CN108948100B - Preparation and application of two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials - Google Patents
Preparation and application of two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials Download PDFInfo
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
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Abstract
The invention relates to preparation and application of two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials. The invention aims to solve the problem that the capacity of a plurality of polyacid-based metal organic framework materials as electrode materials of a super capacitor is not high, and provides a material capable of improving the capacity of the polyacid-based metal organic framework materials as electrodes of the super capacitor and a preparation method thereof. The chemical formulas of the two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials are respectively [ Cu ]IICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O (1) and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2O (2), wherein btx is 1, 4-bis (triazol-1-methyl) benzene. The method comprises the following steps: the materials 1 and 2 are respectively prepared by adding polyacid, metal copper salt and organic ligand into distilled water, stirring uniformly, adjusting pH value, and reacting at 160 ℃ for 3 days. The invention can obtain two three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materials, and the specific capacitance values of the two materials are respectively measured to be 138.4F g under the current density of 2A/g‑1(1) And 82.1F g‑1(2) A research model is provided for improving the super-electric performance of the polyacid-based metal-organic framework material by only changing the polyacid species.
Description
Technical Field
The invention relates to preparation and application of two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials.
Background
Polyacids (POMs) are a class of polyoxometalate materials, generally have a rich structure, and have rapid multi-electron transfer capability. Therefore, the polyacid is widely researched in the aspects of catalysis, nanotechnology, biomedicine, material science and the like, and particularly shows a wide application prospect in the fields of electricity storage materials and the like. Keggin polyacid, one of the most traditional polyacid, has been considered for application in the field of electricity storage, such as phosphomolybdic acid exhibiting a reduction capability of 24 electrons during discharge, a theoretical capacity of 270 mAh/g, higher than that of Li, a commercial cathode material2CoO2(140 mAh/g). However, the high solubility of polyacid in water and poor conductivity inhibits its application in the field of water-based supercapacitors.
Metal-Organic Frameworks (MOFs) are a class of materials formed from Metal ions and Organic ligands, generally having a rich structure, especially a channel structure, and thus exhibiting a high specific surface area. Therefore, metal organic framework materials are highly favored in the field of catalysis and have been rapidly developed. However, its poor conductivity limits its application in the electrochemical field.
Therefore, polyacid is introduced into the Metal-Organic framework structure to form a polyacid-based Metal-Organic Frameworks (POMOFs), so that the multi-electron transfer capability of the POMs can be exerted, and the abundant structure and excellent performance of the MOFs can be inherited. Therefore, the two fields of POMs and MOFs are organically combined, the functions of the POMs and the MOFs can be perfectly combined, the advantages of each component can be fully exerted, and the defects of each component can be made up. In addition, the combination of a polyacid with a metal-organic framework material to produce a crystalline material rather than an amorphous material will further enhance the conductivity of the material. Meanwhile, the combination of different types of polyacid and the metal-organic framework material can also enable the whole material to have different electrochemical activities. Therefore, the two isomorphic materials provide a research model for only changing the types of the polyacid to improve the super-electric property of the polyacid-based metal-organic framework material, and have certain guiding significance for reasonably designing and assembling other novel polyacid-based metal-organic framework super-capacitor materials in the future.
Disclosure of Invention
The invention aims to solve the problem that the capacitance performance of a plurality of polyacid-based metal organic framework materials as electrode materials of a super capacitor is not high, and provides a preparation method of a material capable of improving the capacitance performance.
