CN109651620A - A kind of nickel metal coordinating polymer and preparation method thereof - Google Patents
A kind of nickel metal coordinating polymer and preparation method thereof Download PDFInfo
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- CN109651620A CN109651620A CN201811406146.0A CN201811406146A CN109651620A CN 109651620 A CN109651620 A CN 109651620A CN 201811406146 A CN201811406146 A CN 201811406146A CN 109651620 A CN109651620 A CN 109651620A
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- nickel metal
- benzene
- ppda
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 26
- 229920000642 polymer Polymers 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000013256 coordination polymer Substances 0.000 claims abstract description 20
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 19
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 9
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 241000579895 Chlorostilbon Species 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005485 electric heating Methods 0.000 claims description 8
- 229910052876 emerald Inorganic materials 0.000 claims description 8
- 239000010976 emerald Substances 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 15
- 238000011160 research Methods 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 29
- 239000000243 solution Substances 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- -1 nickel metal complex Chemical class 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 5
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 239000006181 electrochemical material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- WXKKDBZRLLTFGW-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C1=CC=CC=C1 Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C1=CC=CC=C1 WXKKDBZRLLTFGW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229920005565 cyclic polymer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003639 trimesic acids Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (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)
Abstract
A kind of nickel metal coordinating polymer disclosed by the invention, has three-dimensional porous supramolecular network structure, and chemical formula is { [Ni (ppda) (mbib)] H2O}n, wherein ppda is represented to phenylenediacetic Acid, and bib represents bis- (1- imidazole radicals) benzene of 1,3-, which belongs to rhombic system, space group Pna21.One-dimensional ring is formed with " V " shape formula and W metal bridging to the carboxyl of phenylenediacetic Acid, adjacent one-dimensional ring forms two-dimentional oversubscription sublayer by Hydrogenbond, pass through 1, bis- (1- imidazole radicals) benzene of 3-) ligand phenyl ring between π-π effect, three-dimensional porous supramolecular network structure is formed, research is expanded to the electrochemistry of Ni coordination polymer and has established certain basis.The present invention uses the preparation method of hydrothermal synthesis, easy to operate, and mild condition, yield are high, reproducibility is good and can understand reaction process.
Description
Technical field
The invention belongs to nickel metal complex materials technical fields, are related to a kind of nickel metal coordinating polymer, further relate to this
The preparation method of complex.
Background technique
In recent years, it designs and constructs based on the supermolecular mechanism between metal and organic ligand with conductive, magnetic, luminous
Etc. the supramolecular chemistry systems of properties have become in the fields such as modern chemistry, material science the very active and research full of prospect
One of theme.Studies have shown that polybasic carboxylic acid is widely used in construction structure novelty, performance because of its a variety of flexible bonding pattern
Unique one-dimensional, two and three dimensions super molecular complex, existing research focus mostly in aromatic series polybasic carboxylic acid complex.Due to more
The Biodiversity Characteristics of the dihedral angle of the carboxyl plane and phenyl ring interplanar of carboxylic acid ylidene ligands, allow to for metal center being fixed to
Different directions are to show unique advantage: be especially rigid more carboxyl benzene ligand trimesic acids, M-phthalic acid,
It is steady that terephthalic acid (TPA), phthalic acid etc. can construct out a variety of different, strong rigid with form and excellent heat from metal ion
Qualitative coordination polymer and obtained extensive research.But currently with equal benzene triacetic acid, phenylenediacetic Acid, to benzene two
The research that acetic acid, phthalic acid construct coordination polymer as polycarboxylic acid ylidene ligands is very few, the coordination polymer of some reports
Preparation process is complicated, is not easy to repeat；Actually these ligands have preferable flexibility characteristics, can match for the multidimensional of synthesizing new
Position polymer provides wider array of range of choice.
