Difunctional multi-acid-group metal organic framework material

Abstract

The invention discloses a difunctional polyacid-based metal organic framework material, belongs to the technical field of electrochemistry and catalytic chemistry difunctions, and particularly relates to a polyacid-based metal organic framework material, a preparation method thereof, a supercapacitor of the polyacid-based metal organic framework material and application of the polyacid-based metal organic framework material in catalytic synthesis of sulfoxide compounds. The polyacid-based metal organic framework material as a supercapacitor electrode material has very good electrochemical capacity, when the current density is 1A. G <-1 >, the capacitance is 447.5 F.g <-1 >, 278.6 F.g <-1 >, 204.2 F.g <-1 >, 391.9 F.g <-1 > and 289.6 F.g <-1 > respectively, and the capacitance can be kept at 90% or above after 1000 times of constant-current charge-discharge cycles, and the catalytic material can be used as a heterogeneous catalyst and can be applied to the field of high-performance lithium ion batteries, such as lithium ion batteries, lithium ion batteries, lithium ion batteries, lithium ion batteries, lithium ion batteries, lithium ion batteries, lithium ion batteries, lithium ion batteries, lithium ion batteries, lithium ion batteries, lithium ion batteries, lithium ion batteries and lithium ion batteries. The catalyst has excellent catalytic activity in selective catalytic oxidation of thioether compounds, and the selectivity and the conversion rate can reach 99% or above; the catalyst can be repeatedly used for more than 8 times, and the structure and the catalytic activity are not changed; and the preparation process of the polyacid-based catalyst is simple, the condition is mild, the product purity is high, and the polyacid-based catalyst has potential application value in the fields of electrochemistry and catalysis.

Description

Technical Field

[0001] This invention belongs to the fields of electrochemistry and catalytic chemistry, specifically relating to a polyacid-based metal-organic framework material, its preparation method, and its application in supercapacitors and the efficient synthesis of benzyl sulfoxide compounds through selective catalytic oxidation of benzyl sulfide compounds. Background Technology

[0002] Against the backdrop of continuously growing global energy demand and increasingly severe environmental problems, the development of efficient and clean energy storage technologies has become a focus of scientific research. Supercapacitors, as a highly efficient energy storage device, have attracted much attention due to their advantages such as rapid charge and discharge capabilities, high power density, and long cycle life. Their performance largely depends on the characteristics of the electrode materials, but traditional materials such as metal oxides or conductive polymers face problems such as high cost and environmental pollution. Therefore, finding new, environmentally friendly, low-cost, and high-performance electrode materials is one of the current research priorities.

[0003] The selective oxidation of sulfides has always been a research hotspot. On the one hand, their oxidation products, sulfoxides and sulfones, have important applications in medicine, pesticides, and organic synthesis, and the selective oxidation of organosulfides is an effective way to obtain these compounds. On the other hand, sulfide compounds are widely found in petroleum products such as gasoline and diesel, and are the most abundant sulfur-containing substances in them; these sulfur-containing compounds, when burned at high temperatures, produce SO₂. x It can cause acid rain and acid fog, resulting in environmental pollution and harming human health. For oil desulfurization, catalytic oxidation can convert sulfides into more polar sulfones or sulfoxides, which can then be separated from the oil phase using an extractant, achieving the desulfurization goal. This oxidative desulfurization process has been widely studied in recent years due to its high efficiency and practicality. Compared with other desulfurization technologies, oxidative desulfurization (especially deep desulfurization) shows significant potential and has the advantages of low cost and simple operation. However, current sulfide oxidation processes often require the use of large amounts of volatile organic solvents, chemical oxidants, and precious metal catalysts, posing a serious threat to the environment. Therefore, developing a milder and cleaner sulfide oxidation technology is of significant research importance.

