CN114496587B - Polyacid metal organic framework crystal and preparation method and application thereof - Google Patents
Polyacid metal organic framework crystal and preparation method and application thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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- 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 OR LIGHT-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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- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
Abstract
A polyacid metal organic framework crystal and a preparation method and application thereof relate to a polyacid crystal and a preparation method and application thereof. Solves the problems of low specific capacitance and poor stability of polyacid as electrode material. The chemical formula of the polyacid metal organic framework crystal is [ AsW ] 12 O 40 ][Cu 5 (pz) 6 (H 2 O) 4 ]. The method comprises the following steps: h 2 WO 4 、NaAsO 2 、CuCl 2 ·2H 2 Placing O and pyrazine in a container, adding solvent, adjusting pH, and crystallizing. Application: is used for preparing electrode materials.
Description
Technical Field
The invention relates to polyacid crystals, a preparation method and application thereof.
Background
With the rapid development of global economy, there is an urgent need for efficient, clean and sustainable new energy sources, and super capacitors as new power sources are often used for emerging wearable electronic devices, multi-power automobiles, intermittent energy supply balance systems, and the like. The stable electrochemical performance of the supercapacitor derives from the electrode material, and the composition and structure of the electrode material are the central factors determining the performance of the supercapacitor. Therefore, research on flexible electrode materials with high energy density, high power density and long cycle life is one of important links of national economic development.
Polyacids (POMs) are molecular cluster compounds with nanometer size, have various structures, strong modifiable property and adjustable physicochemical properties, and the properties lead the polyacids to have wide application prospects in various fields such as catalysis, electrochemistry and the like. In addition, POMs have molecular conductivity capability that allows for rapid and reversible multiple electron transfer reactions without changing structure, which makes them exhibit application potential in the supercapacitor field. However, polyacid crystals have low specific capacitance and poor cycling stability as electrode materials, limiting their application in the field of supercapacitors.
In recent years, in order to overcome these disadvantages, researchers have been working on compounding POMs with structurally stable, high conductivity carbon materials, and experimental results have shown that the specific capacitance and the cyclic stability of such composite structures are not ideal.
Disclosure of Invention
The invention aims to solve the problems of low specific capacitance and poor stability of polyacid serving as an electrode material, and provides a polyacid metal organic framework crystal, a preparation method and application thereof.
A polyacid metal-organic framework crystal has a chemical formula of [ AsW ] 12 O 40 ][Cu 5 (pz) 6 (H 2 O) 4 ]Wherein pz is pyrazine, the crystal system is triclinic system, the space group is P-1, and the unit cell parameter is α＝61.5250(10)°，β＝71.8400(10)°，γ＝70.6120(10)°。
The preparation method of the polyacid metal organic framework crystal comprises the following steps:
1. will H 2 WO 4 、NaAsO 2 、CuCl 2 ·2H 2 Placing O and pyrazine in a container, adding a solvent, stirring at room temperature and stirring speed of 200-300 rpm until the mixture is uniform, and finally regulating pH to 4.5-6.5 to obtain a reaction solution;
said H 2 WO 4 With NaAsO 2 The molar ratio of (3) is 1 (0.37-0.57);
said H 2 WO 4 With CuCl 2 ·2H 2 The mol ratio of O is 1 (0.75-0.95);
said H 2 WO 4 The molar ratio of the compound to the pyrazine is 1 (0.74-0.94);
said H 2 WO 4 The mol ratio of the solvent to the solvent is 1 (0.31-0.51);
2. adding the reaction solution into a polytetrafluoroethylene reaction kettle according to the volume filling degree of the polytetrafluoroethylene reaction kettle being 65-85%, crystallizing for 85-100 h at 150-165 ℃, naturally cooling to room temperature to obtain blue blocky crystals, repeatedly flushing the crystals with distilled water, and drying to obtain polyacid metal-organic frame crystals;
the chemical formula of the polyacid metal organic framework crystal is [ AsW ] 12 O 40 ][Cu 5 (pz) 6 (H 2 O) 4 ]Wherein pz is pyrazine, the crystal system is triclinic system, the space group is P-1, and the unit cell parameter is α＝61.5250(10)°，β＝71.8400(10)°，γ＝70.6120(10)°。
The application of polyacid metal organic frame crystal is used for preparing electrode materials.
