CN109354698A - Bimetal nano phosphate, preparation method and application based on metal-organic framework object - Google Patents
Bimetal nano phosphate, preparation method and application based on metal-organic framework object Download PDFInfo
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- CN109354698A CN109354698A CN201811307928.9A CN201811307928A CN109354698A CN 109354698 A CN109354698 A CN 109354698A CN 201811307928 A CN201811307928 A CN 201811307928A CN 109354698 A CN109354698 A CN 109354698A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 71
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 54
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 239000010452 phosphate Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 64
- 239000000463 material Substances 0.000 claims abstract description 39
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 17
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000021317 phosphate Nutrition 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 230000001376 precipitating effect Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000011258 core-shell material Substances 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011149 active material Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 239000013256 coordination polymer Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 4
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000026731 phosphorylation Effects 0.000 description 2
- 238000006366 phosphorylation reaction Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910003873 O—P—O Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RDFYLEVYNJBTGY-UHFFFAOYSA-N [Ni++].O[N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ni++].O[N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O RDFYLEVYNJBTGY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- AHBDJJPEQJQYMC-UHFFFAOYSA-N ethanol nickel(2+) dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] AHBDJJPEQJQYMC-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of bimetal nano method for production of phosphate salt based on metal-organic framework object, the bimetal nano phosphate prepares metal-organic framework object using cobalt nitrate, 2-methylimidazole as raw material, then another nitrate nickel nitrate treatment metal-organic framework object is utilized, the pattern of metal-organic framework object is maintained in the upper formation layered double hydroxide of metal-organic framework object, it realizes syntype transformation, obtains presoma；The present invention performs etching obtained presoma using phosphate, and the hollow core-shell structure of formation increases the specific surface area of material, capacitive property with higher.Bimetal nano method for production of phosphate salt provided by the invention based on metal-organic framework object, raw material is cheap and easy to get, easy to operate, avoids high energy consumption, obtains bimetal nano phosphate capacitive property with higher, can be used in preparing capacitor element.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of bimetal nano phosphorus based on metal-organic framework object
Hydrochlorate, preparation method and application.
Background technique
Metal-organic framework object (Metal-organic Frameworks, MOFs) is by metal ion and organic ligand
The paracrystalline porous material that self assembly is constructed, MOFs has many advantages, such as porosity, large specific surface area, so in recent years
That there is huge application prospect in the electrode material field as capacitor.Contain a large amount of metal ion in MOFs structure,
With structure diversity, major element and lanthanide series can be extended to from transition elements by constructing metallic element.Due to MOFs
The shortcomings that it is pyrolysismethod that material, which prepares the common method of metal oxide, needs the condition of high temperature and pressure, this results in high energy consumption.
And transition metal phosphate is seldom reported, the phosphate of especially double transition metal is reported less.P element is N race element
In with multivalent state nonmetalloid, be most widely used coordination atom in Coordinative Chemistry, a large amount of phosphide is extensive
Applied to fields such as lithium ion battery, supercapacitor, electro-catalysis, photocatalysis, metal phosphide have stronger electric conductivity and
Mechanical strength.The open structure of transition metal phosphate and different patterns assign its a large amount of reactivity site, Ke Yijin
The a large amount of redox reaction of row, and the P-O covalent bond in structure is relatively strong, makes it have chemical stability.PO4 3-It can
To enhance the electric conductivity of MOFs, improves interface Faradaic processes and improve the oxidation-reduction process of metal center, and two kinds
There is synergistic effect, these advantages are that transition metal phosphate and double transition metal phosphates become electrode for capacitors between metal
Material provides unlimited possibility.
So far, the synthesis majority of nano phosphate be using the precipitation method or hydro-thermal method, and it is most present it is flower-shaped,
Sheet and graininess, this structure due to lesser specific surface area, be unfavorable for electrolyte infiltration and ion transport from
And the generation of redox reaction is hindered, prevent it from obtaining higher specific capacity and stability, and with metal-organic framework object
Hollow structure for the nano phosphate of template preparation is seldom, therefore significantly limits and received with Metal-organic frame synthesis
The phosphatic large-scale application of rice.
