CN114808138A - Preparation and application of octahedral magic cube-shaped Keggin type copper phosphomolybdate crystalline material - Google Patents
Preparation and application of octahedral magic cube-shaped Keggin type copper phosphomolybdate crystalline material Download PDFInfo
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- 239000002178 crystalline material Substances 0.000 title claims abstract description 81
- 239000010949 copper Substances 0.000 title claims abstract description 77
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000003990 capacitor Substances 0.000 claims abstract description 11
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- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 27
- 239000013110 organic ligand Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 13
- 229910001431 copper ion Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000001450 anions Chemical group 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000000840 electrochemical analysis Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
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- 239000007772 electrode material Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
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- 239000012621 metal-organic framework Substances 0.000 description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 2
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- 230000002441 reversible effect Effects 0.000 description 2
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- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910016525 CuMo Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 238000005498 polishing Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- 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
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention relates to a preparation method and application of an octahedral magic cube type Keggin type copper phosphomolybdate based crystalline material. The invention aims to solve the problems of poor stability and low conductivity of some polyacid crystalline materials serving as electrode materials of a super capacitor in a solution, and provides a preparation method capable of improving the capacitance performance of the polyacid crystalline materials serving as the electrode materials of the super capacitor. The chemical formula of the octahedral magic cube type Keggin type copper phosphomolybdate based crystalline material is [ Cu (H) 2 O) 2 H 4 (pybta) 4 ](PMo 12 O 40 ) 2 ·2H 2 O, wherein the pybta is 1-pyridine-3-methylene-1H-benzotriazole. Synthesis methodPhosphomolybdic acid, copper acetate and pybta are added into distilled water and stirred uniformly, the pH value is adjusted, the mixture reacts for 4 days at the temperature of 140 ℃, and the specific capacitance value of an electrode material prepared from the obtained crystalline material is 556F/g under the current density of 1A/g. Provides a technical route for constructing an octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material to improve the super-electric performance.
Description
Technical Field
The invention relates to a preparation method and application of an octahedral magic cube type Keggin type copper phosphomolybdate based crystalline material.
Background
The super capacitor is a green and environment-friendly energy storage device which is physically transferred by charges, rapidly charged and discharged and is not influenced by temperature, so that the super capacitor is longer in service life, has higher power density and wide temperature application range, is low in cost, is non-toxic and pollution-free, and is one of energy storage devices which pay attention to at present in large quantities. Whether precise energy storage with small capacity or large-scale electric energy storage, it exhibits excellent characteristics from single energy storage to hybrid energy storage used in conjunction with a secondary battery or a fuel cell.
Polyoxometalates (POMs) (also called polyacid) are nano oxide clusters with reversible oxidation activity, have the characteristics of structure modification, adjustable physicochemical properties and the like, and can be used as basic materials for various applications. The molecular clusters are very stable, and show strong and stable interaction when being combined with various crystal materials, so that the molecular clusters have wide application prospects in the field of water-based supercapacitors.
Phosphomolybdates are an important branch of the development of polyacid chemistry. Due to the various coordination modes of the molybdenum, the geometrical configuration of the molybdenum also presents diversification, such as tetrahedron, triangular bipyramid, octahedron and the like. Due to the abundant structure, reversible redox property, nanoscale size and excellent electrochemical performance, the composite material has a wide application prospect in the aspects of material synthesis, electrocatalysis, supercapacitors and the like. However, phosphomolybdate has good solubility in water and some organic solvents, and the phosphomolybdate as a capacitor electrode material affects the cycle life of the electrode. Meanwhile, the polyacid material has poor conductivity, and the transmission of electrolyte ions and electrons in the electrode is limited, so that the capacitance, rate capability and cycle characteristics of the electrode material are not ideal. In order to solve the problems of high water solubility, poor conductivity and the like of polyacid, polyacid is used as a pre-assembly precursor, a metal organic framework is introduced, and a polyacid-based metal organic framework crystal material is prepared and applied to the field of supercapacitors.
Disclosure of Invention
The invention aims to solve the problems of poor stability and low conductivity of the polyacid salt serving as the electrode material of the supercapacitor in the solution. In order to improve the capacitance performance of the material, the invention provides a preparation method of an octahedral magic cube-shaped Keggin type copper phosphomolybdate crystalline material.