The beneficial effects of the invention are as follows: the invention constructs POMOFs polyacid metal organic frame, prepares a novel Keggin structure arsenic tungsten metal organic frame crystal, [ AsW ] 12 O 40 ][Cu 5 (pz) 6 (H 2 O) 4 ](abbreviated as AsW) 12 ) So that the composite material is compounded with PPy and fully utilizes the AsW 12 And PPy, coating it on carbon cloth (abbreviated as CC) to obtain AsW 12 /PPy/CC electrode. The electrochemical activity and the cycling stability of the polyacid-based electrode material are improved. When the current density is 1 A.g -1 When the specific capacitance reaches 1510 F.g -1 . At a current density of 2 A.g -1 Next, asW is carried out 12 The ratio PPy/CC is used as a working electrode to circulate 5000 times, and the specific capacitance retention rate is 96.7 percent.
The invention is used for polyacid metal organic framework crystals, and a preparation method and application thereof.
Drawings
FIG. 1 shows an AsW prepared in example one 12 An ellipsoidal diagram of the crystal;
FIG. 2 is a schematic diagram of a metal organic framework composed of copper atoms and pyrazine organic ligands according to an embodiment;
FIG. 3 is an AsW prepared in example one 12 Schematic representation of the three-dimensional structure of the crystal;
FIG. 4 shows an AsW prepared in example one 12 XRD pattern of the crystal, 1 is simulation, 2 is experiment;
FIG. 5 is an AsW prepared in example one 12 Infrared spectrogram of the crystal;
FIG. 6 shows an AsW prepared in example two steps one 12 A profile of/PPy;
FIG. 7 is an AsW prepared in example two 12 The cyclic voltammogram of the/PPy/CC electrode is 1 to 5 mV.s -1 2 is 10 mV.s -1 3 is 20 mV.s -1 4 is 50 mV.s -1 ；
FIG. 8 is an AsW prepared in example two 12 Constant current charge-discharge curve of/PPy/CC electrode, 1 is 1A.g -1 2 is 2A.g -1 3 is 5 A.g -1 4 is 10A.g -1 ；
FIG. 9 is an AsW prepared in example two 12 Nyquist curve of the/PPy/CC electrode;
FIG. 10 is an AsW prepared in example two 12 Cycling stability curve of/PPy/CC electrode.
Detailed Description
The first embodiment is as follows: the polyacid metal organic framework crystal has a chemical formula of [ AsW ] 12 O 40 ][Cu 5 (pz) 6 (H 2 O) 4 ]Wherein pz is pyrazine and the crystal system is triclinic system, emptyThe inter group is P-1, and the unit cell parameter isα＝61.5250(10)°，β＝71.8400(10)°，γ＝70.6120(10)°。
In order to improve the electrochemical properties of the POMs, the transition metal complex is combined with the POMs as a secondary structure to generate POMOFs, and compared with the POMOFs and the POMs, the POMOFs and the POMs have large specific surface area and more holes, so that more reaction sites can be provided for electrochemical energy storage, and electron transmission is facilitated. Polypyrrole (PPy) has high conductivity, good environmental stability, reversible electrochemical oxidation-reduction property and strong charge storage capacity, and is an ideal electrode material of a polymer secondary battery, so that the novel POMOFs is designed, and is compounded with PPy and coated on carbon cloth to prepare the POMOFs/PPy/CC electrode, and the POMOFs/PPy/CC electrode possibly has good electrochemical energy storage property.
The beneficial effects of this embodiment are: the embodiment constructs a POMOFs polyacid metal organic framework, prepares a novel Keggin structure arsenic-tungsten metal organic framework crystal, [ AsW ] 12 O 40 ][Cu 5 (pz) 6 (H 2 O) 4 ](abbreviated as AsW) 12 ) So that the composite material is compounded with PPy and fully utilizes the AsW 12 And PPy, coating it on carbon cloth (abbreviated as CC) to obtain AsW 12 /PPy/CC electrode. The electrochemical activity and the cycling stability of the polyacid-based electrode material are improved. When the current density is 1 A.g -1 When the specific capacitance reaches 1510 F.g -1 . At a current density of 2 A.g -1 Next, asW is carried out 12 The ratio PPy/CC is used as a working electrode to circulate 5000 times, and the specific capacitance retention rate is 96.7 percent.