Summary of the invention
In order to solve the technical problems such as high energy consumption caused by the methods of pyrolysis, the present invention with metal nitrate cobalt nitrate with have
Machine ligand 2-methylimidazole reacts in organic solvent for raw material obtains metal-organic framework object, then with another metal nitre
After hydrochlorate nickel nitrate treatment, further with phosphate treated obtain it is a kind of based on metal-organic framework object have hollow core
The bimetal nano phosphate of shell structure.This method is easy to operate, avoids high energy consumption；Furthermore this method can be good at controlling and receive
The pattern of rice material improves its condenser capacity.
The object of the present invention is to provide a kind of above-mentioned bimetal nano phosphate based on metal-organic framework object
It is a further object of the present invention to provide a kind of above-mentioned bimetal nano based on metal-organic framework object is phosphatic
The bimetal nano phosphate that preparation method obtains.
Another object of the present invention is to provide a kind of above-mentioned bimetal nano phosphate in preparing capacitive property material
Using.
Purpose according to the present invention, the present invention provide a kind of bimetal nano phosphate based on metal-organic framework object
Preparation method, comprising the following steps:
(1) it prepares metal-organic framework object: taking cobalt nitrate and 2-methylimidazole, be dissolved in organic solvent, be stirred
Even, room temperature stands 20-26h, and filtering takes precipitating, organic solvent or filtrate washing precipitating, then dries at 65-75 DEG C, obtain gold
Category-organic framework (MOFs)；
(2) prepare presoma: the metal-organic framework object and nickel nitrate for taking step (1) to obtain are dissolved in solvent, stir
Reaction is mixed, precursor solution is obtained；
(3) it prepares target product: phosphate is added into precursor solution obtained in step (2), stir, then exist
70-110 DEG C of reaction 10-20h, centrifugation, is precipitated, is washed respectively with water and dehydrated alcohol, then in 65-75 DEG C of drying, obtained
To the bimetal nano phosphate.
Preferably, in step (1), the molar ratio of the cobalt nitrate and 2-methylimidazole is 1:4-5.
Preferably, in step (1), the organic solvent that the cobalt nitrate is reacted with 2-methylimidazole includes methanol.
Preferably, in step (1), cobalt nitrate 1mol is dissolved in every 500ml organic solvent, dissolves 2-methylimidazole 4-
5mol。
Preferably, in step (2), the mass ratio of the metal-organic framework object and nickel nitrate is 1-3:4.
Preferably, in step (2), the rate of the stirring is 150-500r/min, time 30-45min.
Preferably, in step (2), the solvent of the metal-organic framework object and the nitric acid nickel reactant includes anhydrous second
Alcohol.
Preferably, in step (3), the phosphate is sodium phosphate, the metal-organic framework object and the sodium phosphate
Mass ratio is 5:4.
Preferably, in step (3), the time of the stirring is 45-70min.
Bimetal nano method for production of phosphate salt provided by the invention based on metal-organic framework object, it is preferable that tool
Body the following steps are included:
(1) prepare metal-organic framework object: taking cobalt nitrate and 2-methylimidazole, according to mole for 1:4-5 be dissolved in it is organic molten
In agent methanol, wherein dissolving cobalt nitrate 1mol in the methanol of every 500ml, the period that stirs evenly is uniformly mixed, and room temperature stands 20-
26h, filtering take precipitating, organic solvent or filtrate washing precipitating, then dry at 65-75 DEG C, obtain metal-organic framework object
(ZIF-67)；
(2) prepare presoma: the metal-organic framework object (ZIF-67) for taking step (1) to obtain is dissolved in containing nickel nitrate
Ethanol solution in, wherein the mass ratio of ZIF-67 and nickel nitrate be 1-3:4, be stirred to react 30-45min, obtain forerunner
Liquid solution (ZIF-67-LDH)；
(3) it prepares target product: sodium phosphate is added to precursor solution (ZIF-67-LDH) obtained in step (2) is middle,
Stirring, then in 70-110 DEG C of reaction 10-20h, centrifugation is precipitated, is washed respectively with water and dehydrated alcohol, then in 65-
75 DEG C of dryings obtain the bimetal nano phosphate (ZIF-67-CNP).
The present invention provides the bimetal nano phosphate for the metal-organic framework object that above-mentioned method is prepared.