The two three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materials have chemical formulas of [ Cu ]IICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O (1) and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2O (2) wherein btx is 1, 4-bis (triazol-1-methyl) benzene; the crystal appearance is respectively in green and black blocks; the crystal systems are all triclinic crystal systems; the space groups are all P-1; cell parameters are respectivelya=13.2381(4) Å，b=13.4004(4) Å，c=14.6492(5) Å，α= 108.492(3)°，β=92.529(3)°，γ=97.260(3)°，V=2434.96(14) Å3Anda=13.126(2) Å，b=13.321(2)Å，c=14.537(2) Å，α=108.382(4)°，β=92.714(4)°，γ=96.899(4)°，V=2384.7(7) Å3。
the preparation and application of the two three-dimensional pseudo-rotaxane type polyacid-based metal organic frameworks as the electrode material of the supercapacitor are completed according to the following steps:
firstly, preparing a reaction solution with a pH value of 2: will K4Na6[α-1,2-PW10Ti2O39]2·14H2Adding O or silicomolybdic acid, copper salt and 1, 4-bis (triazole-1-methyl) benzene into distilled water, stirring uniformly, and then adjusting the pH value of the suspension to 2;
k in step (a)4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The molar ratio of O to the metal salt is 1 (1-3);
in the first stepSaid K4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The molar ratio of O to 1, 4-bis (triazole-1-methyl) benzene is 1 (1-2);
k in step (a)4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The volume ratio of the O substance to the distilled water is 0.12mmol (10-20 mL);
preparing two three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materials: transferring the reaction solution with the pH value of 2 prepared in the step one into a polytetrafluoroethylene reaction kettle, reacting for 3 days at the temperature of 160 ℃, cooling the temperature of the reaction solution to room temperature, and washing to obtain green or black blocky crystals, wherein the green or black blocky crystals have a three-dimensional pseudo-rotaxane type structure; the chemical formulas of the two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials in the step two are respectively [ Cu ]IICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O (1) and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2O (2) wherein btx is 1, 4-bis (triazol-1-methyl) benzene; the crystal appearance is respectively in green and black blocks; the crystal systems are all triclinic crystal systems; the space groups are all P-1; cell parameters are respectivelya=13.2381(4) Å，b=13.4004(4) Å，c=14.6492(5) Å，α= 108.492(3)°，β=92.529(3)°，γ=97.260(3)°，V=2434.96(14) Å3Anda=13.126(2) Å，b=13.321(2)Å，c=14.537(2) Å，α=108.382(4)°，β=92.714(4)°，γ=96.899(4)°，V=2384.7(7) Å3；
preparing two three-dimensional pseudo-rotaxane type polyacid-based metal organic frameworks as electrode materials of the supercapacitor: 2.5 mm of each of the two three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materialsUniformly grinding g of the metal oxide and 2.5 mg of acetylene black respectively, adding the ground metal oxide and the acetylene black into 500 microliters of water, performing ultrasonic treatment for 3 hours to obtain uniformly dispersed mixed liquid, dripping 10 microliters of the mixed liquid on a pretreated glassy carbon electrode, standing the glass carbon electrode at room temperature for 3 hours, then dripping 2.5 microliters of Nafion solution, and standing the glass carbon electrode at room temperature for 1 hour to obtain two working electrodes modified by the three-dimensional pseudo-rotaxane type polyacid-organic framework material respectively; under the condition that dilute sulfuric acid is used as an electrolyte solution, the modified working electrode in the step three is used for the first time to improve the capacitance performance of the polyacid-based metal organic framework material as the electrode material of the supercapacitor by only changing the polyacid species, and the specific capacitance values of the polyacid-based metal organic framework material are respectively 138.4F g under the current density of 2A/g-1(1) And 82.1F g-1(2) After 1000 cycles of charge and discharge, the specific capacitance value can be kept above the initial 97%.
Compared with the prior art, the implementation mode has the following characteristics:
firstly, the embodiment adopts a hydrothermal synthesis technology, and two ends of organic ligand 1, 4-bis (triazole-1-methyl) benzene with low original solubility in a water system are respectively connected through metal at a certain temperature and under a certain pressure, and then isolated polyoxometalate clusters can be connected in series, so that two novel three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials can be prepared for the first time; taking the material 2 as an example, a two-dimensional Cu2-btx-Cu3 structure and a one-dimensional Cu1-btx structure are connected in a polyacid mode, so that a three-dimensional covalently connected polyacid-based metal organic framework cavity structure is formed, and meanwhile, a free one-dimensional Cu4-btx structure is used as a molecular axis to penetrate into the three-dimensional covalently connected polyacid-based metal organic framework cavity structure to form a novel one-dimensional + three-dimensional quasi-rotaxane type polyacid-based metal organic framework material;
secondly, the two three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materials prepared by the embodiment are used as electrode materials of the super capacitor. The specific capacitance values at a current density of 2A/g were respectively found to be 138.4F g-1(1) And 82.1F g-1(2). Since the two electrode materials belong to homogeneous materials, the difference in specific capacitive properties is only derived from the difference in polyacid species. Thus, the results may indicate that for polyacid-based metal-organic frameworks crystalsThe specific capacitance performance of the material as a super capacitor electrode material is greatly influenced by the types of bulk materials and polyacid. Therefore, the method provides a research model for improving the performance of the super capacitor of the polyacid-based metal-organic framework material by only changing the polyacid species; thirdly, the embodiment can overcome the problems of high solubility and low conductivity of the traditional polyacid electrode material in water. The main reasons are: (1) the polyacid-based metal-organic framework material is prepared into crystals by a hydrothermal method, and is not only hardly dissolved in water any more, but also the conductivity of the polyacid-based metal-organic framework material is improved, so that the polyacid-based metal-organic framework material is favorably applied to the electrode material of the water system supercapacitor; (2) in the crystal material, the conductivity of the material is further improved by introducing nitrogen element in organic ligand 1, 4-bis (triazole-1-methyl) benzene; (3) the polyacid-based metal-organic framework material is hardly dissolved in water, so that higher cycling stability can be maintained in the constant-current charge and discharge process.
