CN109651620B - Nickel metal coordination polymer and preparation method thereof - Google Patents
Nickel metal coordination polymer and preparation method thereof Download PDFInfo
- Publication number
- CN109651620B CN109651620B CN201811406146.0A CN201811406146A CN109651620B CN 109651620 B CN109651620 B CN 109651620B CN 201811406146 A CN201811406146 A CN 201811406146A CN 109651620 B CN109651620 B CN 109651620B
- Authority
- CN
- China
- Prior art keywords
- coordination polymer
- benzene
- imidazolyl
- bis
- ppda
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 42
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- SLWIPPZWFZGHEU-UHFFFAOYSA-N 2-[4-(carboxymethyl)phenyl]acetic acid Chemical group OC(=O)CC1=CC=C(CC(O)=O)C=C1 SLWIPPZWFZGHEU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- GDWGYEKGZJOUHE-UHFFFAOYSA-N 1-(3-imidazol-1-ylphenyl)imidazole Chemical group C1=NC=CN1C1=CC=CC(N2C=NC=C2)=C1 GDWGYEKGZJOUHE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 claims description 8
- 238000005485 electric heating Methods 0.000 claims description 8
- 238000005303 weighing Methods 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
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 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
- 239000003446 ligand Substances 0.000 abstract description 15
- 238000011160 research Methods 0.000 abstract description 7
- 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
- 230000009471 action Effects 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- -1 nickel metal complex Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 5
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000006181 electrochemical material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- GDYYIJNDPMFMTB-UHFFFAOYSA-N 2-[3-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC(CC(O)=O)=C1 GDYYIJNDPMFMTB-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000002131 composite material Substances 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000921 elemental analysis 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
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 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
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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
- H01G11/24—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
Landscapes
- 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
The invention discloses a nickel metal coordination polymer, which has a three-dimensional porous supermoleculeNetwork structure of the formula { [ Ni (ppda) ((mbib))]·H
2O}
nWherein ppda represents p-phenylenediacetic acid, bib represents 1, 3-bis (1-imidazolyl) benzene, and the coordination polymer belongs to an orthorhombic system and has a space group Pna 21. Carboxyl of p-phenylenediacetic acid is bridged with metal Ni in a V form to form a one-dimensional ring, adjacent one-dimensional rings are combined through hydrogen bonds to form a two-dimensional supermolecular layer, and a three-dimensional porous supermolecular network structure is formed through pi-pi action between benzene rings of 1, 3-bis (1-imidazolyl) benzene ligands, so that a certain foundation is laid for electrochemical development research of Ni coordination polymers. The preparation method adopts a hydrothermal synthesis method, is simple to operate, has mild conditions, high yield and good reproducibility, and can understand the reaction process.
Description
Technical Field
The invention belongs to the technical field of nickel metal complex materials, relates to a nickel metal coordination polymer, and further relates to a preparation method of the complex.
Background
In recent years, designing and constructing a supramolecular chemical system with the properties of conductivity, magnetism, luminescence and the like based on the supramolecular action between metal and organic ligand has become one of the active and promising research subjects in the fields of modern chemistry, material science and the like. Researches show that polycarboxylic acid is widely used for constructing one-dimensional, two-dimensional and three-dimensional supramolecular complexes with novel structures and unique performances due to various flexible bonding modes, and the researches are mostly focused on aromatic polycarboxylic acid complexes. Due to the diversity of dihedral angles between the carboxyl plane and the benzene ring plane of polycarboxylic acid-based ligands, it is possible to fix the metal center in different directions and thus present unique advantages: in particular, it has been widely studied that a variety of coordination polymers having different forms, strong rigidity and excellent thermal stability can be constructed with metal ions by using rigid polycarboxyphenyl ligands, such as trimesic acid, isophthalic acid, terephthalic acid and phthalic acid. However, at present, researches on constructing coordination polymers by using pyromellitic acid, m-phenylenediacetic acid, p-phenylenediacetic acid and o-phenylenediacetic acid as polycarboxylic-based ligands are few, and some reported coordination polymers have complex preparation processes and are not easy to repeat; in fact, the ligands have the characteristic of better flexibility, and can provide a wider selection range for synthesizing novel multidimensional coordination polymers.