It is provided by the invention above-mentioned capacitor material to be prepared based on the bimetal nano phosphate of metal-organic framework object
Application in material.
Bimetal nano phosphate provided by the invention based on metal-organic framework object has hollow core-shell structure, increases
Specific surface area is added, capacitive property with higher can be used in preparing capacitance material, further be used for the capacitance material
Prepare capacitor element.
The present invention prepares electrode using above-mentioned bimetal nano phosphate, and the electrode is prepared by the following steps to obtain: claiming
Above-mentioned bimetal nano phosphate, superconduction carbon black, polytetrafluoroethyl-ne aqueous solution are taken, is added in ethyl alcohol, ultrasound is dried, coating
To nickel material, the electrode, the mass ratio of the bimetal nano phosphate, superconduction carbon black and polytetrafluoroethyl-ne aqueous solution are obtained
For 8:1:20 (mg/mg/ul), the mass fraction of polytetrafluoroethyl-ne aqueous solution is 5%.
The invention has the benefit that
The present invention provides a kind of bimetal nano method for production of phosphate salt based on metal-organic framework object, described double
Metal nano phosphate prepares metal-organic framework object using cobalt nitrate, 2-methylimidazole as raw material, then utilizes another nitric acid
Salt nickel nitrate treatment metal-organic framework object, in the upper formation layered double hydroxide (LDH) of metal-organic framework object
To maintain the pattern of metal-organic framework object, realizes syntype transformation, obtain presoma；The present invention is using phosphate to obtaining
Presoma performs etching, and the hollow core-shell structure of formation increases the specific surface area of material, thus capacitive property with higher.
Bimetal nano method for production of phosphate salt provided by the invention based on metal-organic framework object, raw material is cheap and easy to get, operation
Simply, high energy consumption is avoided, bimetal nano phosphate capacitive property with higher is obtained, the material of capacity cell can be prepared
Material.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1: the test XRD spectra for the ZIF-67 crystalline material being prepared in embodiment 1；
Fig. 2: the test XRD spectra and JCPDS standard spectrogram for the ZIF-67-CNP material being prepared in embodiment 1；
Fig. 3: specific surface area (BET) test chart of ZIF-67-CNP material in embodiment 1；
Fig. 4: the pore-size distribution test chart of ZIF-67-CNP material in embodiment 1；
Fig. 5: the infrared spectrum test chart of ZIF-67, ZIF-67-CNP material in embodiment 1；
Fig. 6: the EDS spectrogram of ZIF-67-LDH-CNP material in embodiment 1；
Fig. 7: ZIF-67 electron scanning micrograph (SEM) in embodiment 1；
Fig. 8: the phosphatic Scanning Electron of bimetal nano prepared under the conditions of the hot temperature of different solvents in embodiment 1-6 is aobvious
Micro mirror figure；
Wherein a is embodiment 2, and b is embodiment 3, and c is embodiment 4, and d is embodiment 5, and e is embodiment 1, and f is embodiment
6；
Fig. 9: electron scanning micrograph (SEM) spectrogram of ZIF-67-LDH-CNP material and transmission electricity in embodiment 1
Sub- microscope photo (TEM) spectrogram；
Figure 10: ZIF-67-LDH-CNP (the being named as ZIF-67-LDH-CNP-110) material that is prepared in embodiment 1 and
The performance of the supercapacitor test chart for the material that comparative example 1-3 is obtained；
Wherein a corresponds to ZIF-67-LDH-CNP-110, ZIF-67-LDH, ZIF-67-CNP, ZIF-67-CP in 10mVs-1
When CV curve；The constant current charge-discharge curve of b respective material；C corresponds to the capacitor under different current densities；D corresponds to material
Cyclical stability；
