar, and fully grinding to obtain uniform black paste. And uniformly smearing the black electrode slurry on the foam nickel after washing and drying, and putting the foam nickel into a vacuum drying oven for drying at 50 ℃ for 24 hours to obtain the electrode slice. The prepared electrode slice is used as a working electrode, and is placed in a three-electrode system together with a platinum wire counter electrode and an Ag/AgCl reference electrode, and an electrochemical workstation is used for carrying out electrochemical performance test.
The SEM spectrum of Ni-BTC obtained in example 2 is shown in FIG. 1 b, and the material structure is a rod-like structure composed of orderly stacked lamellar structures. As shown in figure 2, the XRD pattern of the prepared Ni-BTC mainly appears near 8.46 degrees, 15.03 degrees, 15.96 degrees and 17.07 degrees, and accords with the XRD pattern characteristics of Ni-MOF (PCPDFNo. 35-1676).
Example 3
Weighing 4mmol of nickel nitrate hexahydrate Ni (NO) 3 ) 2 ·6H 2 O, dissolving in 15mLN, N-Dimethylformamide (DMF), and carrying out ultrasonic dissolution for 20min to obtain a green solution A; 2mmol of 2, 5-dihydroxyterephthalic acid (H) was weighed out 4 DOBDC) is dissolved in 15mLN, N-Dimethylformamide (DMF) and subjected to ultrasonic dissolution for 20min to obtain yellow solution B; mixing A, B solution, pouring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, putting the reaction kettle into a baking oven, reacting for 24 hours at 140 ℃, taking out the reaction kettle after the reaction is finished, and cooling the reaction kettle to room temperature; respectively centrifugally washing the obtained reddish brown solution with N, N-Dimethylformamide (DMF), deionized water, absolute methanol and dichloromethane once to leave lower layer ginger yellow powder; and (3) putting the cleaned ginger yellow powder into a vacuum drying oven, and drying at 60 ℃ for 12 hours to obtain the ginger yellow powder, namely the nickel-based metal organic framework, namely the Ni-DOBDC.
Ni-DOBDC powder, acetylene black and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 7:2:1, adding a proper amount of absolute ethyl alcohol dropwise into a mortar, and fully grinding to obtain uniform black paste. And uniformly smearing the black electrode slurry on the foam nickel after washing and drying, and putting the foam nickel into a vacuum drying oven for drying at 50 ℃ for 24 hours to obtain the electrode slice. The prepared electrode slice is used as a working electrode, and is placed in a three-electrode system together with a platinum wire counter electrode and an Ag/AgCl reference electrode, and an electrochemical workstation is used for carrying out electrochemical performance test.
The SEM image of Ni-DOBDC obtained in example 3 is shown in FIG. 1 c, and the material structure is a spherical structure composed of fine lamellar structures. The XRD pattern of the prepared Ni-DOBDC is shown in figure 2, and characteristic peaks mainly appear near 6.83 degrees and 11.84 degrees, which accord with the XRD pattern characteristics of MOF-74.
Example 4
2mmol of nickel nitrate hexahydrate Ni (NO) was weighed out 3 ) 2 ·6H 2 O, 2mmol ferric nitrate nonahydrate Fe (NO) 3 ) 3 ·9H 2 O, dissolving in 15mLN, N-Dimethylformamide (DMF), and carrying out ultrasonic dissolution for 20min to obtain yellow solution A; 2mmol of 2, 5-dihydroxyterephthalic acid (H) was weighed out 4 DOBDC) is dissolved in 15mLN, N-Dimethylformamide (DMF) and subjected to ultrasonic dissolution for 20min to obtain yellow solution B; mixing A, B solution, pouring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, putting the reaction kettle into an oven, reacting for 24 hours at 140 ℃, taking out the reaction kettle after the reaction is finished, and cooling the reaction kettle to room temperature; the brown solution is respectively centrifugally washed once by N, N-Dimethylformamide (DMF), deionized water, absolute methanol and methylene dichloride, and lower green powder is left; and (3) placing the cleaned reddish brown powder into a vacuum drying oven, and drying at 60 ℃ for 12 hours to obtain the reddish brown powder, namely the nickel-based metal organic framework, and marking the nickel-based metal organic framework as NiFe-DOBDC.
NiFe-DOBDC powder, acetylene black and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 7:2:1, adding a proper amount of absolute ethyl alcohol dropwise into a mortar, and fully grinding to obtain uniform black paste. And uniformly smearing the black electrode slurry on the foam nickel after washing and drying, and putting the foam nickel into a vacuum drying oven for drying at 50 ℃ for 24 hours to obtain the electrode slice. The prepared electrode slice is used as a working electrode, and is placed in a three-electrode system together with a platinum wire counter electrode and an Ag/AgCl reference electrode, and an electrochemical workstation is used for carrying out electrochemical performance test.