In order to solve the technical problems, the invention is realized by the following technical scheme:
firstly, preparing a reaction solution with a pH value of 2.5-3.0: adding phosphomolybdic acid, copper acetate and 1-pyridine-3-methylene-1H-benzotriazole into distilled water, uniformly stirring, and then adjusting the pH value of the suspension to 2.5-3.0 to obtain a reaction solution with the pH value of 2.5-3.0;
the molar ratio of the phosphomolybdic acid to the copper acetate in the first step is as follows: 1.0 (6.0-7.0);
the molar ratio of the phosphomolybdic acid to the 1-pyridine-3-methylene-1H-benzotriazole in the first step is as follows: 1.0 (0.9-1.1);
the volume ratio of the phosphomolybdic acid substance to the distilled water in the first step is as follows: 0.16mmol:15 mL.
Secondly, transferring the reaction liquid with the pH value of 2.5-3.0 prepared in the step one into a polytetrafluoroethylene reaction kettle, reacting at the temperature of 140 ℃ for 4 days, cooling the reaction liquid to room temperature, and washing to obtain green blocky crystals, namely the octahedral magic cube-shaped Keggin type phosphomolybdic acid copper-based crystalline material, wherein the chemical formula of the crystalline material is [ Cu (H) 2 O) 2 H 4 (pybta) 4 ](PMo 12 O 40 ) 2 ·2H 2 O, wherein the pybta is 1-pyridine-3-methylene-1H-benzotriazole; the appearance of the crystal is green block; the crystal is orthorhombic; the space group is Pbca; cell parameters of
b＝21.165(7)，
α＝90°，β＝90°，γ＝90°，
Thirdly, preparing the working electrode of the super capacitor of the octahedral magic cube type Keggin type copper phosphomolybdate based crystalline material: grinding 10mg of Keggin type copper phosphomolybdate crystalline material and 10mg of acetylene black uniformly, adding the ground material into 1mL of water, carrying out ultrasonic treatment for 2h to obtain a uniformly dispersed mixed solution, dripping 10 mu L of the mixed solution on a pretreated glassy carbon electrode, standing at room temperature for 10h, dripping 5 mu L of Nafion solution, and standing at room temperature for 1h to obtain the working electrode.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material is successfully prepared by using 1-pyridine-3-methylene-1H-benzotriazole organic ligand, copper acetate and phosphomolybdic acid through a one-step hydrothermal synthesis method for the first time. The single crystal X-ray diffraction result shows that the structural unit of the crystalline material prepared by the invention is an octahedral magic cube-shaped space structure. The structural unit takes copper ions as a symmetrical center, and the copper ions, four organic ligands and two coordinated waters form a windmill structure. Meanwhile, hydrogen atoms on carbon atoms and water cluster oxygen atoms in molecules in the organic ligand respectively form hydrogen bonds with terminal oxygen and bridging oxygen on phosphomolybdic acid, and phosphomolybdic acid molecules are distributed at six vertex positions of an octahedral structure taking copper ions as centers through the action of the hydrogen bonds to form a primary structural unit in the shape of an octahedron magic cube.
As polyacid and metal in crystalline material molecules and polyacid and ligand can be mutually connected through hydrogen bond interaction, the conduction path of electrons and protons is increased from water cluster-metal-organic ligand to organic ligand-polyacid-water cluster-metal-organic ligand, and the performance of the super capacitor of the supermolecule crystalline material can be improved by the increase of the multi-electron/proton transmission channel.
Secondly, the octahedral magic cube-shaped Keggin type copper phosphomolybdate crystalline material prepared by the embodiment is used as an electrode material of a super capacitor. It was found to have a specific capacitance value of 556F/g at a current density of 1A/g. The results can show that the unique structure increases an electron/proton conduction path, so that the electron/proton conduction becomes easier and faster, and the stability and the electrical conductivity of the supercapacitor are improved.
Drawings
FIG. 1 is a diagram of the basic structural units of an octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material according to an embodiment.
FIG. 2 is a schematic diagram of an octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material according to an example: a represents a single-layer octahedral magic cube-shaped Keggin type phosphomolybdic acid copper-based crystalline material along the c-axis direction, b represents a schematic diagram of the octahedral magic cube-shaped Keggin type phosphomolybdic acid copper-based crystalline material along the a-axis direction, and c represents a structural unit formed by phosphomolybdic acid, copper ions, organic ligands and water clusters.