Figure 11: the Current Voltage of the ZIF-67-LDH-CNP material prepared at the hot temperature of different solvents in embodiment 1-6 is bent
Line chart (CV curve)；
Wherein a is the CV curve of the ZIF-67-LDH-CNP-T25 of embodiment 2, and b is the ZIF-67-LDH- of embodiment 3
The CV curve of CNP-T50, c are the CV curve of the ZIF-67-LDH-CNP-T70 of embodiment 4, and d is the ZIF-67- of embodiment 5
The CV curve of LDH-CNP-T90, e are the CV curve of the ZIF-67-LDH-CNP-T110 of embodiment 1, and f is the ZIF- of embodiment 6
The CV curve of 67-LDH-CNP-T130；
Figure 12: the ZIF-67-LDH-CNP material prepared at the hot temperature of different solvents in embodiment 1-6 is in different electric currents
Under constant current charge-discharge curve (GCD curve) figure；
Wherein a is the GCD curve of the ZIF-67-LDH-CNP-T25 of embodiment 2, and b is the ZIF-67-LDH- of embodiment 3
The GCD curve of CNP-T50, c are the GCD curve of the ZIF-67-LDH-CNP-T70 of embodiment 4, and d is the ZIF-67- of embodiment 5
The GCD curve of LDH-CNP-T90, e are the GCD curve of the ZIF-67-LDH-CNP-T110 of embodiment 1, and f is embodiment 6
The GCD curve of ZIF-67-LDH-CNP-T130；
Figure 13: the super electricity of the ZIF-67-LDH-CNP material prepared under difference ZIF-67 quality requirements in embodiment 7-10
Container performance test chart；
Wherein a is the CV curve of the ZIF-67-LDH-CNP-m40 of embodiment 7, and b is the ZIF-67-LDH- of embodiment 8
The CV curve of CNP-m60, c are the CV curve of the ZIF-67-LDH-CNP-m100 of embodiment 9, and d is the ZIF-67- of embodiment 10
The CV curve of LDH-CNP-m120；
Figure 14: the different electricity of the ZIF-67-LDH-CNP material prepared under difference ZIF-67 quality requirements in embodiment 7-10
Constant current charge-discharge curve (GCD curve) figure flowed down；
Wherein a is the GCD curve of the ZIF-67-LDH-CNP-m40 of embodiment 7, and b is the ZIF-67-LDH- of embodiment 8
The GCD curve of CNP-m60, c are the GCD curve of the ZIF-67-LDH-CNP-m100 of embodiment 9, and d is the ZIF- of embodiment 10
The GCD curve of 67-LDH-CNP-m120；
Figure 15: the performance of the supercapacitor of ZIF-67-LDH, ZIF-67-CP, ZIF-67-CN material is surveyed in comparative example 1-3
Attempt；
Wherein a is the CV curve of the ZIF-67-LDH of the comparative example 2 of comparative example 1, and b is the CV curve of ZIF-67-CP, and c is
The CV curve of the ZIF-67-CNP of comparative example 3, d are the GCD curve of the ZIF-67-LDH of comparative example 1, and e is the ZIF- of comparative example 2
The GCD curve of 67-CP, f are the GCD curve of the ZIF-67-CNP of comparative example 3.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Embodiment 1
A kind of bimetal nano method for production of phosphate salt based on metal-organic framework object, comprising the following steps:
(1) cobalt nitrate and 2-methylimidazole the preparation of metal-organic framework object (ZIF-67): are weighed according to molar ratio 1:4
It is dissolved in organic solvent methanol 500mL respectively, wherein cobalt nitrate 1mol, 2-methylimidazole 4mol, stirring is uniformly mixed it, room temperature
Lower standing for 24 hours, filters above-mentioned reaction solution, precipitating is washed with mother liquor, required crystalline material metal-is dried to obtain at 70 DEG C to be had
Machine frame object ZIF-67；
(2) it the preparation of presoma (ZIF-67-LDH): weighs 100mgZIF-67 and is dissolved in containing 160mgNi (NO3)2Nothing
The solution of ZIF-67-LDH can be obtained in hydrous ethanol solution, strong stirring 30min, stirring rate 500r/min；
(3) 80mgNa the preparation of ZIF-67-CNP: is added in step (2) acquired solution3PO4Distilled water solution, stir 1h
It is packed into reaction kettle afterwards and reacts 15h at 110 DEG C, obtained precipitating is centrifuged, is respectively washed 3 times with deionized water and dehydrated alcohol
Dry 12h, can be obtained target product ZIF-67-CNP at 70 DEG C.