[0004] Polyoxometalates (polyacids) are an important class of polynuclear clusters, possessing reversible electron transfer properties and the ability to maintain structural stability even after undergoing multiple rapid electron transfers, making them potential ideal electrode materials for supercapacitors and catalytic oxidation materials. However, the high solubility and low conductivity of traditional polyacid clusters lead to poor cycle stability and capacitive performance. To address these issues of easy solubility and deactivation of active sites, researchers often synthesize polyacid composites using various carbon materials such as graphene and various polymers as supports for heterogeneous catalytic oxidation. However, such composite systems often suffer from defects such as unclear structural composition, low loading rate, deactivation of active sites, or polyacid leaching.

[0005] To this end, the present study proposes a molecular recombination and tailoring strategy: taking the classic Keggin-type polyacid as the core, combining with specific metal-organic subunits, using the "bridge" effect and synergistic effect of the latter, and designing and preparing polyoxometalate-based metal-organic framework (POMOFs) with multiple electrochemical and catalytic active sites. This strategy aims to achieve efficient and selective oxidation of sulfide compounds, which has important theoretical value and practical significance.

[0006] Current research shows that polyoxometalate-based metal-organic framework materials can effectively solve the above electrochemical and catalytic problems. It not only combines the dual advantages of polyoxometalate and metal-organic framework materials, but also significantly improves the structural stability and thermal stability of the material. Therefore, developing polyoxometalate-based metal-organic framework materials with novel structures, high electrochemical capacity and efficient catalytic oxidation of sulfide compounds is an urgent and significant research topic. SUMMARY

[0007] The present application aims to provide a polyoxometalate-based metal-organic framework material, which is composed of transition metal silver ions or copper ions or cobalt ions, BTYE coordination and {SiMo 12 O 40} 4- form a multi-dimensional polyoxometalate metal framework material, which has stable structure and is conducive to electrochemical and catalytic reaction recycling, and has multiple electrons {SiMo 12 O 40} 4- and transition metal ions dispersed in the framework material can fully transfer electrons quickly, which is conducive to improving electrochemical and catalytic activity.

[0008] The second object of the present application is to provide a preparation method of a polyoxometalate-based metal-organic framework material, which is simple, low in cost and conducive to large-scale production.

[0009] The third object of the present application is to provide an application of a polyoxometalate-based metal-organic framework material, which is used as an electrode material for supercapacitors and as a catalyst for sulfide compound oxidation reactions. It not only has good electrochemical capacity and cycle stability, but also has good catalytic activity and selectivity as a catalyst, and can be reused to reduce costs.

[0010] In order to achieve the above technical purposes, the present application provides a preparation method of a polyoxometalate-based metal-organic framework material, which has the chemical formula

[0011] [{Co2(BTYE)4}{SiMo 12 O 40}](4), (BTYE = 1,2-bis(4H-1,2,4-triazol-4-yl)ethane).

[0012] Compound 1 is monoclinic, space group P21 / c; the cell parameters of the compound are β = 93.3590(14)°, Compound 2 is triclinic, space group P-1; c = 17.5598(4), α = 75.1010(10)°, β = 81.1600(10)°, γ = 73.5020(10)°, Compound 3 is triclinic, space group P1; α = 81.7942(17)°, β = 65.4177(16)°, γ = 77.2034(16)°, Compound 4 is monoclinic, space group Pc; β = 115.444(4)°, Compound 5 is monoclinic, space group P1; α = 70.994(5)°, β = 64.558(4)°, γ = 76.980(4)°,

[0013] Structure of the polyacid-based metal organic framework material 1 of the application: there are half of the crystallographic independent {SiMo 12 O 40} 4- ions, two silver ions, one half 1,2-bis(4H-1,2,4-triazol-4-yl)ethane (BTYE). Two silver ions adopt different coordination modes: Ag1 adopts five-coordination to form a square pyramid structure, and Ag2 adopts six-coordination to form an octahedral configuration. Two silver ions are bridged by BTYE to form a binuclear structure {Ag2(BTYE)2}, eight anions and eight BTYE are connected to form an octanuclear structure {Ag8(BTYE)8}, the binuclear structure {Ag2(BTYE)2} and the octanuclear structure {Ag8(BTYE)8} are connected by shared anions and BTYE to form a two-dimensional metal complex layer, and the layers are connected by anions and coordination along the c-axis to form a three-dimensional metal organic framework structure, {SiMo 12 O 40} 4- Anion hexadentate coordination fills in one-dimensional channels to form a three-dimensional polyacid-based metal organic framework material.