FIG. 3 is a schematic diagram of a primary structural unit of an octahedral magic cube-shaped Keggin-type copper phosphomolybdate based crystalline material according to an embodiment.
FIG. 4 is a schematic diagram showing the connection between the interlayer polyacid and the ligand of the octahedral magic cube-shaped Keggin-type copper phosphomolybdate based crystalline material in the example.
FIG. 5 is an infrared spectrum of an octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material of example.
FIG. 6 is a powder X-ray diffraction pattern of the octahedral magic cube-like Keggin-type copper phosphomolybdate crystalline material of example.
FIG. 7 shows an example of an octahedral magic cube-shaped Keggin-type copper phosphomolybdate crystalline material as a working electrode at 0.5M (H) 2 SO 4 -Na 2 SO 4 ) Cyclic voltammograms at sweep rates in the electrolyte of 5, 10, 30, 50, 70, 90 and 100mV/s, respectively.
FIG. 8 shows an example of an octahedral magic cube-like Keggin-type copper phosphomolybdate crystalline material as a working electrode at 0.5M (H) 2 SO 4 -Na 2 SO 4 ) And the current density in the electrolyte is respectively 1, 2, 3, 5, 8 and 10A/g.
FIG. 9 shows an example of an octahedral magic cube-shaped Keggin-type copper phosphomolybdate based crystalline material as a working electrode at 0.5M (H) 2 SO 4 -Na 2 SO 4 ) In the electrolyteWhen the current density is 10A/g, the specific capacitance retention rate of the constant current charging/discharging is schematic diagram for 1000 circles.
Detailed Description
The technical solutions of the present invention are not limited to the specific embodiments listed below, which are only used to illustrate the present invention and are not limited to the technical solutions described in the embodiments of the present invention. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result. So long as the use requirements are met, the invention is within the protection scope.
The first embodiment is as follows: the present embodiment describes an octahedral magic cube-like Keggin-type copper phosphomolybdate crystalline material having a molecular formula of C 48 H 52 N 16 P 2 CuMo 24 O 84 The basic structural unit contains 1 metallic copper ion, two 1-imidazole-1-methylene-1H-benzotriazole organic ligands and one PMo 12 O 40 3- A polyacid anion and two water molecules. Wherein copper ions are respectively coordinated with coordinated water O1W and nitrogen atoms N2 and N4 in organic ligands to form a windmill-shaped metal organic ligand structural unit Cu (H) 2 O) 2 (pybta) 4 The hydrogen atoms on the oxygen atoms O1W and O2W of the water cluster in the molecule are respectively connected with PMo 12 O 40 3- The terminal oxygen O37, O18 and the bridging oxygen O31 on the polyacid anion form hydrogen bonds, and PMo is formed through the action of the hydrogen bonds 12 O 40 3- The polyacid clusters are distributed at six vertex positions of an octahedral structure taking copper ions as the center to form an octahedral magic cube-shaped unit structure.
The second embodiment is as follows: the preparation method of the octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material supercapacitor electrode material according to the embodiment is completed according to the following steps:
firstly, preparing a reaction solution with a pH value of 2.5-3.0: adding phosphomolybdic acid, copper acetate and 1-pyridine-3-methylene-1H-benzotriazole into distilled water, uniformly stirring, and then adjusting the pH value of the suspension to 2.5-3.0 to obtain a reaction solution with the pH value of 2.5-3.0;
the molar ratio of the phosphomolybdic acid to the copper acetate in the first step is as follows: 1.0 (6.0-7.0);
the molar ratio of the phosphomolybdic acid to the 1-pyridine-3-methylene-1H-benzotriazole in the first step is as follows: 1.0 (0.9-1.1);
the volume ratio of the phosphomolybdic acid substance to the distilled water in the first step is as follows: 0.16mmol:15 mL.