The preparation of active material electrode: the ZIF-67-CNP material for taking 16mg to synthesize, 2mg superconduction carbon black, 40ul mass point
The polytetrafluoroethyl-ne aqueous solution of number 5%, is put into 2mL ethyl alcohol, ultrasonic 30min.Then 70 DEG C are placed in, dries, will dry in baking oven
Mixing material after dry is applied in the nickel foam of 1x2cm2, and then tabletting is made into electrode.
Embodiment 2
(1) preparation of ZIF-67 metal-organic framework object is the same as embodiment 1.
(2) preparation of ZIF-67-LDH is the same as embodiment 1.
(3) 80mgNa the preparation of ZIF-67-CNP: is added in step (2) acquired solution3PO4Distilled water solution, stir 1h
15h is reacted at 25 DEG C afterwards, obtained precipitating is centrifuged, with deionized water and dehydrated alcohol respectively wash 3 times at 70 DEG C do
Dry 12h, can be obtained target product.
The preparation of active material electrode is the same as embodiment 1.
Embodiment 3
(1) preparation of ZIF-67 metal-organic framework object is the same as embodiment 1.
(2) preparation of ZIF-67-LDH is the same as embodiment 1.
(3) 80mgNa the preparation of ZIF-67-CNP: is added in step (2) acquired solution3PO4Distilled water solution, stir 1h
15h is reacted at 50 DEG C afterwards, obtained precipitating is centrifuged, with deionized water and dehydrated alcohol respectively wash 3 times at 70 DEG C do
Dry 12h, can be obtained target product.
The preparation of active material electrode is the same as embodiment 1.
Embodiment 4
(1) preparation of ZIF-67 metal-organic framework object is the same as embodiment 1.
(2) preparation of ZIF-67-LDH is the same as embodiment 1.
(3) 80mgNa the preparation of ZIF-67-CNP: is added in step (2) acquired solution3PO4Distilled water solution, stir 1h
15h is reacted at 70 DEG C afterwards, obtained precipitating is centrifuged, with deionized water and dehydrated alcohol respectively wash 3 times at 70 DEG C do
Dry 12h, can be obtained target product.
The preparation of active material electrode is the same as embodiment 1.
Embodiment 5
(1) preparation of ZIF-67 metal-organic framework object is the same as embodiment 1.
(2) preparation of ZIF-67-LDH is the same as embodiment 1.
(3) 80mgNa the preparation of ZIF-67-CNP: is added in step (2) acquired solution3PO4Distilled water solution, stir 1h
15h is reacted at 90 DEG C afterwards, obtained precipitating is centrifuged, with deionized water and dehydrated alcohol respectively wash 3 times at 70 DEG C do
Dry 12h, can be obtained target product.
The preparation of active material electrode is the same as embodiment 1.
Embodiment 6
(1) preparation of ZIF-67 metal-organic framework object is the same as embodiment 1.
(2) preparation of ZIF-67-LDH is the same as embodiment 1.
(3) it the preparation of ZIF-67-CNP: is added in step (2) acquired solution and contains 80mgNa3PO4Distilled water solution, stirring
15h is reacted after 1h at 130 DEG C, obtained precipitating is centrifuged, and respectively washs 3 times at 70 DEG C with deionized water and dehydrated alcohol
Dry 12h, can be obtained target product.
The preparation of active material electrode is the same as embodiment 1.
Embodiment 7
(1) preparation of ZIF-67 metal-organic framework object is the same as embodiment 1.
(2) it the preparation of ZIF-67-LDH: weighs 40mgZIF-67 and is dissolved in containing 160mgNi (NO3)2Dehydrated alcohol it is molten
The solution of ZIF-67-LDH can be obtained in liquid, strong stirring 30min；
(3) preparation of ZIF-67-CNP is the same as embodiment 1.