The novel three-dimensional coordination polymer is synthesized by nickel acetate metal salt and a p-phenylenediacetic acid ligand under the hydrothermal reaction condition, and the structure and the electrochemical performance of the novel three-dimensional coordination polymer are characterized.
Disclosure of Invention
The invention aims to provide a nickel metal coordination polymer, provides an electrochemical material, synthesizes a nickel metal complex with a three-dimensional structure by utilizing the good flexibility of p-phenylenediacetic acid, and provides a theoretical basis for the research of developing nickel metal elements.
The invention also aims to provide a preparation method of the nickel metal coordination polymer, which solves the problems of complex preparation process and low reproducibility in the prior art.
The invention adopts the technical scheme that a nickel metal coordination polymer has a three-dimensional porous reticular supermolecular structure with a chemical formula of { [ Ni (ppda) ((mbib))]·H
2O}
nWherein, ppda represents p-phenylenediacetic acid; bib represents 1, 3-bis (1-imidazolyl) benzene;
the coordination polymer belongs to an orthorhombic system, the space group is Pna21, the unit cell parameters are a-18.5939 (8) nm, b-7.6992 (3) nm, c-14.9541 (7) nm, α - β -gamma-90 DEG, and V-2140.80 (16) nm
3，Z＝4，μ＝0.949mm
-1；
The invention also provides a preparation method of the nickel metal coordination polymer, which comprises the following steps:
and 2, placing the mixed solution I in a 25mL reaction kettle, quickly heating to a certain temperature in an electric heating constant-temperature air-blowing drying oven, reacting at a constant temperature for a period of time, cooling to room temperature, taking out the reaction kettle to obtain a mixed solution II, filtering, washing and drying the mixed solution II to obtain emerald green blocky crystals, namely the nickel metal coordination polymer.
Yet another feature of the present invention is that,
in the step 1, the molar concentration ratio of nickel acetate, p-phenylenediacetic acid, 1, 3-bis (1-imidazolyl) benzene) and KOH is 1:1:1: 1.
In the step 2, the heating rate is 20 ℃/h-50 ℃/h, the temperature of the constant temperature reaction is 150-200 ℃, and the reaction time is 48-96 h.
The cooling rate in the step 2 is 10-20 ℃/h.
The prepared coordination polymer has a three-dimensional porous reticular supramolecular structure and has a chemical formula { [ Ni (ppda) ((mbib))]·H
2O}
nWherein, ppda represents p-phenylenediacetic acid; bib represents 1, 3-bis (1-imidazolyl) benzene;
the coordination polymer belongs to an orthorhombic system, the space group is Pna21, the unit cell parameters are a-18.5939 (8) nm, b-7.6992 (3) nm, c-14.9541 (7) nm, α - β -gamma-90 DEG, and V-2140.80 (16) nm
3，Z＝4，μ＝0.949mm
-1。
The prepared coordination polymer is applied as a capacitor material.
The invention has the beneficial effects that the nickel metal coordination polymer and the preparation method thereof provide a new electrochemical material { [ Ni (ppda) () ] (mbib)]·H
2O}
nThe coordination number of Ni1 in the coordination polymer is 6, wherein carboxyl of the p-phenylene diacetic acid is bridged with metal Ni1 in a V form to form a one-dimensional ring of a polymer belt moving along one direction, adjacent one-dimensional rings are bonded together through strong intermolecular hydrogen to form a two-dimensional supermolecular layer, in addition, a three-dimensional porous supermolecular network structure with face-to-face orientation is formed through pi-pi interaction between benzene rings of the 1, 3-bis (1-imidazolyl) benzene ligand, a certain foundation is laid for electrochemical development research of the Ni coordination polymer, and the nickel metal complex with the three-dimensional structure is synthesized by utilizing good flexibility of the p-phenylene diacetic acid. The preparation method adopts a hydrothermal synthesis method, is simple to operate, has mild conditions, high yield and good reproducibility, and can understand the reaction process.