Secondly, preparing an octahedral magic cube type Keggin type copper phosphomolybdate crystalline material: transferring the reaction solution prepared in the step one into a polytetrafluoroethylene reaction kettle, reacting for 4 days at the temperature of 140 ℃, cooling the temperature of the reaction solution to room temperature, and washing to obtain green blocky crystals, namely the octahedral magic cube-shaped Keggin type phosphomolybdic acid copper-based crystalline material, wherein the chemical formula of the crystalline material is [ Cu (H) 2 O) 2 H 4 (pybta) 4 ](PMo 12 O 40 ) 2 ·2H 2 O, wherein the pybta is 1-pyridine-3-methylene-1H-benzotriazole; the appearance of the crystal is green block; the crystal is orthorhombic; the space group is Pbca; cell parameters of
b＝21.165(7)，
α＝90°，β＝90°，γ＝90°，
Thirdly, preparing the working electrode of the super capacitor of the octahedral magic cube type Keggin type copper phosphomolybdate based crystalline material: and grinding 10mg of the metal organic supermolecule phosphomolybdic acid crystalline material and 10mg of acetylene black uniformly, adding the ground materials into 1mL of water, carrying out ultrasonic treatment for 2h to obtain a uniformly dispersed mixed solution, dripping 10 mu L of the mixed solution on a pretreated glassy carbon electrode, standing at room temperature for 10h, then dripping 5 mu L of Nafion solution, and standing at room temperature for 1h to obtain a working electrode modified by the metal organic supermolecule phosphomolybdic acid crystalline material for electrochemical testing.
The glassy carbon electrode in the third step needs to be pretreated, and the specific process is as follows: firstly, polishing a glassy carbon electrode by using aluminium oxide powder with the diameters of 1 micrometer, 0.3 micrometer and 0.05 micrometer, then carrying out ultrasonic treatment in absolute ethyl alcohol and deionized water for 2 minutes, completely cleaning, finally carrying out cyclic voltammetry in a potassium ferricyanide and potassium chloride mixed solution, wherein the scanning potential range is 0-0.6V, and carrying out post-modification on the glassy carbon electrode when the peak potential difference of an oxidation peak and a reduction peak in a cyclic voltammogram is less than 80 mV. Meanwhile, a three-electrode system is selected in the electrochemical test, a glassy carbon electrode or a post-modified glassy carbon electrode is used as a working electrode, a silver/silver chloride electrode is used as a reference electrode, and platinum is used as a counter electrode.
The third concrete implementation mode: in the preparation method of the octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material in the second step of the specific embodiment, the molar ratio of the 1-pyridine-3-methylene-1H-benzotriazole, the copper acetate and the phosphomolybdic acid is 1.0 (6.0-7.0): 1.0.
The fourth concrete implementation mode: the present embodiment is different from the second embodiment in that: the copper acetate in the step one can be replaced by copper chloride, copper nitrate or copper sulfate. The others are the same as in the first to third embodiments.
The fifth concrete implementation mode: in the preparation method of the octahedral magic cube-shaped Keggin-type copper phosphomolybdate crystalline material in the first step of the second specific embodiment, the volume ratio of the mole number of the phosphomolybdic acid to the distilled water is 0.16mmol:15 mL.
The sixth specific implementation mode: the present embodiment is different from the second embodiment in that: in the step one, the pH value of the reaction solution is adjusted to 2.5-3.0, and HNO with the molar concentration of 1mol/L is used 3 Solution and NaOH solution. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the present embodiment is different from the second embodiment in that: and the reaction temperature in the second step is 140-160 ℃, and the reaction time is 3-5 days. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: in the third step of the second specific embodiment, the volume ratio of the mass of the prepared octahedral magic cube-shaped Keggin type copper phosphomolybdate crystalline material to the volume of the acetylene black to the distilled water is 1mg:1mg:0.1 mL.
The following examples were used to demonstrate the beneficial effects of the present invention:
example (a) - (b): a preparation method of an octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material is realized by the following steps:
firstly, preparing a reaction solution with a pH value of 3.0: uniformly dispersing 0.16mmol of phosphomolybdic acid, 1.10mmol of copper acetate and 0.16mmol of 1-pyridine-3-methylene-1H-benzotriazole into 15mL of distilled water, and then using 1mol/L of HNO 3 The pH value of the reaction solution was adjusted to 3.0 by the solution and 1mol/L NaOH solution to obtain a reaction solution having a pH value of 3.0.
Secondly, transferring the prepared reaction liquid with the pH value of 3.0 into a 25mL polytetrafluoroethylene reaction kettle, reacting at the temperature of 140 ℃ for 4 days, cooling the reaction liquid to room temperature, and washing to obtain green blocky crystals, namely the octahedral magic-cube Keggin type copper phosphomolybdate crystalline material.