The preparation of active material electrode is the same as embodiment 1.
Embodiment 8
(1) preparation of ZIF-67 metal-organic framework object is the same as embodiment 1.
(2) it the preparation of ZIF-67-LDH: weighs 60mgZIF-67 and is dissolved in containing 160mgNi (NO3)2Dehydrated alcohol it is molten
The solution of ZIF-67-LDH can be obtained in liquid, strong stirring 30min；
(3) preparation of ZIF-67-CNP is the same as embodiment 1.
The preparation of active material electrode is the same as embodiment 1.
Embodiment 9
(1) preparation of ZIF-67 metal-organic framework object is the same as embodiment 1.
(2) it the preparation of ZIF-67-LDH: weighs 100mgZIF-67 and is dissolved in containing 160mgNi (NO3)2Dehydrated alcohol it is molten
The solution of ZIF-67-LDH can be obtained in liquid, strong stirring 30min；
(3) preparation of ZIF-67-CNP is the same as embodiment 1.
The preparation of active material electrode is the same as embodiment 1.
Embodiment 10
(1) preparation of ZIF-67 metal-organic framework object is the same as embodiment 1.
(2) it the preparation of ZIF-67-LDH: weighs 120mgZIF-67 and is dissolved in the dehydrated alcohol containing 160mg Ni (NO3) 2
The solution of ZIF-67-LDH can be obtained in solution, strong stirring 30min；
(3) preparation of ZIF-67-CNP is the same as embodiment 1.
The preparation of active material electrode is the same as embodiment 1.
Embodiment 11
A kind of bimetal nano method for production of phosphate salt based on metal-organic framework object, comprising the following steps:
(1) cobalt nitrate and 2-methylimidazole the preparation of metal-organic framework object (ZIF-67): are weighed according to molar ratio 1:5
It is dissolved in organic solvent methanol 500mL respectively, wherein cobalt nitrate 1mol, 2-methylimidazole 5mol, stirring is uniformly mixed it, room temperature
Lower standing 20h, filters above-mentioned reaction solution, and precipitating is washed with mother liquor, and required crystalline material metal-is dried to obtain at 65 DEG C to be had
Machine frame object ZIF-67；
(2) it the preparation of presoma (ZIF-67-LDH): weighs 100mgZIF-67 and is dissolved in containing 160mgNi (NO3)2Nothing
The solution of ZIF-67-LDH can be obtained with the rate stirring 45min of 150r/min for hydrous ethanol solution；
(3) 80mgNa the preparation of ZIF-67-CNP: is added in step (2) acquired solution3PO4Distilled water solution, stirring
It is packed into reaction kettle after 70min and reacts 15h at 110 DEG C, obtained precipitating is centrifuged, is respectively washed with deionized water and dehydrated alcohol
3 times dry 14h at 65 DEG C are washed, target product can be obtained.
Embodiment 12
A kind of bimetal nano method for production of phosphate salt based on metal-organic framework object, comprising the following steps:
(1) cobalt nitrate and 2-methylimidazole the preparation of metal-organic framework object (ZIF-67): are weighed according to molar ratio 1:5
It is dissolved in organic solvent methanol 500mL respectively, wherein cobalt nitrate 1mol, 2-methylimidazole 5mol, stirring is uniformly mixed it, room temperature
Lower standing 26h, filters above-mentioned reaction solution, and precipitating is washed with mother liquor, and required crystalline material metal-is dried to obtain at 75 DEG C to be had
Machine frame object ZIF-67；
(2) it the preparation of presoma (ZIF-67-LDH): weighs 100mgZIF-67 and is dissolved in containing 160mgNi (NO3)2Nothing
The solution of ZIF-67-LDH can be obtained with the rate stirring 30min of 500r/min for hydrous ethanol solution；
(3) 80mgNa the preparation of ZIF-67-CNP: is added in step (2) acquired solution3PO4Distilled water solution, stirring
It is packed into reaction kettle after 45min and reacts 15h at 110 DEG C, obtained precipitating is centrifuged, is respectively washed with deionized water and dehydrated alcohol
3 times dry 11h at 75 DEG C are washed, target product can be obtained.