Drawings
FIG. 1 is a coordination environment of Ni atoms in a coordination polymer obtained in example 1 of the present invention;
FIG. 2 shows a one-dimensional cyclic structure of a coordination polymer obtained in example 1 of the present invention;
FIG. 3 is a three-dimensional network structure of a coordination polymer obtained in example 1 of the present invention;
FIG. 4 is a thermogravimetric analysis of a coordination polymer obtained in example 1 of the present invention;
FIG. 5 is a cyclic voltammogram of the coordination polymer obtained in example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a nickel metal coordination polymer, which has a three-dimensional porous supermolecular network structure and has the chemical formula { [ Ni (ppda) ()]·H
2O}
nWherein, ppda represents p-phenylenediacetic acid; bib represents 1, 3-bis (1-imidazolyl) benzene;
{[Ni(ppda)(mbib)]·H
2O}
nthe coordination polymers all belong to the orthorhombic system and have the space group of Pna21 { [ Ni (ppda) ("mbib")]·H
2O}
nThe unit cell parameters of (1) are a-18.5939 (8) nm, b-7.6992 (3) nm, c-14.9541 (7) nm, α - β - γ -90 ° and V-2140.80 (16) nm
3，Z＝4，μ＝0.949mm
-1；
The invention relates to a preparation method of a nickel metal coordination polymer, which comprises the following steps:
in the step 1, the molar concentration ratio of nickel acetate, p-phenylenediacetic acid, 1, 3-bis (1-imidazolyl) benzene and KOH is 1:1:1: 1.
And 2, placing the mixed solution I in a 25mL reaction kettle, quickly heating to a certain temperature in an electric heating constant-temperature air-blowing drying oven, reacting at a constant temperature for a period of time, cooling to room temperature, taking out the reaction kettle to obtain a mixed solution II, filtering, washing and drying the mixed solution II to obtain emerald green blocky crystals, namely the nickel metal coordination polymer.
In the step 2, the heating rate is 20 ℃/h-50 ℃/h, the temperature of the constant temperature reaction is 150-200 ℃, and the reaction time is 48-96 h.
The cooling rate in the step 2 is 10-20 ℃/h.
The prepared complex is applied as an electrochemical material.
The reaction mechanism occurring during the preparation: p-phenylene diacetic acid belongs to binary weak acid, KOH is added to deprotonate the p-phenylene diacetic acid, and according to the soft, hard, acid and alkali rules of the acid-base electron theory: the 'soft-hydrophilic soft-hard-hydrophilic', p-phenylenediacetic acid as soft alkali provides electron pair to form chemical bond coordination covalent bond with empty orbit of soft acid metal ion, the reaction equation is as follows:
example 1
Weighing 0.1mmol of nickel acetate tetrahydrate, 0.1mmol of p-phenylenediacetic acid and 0.1mmol of 1, 3-bis (1-imidazolyl) benzene, adding 12mL of distilled water into a 25mL beaker, dropwise adding 0.1mmol of KOH while stirring to obtain a mixed solution I, and putting the mixed solution I into a 25mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining; putting the reaction kettle into an electric heating constant-temperature air-blowing drying oven, heating from 20 ℃ to 200 ℃ at a heating rate of 50 ℃/h for rapid heating reaction, reacting at 200 ℃ for 72h at a constant temperature, cooling to room temperature at a speed of 10 ℃/h, filtering, washing and drying the reaction solution to obtain a emerald green massive crystal complex, namely { [ Ni (ppda) ((mbib))]·H
2O}
nAnd (3) a complex.
Example 2
Weighing 0.1mmol of nickel acetate tetrahydrate, 0.1mmol of p-phenylenediacetic acid and 0.1mmol of 1, 3-bis (1-imidazolyl) benzene, adding 12mL of distilled water into a 25mL beaker, dropwise adding 0.1mmol of KOH while stirring to obtain a mixed solution I, and putting the mixed solution I into a 25mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining; placing the reaction kettle into an electric heating constant temperature blast drying oven, heating from 20 deg.C to 180 deg.C at a heating rate of 20 deg.C/h, performing rapid heating reaction at 180 deg.C for 48h, cooling to room temperature at a rate of 12 deg.C/h, filtering, washing and drying the reaction solution to obtain emerald green block crystalsComplexes, namely { [ Ni (ppda) ((mbib))]·H
2O}
nAnd (3) a complex.