It is coordinated herein using nickel acetate metal salt with new three-dimensional under hydrothermal reaction condition, is synthesized to phenylenediacetic Acid ligand
Polymer, and the characterization of structure and chemical property has been carried out to it.
Summary of the invention
The object of the present invention is to provide a kind of nickel metal coordinating polymers, provide a kind of electrochemical material, and utilize
To the good flexibility of phenylenediacetic Acid, synthesize the nickel metal complex with three-dimensional structure, for grinding for exploitation nickel metallic element
Study carefully and provides theoretical basis.
It is a further object of the present invention to provide a kind of preparation methods of nickel metal coordinating polymer, solve existing prepared
Journey is complicated, the low problem of reproducibility.
The technical scheme adopted by the invention is that a kind of nickel metal coordinating polymer, has three-dimensional porous netted oversubscription
Minor structure, chemical formula are { [Ni (ppda) (mbib)] H2O}n, wherein ppda is represented to phenylenediacetic Acid；It is bis- that bib represents 1,3-
(1- imidazole radicals) benzene；
The coordination polymer belongs to rhombic system, space group Pna21, and cell parameter is a=18.5939 (8) nm, b
=7.6992 (3) nm, c=14.9541 (7) nm, α=β=γ=90 °, V=2140.80 (16) nm3, Z=4, μ=0.949mm-1；
Another technical solution of the invention is a kind of preparation method of nickel metal coordinating polymer, specific preparation process packet
Include following steps:
Step 1. weighs suitable nickel acetate, (1- imidazole radicals) benzene bis- to phenylenediacetic Acid, 1,3- and suitable deionized water
It is placed in the beaker of 25mL, stirs evenly, suitable KOH is added dropwise while stirring and obtains mixed solution I；
Mixed solution I is placed in 25mL reaction kettle by step 2., in electric heating constant-temperature blowing drying box, quickly heating first
To certain temperature, and isothermal reaction is for a period of time, is then cooled to room temperature, takes out reaction kettle and obtains mixed solution I I, will mix
It closes solution II to be filtered, washed and dried, obtains emerald bulk crystals, i.e. nickel metal coordinating polymer.
Other features of the invention also reside in,
Nickel acetate, (1- imidazole radicals) benzene bis- to phenylenediacetic Acid, 1,3- in step 1) and KOH molar concentration rate be 1:1:1:
1。
Heating rate is 20 DEG C/h-50 DEG C/h in step 2, and the temperature of isothermal reaction is 150 DEG C -200 DEG C, and the reaction time is
48h-96h。
Rate of temperature fall in step 2 is 10 DEG C/h-20 DEG C/h.
The coordination polymer being prepared has three-dimensional porous meshed super molecular structure, and chemical formula is { [Ni (ppda)
(mbib)]·H2O}n, wherein ppda is represented to phenylenediacetic Acid；Bib represents bis- (1- imidazole radicals) benzene of 1,3-；
The coordination polymer belongs to rhombic system, space group Pna21, and cell parameter is a=18.5939 (8) nm, b
=7.6992 (3) nm, c=14.9541 (7) nm, α=β=γ=90 °, V=2140.80 (16) nm3, Z=4, μ=0.949mm-1。
Application of the coordination polymer being prepared as capacitor material.
The invention has the advantages that a kind of nickel metal coordinating polymer and preparation method thereof, provides a kind of new electrification
Learn material { [Ni (ppda) (mbib)] H2O}n(ppda=is to phenylenediacetic Acid；Bib represents bis- (1- imidazole radicals) benzene of 1,3-.Matching
The ligancy of Ni1 is 6 in the polymer of position, wherein the carboxyl to phenylenediacetic Acid is even formed along one with " V " shape formula and W metal Bridge 1
The one-dimensional ring of the polymer belt of a direction movement, adjacent one-dimensional ring are combined together by strong intermolecular hydrogen bonding, form two dimension
Oversubscription sublayer, in addition, passing through bis- (1- imidazole radicals) benzene of 1,3-) ligand phenyl ring between π-π interaction, formed with facing
The three-dimensional porous supramolecular network structure of planar orientation expands research to the electrochemistry of Ni coordination polymer and has established certain basis
And it is utilized and synthesizes the nickel metal complex with three-dimensional structure to the good flexibility of phenylenediacetic Acid.The present invention uses water
The preparation method of thermal synthesis, easy to operate, mild condition, yield are high, reproducibility is good and can understand reaction process.