The second embodiment is as follows: the preparation method of the polyacid metal organic framework crystal comprises the following steps:
1. will H 2 WO 4 、NaAsO 2 、CuCl 2 ·2H 2 Placing O and pyrazine in a container, adding solvent, stirring at room temperature and stirring speed of 200-300 rpmUniformly, and finally, regulating the pH value to be 4.5-6.5 to obtain a reaction solution;
said H 2 WO 4 With NaAsO 2 The molar ratio of (3) is 1 (0.37-0.57);
said H 2 WO 4 With CuCl 2 ·2H 2 The mol ratio of O is 1 (0.75-0.95);
said H 2 WO 4 The molar ratio of the compound to the pyrazine is 1 (0.74-0.94);
said H 2 WO 4 The mol ratio of the solvent to the solvent is 1 (0.31-0.51);
2. adding the reaction solution into a polytetrafluoroethylene reaction kettle according to the volume filling degree of the polytetrafluoroethylene reaction kettle being 65-85%, crystallizing for 85-100 h at 150-165 ℃, naturally cooling to room temperature to obtain blue blocky crystals, repeatedly flushing the crystals with distilled water, and drying to obtain polyacid metal-organic frame crystals;
the chemical formula of the polyacid metal organic framework crystal is [ AsW ] 12 O 40 ][Cu 5 (pz) 6 (H 2 O) 4 ]Wherein pz is pyrazine, the crystal system is triclinic system, the space group is P-1, and the unit cell parameter is α＝61.5250(10)°，β＝71.8400(10)°，γ＝70.6120(10)°。
And a third specific embodiment: the second difference between this embodiment and the specific embodiment is that: the solvent in the first step is distilled water. The other steps are the same as those of the second embodiment.
The specific embodiment IV is as follows: the present embodiment differs from the second or third embodiment in that: in the first step, the pH is adjusted to 4.5-6.5 by using the concentration of 0.1 mol.L -1 ～0.3mol·L -1 Is regulated by HCl of (C). The other steps are the same as those of the second or third embodiment.
Fifth embodiment: the application of the polyacid metal organic framework crystal in the embodiment mode is that the polyacid metal organic framework crystal is used for preparing electrode materials.
Specific embodiment six: the fifth difference between this embodiment and the specific embodiment is that: the polyacid metal organic framework crystal is used for preparing an electrode material and comprises the following steps:
1. preparing slurry:
mixing polyacid metal organic frame crystal with polypyrrole, grinding in an agate mortar, ultrasonically mixing, then placing in a reaction kettle, and reacting for 8-11 h at 160-190 ℃ to obtain AsW 12 PPy, asW 12 Mixing PPy, super P and polyvinylidene fluoride to obtain a mixture, and dropwise adding N-methyl-2-pyrrolidone into the mixture to obtain slurry;
the mass ratio of the polyacid metal organic framework crystal to the polypyrrole is 1 (0.45-0.60); the AsW 12 The mass ratio of the PPy to the Super P is 1 (0.27-0.31); the AsW 12 The mass ratio of PPy to polyvinylidene fluoride is 1 (0.13-0.16); the volume ratio of the mass of the mixture to the N-methyl-2-pyrrolidone is 1mg (0.25-0.35) mL;
2. preparation of AsW 12 /PPy/CC electrode:
immersing the carbon cloth in concentrated nitric acid, heating for 1-3 h at 80-110 ℃, finally cleaning to obtain treated carbon cloth, coating the slurry on the treated carbon cloth, and finally drying to obtain AsW 12 /PPy/CC electrode. The other steps are the same as those of the fifth embodiment.
Seventh embodiment: the present embodiment differs from the fifth or sixth embodiment in that: the polypyrrole in the first step is specifically prepared by the following steps: dissolving methyl orange in deionized water to obtain methyl orange solution, and stirring at 1800-2100 rpm in ice bath to obtain FeCl solution 3 Adding into methyl orange solution, stirring, adding pyrrole, stirring for 22-28 hr under ice bath at 600-700 rpm and darkness, filtering, removing ethanolWashing with ionized water for multiple times and drying to obtain polypyrrole; the volume ratio of the methyl orange to the deionized water is 1g (1150-1250 mL); the methyl orange and FeCl 3 The mass ratio of (4) to (5) is 1; the volume ratio of the methyl orange to the pyrrole is 1g (1.8-2.2) mL. The other steps are the same as those of the fifth or sixth embodiment.
