CN108172418A - Aromatic carboxylic acids class transition metal organic framework and its preparation method and application - Google Patents
Aromatic carboxylic acids class transition metal organic framework and its preparation method and application Download PDFInfo
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- CN108172418A CN108172418A CN201810033140.7A CN201810033140A CN108172418A CN 108172418 A CN108172418 A CN 108172418A CN 201810033140 A CN201810033140 A CN 201810033140A CN 108172418 A CN108172418 A CN 108172418A
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- transition metal
- carboxylic acids
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- -1 Aromatic carboxylic acids Chemical class 0.000 title claims abstract description 43
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 36
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 29
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007772 electrode material Substances 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 27
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000013384 organic framework Substances 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 24
- 238000002474 experimental method Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 7
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical group OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses aromatic carboxylic acids class transition metal organic frameworks and its preparation method and application.Transition metal salt and aromatic carboxylic acids are dissolved in solvent and alkali, then mixed liquor is transferred in autoclave, be ultrasonically treated, first heat up and cool down again, filtered, washing obtains aromatic carboxylic acids class transition metal organic framework.Obtained aromatic carboxylic acids class transition metal organic framework, general formula are：[M’M”7(OH)3(L)6(H2O)x]·yH2O.The electrode material that the aromatic carboxylic acids class transition metal organic framework of preparation is used as ultracapacitor has high capacitance and excellent cyclical stability.
Description
Technical field
The invention belongs to the preparation field of electrode material for super capacitor, more particularly to aromatic carboxylic acids class transition metal is organic
Frame object and its synthetic method.
Background technology
The fast development of global economy, along with the rapid growth of energy demand, development cleaning, sustainable, high-efficiency energy-storage
Device becomes the task of top priority.Ultracapacitor has power density high, has extended cycle life as a kind of important energy storage device
Advantage has been to be concerned by more and more people.
Electrode material is the important component of ultracapacitor, is the key factor for influencing performance of the supercapacitor.It is super
The electrode material of grade capacitor mainly has carbon material, metal oxide materials, conducting polymer materials.Carbon material has the cycle longevity
Many advantages, such as life is long, at low cost, but specific capacitance and oxidation resistance are relatively low.Conducting polymer materials have good electric conductivity
But stability is poor.And although redox reaction can occur for metal oxide, have higher specific capacitance, there are of high cost etc.
Problem.The task of top priority is exactly to find the electrode material with high-performance, environmentally friendly and practical application more simple cheap.
Metal organic frame (MOF) is that a kind of have that porous, specific surface area is high, adjustable aperture and redox reaction site
The features such as new material.MOF materials are used as the electrode material of ultracapacitor, can be divided into two kinds of situations, one kind is used as
Synthesize the masterplate of porous carbon, metal oxide or metal oxide/porous carbide mixture；Another kind is exactly original MOF
Directly as the electrode material of ultracapacitor.Original MOF shows high specific capacitance directly as electrode material, good leads
Electrically, the advantages that having extended cycle life.For example, we have found the copper (Cu-MOF) of tetrafluoro terephthalic acid groups and the metal of cobalt recently
During electrode material of the organic framework (Co-MOF) as ultracapacitor, respectively show 1274F/g (in LiOH, electric current
Density 1A/g；Dalton Trans., 2015,44,19175) and 2474F/g (in KOH, current density 1A/g；ACS
Appl.Mater.Interfaces, 2016,8,4585) specific capacity.But it is generally noted above in two kinds of original MOF materials, uses
Tetrafluoro terephthalic acid (TPA) price it is somewhat expensive, be unfavorable for industrialized production.Therefore, it is (adjacent using cheap aromatic carboxylic acids
Phthalic acid, M-phthalic acid, terephthalic acid (TPA) etc.) come prepare can be as the metal organic frame of electrode material for super capacitor
Object is very necessary
There is presently no with seven core of the synthesis of hydroxy such as transition metal and phthalic acid, M-phthalic acid, terephthalic acid (TPA)
Reports of the cluster MOF as the electrode material of ultracapacitor.