Detailed description of the invention
Fig. 1 is the coordination environment of Ni atom in coordination polymer that the embodiment of the present invention 1 obtains；
Fig. 2 is the one-dimensional cyclic structure for the coordination polymer that the embodiment of the present invention 1 obtains；
Fig. 3 is the tridimensional network for the coordination polymer that the embodiment of the present invention 1 obtains；
Fig. 4 is the thermogravimetric analysis figure for the coordination polymer that the embodiment of the present invention 1 obtains；
Fig. 5 is the coordination polymer cyclic voltammetry curve figure that embodiment 1 obtains.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of nickel metal coordinating polymer of the invention, has three-dimensional porous supermolecule network, and chemical formula is { [Ni
(ppda)(mbib)]·H2O}n, wherein ppda is represented to phenylenediacetic Acid；Bib represents bis- (1- imidazole radicals) benzene of 1,3-；
{[Ni(ppda)(mbib)]·H2O}nCoordination polymer belongs to rhombic system, space group Pna21, { [Ni
(ppda)(mbib)]·H2O}nCell parameter be a=18.5939 (8) nm, b=7.6992 (3) nm, c=14.9541 (7)
Nm, α=β=γ=90 °, V=2140.80 (16) nm3, Z=4, μ=0.949mm-1；
A kind of preparation method of nickel metal coordinating polymer of the invention, specific preparation process include the following steps:
Step 1. weighs suitable nickel acetate, (1- imidazole radicals) benzene bis- to phenylenediacetic Acid, 1,3- and suitable deionized water
It is placed in the beaker of 25mL, stirs evenly, suitable KOH is added dropwise while stirring and obtains mixed solution I；
The molar concentration rate of nickel acetate, (1- imidazole radicals) benzene bis- to phenylenediacetic Acid, 1,3- and KOH is 1:1:1 in step 1:
1。
Mixed solution I is placed in 25mL reaction kettle by step 2., in electric heating constant-temperature blowing drying box, quickly heating first
To certain temperature, and isothermal reaction is for a period of time, is then cooled to room temperature, takes out reaction kettle and obtains mixed solution I I, will mix
It closes solution II to be filtered, washed and dried, obtains emerald bulk crystals, i.e. nickel metal coordinating polymer.
Heating rate is 20 DEG C/h-50 DEG C/h in step 2, and the temperature of isothermal reaction is 150 DEG C -200 DEG C, and the reaction time is
48h-96h。
Rate of temperature fall in step 2 is 10 DEG C/h-20 DEG C/h.
Application of the complex being prepared as electrochemical material.
The reaction mechanism occurred in preparation process: belonging to weak diacid to phenylenediacetic Acid, and KOH is added to make its deprotonation, according to
The Lewis acid-base theoryby of soda acid electron theory: " soft parent is soft, hard parent is hard " provides electronics pair and soft acid as soft base to phenylenediacetic Acid
The unoccupied orbital of metal ion forms chemical bond co-ordinate covalent bond, and reaction equation is as follows:
Embodiment 1
Weigh 0.1mmol four hydration nickel acetates, 0.1mmol to phenylenediacetic Acid, bis- (the 1- imidazoles of 1, the 3- of 0.1mmol
Base) benzene, 12mL distilled water is added in the beaker of 25mL, the KOH that 0.1mmol is added dropwise while stirring obtains mixed solution I, will mix
Solution I is closed to be fitted into using polytetrafluoroethylene (PTFE) as in the 25mL stainless steel autoclave of liner；Reaction kettle is put into electric heating constant temperature drum
In wind drying box, it is warming up to 200 DEG C from 20 DEG C with 50 DEG C/h of heating rate, quickly heating reaction is carried out, in 200 DEG C of isothermal reactions
72h, then room temperature is cooled to the rate of 10 DEG C/h, reaction solution is filtered, washed and dried, emerald bulk crystals is obtained and matches
Close object, i.e. { [Ni (ppda) (mbib)] H2O}nComplex.