Comparative example 1
The preparation of ZIF-67-LDH
With example 1, the ZIF-67-LDH solution that 1 step of embodiment (2) is obtained is dry at 70 DEG C for the preparation of ZIF-67-LDH
It is dry to obtain ZIF-67-LDH.
The preparation of active material electrode is the same as embodiment 1.
Comparative example 2
The preparation of ZIF-67-CP
(1) preparation of ZIF-67 is the same as example 1.
(2) 80mgNa is added in ZIF-67 prepared by step (1)3PO4Aqueous solution, stir 1h after reacted at 110 DEG C
15h, obtained precipitating are centrifuged, and are respectively washed 3 times dry 12h at 70 DEG C with deionized water and dehydrated alcohol, be can be obtained
Target product ZIF-67-CP.
The preparation of active material electrode is the same as embodiment 1.
Comparative example 3
The preparation of ZIF-67-CNP:
(1) preparation of ZIF-67 is the same as example 1.
(2) ZIF-67-LDH): it weighs 100mgZIF-67 and is dissolved in containing 160mgNi (NO3)2Ethanol solution, i.e.,
The solution of ZIF-67-LDH can be obtained；
(3) preparation of ZIF-67-CNP is the same as embodiment 1.
The preparation of active material electrode is the same as embodiment 1.
To disclosed in this invention the description of embodiment be not intended to limit the scope of the invention, but for describing
The present invention.Correspondingly, the scope of the present invention is not limited by embodiment of above, but is carried out by claim or its equivalent
It limits.
Test example
The bimetal nano phosphate that embodiment 1-10 and comparative example are obtained is characterized, and to using its preparation
Electrode carries out capacitive property test.The result is shown in Figure 1-14.
As can be seen from Figure 1 the step of embodiment of the present invention 1 (1) has obtained ZIP-67 corresponding with standard spectrogram.From
It can be seen that the diffraction maximum of the ZIP-67 after phosphorylation completely disappears in Fig. 2, and there is the diffraction of nickel phosphate and cobalt phosphate
Peak illustrates method phosphorylation success provided by the invention.
As can be seen from Figure 3 it can be seen that under the conditions of 77K N2Adsorbance reached 650cm3/ g or more compares table
Area has reached 150m2/g.The specific surface area of superelevation significantly enhance the mass transport process of active material and electrolyte solution, increase
The strong performance of its capacitive property.
Figure 4, it is seen that the aperture for the ZIF-67-CNP that embodiment 1 obtains is in mesoporous scope.
From figure 5 it can be seen that the absorption peak of 2-methylimidazole disappears in ZIF-67, there is the absorption of O-P, O-P-O
Peak illustrates that ZIF-67 is etched by phosphate.
As can be seen from Figure 6 Co:Ni is approximately equal to 2:1, illustrates successfully to prepare bimetal nano phosphate.
As can be seen from Figure 7 ZIF-67 material is the regular dodecahedron structure with smooth surface.
As can be seen from Figure 8 fold has occurred in the material surface prepared under the conditions of 25 DEG C, and phosphate is not by outer
Inside etching ZIF-67, when temperature is increased to 50 DEG C, ZIF-67 ecto-entad is etched into hollow knot by phosphate
Structure, when being increased to 70 DEG C, 90 DEG C, 110 DEG C with temperature, the shell of the hollow structure of material is gradually thinning, but works as temperature liter
When height is to 130 DEG C, this core-shell structure has been totally disrupted, and can not maintain hollow pattern.
As can be seen from Figure 9 the pattern of ZIF-67-CNP is uniform, is hollow shell structurre, and the thickness of shell is
30nm or so.