Drawings
FIG. 1 is a schematic diagram of three parts of a 3D covalent polyacid-based metal organic framework molecular cavity structure according to an example: a ') represents a 2D network structure consisting of a 78-atom Cu2-btx-Cu3-btx-Cu3-btx-Cu2-btx macro-ring structure, a ' ') represents a 1D structure consisting of Cu1-btx, and b) represents a 0D polyacid structure.
FIG. 2 is a schematic diagram of a pseudo-rotaxane structure formed by inserting free chain molecular axes of 1D into a cavity structure of a 3D covalent polyacid-based metal organic framework molecule in example I to form 1D + 3D.
FIG. 3 is an infrared spectrum of two materials with three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework in example.
FIG. 4 is a powder X-ray diffraction pattern of one or two of the materials having a three-dimensional pseudorotaxane-type polyacid-based metal-organic framework.
FIG. 5 shows two examples of three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materials as working electrodes at 1M H2SO4Cyclic voltammograms at sweep rates in the electrolyte of 10, 30, 50, 70 and 90mV/s, respectively.
FIG. 6 shows two examples of three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materials as workElectrodes, at 1M H2SO4And the current density in the electrolyte is respectively 2, 3, 5, 8 and 10A/g.
FIG. 7 shows two examples of three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materials as working electrodes, at 1M H2SO4When the current density in the electrolyte is 10A/g, the constant current charge/discharge is 1000-turn curve.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, which are only used for illustrating 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 chemical formulas of the two materials having a three-dimensional pseudorotaxane-type polyacid-based metal organic framework of the present embodiment are respectively [ Cu ]IICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O (1) and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2O (2) wherein btx is 1, 4-bis (triazol-1-methyl) benzene; the crystal appearance is respectively in green and black blocks; the crystal systems are all triclinic crystal systems; the space groups are all P-1; cell parameters are respectivelya=13.2381(4) Å，b=13.4004(4) Å，c=14.6492(5) Å，α= 108.492(3)°，β=92.529(3)°，γ=97.260(3)°，V=2434.96(14) Å3Anda=13.126(2) Å，b=13.321(2)Å，c=14.537(2) Å，α=108.382(4)°，β=92.714(4)°，γ=96.899(4)°，V=2384.7(7) Å3。
the second embodiment is as follows: the preparation method of the two polyacid-based metal-organic framework supercapacitor electrode materials of the embodiment is completed according to the following steps:
firstly, preparing a reaction solution with a pH value of 2: will K4Na6[α-1,2-PW10Ti2O39]2·14H2Adding O or silicomolybdic acid, copper salt and 1, 4-bis (triazole-1-methyl) benzene into distilled water, stirring uniformly, and then adjusting the pH value of the suspension to 2;
k in step (a)4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The molar ratio of O to the metal salt is 1 (1-3);
k in step (a)4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The molar ratio of O to 1, 4-bis (triazole-1-methyl) benzene is 1 (1-2);
k in step (a)4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The amount of O substance and the volume of distilled water are 0.12mmol (10-20 mL);
preparing two polyacid-based metal organic framework supercapacitor electrode materials: transferring the reaction solution with the pH value of 2 into a polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 3 days, cooling the reaction solution to room temperature, and washing to obtain green or black blocky crystals, wherein the green or black blocky crystals have a three-dimensional pseudo-rotaxane type structure; the chemical formulas of the two polyacid-based metal organic framework supercapacitor electrode materials in the step two are respectively [ Cu ]IICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O (1) and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2O (2) wherein btx is 1, 4-bis (triazol-1-methyl) benzene; the crystal appearance is respectively in green and black blocks; crystal system is allIs a triclinic system; the space groups are all P-1; cell parameters are respectivelya=13.2381(4) Å，b=13.4004(4) Å，c=14.6492(5) Å，α= 108.492(3)°，β=92.529(3)°，γ=97.260(3)°，V=2434.96(14) Å3Anda=13.126(2) Å，b=13.321(2)Å，c=14.537(2) Å，α=108.382(4)°，β=92.714(4)°，γ=96.899(4)°，V=2384.7(7) Å3；