The structure of an octahedral magic cube Keggin type copper phosphomolybdate crystalline material prepared in the example is determined:
conclusion:x-ray crystallographic parameters: see table 1.
TABLE 1 two materials crystallography parameters
a R 1 ＝∑║F o │─│F c ║/∑│F o │. b wR 2 ＝{∑[w(F o 2 ─F c 2 ) 2 ]/∑[w(F o 2 ) 2 ]} 1/2
an octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material is an orthorhombic system, namely a Pbca space group. The basic structural unit of the crystalline material contains 1 metallic copper ion, two 1-imidazole-1-methylene-1H-benzotriazole organic ligands and one PMo 12 O 40 3- Polyacid anion and two water molecules (as shown in figure 1). Wherein copper ions are respectively coordinated with coordinated water O1W and nitrogen atoms N2 and N4 in organic ligands to form a windmill-shaped metal organic ligand structural unit Cu (H) 2 O) 2 (pybta) 4 The hydrogen atom on the oxygen atom O2W of the water cluster in the molecule is respectively connected with PMo 12 O 40 3- The terminal oxygen O37, O18 and the bridging oxygen O31 on the polyacid anion form hydrogen bonds to enable PMo 12 O 40 3- The polyacid clusters are distributed at six vertex positions of an octahedral structure with copper ions as the center to form an octahedral magic cube-shaped unit structure (as shown in fig. 2c and fig. 3).
Analyzing from the topological point of view, if each metal organic ligand structural unit Cu (H) 2 O) 2 (pybta) 4 And PMo 12 O 40 3- The oxygen atoms O37, O18 and O31 in the polyacid anion are connected by hydrogen bonds, each PMo 12 O 40 3- The polyacid anions are respectively connected with three metal organic ligand structural units, and the connection is infinitely repeated in the mode to form a two-dimensional plane structure along the direction of the a axis.
At the same time, PMo in the two-dimensional plane described above 12 O 40 3- The terminal oxygen (O35, O34, O38) and the bridging oxygen (O14, O21) of the polyacid anion respectively form hydrogen bonds with hydrogen atoms (H14, H6, H21, H8b) on carbon atoms in interlayer metal organic ligand structural units, and extend infinitely in such a way to form an octahedral magic cube-shaped Keggin type copper phosphomolybdate based three-dimensional supramolecular crystalline material (as shown in figure 4).
FIG. 1 is a diagram of the basic structural units of an octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material according to an embodiment.
FIG. 2 is a schematic diagram of an octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material according to an example: a represents a single-layer octahedral magic cube-shaped Keggin type phosphomolybdic acid copper-based crystalline material along the c-axis direction, b represents a schematic diagram of the octahedral magic cube-shaped Keggin type phosphomolybdic acid copper-based crystalline material along the a-axis direction, and c represents a structural unit formed by phosphomolybdic acid, copper ions, organic ligands and water clusters.
FIG. 3 is a schematic diagram of a primary structural unit of an octahedral magic cube-shaped Keggin-type copper phosphomolybdate based crystalline material according to an embodiment.
FIG. 4 is a schematic diagram showing the connection between the interlayer polyacid and the ligand of the octahedral magic cube-shaped Keggin-type copper phosphomolybdate based crystalline material in the example.
(II) the octahedral magic cube type Keggin phosphomolybdic acid copper-based crystalline material [ Cu (H) prepared in the first embodiment 2 O) 2 H 4 (pybta) 4 ](PMo 12 O 40 ) 2 ·2H 2 Performing infrared spectrum characterization on the obtained product to obtain an infrared spectrum of the phosphomolybdic acid metal organic supramolecular crystalline material, wherein the infrared spectrum is shown in figure 5 and is 1064,969,877and 794cm -1 The characteristic peaks of (A) are attributed to v (P-O), v (Mo ═ Ot), v (Mo-Ob-Mo) and v (Mo-Oc-Mo) stretching vibration; the vibration peak is 1100-1650 cm -1 In the range of 3444cm attributable to organic ligands -1 Belonging to the stretching vibration peak of water molecules in the compound.
FIG. 5 is an infrared spectrum of an octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material of example.