As can be seen from Figure 10 under different current densities, when current density is 1,2,4,6,8 and 10A/g, this hair
The capacitance for the electrode that bright embodiment 1 obtains is respectively that its capacitance is respectively 1416,1316,1160,1044,960 and 860F/
g。
As can be seen from Figure 11 as the increase of sweep speed, CV shape remain unchanged, illustrate to obtain under condition of different temperatures
The stability of the material arrived is good.It can be seen that as the temperature rises from the result of Figure 12, capacitance gradually increases,
When temperature is higher than 130 DEG C lower than 50 DEG C, capacitance is small；Therefore the phosphatic preparation temperature of bimetal nano provided by the invention exists
It is 70-110 DEG C, the capacitance of obtained material is big.It can be seen that 7-10 of the embodiment of the present invention different from the result of Figure 13
Under different scanning rates, CV shape remains unchanged the bimetal nano phosphate being prepared under material rate, material it is steady
Qualitative energy.The capacitance of material provided by the invention is big as can be seen from Figure 14.
As can be seen from Figure 15 ZIF-67-CP that comparative example 1 obtains ZIF-67-LDH, comparative example 2 obtain, comparative example
The capacity of 3 obtained ZIF-67-CNP is 460,202,640Fg respectively-1, illustrate by forming LDH and carrying out phosphate etching
It can be improved the capacitive property of supercapacitor.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of bimetal nano method for production of phosphate salt based on metal-organic framework object, which is characterized in that including following
Step:
(1) it prepares metal-organic framework object: taking cobalt nitrate and 2-methylimidazole, be dissolved in organic solvent, be uniformly mixed,
Room temperature stands 20-26h, and filtering takes precipitating, organic solvent or filtrate washing precipitating, then dries at 65-75 DEG C, obtain metal-
Organic framework；
(2) prepare presoma: the metal-organic framework object and nickel nitrate for taking step (1) to obtain are dissolved in solvent, and stirring is anti-
It answers, obtains precursor solution；
(3) it prepares target product: phosphate is added into precursor solution obtained in step (2), stir, then in 70-110
DEG C reaction 10-20h, centrifugation is precipitated, is washed respectively with water and dehydrated alcohol, then in 65-75 DEG C of drying, is obtained described
Bimetal nano phosphate.
2. the bimetal nano processes for producing phosphates according to claim 1 based on metal-organic framework object, feature
It is, in step (1), the molar ratio of the cobalt nitrate and 2-methylimidazole is 1:4-5.
3. the bimetal nano processes for producing phosphates according to claim 1 based on metal-organic framework object, feature
It is, in step (1), the organic solvent that the cobalt nitrate is reacted with 2-methylimidazole includes methanol.
4. the bimetal nano processes for producing phosphates according to claim 1 based on metal-organic framework object, feature
It is, in step (2), the mass ratio of the metal-organic framework object and nickel nitrate is 1-3:4.
5. the bimetal nano processes for producing phosphates according to claim 1 based on metal-organic framework object, feature
It is, in step (2), the rate of the stirring is 150-500r/min, and the time of stirring is 30-45min.
6. the bimetal nano processes for producing phosphates according to claim 1 based on metal-organic framework object, feature
It is, in step (2), the solvent of the metal-organic framework object and the nitric acid nickel reactant includes dehydrated alcohol.
7. the bimetal nano processes for producing phosphates according to claim 1 based on metal-organic framework object, feature
It is, in step (3), the phosphate is sodium phosphate, and the mass ratio of the metal-organic framework object and the sodium phosphate is 5:
4。
8. bimetal nano method for production of phosphate salt according to claim 1, which is characterized in that described in step (3)
The time of stirring is 45-70min.
9. the bimetal nano phosphate for the metal-organic framework object that any method of claim 1-8 is prepared.
10. it is as claimed in claim 9 based on the bimetal nano phosphate of metal-organic framework object in preparing capacitance material
Using.
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| CN114920228B (en) * | 2022-05-25 | 2024-04-19 | 重庆良伊生物科技有限公司 | Transition metal phosphate nano enzyme material and preparation method and application thereof |
| CN116632219A (en) * | 2023-07-19 | 2023-08-22 | 兰溪博观循环科技有限公司 | Metal phosphate composite material with core-shell structure, and preparation method and application thereof |
| CN116632219B (en) * | 2023-07-19 | 2023-10-24 | 兰溪博观循环科技有限公司 | Metal phosphate composite material with core-shell structure, and preparation method and application thereof |
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