The SEM of NiFe-DOBDC obtained in example 4 is shown in FIG. 1 d as a block structure showing lamellar structure. The XRD pattern of the prepared NiFe-DOBDC is shown in figure 2, and characteristic peaks mainly appear near 6.75 degrees and 11.85 degrees, and accord with the XRD pattern characteristics of MOF-74.
Example 5
4mmol of nickel chloride hexahydrate (NiCl) was weighed out 2 ·6H 2 O), 2mmol of cobalt nitrate hexahydrate Co (NO) 3 ) 2 ·6H 2 O, dissolving in 15mLN, N-Dimethylformamide (DMF), and carrying out ultrasonic dissolution for 20min to obtain pink solution A; 2mmol of 2, 5-dihydroxyterephthalic acid (H) was weighed out 4 DOBDC) is dissolved in 15mLN, N-Dimethylformamide (DMF) and subjected to ultrasonic dissolution for 20min to obtain yellow solution B; a, B solution is mixed and poured into a 50mL polytetrafluoroethylene high-pressure reaction kettle, and the reaction kettle is put into an ovenReacting for 12 hours at 140 ℃, taking out the reaction kettle after the reaction is finished, and cooling to room temperature; the obtained yellowish-brown solution is respectively centrifugally washed once by N, N-Dimethylformamide (DMF), deionized water, absolute methanol and methylene dichloride, and lower brown powder is left; and (3) placing the cleaned brown powder into a vacuum drying oven, and drying at 60 ℃ for 12 hours to obtain the brown powder, namely the nickel-based metal organic framework, which is marked as NiCo-DOBDC.
NiCo-DOBDC powder, acetylene black and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 7:2:1, adding a proper amount of absolute ethyl alcohol dropwise into a mortar, and fully grinding to obtain uniform black paste. And uniformly smearing the black electrode slurry on the foam nickel after washing and drying, and putting the foam nickel into a vacuum drying oven for drying at 50 ℃ for 24 hours to obtain the electrode slice. The prepared electrode slice is used as a working electrode, and is placed in a three-electrode system together with a platinum wire counter electrode and an Ag/AgCl reference electrode, and an electrochemical workstation is used for carrying out electrochemical performance test.
The SEM of NiCo-DOBDC obtained in example 5 is shown in FIG. 1 e as a stacked lamellar structure. The XRD pattern of the prepared NiCo-DOBDC is shown in figure 2, and the characteristic peaks mainly appear near 6.87 degrees and 11.85 degrees, which accord with the XRD pattern characteristics of MOF-74.
Example 6
2mmol of nickel chloride hexahydrate (NiCl) was weighed out 2 ·6H 2 O), 1mmol ferric nitrate nonahydrate Fe (NO) 3 ) 3 ·9H 2 O, 1mmol cobalt nitrate hexahydrate Co (NO) 3 ) 2 ·6H 2 O, dissolving in 15mLN, N-Dimethylformamide (DMF), and performing ultrasonic dissolution for 20min to obtain reddish brown solution A; 2mmol of 2, 5-dihydroxyterephthalic acid (H) was weighed out 4 DOBDC) is dissolved in 15mLN, N-Dimethylformamide (DMF) and subjected to ultrasonic dissolution for 20min to obtain yellow solution B; mixing A, B solution, pouring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, putting the reaction kettle into a baking oven, reacting for 12 hours at 140 ℃, taking out the reaction kettle after the reaction is finished, and cooling the reaction kettle to room temperature; the obtained dark brown solution is respectively centrifugally washed once by N, N-Dimethylformamide (DMF), deionized water, absolute methanol and methylene dichloride, and lower dark brown powder is left; placing the cleaned dark brown powder into vacuum dryingDrying in a drying box at 60 ℃ for 12 hours to obtain dark brown powder, namely the nickel-based metal organic framework, which is recorded as NiCoFe-DOBDC.
NiCoFe-DOBDC powder, acetylene black and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 7:2:1, adding a proper amount of absolute ethyl alcohol dropwise into a mortar, and fully grinding to obtain uniform black paste. And uniformly smearing the black electrode slurry on the foam nickel after washing and drying, and putting the foam nickel into a vacuum drying oven for drying at 50 ℃ for 24 hours to obtain the electrode slice. The prepared electrode slice is used as a working electrode, and is placed in a three-electrode system together with a platinum wire counter electrode and an Ag/AgCl reference electrode, and an electrochemical workstation is used for carrying out electrochemical performance test.