(III) the octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material [ Cu (H) 2 O) 2 H 4 (pybta) 4 ](PMo 12 O 40 ) 2 ·2H 2 And performing powder X-ray diffraction measurement on the O to obtain a powder X-ray diffraction spectrogram of the Keggin type copper phosphomolybdate crystalline material. As shown in fig. 6, the peak positions of the experimentally measured spectrum and the spectrum obtained by crystal simulation are consistent, and it can be determined that the experimentally obtained crystal structure is a structure analyzed by software, and the purity of the crystal is very high.
FIG. 6 is a powder X-ray diffraction pattern of the octahedral magic cube-like Keggin-type copper phosphomolybdate crystalline material of example.
(IV) an octahedral magic cube K prepared in example oneeggin type copper phosphomolybdate based crystalline material [ Cu (H) 2 O) 2 H 4 (pybta) 4 ](PMo 12 O 40 ) 2 ·2H 2 And O, performing electrochemical performance test. Through a three-electrode system at 0.5M (H) 2 SO 4 -Na 2 SO 4 ) In the electrolyte, the crystalline material is prepared into a modified glassy carbon electrode as a working electrode, a silver/silver chloride electrode as a reference electrode and platinum as a counter electrode. The working electrode was subjected to cyclic voltammetry measurements at sweep rates of 5, 10, 30, 50, 70, 90 and 100mV/s, respectively, as shown in FIG. 7. The cyclic voltammetry test result shows a plurality of pairs of redox peaks, which indicates that the crystalline material belongs to a pseudocapacitance super capacitor material. The specific capacitance values were 556, 488, 463, 431, 399, and 385F/g when the current densities were 1, 2, 3, 5, 8, and 10A/g, respectively, as shown in FIG. 8. When the current density is 10A/g, the constant current is charged/discharged for 1000 circles, and the specific capacitance of the crystalline material is kept at 92.2 percent, as shown in figure 9.
FIG. 7 shows an example of an octahedral magic cube-shaped Keggin-type copper phosphomolybdate crystalline material as a working electrode at 0.5M (H) 2 SO 4 -Na 2 SO 4 ) Cyclic voltammograms at sweep rates in the electrolyte of 5, 10, 30, 50, 70, 90 and 100mV/s, respectively.
FIG. 8 shows an example of an octahedral magic cube-like Keggin-type copper phosphomolybdate crystalline material as a working electrode at 0.5M (H) 2 SO 4 -Na 2 SO 4 ) And the current density in the electrolyte is respectively 1, 2, 3, 5, 8 and 10A/g.
FIG. 9 shows an example of an octahedral magic cube-shaped Keggin-type copper phosphomolybdate based crystalline material as a working electrode at 0.5M (H) 2 SO 4 -Na 2 SO 4 ) When the current density in the electrolyte is 10A/g, the specific capacitance retention rate of the constant current charging/discharging is 1000 circles.
In summary, the following steps: the octahedral magic cube-shaped Keggin type copper phosphomolybdate crystalline material is successfully prepared by a hydrothermal synthesis method, and is used for successfully preparing a supercapacitor electrode material.
Claims (9)
1. An octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material with a chemical formula of [ Cu (H) 2 O) 2 H 4 (pybta) 4 ](PMo 12 O 40 ) 2 ·2H 2 O, wherein the pybta is 1-pyridine-3-methylene-1H-benzotriazole; the appearance of the crystal is green block; the crystal is orthorhombic; the space group is Pbca; cell parameters of
b＝21.165(7)，
α＝90°，β＝90°，γ＝90°，
2. An octahedral magic cube-shaped Keggin type copper phosphomolybdate crystalline material is characterized in that a preparation method of a novel copper phosphomolybdate crystalline material is completed according to the following steps:
firstly, preparing a reaction solution with a pH value of 2.5-3.0: adding phosphomolybdic acid, copper acetate and 1-pyridine-3-methylene-1H-benzotriazole into distilled water, uniformly stirring, and then adjusting the pH value of the suspension to 2.5-3.0 to obtain a reaction solution with the pH value of 2.5-3.0;
the molar ratio of the phosphomolybdic acid to the copper acetate in the first step is as follows: 1.0 (6.0-7.0);
the molar ratio of the phosphomolybdic acid to the 1-pyridine-3-methylene-1H-benzotriazole in the first step is as follows: 1.0 (0.9-1.1);
the volume ratio of the phosphomolybdic acid substance to the distilled water in the first step is as follows: 0.16mmol:15 mL.