[0014] Structure of the polyacid-based metal organic framework material 2 of the application: there are two half of the crystallographic independent {SiMo 12 O 40}4- ions, four copper ions, three half 1,2-bis(4H-1,2,4-triazol-4-yl)ethane (BTYE). The four copper ions all adopt three different coordination modes: Cu1 adopts six-coordination to form an octahedral configuration, Cu2 and Cu3 adopt three-coordination to form a trigonal configuration, Cu4 and Cu5 adopt four-coordination to form a tetrahedral configuration structure. Six copper ions and six BTYE connect to form a six-core structure {Cu6(BTYE)6}, eight copper ions and six BTYE, two oxygen atoms form an eight-core structure {Cu8BTYE6(μ2-O)2}, the six-core structure {Cu6(BTYE)6} and the eight-core structure {Cu8BTYE6(μ2-O)2} form a two-dimensional metal-organic layer through sharing BTYE ligands and copper ions, and the two-dimensional layer is connected by anions along the a axis to form a three-dimensional metal-organic framework material structure, and then {SiMo 12 O 40} 4- The anions form two different coordination modes to fill in the one-dimensional channel to form a three-dimensional polyacid-based metal-organic framework material.

[0015] Structure of the polyacid-based metal-organic framework material 3 of the application: there is a half of a crystallographically independent {SiMo 12 O 40} 4- ions, one half copper ion, one half 1,2-bis(4H-1,2,4-triazol-4-yl)ethane (BTYE). The two copper ions all adopt different coordination modes: Cu1 adopts three-coordination to form a trigonal configuration, and Cu2 adopts six-coordination to form an octahedral configuration. Two Cu1, two Cu2 form a double ring structure {Cu4BTYE3} by sharing three BTYE ligands, and the double ring structure forms a one-dimensional metal-organic chain through bridging BTYE, and then {SiMo 12 O 40} 4- A one-dimensional inorganic chain is formed by sharing Cu ions, and the two inorganic chains are connected with each other to form a three-dimensional polyacid-based metal-organic framework material.

[0016] Structure of the polyacid-based metal-organic framework material 4 of the application: there is one crystallographically independent {SiMo 12 O 40} 4- ions, two cobalt ions, four 1,2-bis(4H-1,2,4-triazol-4-yl)ethane (BTYE). The two cobalt ions all adopt five-coordination to form a trigonal bipyramid, and the four cobalt ions are connected by BTYE to form a four-core structure {Co4(BTYE)4}, and the four-core structure forms a two-dimensional metal-organic layer structure through sharing ligands and cobalt ions. Then, {SiMo 12 O 40}4- The adjacent two-dimensional layers are connected to form a three-dimensional polyoxometallic metal-organic framework material.

[0017] The structure of the polyoxometallic metal-organic framework material 5 of the present application: there is one crystallographic independent {SiMo 12 O 40} 4- An ion, one cobalt ion, three 1,2-bis(4H-1,2,4-triazole-4-yl)ethane (BTYE). The cobalt ion adopts six-coordination to form an octahedral configuration, and the cobalt ions are connected by BTYE to form a one-dimensional chain.

[0018] A preparation method of a polyoxometallic metal-organic framework material, which is obtained by hydrothermal and solvothermal synthesis, and the preparation method comprises the following steps:

[0019] A precursor H4[SiMo 12 O 40 ]·xH2O (Inorg. Chem. 1983, 22, 207-216) is synthesized by a conventional method,

[0020] H4[SiMo 12 O 40 ]·xH2O is dissolved in water, then silver / copper / cobalt salt and ligand BTYE are added, stirring for 0.5-1 h, adjusting pH=2-4 with nitric acid, continuing to stir for 0.5-1 h, then transferring to a polytetrafluoroethylene reaction kettle, heating at 120-180 DEG C in an oven for 2-5 days, slowly cooling to room temperature, to obtain a polyoxometallic metal-organic framework material, and washing and drying to obtain polyoxometallic metal-organic framework materials 1, 2 and 4;