Embodiment 2
Weigh 0.1mmol four hydration nickel acetates, 0.1mmol to phenylenediacetic Acid, bis- (the 1- imidazoles of 1, the 3- of 0.1mmol
Base) benzene, 12mL distilled water is added in the beaker of 25mL, the KOH that 0.1mmol is added dropwise while stirring obtains mixed solution I, will mix
Solution I is closed to be fitted into using polytetrafluoroethylene (PTFE) as in the 25mL stainless steel autoclave of liner；Reaction kettle is put into electric heating constant temperature drum
In wind drying box, it is warming up to 180 DEG C from 20 DEG C with 20 DEG C/h of heating rate, quickly heating reaction is carried out, in 180 DEG C of isothermal reactions
48h, then room temperature is cooled to the rate of 12 DEG C/h, reaction solution is filtered, washed and dried, obtain emerald bulk crystals
Complex, i.e. { [Ni (ppda) (mbib)] H2O}nComplex.
Embodiment 3
Weigh 0.1mmol four hydration nickel acetates, 0.1mmol to phenylenediacetic Acid, bis- (the 1- imidazoles of 1, the 3- of 0.1mmol
Base) benzene, 12mL distilled water is added in the beaker of 25mL, the potassium hydroxide that 0.1mmol is added dropwise while stirring obtains mixed solution
Mixed solution I is fitted into using polytetrafluoroethylene (PTFE) as in the 25mL stainless steel autoclave of liner by I；Reaction kettle is put into electric heating
In constant temperature blast drying oven, it is warming up to 160 DEG C from 20 DEG C with 50 DEG C/h of heating rate, quickly heating reaction is carried out, in 160 DEG C of perseverances
Temperature reaction 72h, then room temperature is cooled to the rate of 10 DEG C/h, reaction solution is filtered, washed and dried, emerald bulk is obtained
Crystal complex, i.e. { [Ni (ppda) (mbib)] H2O}nComplex.
Embodiment 4
Weigh 0.1mmol four hydration nickel acetates, 0.1mmol to phenylenediacetic Acid, bis- (the 1- imidazoles of 1, the 3- of 0.1mmol
Base) benzene, 12mL distilled water is added in the beaker of 25mL, the potassium hydroxide that 0.1mmol is added dropwise while stirring obtains mixed solution
Mixed solution I is fitted into using polytetrafluoroethylene (PTFE) as in the 25mL stainless steel autoclave of liner by I；Reaction kettle is put into electric heating
In constant temperature blast drying oven, it is warming up to 150 DEG C from 30 DEG C with 40 DEG C/h of heating rate, quickly heating reaction is carried out, in 150 DEG C of perseverances
Temperature reaction 96h, then room temperature is cooled to the rate of 15 DEG C/h, reaction solution is filtered, washed and dried, emerald bulk is obtained
Crystal complex, i.e. { [Ni (ppda) (mbib)] H2O}nComplex.