Invention content
The purpose of the present invention is intended to provide a kind of simple and practicable aromatic carboxylic acids class transition metal organic framework material
Preparation method, and study its performance as electrode material for super capacitor.This method is using the raw material being easy to get, using liquid phase
Method, high yield have synthesized serial aromatic carboxylic acids class transition metal organic framework material.This method is simple for process, inexpensive,
Low energy consumption, and favorable reproducibility is had excellent performance.Prepared aromatic carboxylic acids class transition metal organic framework is used as ultracapacitor
Electrode material has high capacitance and excellent cyclical stability, wherein Ni-based aromatic carboxylic acids class transition metal organic framework
([KNi7(OH)3(L1)6(H2O)4]·10H2O, L=M-phthalic acid) it is shown as super capacitance electrode material
Specific capacity may be up to 1667Fg-1, after recycling 2000 times, capacity retention ratio is more than 80%.
Aromatic carboxylic acids class transition metal organic framework provided by the invention, general formula are：
[M’M”7(OH)3(L)6(H2O)x]·yH2O。
Wherein, M ' is one kind in lithium, sodium, potassium ion；M " is one kind in manganese, cobalt, nickel, copper, zinc, iron, cadmium ion；
Wherein, L is one kind in phthalic acid, terephthalic acid (TPA), M-phthalic acid.X is 2-6；Y is 2-12.
The present invention also provides the synthetic method of above-mentioned aromatic carboxylic acids class transition metal organic framework, as steps described below
It carries out：
By transition metal salt and aromatic carboxylic acids, it is dissolved in suitable solvent and alkali, mixed liquor is then transferred to autoclave
In, it is ultrasonically treated, first heats up and cool down again, filter, washing obtains aromatic carboxylic acids class transition metal organic framework.
Wherein, transition metal salt：Aromatic carboxylic acids (molar ratio)=6:5-5:8.
Wherein, the transition metal salt is a kind of soluble-salt in manganese, cobalt, nickel, copper, zinc, iron, cadmium etc..
Wherein, the aromatic carboxylic acids is one kind in phthalic acid, terephthalic acid (TPA), M-phthalic acid；
Wherein, the solvent is water, organic solvent or their mixture.Organic solvent is methanol, ethyl alcohol or propyl alcohol.
Wherein, the alkali is KOH, NaOH or LiOH.Its is a concentration of：1.0~2.5mol/L, dosage are：0.25~
0.75mL。
Wherein, the sonication treatment time is：0.5~1h.
Wherein, the range of reaction temperature in the autoclave is 150~170 DEG C, the 3 days reaction time, after reaction was completed
Cooling, drops to room temperature (25 DEG C) and filters afterwards, and filtering products therefrom is washed for several times with methanol or ethyl alcohol.
The present invention also provides the application of aromatic carboxylic acids class transition metal organic framework obtained, which uses
Make electrode material for super capacitor.
Advantages of the present invention：The present invention prepares aromatic carboxylic acids class transition metal with transition metal salt and aromatic carboxylic acids machine frame
Frame object material, preparation method simple process and low cost, low energy consumption, and favorable reproducibility is had excellent performance, at high temperature under high pressure, high pressure
Kettle reaction is safer.The electrode material that prepared aromatic carboxylic acids class transition metal organic framework is used as ultracapacitor has
There are high capacitance and excellent cyclical stability, be a kind of completely new inorganic-organic hybridization electrode material, seven core of hydroxyl obtained
Cluster MOF material structures are stablized, and the alkali metal ion contained is conducive to the diffusion and transmission of alkali metal ion in electrode material,
Electrode material for super capacitor field, has broad application prospects.