The SEM of NiCoFe-DOBDC obtained in example 6 is shown in FIG. 1 f as a lamellar structure. The XRD pattern of the prepared NiCoFe-DOBDC is shown in figure 2, and characteristic peaks mainly appear near 6.83 degrees and 11.83 degrees, which accord with the XRD pattern characteristics of MOF-74.
Test case
The electrode materials prepared in examples 1 to 6 were subjected to electrical property tests, including GCD, EIS, CV and cyclic stability, respectively, under a three-electrode system of 4m koh, and the calculated specific capacitance values after fitting according to GCD, EIS, CV measurement data are shown in table 1, and the cyclic stability detection results are shown in table 2.
TABLE 1 specific capacitances of the electrode materials at current densities of 1, 2,5, 8, 10A/g
TABLE 2 specific capacitance retention of electrode materials after 3000 cycles at a current density of 10A/g
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Efficiency of | 56.34％ | 50.61％ | 50.68％ | 83.59％ | 84.79％ | 89.92％ |
In summary, the invention provides a nickel-based metal organic framework material prepared based on a one-step solvothermal synthesis method, which is characterized in that the shape and structure of the material are adjusted by further doping bimetal, so that the water stability and electrochemical performance of the material are improved. The material synthesis method is simple and convenient, the used instrument and reagent are simple, and the generated acid-base waste liquid is less. The successfully synthesized nano lamellar structure greatly improves the defect of insufficient electrochemical performance of the massive nickel-based metal organic framework, greatly improves the cycle performance of the material when being used as a pseudocapacitance electrode material, and provides basic research support for the application of the nickel-based metal organic framework to the pseudocapacitance electrode material.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (6)
1. The synthesis method of the nickel-based metal organic framework prepared on the basis of the solvothermal synthesis method is characterized by comprising the following steps of:
(1) Dissolving metal salt in an organic solvent to obtain a solution A;
(2) Dissolving an organic ligand in an organic solvent to obtain a solution B;
(3) Adding the solution A and the solution B into a reaction kettle for solvothermal reaction;
(4) Filtering, washing and drying a solid product obtained by the reaction to obtain a nickel-based metal organic framework;
the metal salt is nickel salt, cobalt salt and ferric salt;
the organic ligand is 2, 5-dihydroxyterephthalic acid;
the molar ratio of the metal ions in the metal salt to the organic ligand is 2:1.
2. The synthesis according to claim 1, wherein the nickel salt is nickel nitrate and/or nickel chloride.
3. The method according to any one of claims 1 to 2, wherein the solvothermal reaction is carried out at a temperature of 120 to 200 ℃ for a period of 12 to 24 hours.
4. The synthesis method according to any one of claims 1 to 2, wherein the organic solvent in step (1) and step (2) is N, N-dimethylformamide.
5. The nickel-based metal organic framework synthesized by the synthesis method according to any one of claims 1 to 4.
6. The use of the nickel-based metal organic framework according to claim 5 in electrode materials of batteries, capacitors or supercapacitors.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104979104A (en) * | 2015-07-02 | 2015-10-14 | 上海应用技术学院 | Preparation method of Ni-MOF electrode material |
| CN104992848A (en) * | 2015-06-30 | 2015-10-21 | 中国地质大学（武汉） | Binary metal organic framework material applied to super capacitor and preparation method for binary metal organic framework material |
| CN109166733A (en) * | 2018-09-30 | 2019-01-08 | 北京印刷学院 | A kind of method that hydro-thermal method prepares Ni/Co base MOF material |
| CN109400906A (en) * | 2018-12-12 | 2019-03-01 | 太原理工大学 | The method of more metal MOFs materials is directly prepared using bimetal complex |
| CN109553779A (en) * | 2018-11-20 | 2019-04-02 | 三峡大学 | A kind of preparation method and application of three-dimensional manometer flower metal-organic framework material |
| CN110085446A (en) * | 2019-04-11 | 2019-08-02 | 北京工业大学 | A kind of preparation method of original position Ni doping Co-MOF-74 electrode material for super capacitor |