[0021] H4[SiMo 12 O 40 ]·xH2O is dissolved in a mixed solution of water and ethanol, then copper / cobalt salt and ligand BTYE are added, stirring for 0.5-1 h, adjusting pH=2-4 with nitric acid, continuing to stir for 0.5-1 h, then transferring to a polytetrafluoroethylene reaction kettle, heating at 120-180 DEG C in an oven for 2-5 days, slowly cooling to room temperature, to obtain a polyoxometallic metal-organic framework material, and washing and drying to obtain polyoxometallic metal-organic framework materials 3 and 5;

[0022] The substance amount ratio of H4[SiMo 12 O 40 ]·xH2O, silver / copper / cobalt salt and BTYE is 1:3-6:1-3;

[0023] A supercapacitor performance research of a polyoxometallic metal-organic framework crystal as an electrode material, and the operation is as follows:

[0024] The three-electrode system is used, dilute sulfuric acid is used as an electrolyte solution, an Ag / AgCl electrode is used as a reference electrode, and a platinum electrode is used as a counter electrode, and the supercapacitor performance is tested by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS).

[0025] A catalytic application of a polyacid-based metal organic framework material in selective catalytic oxidation of sulfide to sulfoxide compounds is as follows:

[0026] The experimental conditions for selective catalytic oxidation of sulfide compounds are as follows: benzyl sulfide compounds, polyacid-based metal organic framework materials and internal standard naphthalene are added to a methanol solution for mixing, after stirring and heating to 50 DEG C, hydrogen peroxide is added, and under stirring conditions, the reaction is carried out for a period of time, wherein the molar ratio of benzyl sulfide compounds, polyacid-based metal organic framework materials and oxidizing agent is 100:1:100-150, qualitative analysis is carried out by gas chromatography, and the selective catalytic path is as follows:

[0027]

[0028] The beneficial effects of the present application are:

[0029] (1) The present application synthesizes a novel polyacid-based metal organic framework material by hydrothermal and solvothermal methods under different temperature and solvent conditions with different metal ions;

[0030] (2) The metal organic framework material described in the present application has high capacitance in supercapacitor performance, and can also maintain good stability in cyclic galvanostatic charge-discharge.

[0031] (3) The metal organic framework material described in the present application has high catalytic activity in the reaction of catalytic oxidation of sulfide to sulfoxide compounds, and the conversion rate and selectivity can reach more than 99%; in addition, the preparation of the catalyst is simple;

[0032] (4) The catalyst described in the present application can be recycled and reused by simple filtration, washing and drying, and the catalyst can still maintain excellent catalytic activity after 5 cycles of reuse; BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 Synthesis path of the polyacid-based metal organic framework material of the present application

[0034] Figure 2 Asymmetric unit of the polyacid-based metal organic framework material 1 of the present application

[0035] Figure 3(a) a binuclear subunit of the polyacid-based metal organic framework material 1 of the present application; (b) a one-dimensional metal complex of the polyacid-based metal organic framework material 1; (c) an octanuclear subunit of the polyacid-based metal organic framework material 1; (d) a two-dimensional metal complex of the polyacid-based metal organic framework material 1; (e) a three-dimensional framework structure of the polyacid-based metal organic framework material 1.

[0036] Figure 4 (a) a three-dimensional metal organic framework material of the polyacid-based metal organic framework material of the present application; (b) a connection mode of polyacid and silver of the polyacid-based metal organic framework material of the present application; (c) a three-dimensional polyacid-based metal organic framework structure of the polyacid-based metal organic framework material of the present application.