And secondly, transferring the reaction solution with the pH value of 2.5-3.0 prepared in the step one into a polytetrafluoroethylene reaction kettle, reacting at the temperature of 140 ℃ for 4 days, cooling the reaction solution to room temperature, and washing to obtain green blocky crystals, namely the octahedral magic cube-shaped Keggin type copper phosphomolybdate crystalline state material.
The chemical formula of the octahedral magic cube type Keggin type copper phosphomolybdate based crystalline material in the second step is [ Cu (H) 2 O) 2 H 4 (pybta) 4 ](PMo 12 O 40 ) 2 ·2H 2 O, wherein the pybta is 1-pyridine-3-methylene-1H-benzotriazole; the appearance of the crystal is green block; the crystal is orthorhombic; the space group is Pbca; cell parameters of
b＝21.165(7)，
α＝90°，β＝90°，γ＝90°，
3. The method for preparing the octahedral magic cube-shaped Keggin-type copper phosphomolybdate crystalline material according to claim 2, wherein the copper acetate is replaced by copper chloride, copper nitrate or copper sulfate in the first step.
4. The preparation method of the octahedral magic cube-shaped Keggin-type copper phosphomolybdate based crystalline material according to claim 2, wherein the molar ratio of the 1-pyridine-3-methylene-1H-benzotriazole, copper acetate and phosphomolybdic acid in the step one is 1.0 (6.0-7.0): 1.0, and the structural formula of the organic ligand 1-pyridine-3-methylene-1H-benzotriazole in the step one is shown in the specification
5. The method for synthesizing the octahedral magic cube-shaped Keggin-type copper phosphomolybdate crystalline material according to claim 2, wherein the volume ratio of the mole number of the phosphomolybdic acid to the distilled water in the step one is 0.16mmol:15 mL.
6. The method for synthesizing the octahedral magic cube-shaped Keggin-type copper phosphomolybdate crystalline material according to claim 2, wherein in the step one, the pH value of the reaction solution is adjusted to 2.5-3.0, and HNO with the substance amount concentration of 1mol/L is used 3 The solution and NaOH solution with the amount concentration of the substances of 1 mol/L.
7. The method for preparing the octahedral magic cube-shaped Keggin-type copper phosphomolybdate crystalline material according to claim 2, wherein the reaction temperature in the second step is 140-160 ℃ and the reaction time is 3-5 days.
8. An octahedral magic cube-shaped Keggin type copper phosphomolybdate based crystalline material is characterized in that unlike other types of polyacid-based metal organic crystalline material structures, copper ions in molecules of the material are respectively coordinated with coordinated water O1W and nitrogen atoms N2 and N4 in organic ligands to form a windmill-shaped metal organic ligand structural unit Cu (H) 2 O) 2 (pybta) 4 The hydrogen atoms on the oxygen atoms O1W and O2W of the water cluster in the molecule are respectively connected with PMo 12 O 40 3- The terminal oxygen O37, O18 and the bridging oxygen O31 on the polyacid anion form hydrogen bonds, and PMo is formed through the action of the hydrogen bonds 12 O 40 3- The polyacid clusters are distributed at six vertex positions of an octahedral structure taking copper ions as the center to form a primary structural unit in an octahedral magic cube shape.
9. Preparing a working electrode of a super capacitor made of an octahedral magic cube type Keggin type copper phosphomolybdate based crystalline material: and uniformly grinding 10mg of metal organic supermolecule phosphomolybdate polymer and 10mg of acetylene black, adding the mixture into 1mL of water, performing ultrasonic treatment for 2h to obtain uniformly dispersed mixed solution, dripping 10 mu L of the mixed solution on a pretreated glassy carbon electrode, standing at room temperature for 10h, then dripping 5 mu L of Nafion solution, and standing at room temperature for 1h to obtain the Keggin type copper phosphomolybdate crystalline material modified working electrode for electrochemical test.
The electrode prepared by the method can form multi-channel electron/proton transmission among organic ligands, polyacid, water clusters, metal and organic ligands, realizes the improvement of the specific capacitance value of the polyacid-based metal organic crystalline material, and realizes the method for preparing the working electrode of the polyacid-based water system supercapacitor.
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