Description of the drawings
Fig. 1 is [KNi7(OH)3(L1)6(H2O)4]·10H2O(L1=M-phthalic acid) CV figure；
Fig. 2 is [KNi7(OH)3(L1)6(H2O)4]·10H2O(L1=M-phthalic acid) charge and discharge electrograph；
Fig. 3 is [KNi7(OH)3(L1)6(H2O)4]·10H2O(L1=M-phthalic acid) cycle life figure；
Fig. 4 is [KNi7(OH)3(L2)6(H2O)4]·10H2O(L2=phthalic acid) bipolar electrode CV figure；
Fig. 5 is [KNi7(OH)3(L1)6(H2O)4]·10H2O(L1=M-phthalic acid) powder X-ray diffractogram；
Fig. 6 is [KNi7(OH)3(L1)6(H2O)4]·10H2The structure chart of O (L=M-phthalic acids)；
Specific embodiment
Below by specific embodiment, the invention will be further described.
Embodiment 1
Four water nickel acetates (0.124g, 0.5mmol) are weighed, M-phthalic acid (is abbreviated as mp, similarly hereinafter) in molecular formula
(0.066g, 0.40mmol) is dissolved in the mixed liquor of the KOH solution of 0.5mL 2mol/L and the methanol of 12mL, Ran Houzhuan
It moves on in the autoclave of 50mL, is ultrasonically treated 1h, put and be warming up to 160 DEG C in an oven, burn 3 days, cool down after reaction was completed, drop to
Room temperature (25 DEG C) filters afterwards, washs filtering products therefrom for several times with methanol or ethyl alcohol, obtains powder, dry, obtains product [KNi7
(OH)3(mp)6(H2O)4]·10H2O。
As the active material of electrode material, according to active material：Acetylene black：Adhesive (PTFE)=75：15：10
Mass ratio, electrode material is made, by its chemical property of its system investigation in three electrodes.From the cyclic voltammogram of Fig. 1
It can be seen that a pair of of redox peaks, illustrate that the electrode material has good invertibity.It can be seen that from the charge and discharge electrograph of Fig. 2
The specific capacitance of the electrode material reaches 1667Fg-1(current density 1Ag-1).Fig. 3 is specific capacitance after recycling 2000 times
Maintenance dose for 83.3%, illustrate that it has extended cycle life.
Fig. 4 is the cyclic voltammogram of bipolar electrode system, and as can be seen from the figure potential windows increase, and can be improved asymmetric super
The energy density of grade capacitor.
Fig. 5 is x-ray diffractogram of powder, and it is [KNi to illustrate product7(OH)3(L1)6(H2O)4]·10H2O (L=isophthalic two
Formic acid).
Fig. 6 is [KNi7(OH)3(L1)6(H2O)4]·10H2The structure chart of O (L=M-phthalic acids), resulting product knot
Structure is：Seven core clustering architecture of hydroxyl.
Embodiment 2
Experimental method with embodiment 1, only by M-phthalic acid be changed to phthalic acid (op is abbreviated as in molecular formula, under
(0.066g, 0.40mmol) is to get compound [KNi together)7(OH)3(op)6(H2O)4]·10H2O。
Embodiment 3
Experimental method with embodiment 1, only by M-phthalic acid be changed to terephthalic acid (TPA) (pp is abbreviated as in molecular formula, under
(0.066g, 0.40mmol) is to get compound [KNi together)7(OH)3(pp)6(H2O)4]·10H2O。
Embodiment 4
Four water nickel acetates (0.124g, 0.5mmol) are only changed to four water cobalt acetates by experimental method with embodiment 1
(0.062g, 0.25mmol) is to get compound [KCo7(OH)3(mp)6(H2O)6]·8H2O。
Embodiment 5
M-phthalic acid is only changed to phthalic acid (0.066g, 0.40mmol), i.e., by experimental method with embodiment 4
Obtain compound [KCo7(OH)3(op)6(H2O)6]·8H2O。
Embodiment 6
M-phthalic acid is only changed to terephthalic acid (TPA) (0.066g, 0.40mmol), i.e., by experimental method with embodiment 4
Obtain compound [KCo7(OH)3(pp)6(H2O)6]·8H2O。
Embodiment 7
Four water nickel acetates (0.124g, 0.5mmol) are only changed to four water manganese acetates by experimental method with embodiment 1
(0.1225g, 0.5mmol) is to get compound [KMn7(OH)3(mp)6(H2O)2]·6H2O。
Embodiment 8