Eighth embodiment: the present embodiment differs from the fifth to seventh embodiments in that: the ultrasonic mixing in the first step is specifically ultrasonic for 20-40 min under the conditions that the ultrasonic power is 40-60W and the working frequency is 30-50 KHz. The other steps are the same as those of the fifth to seventh embodiments.
Detailed description nine: the present embodiment differs from the fifth to eighth embodiments in that: the second step of cleaning is to ultrasonically clean the waste water three times by using ethanol and distilled water respectively; the drying in the second step is specifically carried out for 5-7 h under the condition that the temperature is 100-120 ℃; and in the second step, the mass percentage of the concentrated nitric acid is 65-68%. The other steps are the same as those of the fifth to eighth embodiments.
Detailed description ten: the present embodiment differs from one of the fifth to ninth embodiments in that: in the second step, the coating amount is 2mg/cm 2 ～4mg/cm 2 The slurry was coated on the treated carbon cloth. The other steps are the same as those of the fifth to ninth embodiments.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the polyacid metal organic framework crystal is prepared by the following steps:
1. 0.6014g (2.41 mmol) of H 2 WO 4 、0.1478g(1.14mmol)NaAsO 2 、0.3451g(2.02mmol)CuCl 2 ·2H 2 Placing O and 0.1606g (2.01 mmol) pyrazine in a container, adding 18mL (1.00 mol) solvent, stirring at room temperature and stirring speed of 250 rpm until the mixture is uniform, and finally regulating pH to 5.6 to obtain a reaction solution;
2. adding the reaction solution into a 20mL polytetrafluoroethylene reaction kettle according to the volume filling degree of the polytetrafluoroethylene reaction kettle being 70%, crystallizing for 96 hours at 160 ℃, naturally cooling to room temperature to obtain blue blocky crystals, repeatedly flushing the crystals with distilled water, and drying to obtain polyacid metal-organic framework crystals;
the solvent in the first step is distilled water;
in the first step, the pH was adjusted to 5.6 by using a concentration of 0.2 mol.L -1 Is regulated by HCl of (C).
The polyacid metal organic framework crystal prepared in example one is abbreviated as AsW 12 。
The polyacid metal organic framework crystals prepared by this example were calculated to give a yield of 32% calculated as tungsten.
The polyacid metal organic framework crystal prepared in the first embodiment is subjected to crystal structure measurement, and the specific process is as follows:
selecting a crystal with proper size (0.24X0.26X0.26 mm), placing on a Bruker Smart CCD surface detection X-ray diffractometer in Germany, scanning in omega mode, analyzing the crystal structure by using SHELXL-2015 software package program by adopting a direct method, obtaining the position of hydrogen atom by adopting a theoretical hydrogenation method, and obtaining the position of hydrogen atom by adopting a least square method F 2 And (5) finishing.
TABLE 1AsW 12 Crystallographic parameters of the crystal
R 1 ＝∑||F o |-|F c ||/∑|F o |,wR 2 ＝{Rw[(F o ) 2 -(F c ) 2 ] 2 /Rw[(F o ) 2 ] 2 } 1/2
FIG. 1 shows an AsW prepared in example one 12 An ellipsoidal diagram of the crystal; as can be seen from the figure, asW 12 The crystal is composed of polyanion with Keggin structure, copper atom andpyrazine organic ligands.
FIG. 2 is a schematic diagram of a metal organic framework composed of copper atoms and pyrazine organic ligands according to an embodiment; from the figure, it can be seen that copper atoms and pyrazines form a two-dimensional layered metal organic framework.
FIG. 3 is an AsW prepared in example one 12 Schematic representation of the three-dimensional structure of the crystal; from the figure, it can be seen that polyanions are embedded in the Cu-pz metal organic framework to form a three-dimensional structure.
FIG. 4 shows an AsW prepared in example one 12 XRD pattern of the crystal, 1 is simulation, 2 is experiment; as can be seen from the figure, asW 12 The X-ray powder diffraction of the crystal material is consistent with the key diffraction peak positions in the diffraction pattern fitted by the X-ray single crystal diffraction. Wherein the intensities of the diffraction peaks are slightly different due to the preferred orientation of the single crystal powder, and the test result shows that the AsW 12 The crystals are pure phases.
FIG. 5 is an AsW prepared in example one 12 Infrared spectrogram of the crystal; as can be seen, 948cm -1 The absorption peak average belongs to the characteristic vibration peak of v (As-O), 871-554cm -1 The absorption peak average attribute between the two is v (W-O t )，ν(W-O b )，ν(W-O c ) Is characterized by a peak of vibration; 2974-1056cm -1 Absorption bands within the range are attributed to the characteristic vibrational peaks of pyrazine; at 3453cm -1 The broad peak of (2) is the characteristic vibration peak of water molecule.
Embodiment two: the application of polyacid metal organic frame crystal is used for preparing electrode materials.
The polyacid metal organic framework crystal is used for preparing an electrode material and comprises the following steps:
1. preparing slurry:
mixing 3.33mg of polyacid metal organic framework crystal and 1.67mg of polypyrrole, grinding in an agate mortar, ultrasonically mixing, then placing in a reaction kettle, and reacting for 10 hours at 180 ℃ to obtain AsW 12 PPy, 5mg AsW 12 PPy, super P and polyvinylidene fluoride to obtain a mixture, 2mL of N-methyl-2-pyrrolidone was added dropwise to 7.14mg of the mixtureObtaining slurry;
the AsW 12 The mass ratio of PPy to Super P is 7:2; the AsW 12 The mass ratio of PPy to polyvinylidene fluoride is 7:1;
2. preparation of AsW 12 /PPy/CC electrode:
immersing carbon cloth in concentrated nitric acid, heating at 100deg.C for 2 hr, cleaning to obtain treated carbon cloth, coating slurry on the treated carbon cloth, and oven drying to obtain AsW 12 /PPy/CC electrode.
The polypyrrole in the first step is specifically prepared by the following steps: 0.05g of methyl orange is dissolved in 60mL of deionized water to obtain methyl orange solution, and 0.243g of FeCl is added under the conditions of ice bath and stirring speed of 2000 rpm 3 Adding into methyl orange solution, stirring, adding 105 μl of pyrrole, stirring under ice bath at 650 rpm in dark for 24 hr, filtering, washing with ethanol and deionized water for several times, and drying to obtain polypyrrole.
The ultrasonic mixing in the first step is specifically ultrasonic for 30min under the conditions that the ultrasonic power is 50W and the working frequency is 40 KHz.
The second step of cleaning is to ultrasonically clean the waste water three times by using ethanol and distilled water respectively; the drying in the second step is specifically carried out for 6 hours under the condition that the temperature is 110 ℃; and in the second step, the mass percentage of the concentrated nitric acid is 65-68%.
In the second step, the coating amount is 3.5mg/cm 2 The slurry was coated on a treated carbon cloth (1 cm. Times.1 cm).
FIG. 6 shows an AsW prepared in example two steps one 12 A profile of/PPy; as can be seen from the figure, asW 12 Attached to PPy.
Electrochemical testing: platinum sheet was used as a counter electrode, ag/AgCl as a reference electrode, asW prepared in example two 12 the/PPy/CC electrode is a working electrode, and the electrolyte is 0.5M H 2 SO 4 A solution. Cyclic Voltammograms (CVs), constant current charge-discharge (GCD) and Electrochemical Impedance Spectroscopy (EIS) were tested, respectively.
FIG. 7 is an AsW prepared in example two 12 The cyclic voltammogram of the/PPy/CC electrode is 1 to 5 mV.s -1 2 is 10 mV.s -1 3 is 20 mV.s -1 4 is 50 mV.s -1 The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from the figure, the redox reaction occurs, and the redox peak is remarkable. In addition, as the sweep rate increases, the anode/cathode peak potential shifts to higher/lower voltages, exhibiting good capacitive behavior and storage characteristics.
FIG. 8 is an AsW prepared in example two 12 Constant current charge-discharge curve of/PPy/CC electrode, 1 is 1A.g -1 2 is 2A.g -1 3 is 5 A.g -1 4 is 10A.g -1 The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from the graph, the calculated specific capacitances are 1510 F.g -1 、1440F·g -1 、1276F·g -1 And 1075 F.g -1 When the current density is 1 A.g -1 The specific capacitance is the largest.
FIG. 9 is an AsW prepared in example two 12 Nyquist curve of the/PPy/CC electrode; from the figure, the solution resistance in the high frequency region is about 0.75Ω, the slope in the low frequency region is close to 45 °, and the electrode process is controlled by both the charge transfer and diffusion processes.
FIG. 10 is an AsW prepared in example two 12 a/PPy/CC electrode cycling stability curve; as can be seen from the graph, the current density was 2 A.g -1 Next, asW is carried out 12 The ratio of the specific capacitance retention rate obtained by cycling/PPy/CC as a working electrode for 5000 times is 96.7%, which shows that AsW 12 The PPy/CC has better cycle stability as a working electrode.
Claims (10)
1. A polyacid metal-organic framework crystal is characterized in that the chemical formula of the polyacid metal-organic framework crystal is [ AsW ] 12 O 40 ][Cu 5 (pz) 6 (H 2 O) 4 ]Wherein pz is pyrazine, the crystal system is triclinic, the space group is P-1, the unit cell parameters are a= 11.8287 (8) a, b= 12.4958 (8) a, c= 12.5578 (8) a, α= 61.5250 (10) °, β= 71.8400 (10) °, γ= 70.6120 (10) °.
2. The method for preparing a polyacid metal-organic framework crystal according to claim 1, which is characterized by comprising the following steps:
1. will H 2 WO 4 、NaAsO 2 、CuCl 2 ·2H 2 Placing O and pyrazine in a container, adding a solvent, stirring at room temperature and stirring speed of 200-300 rpm until the mixture is uniform, and finally regulating pH to 4.5-6.5 to obtain a reaction solution;
said H 2 WO 4 With NaAsO 2 The molar ratio of (1), (0.37-0.57);
said H 2 WO 4 With CuCl 2 ·2H 2 The mol ratio of O is 1 (0.75-0.95);
said H 2 WO 4 The molar ratio of the compound to the pyrazine is 1 (0.74-0.94);
said H 2 WO 4 The molar ratio of the solvent to the solvent is 1 (0.31-0.51);
2. adding the reaction solution into a polytetrafluoroethylene reaction kettle according to the volume filling degree of the polytetrafluoroethylene reaction kettle being 65% -85%, crystallizing for 85-100 hours at the temperature of 150-165 ℃, naturally cooling to room temperature to obtain blue blocky crystals, repeatedly flushing the crystals with distilled water, and drying to obtain polyacid metal organic frame crystals.
3. The method for preparing a polyacid metal-organic framework crystal according to claim 2, wherein the solvent in the first step is distilled water.
4. The method for preparing a polyacid metal organic framework crystal according to claim 2, wherein the step one of adjusting the pH to 4.5-6.5 is performed at a concentration of 0.1 mol.L -1 ~0.3mol·L -1 Is regulated by HCl of (C).
5. Use of a polyacid metal-organic framework crystal according to claim 1, characterized in that the polyacid metal-organic framework crystal is used for the preparation of electrode materials.
6. The use of a polyacid metal organic framework crystal according to claim 5, characterized in that the polyacid metal organic framework crystal is used for preparing an electrode material by the following steps:
1. preparing slurry:
mixing polyacid metal organic frame crystal with polypyrrole, grinding in an agate mortar, ultrasonically mixing, then placing in a reaction kettle, and reacting for 8-11 h at 160-190 ℃ to obtain AsW 12 PPy, asW 12 Mixing PPy, super P and polyvinylidene fluoride to obtain a mixture, and dropwise adding N-methyl-2-pyrrolidone into the mixture to obtain slurry;
the mass ratio of the polyacid metal organic framework crystal to the polypyrrole is 1 (0.45-0.60); the AsW 12 The mass ratio of the PPy to the Super P is 1 (0.27-0.31); the AsW 12 The mass ratio of PPy to polyvinylidene fluoride is 1 (0.13-0.16); the volume ratio of the mass of the mixture to the N-methyl-2-pyrrolidone is 1mg (0.25-0.35) mL;
2. preparation of AsW 12 /PPy/CC electrode:
immersing the carbon cloth in concentrated nitric acid, heating for 1-3 hours at the temperature of 80-110 ℃, finally cleaning to obtain treated carbon cloth, coating the slurry on the treated carbon cloth, and finally drying to obtain the AsW 12 /PPy/CC electrode.
7. The use of a polyacid metal organic framework crystal according to claim 6, characterized in that the polypyrrole in step one is specifically prepared by the following steps: dissolving methyl orange in deionized water to obtain methyl orange solution, and stirring at ice bath speed of 1800-2100 rpm to obtain FeCl solution 3 Adding the polypyrrole into methyl orange solution, stirring uniformly, adding the pyrrole, stirring for 22-28 hours under ice bath, stirring speed of 600-700 rpm and darkness, filtering, washing for many times with ethanol and deionized water, and drying to obtain polypyrrole; the volume ratio of the methyl orange to the deionized water is 1g (1150-1250 mL); the methyl orange and FeCl 3 Is of the mass ratio of1 (4-5); the volume ratio of the methyl orange to the pyrrole is 1g (1.8-2.2) mL.
8. The application of the polyacid metal organic frame crystal according to claim 6, wherein the ultrasonic mixing in the step one is performed under the conditions that ultrasonic power is 40-60W and working frequency is 30-50 KHz, and ultrasonic treatment is performed for 20-40 min.
9. The use of a polyacid metal organic framework crystal according to claim 6, characterized in that the washing in step two is three times of ultrasonic washing with ethanol and distilled water, respectively; the drying in the second step is specifically carried out for 5-7 hours under the condition that the temperature is 100-120 ℃; and in the second step, the mass percentage of the concentrated nitric acid is 65% -68%.
10. The method of claim 6, wherein the polyacid metal organic framework crystal is coated in an amount of 2mg/cm 2 ~4mg/cm 2 The slurry was coated on the treated carbon cloth.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4833272A (en) * | 1985-04-09 | 1989-05-23 | New Japan Chemical Co., Ltd. | Process for preparing polycarboxylic acid |
| JP2006338997A (en) * | 2005-06-01 | 2006-12-14 | Toshiba Corp | Methanol oxidation catalyst for fuel cell, electrode for direct methanol fuel cell, and direct methanol fuel cell |
| CN101869851A (en) * | 2010-05-14 | 2010-10-27 | 东北师范大学 | Supported polyoxometallate crystalline catalyst and preparation method thereof |
| CN110117049A (en) * | 2019-05-07 | 2019-08-13 | 河海大学 | A kind of preparation method of metal-organic framework/polypyrrole hydridization conductive electrode |
Family Cites Families (5)
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| CN104804198B (en) * | 2015-04-23 | 2017-07-21 | 吉林大学 | The two-dimension single layer supermolecule polymer of self-supporting and its application in terms of nanometer seperation film |
| CN107910187B (en) * | 2017-08-31 | 2020-05-12 | 哈尔滨理工大学 | Preparation and application of polyacid-based crystalline supercapacitor electrode material |
| CN108440608A (en) * | 2018-04-03 | 2018-08-24 | 黑龙江科技大学 | A kind of hybrid inorganic-organic molybdenum arsenic acid salt crystal and its preparation method and application |
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-
2022
- 2022-03-16 CN CN202210258294.2A patent/CN114496587B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4833272A (en) * | 1985-04-09 | 1989-05-23 | New Japan Chemical Co., Ltd. | Process for preparing polycarboxylic acid |
| JP2006338997A (en) * | 2005-06-01 | 2006-12-14 | Toshiba Corp | Methanol oxidation catalyst for fuel cell, electrode for direct methanol fuel cell, and direct methanol fuel cell |
| CN101869851A (en) * | 2010-05-14 | 2010-10-27 | 东北师范大学 | Supported polyoxometallate crystalline catalyst and preparation method thereof |
| CN110117049A (en) * | 2019-05-07 | 2019-08-13 | 河海大学 | A kind of preparation method of metal-organic framework/polypyrrole hydridization conductive electrode |
Non-Patent Citations (4)
| Title |
|---|
| Assembly-of-cyclic-multi-nuclear-Cu-I--cluster-induc_2010_Journal-of-Molecul;Jingquan Sha;Journal of Molecular Structure;第975卷(第1-3期);211-214 * |
| Hydrothermal Synthesis and Crystal Structure of a Novel Composite Keggin-type Arsenotungstate: [Ni（phen）2][Hphen](AsW12O40);WANG Jing-Ping;结构化学;第26卷(第2期);194-198 * |
| Two novel hybrid compounds based on [MW12O40]5 (M = B, Al) heteropolyanions and copper coordination polymer with bpp ligands;Ying Chen;Inorganica Chimica Acta;第363卷(第14期);3897-3903 * |
| 以AsW12为结构单元的Keggin型多金属氧酸盐合成与性质研究;马秀娟;以AsW12为结构单元的Keggin型多金属氧酸盐合成与性质研究;第34卷(第4期);65-69 * |
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