and thirdly, taking two materials with three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials as working electrode materials, respectively taking 2.5 mg of the two materials and 2.5 mg of acetylene black, grinding the two materials uniformly together, adding the materials into 500 microliters of water, and carrying out ultrasonic treatment for 3 hours to obtain a uniformly dispersed mixed solution. Dripping 10 microliters of the mixed solution on the pretreated glassy carbon electrode, standing for 3 hours at room temperature, then dripping 2.5 microliters of Nafion solution, and standing for 1 hour at room temperature to obtain a polyacid-based metal organic framework material-modified working electrode which can be used for electrochemical testing; the glassy carbon electrode in the third step needs to be pretreated, and the specific process is as follows: first, the diameter of the material is 1, 0.3 and 0.05μPolishing a glassy carbon electrode by using m of aluminum oxide powder, performing ultrasonic treatment in absolute ethyl alcohol and deionized water for 2 minutes, completely cleaning, and finally performing cyclic voltammetry in a potassium ferricyanide and potassium chloride mixed solution, wherein the scanning potential range is 0-0.6V, and when the peak potential difference of an oxidation peak and a reduction peak in a cyclic voltammogram is less than 80 mV, performing post-modification on the glassy carbon electrode. 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: k in the present embodiment4Na6[α-1,2-PW10Ti2O39]2·14H2O was synthesized according to the method described in the literature (He, J.; Wang, X.; Chen, Y.; Liu, J.; Hu, N.; Jia, H. organic Chemistry Communications 2002, 5 (10), 796-. The other steps are the same as those in the second embodiment.
The fourth concrete implementation mode: the present embodiment is different from the second embodiment in that: the metal copper salt is cuprous chloride and cupric acetate respectively. The other steps are the same as those in the second to third embodiments.
The fifth concrete implementation mode: the present embodiment is different from the second embodiment in that: k in step one4Na6[α-1,2-PW10Ti2O39]2·14H2The molar ratio of O or silicomolybdic acid to the metal copper salt is 1: 2. The other steps are the same as those in the second to fourth embodiments.
The sixth specific implementation mode: the present embodiment is different from the second embodiment in that: k in step one4Na6[α-1,2-PW10Ti2O39]2·14H2The molar ratio of O or silicomolybdic acid to 1, 4-bis (triazol-1-methyl) benzene was 2: 3. The other steps are the same as those in the second to fifth embodiments.
The seventh embodiment: the present embodiment is different from the second embodiment in that: k in step one4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The amount of O substance and the volume of distilled water were 0.12mmol:15 mL. The other steps are the same as in embodiments two to six.
The specific implementation mode is eight: the present embodiment is different from the second embodiment in that: in the first step, the pH value of the reaction solution is adjusted to 2 by using HCl solution and NaOH solution, the quantity concentration of which is 1 mol/L. The other steps are the same as those in the second to seventh embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the preparation method of two kinds of metal organic framework materials with three-dimensional pseudo-rotaxane type polyacid comprises the following steps:
firstly, preparing a reaction solution with a pH value of 2: 0.12mmol of K4Na6[α-1,2-PW10Ti2O39]2·14H2O or silicomolybdic acid, 0.24 mmol of metalUniformly dispersing copper salt and 0.18mmol of 1, 4-bis (triazole-1-methyl) benzene into 15mL of distilled water, and adjusting the pH value of the reaction solution to 2 by using 1mol/L HCl solution and 1mol/L NaOH solution to obtain a reaction solution; in the first step, the pH value of the reaction solution is adjusted to 2 by using HCl solution and NaOH solution of which the quantity concentration of substances is 1 mol/L; k in step one4Na6[α-1,2-PW10Ti2O39]2·14H2O is synthesized according to the methods described in the literature (He, J.; Wang, X.; Chen, Y.; Liu, J.; Hu, N.; Jia, H. organic Chemistry Communications 2002, 5 (10), 796-;
preparing two crystal materials with three-dimensional pseudo-rotaxane type polyacid-based metal organic framework: transferring the prepared reaction solution with the pH value of 2 into a 25 mL polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 3 days, cooling the reaction solution to room temperature, and washing to obtain green or black blocky crystals, wherein the green or black blocky crystals have a three-dimensional pseudo-rotaxane type structure.