M-phthalic acid is only changed to terephthalic acid (TPA) (0.066g, 0.40mmol) to obtain the final product by experimental method with embodiment 7
Compound [KMn7(OH)3(pp)6(H2O)2]·6H2O。
Embodiment 9
Experimental method with embodiment 7, only by M-phthalic acid (mp) be changed to phthalic acid (op) (0.066g,
0.40mmol) to get compound [KMn7(OH)3(op)6(H2O)2]·6H2O。
Embodiment 10
Four water nickel acetates (0.124g, 0.5mmol) are only changed to a hydrate water copper acetate by experimental method with embodiment 1
(0.100g, 0.5mmol) is to get compound [KCu7(OH)3(mp)6(H2O)2]·2H2O。
Embodiment 11
M-phthalic acid is only changed to terephthalic acid (TPA) (0.066g, 0.40mmol), i.e., by experimental method with embodiment 10
Obtain compound [KCu7(OH)3(pp)6(H2O)2]·2H2O。
Embodiment 12
M-phthalic acid is only changed to phthalic acid (0.066g, 0.40mmol), i.e., by experimental method with embodiment 10
Obtain compound [KCu7(OH)3(op)6(H2O)2]·2H2O。
Embodiment 13
Four water nickel acetates (0.124g, 0.5mmol) are only changed to zinc acetate (0.109g by experimental method with embodiment 1
0.5mmol) to get compound [KZn7(OH)3(mp)6(H2O)4]·4H2O。
Embodiment 14
M-phthalic acid is only changed to phthalic acid (0.066g, 0.40mmol), i.e., by experimental method with embodiment 13
Obtain compound [KZn7(OH)3(op)6(H2O)4]·4H2O。
Embodiment 15
M-phthalic acid is only changed to terephthalic acid (TPA) (0.066g, 0.40mmol), i.e., by experimental method with embodiment 13
Obtain compound [KZn7(OH)3(pp)6(H2O)4]·4H2O。
Embodiment 16
Experimental method with embodiment 1, only by four water nickel acetates (0.124g, 0.5mmol) be changed to ferric acetate (0.123g,
0.5mmol) to get compound [KFe7(OH)3(mp)6(H2O)6]·12H2O。
Embodiment 17
M-phthalic acid is only changed to phthalic acid (0.066g, 0.40mmol), i.e., by experimental method with embodiment 16
Obtain compound [KFe7(OH)3(op)6(H2O)6]·12H2O。
Embodiment 18
M-phthalic acid is only changed to terephthalic acid (TPA) (0.066g, 0.40mmol), i.e., by experimental method with embodiment 16
Obtain compound [KFe7(OH)3(pp)6(H2O)6]·12H2O。
Embodiment 19
Experimental method with embodiment 1, only by four water nickel acetates (0.124g, 0.5mmol) be changed to cadmium acetate (0.115g,
0.5mmol) to get compound [KCd7(OH)3(mp)6(H2O)4]·8H2O。
Embodiment 20
M-phthalic acid is only changed to phthalic acid (0.066g, 0.40mmol), i.e., by experimental method with embodiment 19
Obtain compound [KCd7(OH)3(op)6(H2O)4]·8H2O
Embodiment 21
M-phthalic acid is only changed to terephthalic acid (TPA) (0.066g, 0.40mmol), i.e., by experimental method with embodiment 19
Obtain compound [KCd7(OH)3(pp)6(H2O)4]·8H2O。
Embodiment 22
2mol/L KOH are only changed to 2mol/LNaOH to get compound [NaNi by experimental method with embodiment 17(OH)3
(mp)6(H2O)4]·10H2O。
Embodiment 23
2mol/L KOH are only changed to 2mol/L LiOH up to compound [LiNi by experimental method with embodiment 17(OH)3
(mp)6(H2O)4]·8H2O。
Embodiment 24
12mL methanol is only changed to the ethyl alcohol of 12mL up to compound [KCd by experimental method with embodiment 197(OH)3
(mp)6(H2O)4]·8H2O。
Embodiment 25
12mL methanol is only changed to 12mL propyl alcohol up to compound [KCd by experimental method with embodiment 197(OH)3(mp)6
(H2O)4]·8H2O。
Claims (9)
1. a kind of aromatic carboxylic acids class transition metal organic framework, it is characterised in that：The aromatic carboxylic acids class transition metal is organic
The general formula of frame object is：
[M’M”7(OH)3(L)6(H2O)x]·yH2O；
Wherein, the M ' is one kind in lithium, sodium, potassium ion；M " is one kind in manganese, cobalt, nickel, copper, zinc, iron, cadmium ion；
The L is one kind in phthalic acid, terephthalic acid (TPA), M-phthalic acid；X is 2-6；Y is 2-12.