Embodiment 5
Weigh 0.1mmol four hydration nickel acetates, 0.1mmol to phenylenediacetic Acid, bis- (the 1- imidazoles of 1, the 3- of 0.1mmol
Base) benzene, 12mL distilled water is added in the beaker of 25mL, the sodium hydroxide that 0.1mmol is added dropwise while stirring obtains mixed solution
Mixed solution I is fitted into using polytetrafluoroethylene (PTFE) as in the 25mL stainless steel autoclave of liner by I；Reaction kettle is put into electric heating
In constant temperature blast drying oven, it is warming up to 200 DEG C from 20 DEG C with 20 DEG C/h of heating rate, quickly heating reaction is carried out, in 200 DEG C of perseverances
Warm crystallization 48h, then room temperature is cooled to the rate of 10 DEG C/h, reaction solution is filtered, washed and dried, emerald bulk is obtained
Crystal complex, i.e. { [Ni (ppda) (mbib)] H2O}nComplex.
{ [Ni (ppda) (mbib)] H that embodiment 1 is prepared2O}nComplex molecule formula is C22H20N4O5Ni, molecule
Amount is 479.13, elemental analysis result experiment value (%.): C 55.06；H is 4.50 calculated values (%.): C 54.89；H is
4.58；
The complex that embodiment 1 is obtained chooses appropriately sized crystal, uses Bruker SMART at room temperature
1000 CCD single crystal X diffraction instrument measure crystal structure.Using through graphite monochromator monochromatization Mo K alpha ray (λ=
0.071073nm), with ω scanning mode, diffracted intensity data are collected.Whole diffracted intensity data are using Lp factor correction and half
Empirical absorption correction.Crystal structure is solved by direct method, and the cell parameter and relevant parameter of complex are as shown in table 1:
The crystallographic data of 1 coordination polymer of table
aR1=Σ | | Fo|–|Fc||/Σ|Fo|,wR2=[Σ w (Fo 2–Fc 2)2/Σw(Fo 2)2]1/2
From the crystal structure analysis of the minimum repetitive unit of coordination polymer it is found that the complex of embodiment 1 belong to it is orthogonal
Crystallographic system, Pna21 space group, each asymmetric cell is comprising central metal Ni (II) ion, one to phenylenediacetic Acid ligand
With bis- (1- imidazole radicals) benzene of 1,3-) ligand, as shown in Figure 1, Ni (II) with from two differences to four on phenylenediacetic Acid ligand
A carboxyl oxygen atom and bis- (1- imidazole radicals) benzene of two 1,3-) on ligand two nitrogen-atoms (Ni (1)-N (1)=2.041 (2),) be coordinated, the bond distance of Ni-O existsIn range.Ni(II)
The octoploids structure of ion presentation distortion, four atoms (N (2), O (1), O (2) and O (3)) composition equatorial planes, and atom O (2)
Axial position is occupied with N (1).
In the complex, two carboxyl deprotonations to phenylenediacetic Acid ligand, to two carboxyls of phenylenediacetic Acid ligand
Using Bidentate State mode, the one-dimensional cyclic polymer to be formed and be moved in one direction is connect with Ni (II) ion bridging
Band, as shown in Fig. 2, the band-like motif of adjacent one-dimensional Polymers has joined together to create two-dimentional oversubscription by strong intermolecular hydrogen bonding
Sublayer, further bis- (1- imidazole radicals) benzene of 1,3- are expanded two-dimensional layer for three-dimensional porous supermolecule with Ni (II) ion by coordination
Reticular structure, the π-π effect between the phenyl ring of bis- (1- imidazole radicals) the benzene ligands of two 1 different, 3- are three knots of complex
Structure is more stable, and structure is as shown in Figure 3.
Complex 1 is done into thermogravimetric analysis, as indicated at 4, for complex 1 in room temperature between 265 DEG C, weightlessness is 3.24%, with
Calculated value: 3.76% very close to.Illustrate that the complex contains the crystallization water, this is with crystallographic structural analysis the result is that identical.It connects down
Come between 280-750 DEG C, ppda and bib ligand decompose, weight loss 81.35%, with calculated value 80.56% very close to.
Last complex starts skeleton and collapses decomposition, and final decomposition product is nickel oxide.