Example 3
Weighing 0.1mmol of nickel acetate tetrahydrate, 0.1mmol of p-phenylenediacetic acid and 0.1mmol of 1, 3-bis (1-imidazolyl) benzene, adding 12mL of distilled water into a 25mL beaker, dropwise adding 0.1mmol of potassium hydroxide while stirring to obtain a mixed solution I, and putting the mixed solution I into a 25mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining; putting the reaction kettle into an electric heating constant-temperature air-blowing drying oven, heating from 20 ℃ to 160 ℃ at a heating rate of 50 ℃/h for rapid heating reaction, reacting at 160 ℃ for 72h at a constant temperature, cooling to room temperature at a speed of 10 ℃/h, filtering, washing and drying the reaction liquid to obtain a emerald green massive crystal complex, namely { [ Ni (ppda) ((mbib))]·H
2O}
nAnd (3) a complex.
Example 4
Weighing 0.1mmol of nickel acetate tetrahydrate, 0.1mmol of p-phenylenediacetic acid and 0.1mmol of 1, 3-bis (1-imidazolyl) benzene, adding 12mL of distilled water into a 25mL beaker, dropwise adding 0.1mmol of potassium hydroxide while stirring to obtain a mixed solution I, and putting the mixed solution I into a 25mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining; putting the reaction kettle into an electric heating constant-temperature air-blowing drying box, heating from 30 ℃ to 150 ℃ at a heating rate of 40 ℃/h for rapid heating reaction, reacting at 150 ℃ for 96h at a constant temperature, cooling to room temperature at a speed of 15 ℃/h, filtering, washing and drying the reaction liquid to obtain a emerald green massive crystal complex, namely { [ Ni (ppda) ((mbib))]·H
2O}
nAnd (3) a complex.
Example 5
Weighing 0.1mmol of nickel acetate tetrahydrate, 0.1mmol of p-phenylenediacetic acid and 0.1mmol of 1, 3-bis (1-imidazolyl) benzene, adding 12mL of distilled water into a 25mL beaker, dropwise adding 0.1mmol of sodium hydroxide while stirring to obtain a mixed solution I, and putting the mixed solution I into a 25mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining; placing the reaction kettle into an electric heating constant-temperature blast drying oven, heating from 20 ℃ to 200 ℃ at a heating rate of 20 ℃/h, carrying out rapid heating reaction, crystallizing at the constant temperature of 200 ℃ for 48h, and cooling to room temperature at a speed of 10 ℃/hThe reaction mixture was filtered, washed and dried to obtain a emerald green massive crystalline complex { [ Ni (ppda) ((mbib))]·H
2O}
nAnd (3) a complex.
EXAMPLE 1 preparation of { [ Ni (ppda) ((mbib))]·H
2O}
nThe molecular formula of the complex is C
22H
20N
4O
5Ni, molecular weight 479.13, elemental analysis results experimental value (%): c is 55.06; h was 4.50 calculated (%): c is 54.89; h is 4.58;
the complex obtained in example 1 was analyzed for crystal structure using Bruker SMART1000 CCD single crystal X-ray diffractometer at room temperature using Mo K α radiation monochromatized with a graphite monochromator (λ 0.071073nm) and collected in an ω -scan manner for diffraction intensity data.
TABLE 1 crystallographic data for coordination polymers
aR
1＝Σ||F
o|–|F
c||/Σ|F
o|,wR
2＝[Σw(F
o 2–F
c 2)
2/Σw(F
o 2)
2]
1/2
As can be seen from the crystal structure analysis of the minimal repeating unit of the coordination polymer, the complex of example 1 belongs to the orthorhombic, Pna21 space group, each asymmetric unit comprising one central metal Ni (ii) ion, one p-phenylenediacetic acid ligand and a 1, 3-bis (1-imidazolyl) benzene ligand, as shown in fig. 1, Ni (ii) reacts with four carboxyl oxygen atoms from two different p-phenylenediacetic acid ligands and two nitrogen atoms from two 1, 3-bis (1-imidazolyl) benzene ligands (Ni (1) -N (1) ═ 2.041(2),
) Coordination, bond length of Ni-O in
Within the range. The Ni (II) ion assumes a distorted octahedral configuration, with four atoms (N (2), O (1), O (2) and O (3)) constituting the equatorial plane and the atoms O (2) and N (1) occupying axial positions.