2. a kind of preparation method of aromatic carboxylic acids class transition metal organic framework according to claim 1, feature exist
In：The preparation method carries out as steps described below：
Transition metal salt and aromatic carboxylic acids are dissolved in solvent and alkali, then mixed liquor is transferred in autoclave, is ultrasonically treated,
It first heats up and cools down again, filter, washing obtains aromatic carboxylic acids class transition metal organic framework.
3. the preparation method of aromatic carboxylic acids class transition metal organic framework according to claim 2, it is characterised in that：Institute
The molar ratio for stating transition metal salt and aromatic carboxylic acids is 6:5-5:8.
4. the preparation method of aromatic carboxylic acids class transition metal organic framework according to claim 2, it is characterised in that：Institute
The solvent stated is water, organic solvent or water and the mixture of organic solvent.
5. the preparation method of aromatic carboxylic acids class transition metal organic framework according to claim 4, it is characterised in that：Institute
The organic solvent stated is methanol, ethyl alcohol or propyl alcohol.
6. the preparation method of aromatic carboxylic acids class transition metal organic framework according to claim 2, it is characterised in that：Institute
The alkali stated be KOH, NaOH or LiOH, it is a concentration of：1.0~2.5mol/L, dosage are：0.25~0.75mL.
7. the preparation method of aromatic carboxylic acids class transition metal organic framework according to claim 2, it is characterised in that：Institute
The sonication treatment time stated is：0.5~1h.
8. the preparation method of aromatic carboxylic acids class transition metal organic framework according to claim 2, it is characterised in that：Institute
Range of reaction temperature in the autoclave stated is 150~170 DEG C, and the reaction time is 3 days.
9. a kind of application of aromatic carboxylic acids class transition metal organic framework according to claim 1, it is characterised in that：Institute
The organic framework stated is used as the electrode material of ultracapacitor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267093A (en) * | 2018-10-09 | 2019-01-25 | 苏州大学 | Ultra-thin Ni-Fe-MOF nanometer sheet and its preparation method and application |
| CN110060875A (en) * | 2019-04-29 | 2019-07-26 | 南京工业大学 | Co base nano-chip arrays electrode and preparation method thereof for supercapacitor |
| CN112103092A (en) * | 2020-07-27 | 2020-12-18 | 浙江工业大学 | Metal cation doped cobalt polysulfide/cobalt hydroxide composite material and preparation method and application thereof |
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2018
- 2018-01-14 CN CN201810033140.7A patent/CN108172418A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267093A (en) * | 2018-10-09 | 2019-01-25 | 苏州大学 | Ultra-thin Ni-Fe-MOF nanometer sheet and its preparation method and application |
| CN110060875A (en) * | 2019-04-29 | 2019-07-26 | 南京工业大学 | Co base nano-chip arrays electrode and preparation method thereof for supercapacitor |
| CN112103092A (en) * | 2020-07-27 | 2020-12-18 | 浙江工业大学 | Metal cation doped cobalt polysulfide/cobalt hydroxide composite material and preparation method and application thereof |
| CN112103092B (en) * | 2020-07-27 | 2022-02-11 | 浙江工业大学 | Metal cation doped cobalt polysulfide/cobalt hydroxide composite material and preparation method and application thereof |
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