Fig. 5 be using cyclic voltammetry (CV) measure complex chemical property, using three-electrode system, saturation it is sweet
Mercury electrode (SCE) makees reference electrode, and copper electrode is auxiliary electrode, and compound nickel foam film makees working electrode, takes water as a solvent,
The concentration of complex is 10-3mol·L-1, 1molL-1KOH solution make supporting electrolyte, scanning range -0.6~0.6V is swept
Retouching rate is 100mVs-1, all occur a pair of of redox peaks on every CV curve, the results showed that Ni (II) → Ni (I) electricity
Son transfer is reversible process, and complex can be used as capacitor material.
Claims (7)
1. a kind of nickel metal coordinating polymer, which is characterized in that there is three-dimensional porous netted supramolecular structure, chemical formula is
{[Ni(ppda)(mbib)]·H2O}n, wherein ppda is represented to phenylenediacetic Acid；Bib represents bis- (1- imidazole radicals) benzene of 1,3-；
The coordination polymer belongs to rhombic system, space group Pna21, and cell parameter is a=18.5939 (8) nm, b=
7.6992 (3) nm, c=14.9541 (7) nm, α=β=γ=90 °, V=2140.80 (16) nm3, Z=4, μ=0.949mm-1。
2. a kind of preparation method of nickel metal coordinating polymer, which is characterized in that specific preparation process includes the following steps:
Step 1. weighs suitable nickel acetate, (1- imidazole radicals) benzene bis- to phenylenediacetic Acid, 1,3- and suitable deionized water and is placed in
It in the beaker of 25mL, stirs evenly, suitable KOH is added dropwise while stirring and obtains mixed solution I；
Mixed solution I is placed in 25mL reaction kettle by step 2., in electric heating constant-temperature blowing drying box, quickly heats up to one first
After determining temperature, and isothermal reaction is for a period of time, is then cooled to room temperature, takes out reaction kettle and obtains mixed solution I I, will mix molten
Liquid II is filtered, washed and dried, and obtains emerald bulk crystals, i.e. nickel metal coordinating polymer.
3. a kind of preparation method of nickel metal coordinating polymer as claimed in claim 2, which is characterized in that in the step 1
Nickel acetate, (1- imidazole radicals) benzene bis- to phenylenediacetic Acid, 1,3-) and KOH molar concentration rate be 1:1:1:1.
4. a kind of preparation method of nickel metal coordinating polymer as claimed in claim 2, which is characterized in that in the step 2
Heating rate is 20 DEG C/h-50 DEG C/h, and the temperature of isothermal reaction is 150 DEG C -200 DEG C, reaction time 48h-96h.
5. a kind of preparation method of nickel metal coordinating polymer as claimed in claim 2, which is characterized in that in the step 2
Rate of temperature fall be 10 DEG C/h-20 DEG C/h.
6. a kind of preparation method of nickel metal coordinating polymer as claimed in claim 2, which is characterized in that is be prepared matches
Position polymer has three-dimensional porous meshed super molecular structure, and chemical formula is { [Ni (ppda) (mbib)] H2O}n, wherein ppda
It represents to phenylenediacetic Acid；Bib represents bis- (1- imidazole radicals) benzene of 1,3-；
The coordination polymer belongs to rhombic system, space group Pna21, and cell parameter is a=18.5939 (8) nm, b=
7.6992 (3) nm, c=14.9541 (7) nm, α=β=γ=90 °, V=2140.80 (16) nm3, Z=4, μ=0.949mm-1。
7. the preparation method as claimed in claim 2 based on Ni (II) complex to phenylenediacetic Acid, which is characterized in that preparation
Application of the obtained coordination polymer as capacitor material.
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| CN111393660A (en) * | 2020-02-21 | 2020-07-10 | 延安大学 | Nickel metal coordination polymer and preparation method and application thereof |
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| CN111393660A (en) * | 2020-02-21 | 2020-07-10 | 延安大学 | Nickel metal coordination polymer and preparation method and application thereof |
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