In the complex, two carboxyl groups of a p-phenylene diacetic acid ligand are deprotonated, the two carboxyl groups of the p-phenylene diacetic acid ligand are in a bidentate chelation coordination mode and are in bridging connection with Ni (II) ions to form a one-dimensional annular polymer band moving along one direction, as shown in figure 2, adjacent one-dimensional polymer band-shaped motifs are combined together through strong intermolecular hydrogen bonds to generate a two-dimensional supermolecular layer, further, 1, 3-bis (1-imidazolyl) benzene expands the two-dimensional layer into a three-dimensional porous supermolecular net structure through coordination and Ni (II) ions, and pi-pi action between benzene rings of two different 1, 3-bis (1-imidazolyl) benzene ligands is that the three-dimensional structure of the complex is more stable, and the structure is as shown in figure 3.
Thermogravimetric analysis is carried out on the complex 1, as shown in 4, the weight loss of the complex 1 is 3.24% between room temperature and 265 ℃, and the calculated value is as follows: 3.76% are very close. It was shown that the complex contained crystal water, which was the same as the result of crystal structure resolution. Next between 280 ℃ and 750 ℃ the ppda and bib ligands decompose with a weight loss of 81.35%, which is very close to the calculated value of 80.56%. And finally, the complex starts to collapse and decompose the skeleton, and the final decomposition product is nickel oxide.
FIG. 5 shows the measurement of the electrochemical properties of the complex by Cyclic Voltammetry (CV), using a three-electrode system, a Saturated Calomel Electrode (SCE) as a reference electrode, a copper electrode as an auxiliary electrode, a composite nickel foam film as a working electrode, water as a solvent, and a complex concentration of 10
-3mol·L
-1，1mol·L
-1The KOH solution is used as a supporting electrolyte, the scanning range is-0.6 to 0.6V, and the scanning speed is 100mV s
-1A pair of redox peaks appear on each CV curve, indicating that the electron transfer of Ni (II) → Ni (I) is reversibleThe complexes are useful as capacitor materials.
Claims (4)
1. A nickel metal coordination polymer, which is characterized by having a three-dimensional porous network supermolecular structure with the chemical formula { [ Ni (ppda) ((mbib))]·H
2O}
nWherein, ppda represents p-phenylenediacetic acid; mbib represents 1, 3-bis (1-imidazolyl) benzene;
the coordination polymer belongs to an orthorhombic system, the space group is Pna21, the unit cell parameters are a-18.5939 (8) nm, b-7.6992 (3) nm, c-14.9541 (7) nm, α - β -gamma-90 DEG, and V-2140.80 (16) nm
3，Z＝4，μ＝0.949mm
-1(ii) a The nickel metal coordination polymer is useful as a capacitor material.
2. The preparation method of the nickel metal coordination polymer is characterized by comprising the following steps:
step 1, weighing a proper amount of nickel acetate, p-phenylenediacetic acid, 1, 3-bis (1-imidazolyl) benzene and a proper amount of deionized water, placing the weighed materials in a 25mL beaker, uniformly stirring, and dropwise adding a proper amount of KOH while stirring to obtain a mixed solution I;
in the step 1, the molar concentration ratio of nickel acetate, p-phenylenediacetic acid, 1, 3-bis (1-imidazolyl) benzene) and KOH is 1:1:1: 1;
step 2, placing the mixed solution I in a 25mL reaction kettle, quickly heating to a certain temperature in an electric heating constant-temperature air-blowing drying oven, reacting at a constant temperature for a period of time, cooling to room temperature, taking out the reaction kettle to obtain a mixed solution II, filtering, washing and drying the mixed solution II to obtain emerald green blocky crystals, namely the nickel metal coordination polymer;
in the step 2, the heating rate is 20-50 ℃/h, the constant temperature reaction temperature is 150-200 ℃, and the reaction time is 48-96 h.