(one) two kinds of crystal materials with three-dimensional pseudo-rotaxane type polyacid-based metal organic framework prepared in the first example are subjected to structure determination:
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
FIG. 1 is a schematic diagram of three parts of a 3D covalent polyacid-based metal organic framework molecular cavity structure according to an example: a ') represents a 2D network structure consisting of a 78-atom Cu2-btx-Cu3-btx-Cu3-btx-Cu2-btx macro-ring structure, a ' ') represents a 1D structure consisting of Cu1-btx, and b) represents a 0D polyacid structure.
FIG. 2 is a schematic diagram of a pseudo-rotaxane structure formed by inserting free chain molecular axes into a 3D covalent polyacid-based metal organic framework molecular cavity structure in example 1D.
(II) two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework crystal materials prepared in example one [ CuIICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2And respectively carrying out infrared spectrum characterization on the O to obtain infrared spectrograms of the two crystal materials with the three-dimensional pseudo-rotaxane type polyacid-organic framework, wherein the infrared spectrograms are shown in figure 3. The infrared spectrogram shows that the material contains both polyacid characteristic peaks and organic ligand characteristic peaks.
FIG. 3 is an infrared spectrum of two crystal materials with three-dimensional pseudo-rotaxane type polyacid-organic frameworks in example.
(III) two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework crystal materials prepared in example one [ CuIICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2And (3) respectively carrying out powder X-ray diffraction measurement to obtain powder X-ray diffraction spectrums of the two crystal materials with the three-dimensional pseudo-rotaxane type polyacid-based metal organic framework, which are shown in figure 4. The powder X-ray diffraction spectrum shows that the peak positions of the experimentally measured spectrum and the spectrum obtained by crystal simulation are consistent, and the purity of the two materials is high.
FIG. 4 is a powder X-ray diffraction pattern of two crystal materials with three-dimensional pseudo-rotaxane type polyacid-based metal organic framework in example.
(IV) two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework crystal materials prepared in example one [ CuIICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2O separately carrying out electrochemical performance measurementAnd (6) testing. By means of a three-electrode system, at 1M H2SO4In the electrolyte, the modified glassy carbon electrodes prepared from the two materials are respectively used as working electrodes, a silver/silver chloride electrode is used as a reference electrode, and platinum is used as a counter electrode. Cyclic voltammetry tests were performed on both crystalline materials at sweep rates of 10, 30, 50, 70 and 90mV/s, respectively, as shown in fig. 5. The cyclic voltammetry test results show a plurality of pairs of redox peaks, which indicates that the two materials both belong to pseudocapacitance super capacitor materials. Specific capacitance values were 82.1, 77.1, 71.4, 67.4, and 64.3F/g (1) and 138.4, 138.1, 135.7, 133.3, and 132.6F/g (2), respectively, when the current densities were 2, 3, 5, 8, and 10A/g, respectively, as shown in FIG. 6. When the current density is 10A/g, the constant current is charged/discharged for 1000 circles, and the specific capacitance of the two polyacid-based crystal materials is kept to be more than 97% of the initial value, as shown in figure 7.
FIG. 5 shows two examples of crystal materials with three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework as working electrodes, at 1M H2SO4Cyclic voltammograms at sweep rates in the electrolyte of 10, 30, 50, 70 and 90mV/s, respectively.
FIG. 6 shows two examples of crystal materials with three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework as working electrodes, at 1M H2SO4And the current density in the electrolyte is respectively 2, 3, 5, 8 and 10A/g.
FIG. 7 shows two examples of crystal materials with three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework as working electrodes, at 1M H2SO4When the current density in the electrolyte is 10A/g, the constant current charge/discharge is 1000-turn curve.
In summary, the following steps: the two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework crystal materials of the first embodiment are successfully prepared by a hydrothermal synthesis method, and when the two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework crystal materials are respectively used as electrode materials of a super capacitor, the specific capacitance values of the two materials are greatly different, and the difference shows that the specific capacitance performance of the super capacitor is greatly influenced by the types of polyacid for the polyacid-based metal organic framework crystal materials. The conclusion has certain academic significance and application prospect for designing and synthesizing more materials with the performance of the super capacitor in the future.
Claims (8)
1. Two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials with chemical formulas of [ Cu ] respectivelyIICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O (1) and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2O (2) wherein btx is 1, 4-bis (triazol-1-methyl) benzene; the crystal appearance is respectively green and black blocks; the crystal systems are all triclinic crystal systems; the space groups are all P-1; cell parameters are respectively
α＝108.492(3)°，β＝92.529(3)°，γ＝97.260(3)°，
And
α＝108.382(4)°，β＝92.714(4)°，γ＝96.899(4)°，
2. the preparation methods of the two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials are characterized in that the preparation methods of the two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials are completed according to the following steps:
firstly, preparing a reaction solution with a pH value of 2: will K4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2Adding O, copper salt and 1, 4-bis (triazole-1-methyl) benzene into distilled water, stirring uniformly, and then adjusting the pH value of the suspension to 2;
k in step (a)4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The molar ratio of O to the metal copper salt is 1 (1-3);
k in step (a)4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The molar ratio of O to 1, 4-bis (triazole-1-methyl) benzene is 1 (1-2);
k in step (a)4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The volume ratio of the O substance to the distilled water is 0.12mmol (10-20 mL);
preparing two three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materials: adding the reaction solution with the pH value of 2 prepared in the step one into a polytetrafluoroethylene reaction kettle, reacting for 3 days at the temperature of 160 ℃, cooling the temperature of the reaction solution to room temperature, and washing to obtain green or black blocky crystals, wherein the green or black blocky crystals have a three-dimensional pseudo-rotaxane type structure;
the chemical formulas of the two three-dimensional pseudo-rotaxane type polyacid-based metal-organic framework materials in the step two are respectively [ Cu ]IICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O (1) and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2O (2) wherein btx is 1, 4-bis (triazol-1-methyl) benzene; the crystal appearance is respectively green and black blocks; the crystal systems are all triclinic crystal systems; the space groups are all P-1; cell parameters are respectively
α＝108.492(3)°，β＝92.529(3)°，γ＝97.260(3)°，
And
α＝108.382(4)°，β＝92.714(4)°，γ＝96.899(4)°，
3. the method for preparing two kinds of three-dimensional pseudorotaxane-type polyacid-based framework materials according to claim 2, wherein the copper metal salts in the first step are cuprous chloride and cupric acetate, respectively.
4. The method for preparing two three-dimensional pseudorotaxane-type polyacid-based metal organic framework materials according to claim 2, wherein K is defined in step one4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The molar ratio of O to the metallic copper salt is 1: 2.
5. The method for preparing two three-dimensional pseudorotaxane-type polyacid-based metal organic framework materials according to claim 2, wherein K is defined in step one4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The molar ratio of O to 1, 4-bis (triazol-1-methyl) benzene was 2: 3.
6. The method of claim 2The preparation method of the two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials is characterized in that K is obtained in the step one4Na6[α-1,2-PW10Ti2O39]2·14H2O or H4[SiMo12O40]·6H2The molar amount of O and the volume of distilled water were 0.12mmol:15 mL.
7. The method for preparing two kinds of three-dimensional pseudorotaxane-type polyacid-based metal organic framework materials according to claim 2, wherein the process of adjusting the pH of the reaction solution to 2 in the first step is adjusted by using HCl solution with a concentration of the substance of 1mol/L to 6mol/L and NaOH solution with a concentration of the substance of 1mol/L to 6 mol/L.
8. The preparation method of the working electrode of the supercapacitor by using the two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials is characterized in that the preparation method of the working electrode of the two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials is completed according to the following steps:
firstly, respectively taking 2.5 mg of two three-dimensional pseudo-rotaxane type polyacid-based metal organic framework materials and 2.5 mg of acetylene black, grinding uniformly, adding into 500 microliters of water, and carrying out ultrasonic treatment for 3 hours to obtain two uniformly dispersed mixed solutions which are respectively marked as a mixed solution A and a mixed solution B;
the two kinds of three-dimensional pseudorotaxane type polyacid-based metal organic framework materials in the first step are [ Cu ] as described in claim 1IICuI 3(H2O)2(btx)5(PWVI 10WV 2O40)]·2H2O (1) and [ Cu ]II 2CuI 2(btx)5(SiMoVI 10MoV 2O40)]·6H2O(2)；
And secondly, dripping 10 microliters of the mixed solution A or the mixed solution B on the pretreated glassy carbon electrode, standing for 3 hours at room temperature, then dripping 2.5 microliters of Nafion solution on the surface of the glassy carbon electrode, and continuously standing for 1 hour at room temperature to respectively obtain two working electrodes modified by the three-dimensional pseudo-rotaxane type polyacid-based metal organic framework material.
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