| CN110787840A (en) * | 2019-11-06 | 2020-02-14 | 中国科学院过程工程研究所 | Bimetallic MOFs catalyst and preparation method and application thereof |
| CN111276341A (en) * | 2020-03-07 | 2020-06-12 | 上海第二工业大学 | Supercapacitor electrode material based on Ni/Co-MOF core-shell structure and preparation method thereof |
| CN111375385A (en) * | 2020-03-05 | 2020-07-07 | 大连理工大学 | Preparation method and application of bimetallic organic framework adsorbent |
| CN113088252A (en) * | 2021-04-01 | 2021-07-09 | 安徽理工大学 | Iron-cobalt-nickel alloy/carbon/graphene ultrathin wave-absorbing material and preparation method thereof |
| CN114438516A (en) * | 2022-02-16 | 2022-05-06 | 中国海洋大学 | Preparation method of porous nickel-iron-based bimetallic organic framework electrocatalyst and application of porous nickel-iron-based bimetallic organic framework electrocatalyst in water oxidation reaction |
| CN115350706A (en) * | 2022-08-29 | 2022-11-18 | 南京信息工程大学 | CO (carbon monoxide) 2 Preparation method of three-element metal MOF (Metal organic framework) derivative catalyst for hydrogenation thermal catalysis |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10695741B2 (en) * | 2016-06-17 | 2020-06-30 | Battelle Memorial Institute | System and process for continuous and controlled production of metal-organic frameworks and metal-organic framework composites |
| CN109267093B (en) * | 2018-10-09 | 2020-04-10 | 苏州大学 | Ultrathin Ni-Fe-MOF nanosheet and preparation method and application thereof |
| JP2023526425A (en) * | 2020-05-22 | 2023-06-21 | ヌマット テクノロジーズ，インコーポレイテッド | Method for refining hydrogen gas used in fuel cells |
-
2023
- 2023-02-03 CN CN202310095212.1A patent/CN115975213B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104992848A (en) * | 2015-06-30 | 2015-10-21 | 中国地质大学（武汉） | Binary metal organic framework material applied to super capacitor and preparation method for binary metal organic framework material |
| CN104979104A (en) * | 2015-07-02 | 2015-10-14 | 上海应用技术学院 | Preparation method of Ni-MOF electrode material |
| CN109166733A (en) * | 2018-09-30 | 2019-01-08 | 北京印刷学院 | A kind of method that hydro-thermal method prepares Ni/Co base MOF material |
| CN109553779A (en) * | 2018-11-20 | 2019-04-02 | 三峡大学 | A kind of preparation method and application of three-dimensional manometer flower metal-organic framework material |
| CN109400906A (en) * | 2018-12-12 | 2019-03-01 | 太原理工大学 | The method of more metal MOFs materials is directly prepared using bimetal complex |
| CN110085446A (en) * | 2019-04-11 | 2019-08-02 | 北京工业大学 | A kind of preparation method of original position Ni doping Co-MOF-74 electrode material for super capacitor |
| CN110787840A (en) * | 2019-11-06 | 2020-02-14 | 中国科学院过程工程研究所 | Bimetallic MOFs catalyst and preparation method and application thereof |
| CN111375385A (en) * | 2020-03-05 | 2020-07-07 | 大连理工大学 | Preparation method and application of bimetallic organic framework adsorbent |
| CN111276341A (en) * | 2020-03-07 | 2020-06-12 | 上海第二工业大学 | Supercapacitor electrode material based on Ni/Co-MOF core-shell structure and preparation method thereof |
| CN113088252A (en) * | 2021-04-01 | 2021-07-09 | 安徽理工大学 | Iron-cobalt-nickel alloy/carbon/graphene ultrathin wave-absorbing material and preparation method thereof |
| CN114438516A (en) * | 2022-02-16 | 2022-05-06 | 中国海洋大学 | Preparation method of porous nickel-iron-based bimetallic organic framework electrocatalyst and application of porous nickel-iron-based bimetallic organic framework electrocatalyst in water oxidation reaction |
| CN115350706A (en) * | 2022-08-29 | 2022-11-18 | 南京信息工程大学 | CO (carbon monoxide) 2 Preparation method of three-element metal MOF (Metal organic framework) derivative catalyst for hydrogenation thermal catalysis |
Non-Patent Citations (3)
| Title |
|---|
| Ambient Fast Synthesis and Active Sites Deciphering of Hierarchical Foam-Like Trimetal-Organic Framework Nanostructures as a Platform for Highly Efficient Oxygen Evolution Electrocatalysis;Qian, QZ等;ADVANCED MATERIALS;第31卷(第23期);1-8 * |
| Bimetal metal-organic framework hollow nanoprisms for enhanced electrochemical oxygen evolution;Sun, FZ等;INTERNATIONAL JOURNAL OF HYDROGEN ENERGY;第48卷(第10期);3942-3951 * |
| Self-sorting multimetal-organic gel electrocatalysts for a highly efficient oxygen evolution reaction;Xiao, YL等;JOURNAL OF MATERIALS CHEMISTRY A;第9卷(第32期);17451-17458 * |
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