3. The method of claim 2, wherein the temperature reduction rate in step 2 is 10 ℃/h to 20 ℃/h.
4. The method of claim 2, wherein the coordination polymer has a three-dimensional porous network supramolecular structure of the formula { [ Ni (ppda) ("mb) ])]·H
2O}
nWherein, ppda represents p-phenylenediacetic acid; mbib represents 1, 3-bis (1-imidazolyl) benzene;
the coordination polymer belongs to an orthorhombic system, the space group is Pna21, the unit cell parameters are a-18.5939 (8) nm, b-7.6992 (3) nm, c-14.9541 (7) nm, α - β -gamma-90 DEG, and V-2140.80 (16) nm
3，Z＝4，μ＝0.949mm
-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811406146.0A CN109651620B (en) | 2018-11-23 | 2018-11-23 | Nickel metal coordination polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811406146.0A CN109651620B (en) | 2018-11-23 | 2018-11-23 | Nickel metal coordination polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109651620A CN109651620A (en) | 2019-04-19 |
| CN109651620B true CN109651620B (en) | 2020-02-11 |
Family
ID=66112220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811406146.0A Active CN109651620B (en) | 2018-11-23 | 2018-11-23 | Nickel metal coordination polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109651620B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041534A (en) * | 2019-05-31 | 2019-07-23 | 安庆师范大学 | A kind of nickel complex and preparation method thereof based on rigid 4- imidazoles ylidene ligands |
| CN111393660B (en) * | 2020-02-21 | 2022-03-08 | 延安大学 | Nickel metal coordination polymer and preparation method and application thereof |
-
2018
- 2018-11-23 CN CN201811406146.0A patent/CN109651620B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109651620A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107602622B (en) | Phosphorized metal organic framework material, preparation method and application thereof | |
| CN109651620B (en) | Nickel metal coordination polymer and preparation method thereof | |
| Wei et al. | Ferrocene-based hyperbranched polymers: a synthetic strategy for shape control and applications as electroactive materials and precursor-derived magnetic ceramics | |
| Wang et al. | Copper (II) metal–organic networks derived from bis (pyridylformyl) piperazine ligands and aromatic polycarboxylates: 2D layered structures and a novel 3, 5-connected binodal 3D topology | |
| WO2017151653A2 (en) | Synthetically modifiable ion channels | |
| CN113549082B (en) | Polyhydroxy compound and preparation method and application thereof | |
| Shi et al. | Thiacalix [4] arene-supported tetradecanuclear cobalt nanocage cluster as precursor to synthesize CoO/Co 9 S 8@ CN composite for supercapacitor application | |
| CN106025178B (en) | It is a kind of to prepare the method for metal oxide and its application in lithium cell cathode material by template of MOF | |
| CN107286185A (en) | A kind of cadmium metal organic framework material and preparation method thereof | |
| CN111471190B (en) | Covalent organic framework material with carborane as starting material and preparation method and application thereof | |
| CN106008586A (en) | POSS-containing high temperature-resistant solid ionic liquid and preparation method thereof | |
| Yang et al. | Ba-MOFs with tetrazole-based acetic acids: unusual configuration, novel topology and high proton conductivity | |
| Li et al. | Development of an interfacial osmosis diffusion method to prepare imine-based covalent organic polymer electrocatalysts for the oxygen evolution reaction | |
| CN113215605B (en) | Method for synthesizing MOF oxygen evolution reaction catalyst by using eutectic solvothermal method | |
| CN109741959A (en) | A kind of graphene/iron-based MOF super capacitor material and preparation method thereof | |
| Yang et al. | Four 3D Co (ii) MOFs based on 2, 4, 6-tris (4-pyridyl)-1, 3, 5-triazine and polycarboxylic acid ligands and their derivatives as efficient electrocatalysts for oxygen reduction reaction | |
| Liu et al. | Three metal complexes derived from 3-methyl-1 H-pyrazole-4-carboxylic acid: synthesis, crystal structures, luminescence and electrocatalytic properties | |
| Liang et al. | One, two, and three-dimensional metal–organic coordination polymers derived from enantiopure organic phosphorate: homochirality, water stability and proton conduction | |
| CN107955182B (en) | Micro-doped composite metal organic framework material, preparation method and application thereof | |
| CN110724166B (en) | Multi-metal oxygen cluster-based covalent organic framework material, preparation method and application thereof | |
| CN115417960B (en) | Stripping method of porphyrin-based covalent organic framework material with ligand drive | |
| CN112778153B (en) | Amido bridged hexacarboxylic acid ligand and metal organic framework material as well as preparation method and application thereof | |
| CN115652363A (en) | Preparation and application of iron-nitrogen-carbon single-atom catalyst for catalytically producing ammonia | |
| CN114854037B (en) | Cobalt (II) complex with semiconductor property and preparation method thereof | |
| Wang et al. | Metal (II)-directed various polyoxometalates-based hybrid compounds: assembly, structures and properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |