CN111690149B - 24-core organic phosphorus copper cluster organic nano-framework packaged polyoxometallate material and preparation method and application thereof - Google Patents

24-core organic phosphorus copper cluster organic nano-framework packaged polyoxometallate material and preparation method and application thereof Download PDF

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CN111690149B
CN111690149B CN202010583631.6A CN202010583631A CN111690149B CN 111690149 B CN111690149 B CN 111690149B CN 202010583631 A CN202010583631 A CN 202010583631A CN 111690149 B CN111690149 B CN 111690149B
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copper cluster
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李少斌
谭效果
张丽
陈越
潘婧
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Abstract

A24-core organic phosphorus copper cluster organic nano-framework packaged polyoxometallate material and a preparation method and application thereof relate to a polyoxometallate crystalline material and a preparation method and application thereof. The invention aims to solve the problems that the existing polyacid-based metal-organic framework crystalline material is difficult to synthesize and cannot be directionally synthesized, and a glassy carbon electrode modified by the polyacid-based metal-organic framework crystalline material has poor capacitance. The chemical formula of the 24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate material is [ HPMo ]12O40]@[Cu4(μ2‑OH)2(C6H5PO3)2(bimb)4]. The method comprises the following steps: firstly, preparing a reaction solution; secondly, hydrothermal reaction. A24-core organic phosphorus copper cluster organic nano-framework packaged polyoxometallate material is used for modifying a glassy carbon electrode. The invention can obtain a 24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate material.

Description

24-core organic phosphorus copper cluster organic nano-framework packaged polyoxometallate material and preparation method and application thereof
Technical Field
The invention relates to a polyoxometallate crystalline material, a preparation method and application thereof.
Background
Metal-organic frameworks (MOFs) have rapidly developed over the past few decades as an emerging porous crystalline material. The substitution of Transition Metal (TM) clusters for the metal structure of MOFs can create an attractive cluster organic framework, which remains largely unexplored. The organic framework cluster has attracted great interest recently due to the attractive and abundant topological structure of the structure composed of secondary building units composed of rigid metal clusters and various organic ligands, and also due to the potential application prospect in the aspects of optics, magnetism, catalysis, gas storage and the like. The design and assembly of novel rigid metal cluster porous framework materials has greater appeal compared to a single metal ion, mainly due to the following reasons: (1) rigid clusters generally have a stable geometry and can maintain their configuration throughout the assembly process, making the structure of the final material more predictable and controllable; (2) the use of larger metal clusters as secondary building units can make the pore size larger; (3) different compositions, sizes and functions provide abundant potential structures for the formation of the metal cluster organic framework.
Polyoxometallate (POMs) as a unique inorganic metal oxide cluster has the characteristics of various configurations, controllable oxidation-reduction potential, changeable oxygen-enriched surface and the like. More importantly, POMs can provide various polyoxoanions as templates to facilitate the formation of a porous clustered organic framework.
One of the international research hotspots on polyacid is to introduce polyacid into MOFs with nanotubes or nanocages to form a polyacid-based Metal-Organic framework crystalline material (pomofos). The addition of the polyacid enables the compound to have structural diversity on one hand, and expands the application on the other hand. The functional materials not only inherit the properties of MOFs materials in the aspects of separation, adsorption and the like, but also can fully exert the excellent catalytic performance of POMs. The synthesis of such materials is relatively difficult because during the autonomous assembly of POMOFs, many conditions affect the formation of the final structure, such as: reaction temperature, pH, type of polyacid anion, secondary organic ligand, stoichiometry, and the like. However, for the above reasons, the prior art has difficulty in directional synthesis, thereby limiting the application of such materials.
In addition, glassy carbon electrodes modified with polyacid-based metal-organic framework crystalline materials have poor capacitance.
Disclosure of Invention
The invention aims to solve the problems that the existing polyacid-based metal-organic framework crystalline material is difficult to synthesize and cannot be directionally synthesized and a glassy carbon electrode modified by the polyacid-based metal-organic framework crystalline material has poor capacitance, and provides a 24-core organic phosphorus copper cluster organic nanometer framework packaging polyoxometalate material and a preparation method and application thereof.
The chemical formula of the 24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate material is [ HPMo ]12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]Wherein bimb is a diimidazole benzene; the crystal is monoclinic; space group is C2/m; unit cell parameter of
Figure BDA0002553633110000021
α＝90°，β＝105.586(4)°，γ＝90°，Z＝2。
A preparation method of 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material is completed according to the following steps:
firstly, preparing a reaction solution:
dissolving phosphomolybdic acid, metal salt, phenylphosphonic acid and diimidazole benzene into a solvent to obtain a reaction solution; adjusting the pH value of the reaction solution to obtain a reaction solution with the pH value of 3.8-4.0;
the molar ratio of the phosphomolybdic acid to the metal salt in the first step is 1 (1.00-1.50);
the molar ratio of the phosphomolybdic acid to the phenylphosphonic acid in the first step is 1 (2.00-2.50);
the molar ratio of the phosphomolybdic acid to the diimidazole benzene in the first step is 1 (3.00-3.50);
the volume ratio of the substance amount of the phosphomolybdic acid to the solvent in the step one is 1mmol (50 mL-100 mL);
secondly, firstly adding a reaction solution with the pH value of 3.8-4.0 into a polytetrafluoroethylene reaction kettle, then reacting in the polytetrafluoroethylene reaction kettle at the temperature of 120-150 ℃, and finally naturally cooling the polytetrafluoroethylene reaction kettle to room temperature to obtain dark green polyhedral crystals, namely 24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate materials;
the chemical formula of the 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material in the second step is [ HPMo ]12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]Wherein bimb is a diimidazole benzene; the crystal is monoclinic; space group is C2/m; unit cell parameter of
Figure BDA0002553633110000022
α＝90°，β＝105.586(4)°，γ＝90°，Z＝2。
A24-core organic phosphorus copper cluster organic nano-framework packaged polyoxometallate material is used for modifying a glassy carbon electrode.
Compared with the prior art, the invention has the following characteristics:
firstly, a 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material is successfully prepared by adopting a simple hydrothermal synthesis technology and utilizing diimidazole benzene, phosphomolybdic acid, copper acetate and phenylphosphonic acid for the first time; in its crystal structure, [ HPMo ]12O40]2-(PMo12) The cluster template is wrapped in a 24-core organic phosphorus copper cluster organic nano framework, and Cu4P2As the organic phosphorus copper cluster organic nano-framework node, the total number of Cu is 64P2Cluster of 2 Cu4P2Clusters each providing 4 Cu2+Ion, another 4 Cu4P2Clusters each providing 1 Cu2+Ions of each Cu2+Ion binding to 2 bimb ligands, Cu4P2The clusters and the bimb are mutually connected to form a highly-open three-dimensional porous MOF structure with a larger pore diameter, and the polyacid is taken as an object to occupy the pore passage and is fused into the frame to further stabilize the whole crystal structure; the material is 24-core organic phosphorus copper cluster organic nano framework Cu4P2Encapsulated polyoxometallate PMo12The novel material of (1);
secondly, the 24-core organic phosphorus copper cluster organic nano framework Cu prepared by the invention4P2The glassy carbon electrode modified by the encapsulated polyoxometallate material has higher specific capacitance and high cycle stability when being applied to a super capacitor, and is prepared in a sulfuric acid solution containing 1mol/L at the current density of 3A g-1Then, a charge-discharge experiment is carried out, and 24-core organic phosphorus copper cluster organic nano framework is used for packaging polyoxometallateIn a material modified glassy carbon electrode system, the current density is 3A g-1Under the condition, the specific capacitance can reach 366.3F g-1At a current density of 3A g-1Under the condition, after 1000 cycles of charge and discharge, the stability of the material can reach 91.4 percent, which is very rare at present. Therefore, the experiment provides an effective strategy for researching, designing and synthesizing the novel multi-core metal cluster organic nano framework frame packaging polyoxometallate material with excellent specific capacitance and cycling stability;
the invention can obtain 24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate material.
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FIG. 1 is a schematic structural diagram of a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in the first embodiment;
FIG. 2 shows the Cu in the 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate structure prepared in the first embodiment4P2A schematic diagram of cluster structure;
FIG. 3 is a schematic structural diagram of a three-dimensional porous polynuclear organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate formed by a 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate material prepared in the first embodiment;
FIG. 4 is a schematic diagram of a topological structure formed by a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in accordance with the first embodiment;
FIG. 5 is an X-ray photoelectron spectrum of a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in the first example;
FIG. 6 is a photoelectron spectrum of Mo in the 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in the first example;
FIG. 7 is an infrared spectrum of a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in accordance with example one;
FIG. 8 is an X-ray diffraction pattern of a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in accordance with example one; wherein 1 is an experimental peak position of the 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment, and 2 is a simulation peak position;
FIG. 9 shows the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometalate material at H of 1mol/L prepared in the first embodiment2SO4Cyclic voltammograms at different sweeping rates in the solution; FIG. 9 shows that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4The sweep rate in the solution is 50mV s -12 is a glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment at 1mol/L H2SO4The sweep rate in the solution is 100mV s-1The cyclic voltammogram of (3) is that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4The sweep rate in the solution is 150mV s-1The cyclic voltammogram of (4) is that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4The sweep rate in the solution is 200mV s-15 is a glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment at 1mol/L H2SO4The sweep rate in the solution is 250mV s-16 is a glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment at 1mol/L H2SO4The sweep rate in the solution is 300mV s-1Cyclic voltammograms of (a);
FIG. 10 is a graph of the linear relationship of the I-I ', II-II ' and III-III ' redox peak currents and sweep rate for a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material modified glassy carbon electrode prepared in example one;
FIG. 11 shows PMo12The charge-discharge comparison schematic diagram of the glassy carbon electrode modified by the material under different current densities; in FIG. 11, 1 is PMo12The glassy carbon electrode modified by the material is 1mol/L H2SO4Current density in solution 3Ag-1Charge and discharge under the conditions shown in the figure, 2 is PMo12The glassy carbon electrode modified by the material is 1mol/L H2SO4Current density in solution 5A g-1Charge and discharge under the conditions shown in the figure, 3 is PMo12The glassy carbon electrode modified by the material is 1mol/L H2SO4Current density in solution 8A g-1Charge and discharge under the conditions shown in the figure, 4 is PMo12The glassy carbon electrode modified by the material is 1mol/L H2SO4Current density in solution 10A g-1A schematic view of charging and discharging under conditions;
fig. 12 is a comparative schematic view of charging and discharging of 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometalate material modified glassy carbon electrode prepared in the first embodiment under different current densities; FIG. 12 shows that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4Current density in solution 3Ag-1A schematic charge-discharge diagram under the conditions, wherein 2 is that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4Current density in solution 5A g-1A schematic charge-discharge diagram under the conditions, wherein 3 is that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4Current density in solution 8A g-1Charge and discharge under the condition, wherein 4 is that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/LH2SO4Current density in solution 10A g-1A schematic view of charging and discharging under conditions;
FIG. 13 shows the glassy carbon electrode modified by 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in the first embodiment at a current density of 8A g-1A schematic of cycling stability under conditions; 1 is the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment and is located at 1 mol-L H2SO4Current density in solution 10A g-1Cycling stability under conditions is shown schematically in FIG. 2 for control PMo12The glassy carbon electrode modified by the material is 1mol/LH2SO4Current density in solution 10A g-1Cycling stability under conditions is shown.
Detailed Description
The technical solutions of the present invention are 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 formula of the 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material is [ HPMo ]12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]Wherein bimb is a diimidazole benzene; the crystal is monoclinic; space group is C2/m; unit cell parameter of
Figure BDA0002553633110000051
Figure BDA0002553633110000052
α＝90°，β＝105.586(4)°，γ＝90°，Z＝2。
The second embodiment is as follows: the preparation method of the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometallate material is completed according to the following steps:
firstly, preparing a reaction solution:
dissolving phosphomolybdic acid, metal salt, phenylphosphonic acid and diimidazole benzene into a solvent to obtain a reaction solution; adjusting the pH value of the reaction solution to obtain a reaction solution with the pH value of 3.8-4.0;
the molar ratio of the phosphomolybdic acid to the metal salt in the first step is 1 (1.00-1.50);
the molar ratio of the phosphomolybdic acid to the phenylphosphonic acid in the first step is 1 (2.00-2.50);
the molar ratio of the phosphomolybdic acid to the diimidazole benzene in the first step is 1 (3.00-3.50);
the volume ratio of the substance amount of the phosphomolybdic acid to the solvent in the step one is 1mmol (50 mL-100 mL);
secondly, firstly adding a reaction solution with the pH value of 3.8-4.0 into a polytetrafluoroethylene reaction kettle, then reacting in the polytetrafluoroethylene reaction kettle at the temperature of 120-150 ℃, and finally naturally cooling the polytetrafluoroethylene reaction kettle to room temperature to obtain dark green polyhedral crystals, namely 24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate materials;
the chemical formula of the 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material in the second step is [ HPMo ]12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]Wherein bimb is a diimidazole benzene; the crystal is monoclinic; space group is C2/m; unit cell parameter of
Figure BDA0002553633110000053
α＝90°，β＝105.586(4)°，γ＝90°，Z＝2。
The structural formula of the diimidazole benzene in this embodiment is
Figure BDA0002553633110000054
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the metal salt in the step one is copper acetate. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the solvent in the first step is one or a mixture of distilled water and anhydrous methanol. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the first step, the pH value of the reaction solution is adjusted to 3.8 by using an HCl solution with the mass concentration of 1-6 mol/L and an NaOH solution with the mass concentration of 1-6 mol/L. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the molar ratio of the phosphomolybdic acid to the metal salt in the first step is 1 (1.00-1.25). The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the molar ratio of the phosphomolybdic acid to the phenylphosphonic acid in the first step is 1 (2.00-2.20). The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the molar ratio of the phosphomolybdic acid to the diimidazole benzene in the first step is 1 (3.00-3.20). The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the volume ratio of the substance amount of the phosphomolybdic acid to the solvent in the step one is 1mmol (70 mL-90 mL); (ii) a The reaction time in the second step is 50-52 h. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is that a 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometallate material is used for modifying a glassy carbon electrode.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the preparation method of the 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material is completed according to the following steps:
firstly, preparing a reaction solution:
dissolving 0.12mmol of phosphomolybdic acid, 0.15mmol of copper acetate, 0.25mmol of phenylphosphonic acid and 0.38mmol of diimidazole benzene into a mixed solution obtained by mixing 6mL of distilled water and 4mL of anhydrous methanol to obtain a reaction solution; adjusting the pH value of the reaction solution to 3.8 to obtain a reaction solution with the pH value of 3.8;
the reaction solution with the pH value of 3.8 in the step one is regulated by using 3mol/L HCl solution and 1mol/L NaOH solution;
secondly, firstly adding the reaction solution with the pH value of 3.8 into a polytetrafluoroethylene reaction kettle, then reacting for 52 hours in the polytetrafluoroethylene reaction kettle with the temperature of 120 ℃, and finally naturally cooling the polytetrafluoroethylene reaction kettle to room temperature to obtain dark green polyhedral crystals, namely the 24-core organic phosphorus copper cluster organic nano framework (Cu)4P2) Encapsulating the polyoxometalate material.
The material of the 24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate prepared in the first embodiment is alpha-Keggin type phosphomolybdic acid;
the yield of the 24-core organic phosphorus copper cluster organic nano framework encapsulation polyoxometalate material prepared in the first example is 51%.
Elemental analysis: the theoretical value (%) of the 24-core organic phosphorus copper cluster organic nano framework encapsulation polyoxometalate material prepared in the first embodiment is 22.07 for C, 1.63 for H, 6.86 for N, 7.78 for Cu and 35.26 for Mo.
The experimental values (%) of the 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in the first example were 22.12 for C, 1.66 for H, 6.90 for N, 7.72 for Cu and 35.15 for Mo.
The results of the above elemental analysis were well matched with the results of single crystal analysis, and it was confirmed that the molecular formula of the compound was C60H53Cu4Mo12P3N16O48；
24-core organic phosphorus copper cluster organic nano-framework encapsulation polyoxometallate material prepared in example one12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]The crystal structure determination is carried out by the following specific processes:
placing the single crystal on Bruker SMART CCD 1000 type X-ray single crystal diffractometer at 293K temperatureColor Cu Ka
Figure BDA0002553633110000071
The collected data temperature was 293K as incident radiation. The absorption correction of the data is carried out by SADABS software, the structure is analyzed by using a SHELXTL software package, the used method is a direct method, the optimization is carried out by using a full matrix least square method, and all non-hydrogen atom coordinates are corrected by adopting anisotropic thermal parameters. And obtaining the hydrogen atom coordinate on the organic group by using a geometric hydrogenation method.
X-ray crystallographic parameters: see table 1.
TABLE 1 crystallographic parameters
Figure BDA0002553633110000072
Figure BDA0002553633110000081
aR1＝∑||Fo|─|Fc||/∑|Fo|,bwR2＝∑[w(Fo 2─Fc 2)2]/∑[w(Fo 2)2]1/2
Description of the X-ray crystal structure: x-ray single crystal diffraction analysis shows that the 24-core organic phosphorus copper cluster organic nano framework (Cu) prepared in the first example4P2) The chemical formula of the packaging polyoxometallate material is [ HPMo ]12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]Molecular formula is C60H53Cu4Mo12P3N16O48Example one prepared 24-core organophosphorus copper cluster organic nano-framework Cu4P2Encapsulation of polyoxometallate materials, polyacid cluster in structure [ HPMo ]12O40]2-The individual is present in the organophosphorus copper cluster organic nano-framework. The unit cell of the material is composed of[ HPMo ]12O40]2-Polyanions (abbreviated PMo)12) 4 Cu ions, 4 bimb ligands, 2. mu.s2-OH and 2C6H5PO3The molecular composition is shown in FIG. 1.
FIG. 1 is a schematic structural diagram of a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in the first embodiment;
example one prepared 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material has 1 crystallographically independent polyacid cluster PMo in the structure12In the 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in the first embodiment, which is surrounded by the organic phosphorus copper cluster organic nano-framework, one interesting structural feature is the presence of two independent secondary structural units; the process of forming the organic nano-framework encapsulation polyoxometallate with the secondary structure unit is as follows: first secondary structural Unit [ Cu4(μ2-OH)2(C6H5PO3)2]2+(Cu4P2)，Cu4P2Is formed by six oxygens of two independent phenylphosphonic acid ligands, and two hydroxyl clusters are connected together by sharing 4 four-coordinate Cu ions to form an organic phosphorus copper cluster organic nanometer framework (the structure is shown in figure 2 in detail). Second Secondary building Block [ HPMo12O40]2-(PMo12) And a classical Keggin type polyacid structure independently exists in a metal organic framework. A Cu4P2With 8 ligands attached, an independent ligand being linked to 2 Cu4P2(see FIG. 3 for structural details).
FIG. 2 shows the Cu in the 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate structure prepared in the first embodiment4P2A schematic diagram of cluster structure;
FIG. 3 is a schematic structural diagram of a three-dimensional porous polynuclear organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate formed by a 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate material prepared in the first embodiment;
from rubbingViewed from the structure, Cu4P2The structural unit is 8 connecting nodes, and the ligand is a 2 connector. One significant structural feature of the main frame is the presence of a Cu-Cu alloy consisting of 64P2And 8 bimb ligands as internal space
Figure BDA0002553633110000091
Figure BDA0002553633110000092
Octahedral nanostructures of (1), PMo12Polyoxoanions as inorganic templates encapsulated into octahedral Cu4P2Nano-mainframe (see figure 4 for structural details).
FIG. 4 is a schematic diagram of a topological structure formed by a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in accordance with the first embodiment;
in summary, the 24-core organic phosphorus copper cluster organic nano-frame encapsulated polyoxometalate material [ HPMo ] prepared in the first embodiment12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]Represents a first example of a 24-core organophosphorus copper cluster organic-nano-framework encapsulated polyoxometalate.
24-core organic phosphorus copper cluster organic nano-framework encapsulation polyoxometallate material prepared in example one12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]XPS test is carried out to obtain 24-core organic phosphorus copper cluster organic nanometer framework packaging polyoxometallate material [ HPMo ] prepared in the first embodiment12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]The photoelectron energy spectrum of (1) is shown in FIGS. 5-6;
FIG. 5 is an X-ray photoelectron spectrum of a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in the first example;
FIG. 6 is a photoelectron spectrum of Mo in the 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in the first example;
as can be seen from FIGS. 5 and 6, sachet PM prepared in example oneO12Cu ions in the clustered metal organic nanotube microporous crystalline material exist in a +2 valence state (figure 5), Mo (3 d)5/2) And Mo (3 d)3/2) The binding energies detected by photoelectron spectroscopy were 232.4eV and 235.5eV, respectively (fig. 6), which are consistent with the valence calculation and charge balance principles.
Performing infrared spectroscopy on the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material prepared in the first embodiment to obtain the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material [ HPMo ]12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]As shown in fig. 7.
FIG. 7 is an infrared spectrum of a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in accordance with example one;
as can be seen from FIG. 7, in the infrared spectrum of the 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometallate material prepared in the first example, the characteristic peak is 1063cm-1,968cm-1,897cm-1And 783cm-1V (P-O), v (Mo ═ Ot), vas(Mo–Ob–Mo)andνas(Mo-Oc-Mo) stretching vibration peak; the vibration peak is 750--1Falling within the range of 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxoanions PMo12And (5) stretching and vibrating. In addition, the vibration peak is 1628--1Belongs to the stretching vibration peak of the ligand in the 24-core organic phosphorus copper cluster organic nanometer framework packaging polyoxometallate material.
An X-ray powder diffraction (PXRD) test was performed on the 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in example one to obtain an X-ray powder diffraction pattern of the 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in example one, as shown in fig. 8.
FIG. 8 is an X-ray diffraction pattern of a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in accordance with example one; wherein 1 is an experimental peak position of the 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment, and 2 is a simulation peak position;
as can be seen from fig. 8, when the experimental X-ray powder diffraction pattern of the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material prepared in the first example is compared with the simulated X-ray powder diffraction pattern of the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material prepared in the first example (1 is the experimental peak position, and 2 is the simulated peak position), the compound [ HPMo ] in PXRD pattern is shown (1 is the experimental peak position, and 2 is the simulated peak position)12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]The experimental peak position and the simulated peak position are basically consistent, which shows that the purity of the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometallate material prepared in the first embodiment is good.
In conclusion, in the present embodiment, a hydrothermal synthesis technology is adopted, and a bidentate ligand 1, 4-bis (1-imidazolyl) benzene, phosphomolybdic acid, copper acetate, and phenylphosphonic acid are used to successfully synthesize the first 24-core organic phosphor copper cluster organic nano-framework encapsulated polyoxometallate material.
The single crystal X-ray diffraction result shows that the 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first example shows that Cu is used for packaging polyoxometallate4P2Organic phosphor copper cluster organic nano frame packaged PMo12A highly open three-dimensional porous POMOF structure of polyoxoanions. Polyacid cluster PMo in the structure12Wrapped in a separate unit by an organic frame.
The prepared 24-core organic phosphorus copper cluster organic nano framework encapsulates the polyoxometallate material modified glassy carbon electrode: in order to investigate the charge and discharge performance of the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material modified glassy carbon electrode as a capacitor, the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material prepared in the first embodiment is difficult to dissolve in water and common organic solvents, so that modification of the Glassy Carbon Electrode (GCE) by the material is the best choice for researching the electrochemical properties of the compound, and the material has the advantages of low cost, easiness in preparation and operation and the like.
Example two: the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is specifically completed according to the following steps:
weighing 10mg of the 24-core organic phosphorus copper cluster organic nano-frame packaged polyoxometallate material prepared in the first embodiment and 10mg of acetylene black, mixing, and grinding for 45min by using an agate mortar to obtain a mixture; taking 16mg of the mixture, fully grinding the mixture for 2 hours by using an agate mortar, and adding 0.25mg of absolute ethyl alcohol and 0.75mL of deionized water into the mixture to obtain mixture powder; the mixture powder was placed in a 4mL small centrifuge tube and dispersed by ultrasound for 45min to give an ink-like liquid. Dropping 5 mu L of printing ink-like liquid on the surface of the treated glassy carbon electrode, standing at room temperature for 5h for drying, and forming a uniformly dispersed film on the surface of the glassy carbon electrode to obtain the glassy carbon electrode modified by the 24-core organic phosphorus copper cluster organic nano-framework packaging polyoxometallate material prepared in the first embodiment; the treated glassy carbon electrode is obtained by the following method:
polishing glassy carbon electrode with 1 μ M, 0.3 μ M and 0.05 μ M alpha-alumina powder for 2min each time, repeatedly rinsing with deionized water, blowing with nitrogen, and placing the polished bare electrode in a mixed solution of 5mM potassium ferricyanide and 0.1M KCl at a scanning range of 0.6V-0.1V and a scanning speed of 50mV s-1Under the conditions of (2), a cyclic voltammogram of the sample was recorded. When the redox peak potential difference in the obtained cyclic voltammetry curve is less than 80mV, the electrode can be used, and the well-treated glassy carbon electrode is obtained.
Example three: PMo12The material modified glassy carbon electrode is specifically completed according to the following steps:
weighing 10mg PMo12The material was mixed with 10mg of acetylene black and ground for 45min with an agate mortar to give a mixture; grinding 16mg of the mixture with agate mortar for 2h, adding 0.25mg of absolute ethyl alcohol and 0.75mL of deionized water, and mixingMixing to obtain mixture powder; the mixture powder was placed in a 4mL small centrifuge tube and ultrasonically dispersed for 45min to obtain a mixed liquid. Dripping 5 mu L of mixed liquid on the surface of the treated glassy carbon electrode, standing at room temperature for 5h for drying, and forming a uniformly dispersed film on the surface of the glassy carbon electrode to obtain PMo12A glassy carbon electrode modified with a material; the treated glassy carbon electrode is obtained by the following method:
polishing glassy carbon electrode with 1 μ M, 0.3 μ M and 0.05 μ M alpha-alumina powder for 2min each time, repeatedly rinsing with deionized water, blowing with nitrogen, and placing the polished bare electrode in a mixed solution of 5mM potassium ferricyanide and 0.1M KCl at a scanning range of 0.6V-0.1V and a scanning speed of 50mV s-1Under the conditions of (2), a cyclic voltammogram of the sample was recorded. When the redox peak potential difference in the obtained cyclic voltammetry curve is less than 80mV, the electrode can be used, and the well-treated glassy carbon electrode is obtained.
The glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4Measuring cyclic voltammograms at different sweeping speeds in the solution; as shown in fig. 9;
FIG. 9 shows the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometalate material at H of 1mol/L prepared in the first embodiment2SO4Cyclic voltammograms at different sweeping rates in the solution; FIG. 9 shows that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4The sweep rate in the solution is 50mV s-12 is a glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment at 1mol/L H2SO4The sweep rate in the solution is 100mV s-1The cyclic voltammogram of (3) is that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4The sweep rate in the solution is 150mV s-1Cyclic voltammogram of (4) 24 nuclei prepared in example oneThe glassy carbon electrode modified by the organic phosphorus copper cluster organic nano framework packaging polyoxometallate material is 1mol/L H2SO4The sweep rate in the solution is 200mV s-15 is a glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment at 1mol/L H2SO4The sweep rate in the solution is 250mV s-16 is a glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment at 1mol/L H2SO4The sweep rate in the solution is 300mV s-1Cyclic voltammograms of (a);
FIG. 10 is a graph of the linear relationship of the I-I ', II-II ' and III-III ' redox peak currents and sweep rate for a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material modified glassy carbon electrode prepared in example one;
as can be seen from fig. 9 and 10, three pairs of reversible redox peaks appear in the potential range from +0.1V to + 0.5V; at a sweeping speed of 50mV s-1Half-wave potential (E) of these three pairs of peaks1/2) These three pairs of peaks are attributed to the redox process of Mo center at 0.46V (I-I '), 0.34V (II-II ') and 0.16V (III-III '), respectively. The first irreversible oxidation peak (I) is attributed to the oxidation of the Mo center. When the sweeping speed is from 50mV s-1Increase to 300mV · s-1In the embodiment one, the cathode peak current and the anode peak current of the glassy carbon electrode modified by the 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material are increased along with the increase of the cathode peak current and the anode peak current, and the current and the sweep speed are in a linear relation; the above results show that the electrochemical behavior of the glassy carbon electrode modified by the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material prepared in the first example is a surface-controlled electrochemical process in the above potential range.
FIG. 11 shows PMo12The charge-discharge comparison schematic diagram of the glassy carbon electrode modified by the material under different current densities; in FIG. 11, 1 is PMo12The glassy carbon electrode modified by the material is 1mol/L H2SO4Current density in solution 3A g-1Charge and discharge under the conditions shown in the figure, 2 is PMo12Material repairDecorated glassy carbon electrode at 1mol/L H2SO4Current density in solution 5A g-1Charge and discharge under the conditions shown in the figure, 3 is PMo12The glassy carbon electrode modified by the material is 1mol/L H2SO4Current density in solution 8A g-1Charge and discharge under the conditions shown in the figure, 4 is PMo12The glassy carbon electrode modified by the material is 1mol/L H2SO4Current density in solution 10A g-1A schematic view of charging and discharging under conditions;
fig. 12 is a comparative schematic view of charging and discharging of 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometalate material modified glassy carbon electrode prepared in the first embodiment under different current densities; FIG. 12 shows that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano-framework encapsulated polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4Current density in solution 3Ag-1A schematic charge-discharge diagram under the conditions, wherein 2 is that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4Current density in solution 5Ag-1A schematic charge-discharge diagram under the conditions, wherein 3 is that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/L H2SO4Current density in solution 8Ag-1Charge and discharge under the condition, wherein 4 is that the glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment is 1mol/LH2SO4Current density in solution of 10Ag-1A schematic view of charging and discharging under conditions;
as can be seen from fig. 11 and 12, the glassy carbon electrode modified by 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material prepared in example one is more than polyoxoanion PMo alone12The glassy carbon electrode modified by the material has high charge and discharge performance. Therefore, the glassy carbon electrode modified by the 24-core organic phosphorus copper cluster organic nano-framework packaging polyoxometallate material prepared in the first embodiment has good application potential for improving the performance of the capacitors of the POMOFs.
On the basis of the electrochemical property research, the cycling stability of the glassy carbon electrode modified by the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material prepared in the first embodiment is further researched, and the result shows that the 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material prepared in the first embodiment has good cycling stability when being used as a capacitor.
As can be seen from fig. 13, in order to examine the cycle stability of the material, a 1000-cycle repeated charge and discharge test was performed thereon. 1 is a glassy carbon electrode modified by 24-core organic phosphorus copper cluster organic nano framework packaging polyoxometallate material prepared in the first embodiment at 1mol/L H2SO4Current density in solution 10A g-1The circulation stability under the condition is shown schematically, and the capacitance retention rate is 95.1%; 2 is control PMo12The glassy carbon electrode modified by the material is 1mol/L H2SO4Current density in solution 10A g-1The cycling stability under the condition is shown schematically, and the capacity retention rate is 61.8%.
In summary, the following steps: the glassy carbon electrode modified by the 24-core organic phosphorus copper cluster organic nano-framework packaging polyoxometallate material prepared in the first embodiment has high capacitor performance and excellent stability, is a potential capacitor material with excellent performance, and has good application potential for improving the capacitor performance of POMOFs.

Claims (10)

1. A24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate material is characterized in that the chemical formula of the 24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate material is [ HPMo ]12O40]@[Cu4(μ2-OH)2(C6H5PO3)2(bimb)4]Wherein bimb is a diimidazole benzene; the crystal is monoclinic; space group is C2/m; the crystallographic parameters are
Figure FDA0002850049350000011
α＝90°，β＝105.586(4)°，γ＝90°，Z＝2。
2. The method for preparing 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometallate material according to claim 1, wherein the method for preparing 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometallate material is completed according to the following steps:
firstly, preparing a reaction solution:
dissolving phosphomolybdic acid, metal salt, phenylphosphonic acid and diimidazole benzene into a solvent to obtain a reaction solution; adjusting the pH value of the reaction solution to obtain a reaction solution with the pH value of 3.8-4.0;
the molar ratio of the phosphomolybdic acid to the metal salt in the first step is 1 (1.00-1.50);
the molar ratio of the phosphomolybdic acid to the phenylphosphonic acid in the first step is 1 (2.00-2.50);
the molar ratio of the phosphomolybdic acid to the diimidazole benzene in the first step is 1 (3.00-3.50);
the volume ratio of the substance amount of the phosphomolybdic acid to the solvent in the step one is 1mmol (50 mL-100 mL);
secondly, firstly adding a reaction solution with the pH value of 3.8-4.0 into a polytetrafluoroethylene reaction kettle, then reacting in the polytetrafluoroethylene reaction kettle at the temperature of 120-150 ℃, and finally naturally cooling the polytetrafluoroethylene reaction kettle to room temperature to obtain dark green polyhedral crystals, namely the 24-core organic phosphorus copper cluster organic nano framework packaged polyoxometallate material.
3. The method according to claim 2, wherein the metal salt in the first step is copper acetate.
4. The method according to claim 2, wherein the solvent in the first step is one or a mixture of distilled water and anhydrous methanol.
5. The method according to claim 2, wherein the pH value of the reaction solution in the first step is adjusted to 3.8 by using HCl solution with a concentration of 1-6 mol/L and NaOH solution with a concentration of 1-6 mol/L.
6. The method for preparing 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometallate material according to claim 2, wherein the molar ratio of phosphomolybdic acid to metal salt in the step one is 1 (1.00-1.25).
7. The method for preparing 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometallate material according to claim 2, wherein the molar ratio of phosphomolybdic acid to phenylphosphonic acid in the step one is 1 (2.00-2.20).
8. The method for preparing 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometalate material according to claim 2, wherein the molar ratio of phosphomolybdic acid to diimidazole benzene in the first step is 1 (3.00-3.20).
9. The method for preparing 24-core organic phosphorus copper cluster organic nano framework encapsulated polyoxometallate material according to claim 2, wherein the volume ratio of the substance of phosphomolybdic acid to the solvent in the step one is 1mmol (70 mL-90 mL); the reaction time in the second step is 50-52 h.
10. The use of a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material according to claim 1, wherein a 24-core organophosphorus copper cluster organic nano-framework encapsulated polyoxometalate material is used for modifying a glassy carbon electrode.
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