[0037] Figure 5 (a) an asymmetric unit of the polyacid-based metal organic framework material 2 of the present application; (b) a hexanuclear subunit of the polyacid-based metal organic framework material 1 of the present application; (c) an octanuclear subunit of the polyacid-based metal organic framework material 2 of the present application; (d) a two-dimensional metal complex of the polyacid-based metal organic framework material 2 of the present application; (e) a three-dimensional framework structure of the polyacid-based metal organic framework material 2 of the present application.

[0038] Figure 6 (a) a three-dimensional metal organic framework material of the polyacid-based metal organic framework material 2 of the present application; (b) a connection mode of polyacid and copper of the polyacid-based metal organic framework material 2 of the present application; (c) a three-dimensional polyacid-based metal organic framework structure of the polyacid-based metal organic framework material 2 of the present application.

[0039] Figure 7 (a) an asymmetric unit of the polyacid-based metal organic framework material 3 of the present application; (b) a one-dimensional metal organic complex of the polyacid-based metal organic framework material 3 of the present application; (c) a one-dimensional inorganic chain of the polyacid-based metal organic framework material 3 of the present application; (d) a two-dimensional polyacid-based metal complex of the polyacid-based metal organic framework material 3 of the present application; (e) a three-dimensional polyacid-based metal organic framework structure of the polyacid-based metal organic framework material 3 of the present application.

[0040] Figure 8 (a) an asymmetric unit of the polyacid-based metal organic framework material 4 of the present application; (b) a tetranuclear subunit of the polyacid-based metal organic framework material 4 of the present application; (c) a two-dimensional metal organic complex of the polyacid-based metal organic framework material 4 of the present application; (d) a three-dimensional polyacid-based metal organic framework structure of the polyacid-based metal organic framework material 4 of the present application.

[0041] Figure 9 (a) an asymmetric unit of the polyacid-based metal organic framework material 5 of the present application; (b) a one-dimensional chain of the polyacid-based metal organic framework material 5 of the present application.

[0042] Figure 10(a-e) cyclic voltammograms of the polyacid-based metal-organic framework materials 1-5 of the present application; (f) cyclic voltammograms of the polyacid-based metal-organic framework materials 1-5 of the present application at a scan rate of 100 mV / s; (g) linear relationship diagram of the redox peaks of the polyacid-based metal-organic framework materials 1-5 of the present application and the scan rate; (h) b value of the polyacid-based metal-organic framework materials 1-5 of the present application; (i) contribution rate of the capacitance of the polyacid-based metal-organic framework material 1 of the present application to the scan rate.

[0043] Figure 11 (a-e) galvanostatic charge-discharge of the polyacid-based metal-organic framework materials 1-5 of the present application; (f) capacitance of the polyacid-based metal-organic framework materials 1-5 of the present application.

[0044] Figure 12 Impedance of the polyacid-based metal-organic framework materials 1-5 of the present application.

[0045] Figure 13 Cyclic capacitance retention rate of the polyacid-based metal-organic framework materials 1-5 of the present application.

[0046] Figure 14 Impedance comparison of the polyacid-based metal-organic framework materials 1-5 of the present application after 1000 times of galvanostatic charge-discharge.

[0047] Figure 15 Results of selective catalytic oxidation of sulfide compounds of the present application.

[0048] Figure 16 Catalytic efficiency of the present application in different solvents.

[0049] Figure 17 Cyclic experiment results of the catalytic oxidation reaction of the present application. DETAILED DESCRIPTION

[0050] The present application will be further described in detail through specific examples, but the present application is only for explaining the present application and is not used to limit the scope of protection of the present application.

[0051] The chemical reagents involved in the following examples are all conventional commercially available products if not otherwise specified.

[0052] Example 1

[0053] Polyacid-based metal-organic framework material

[0054] [{Co2(BTYE)4}{SiMo 12 O 40}](4), The preparation method of the polyacid-based metal-organic framework material of the present application is as follows:

[0055] (1) Precursor H4[SiMo 12 O 40 ]·xH2O (Inorg. Chem. 1983, 22, 207-216) is obtained by a conventional aqueous solution method.

[0056] (2) H4[SiMo 12 O 40 ]·xH2O (0.05 mmol) is dissolved in 10 ml of water, then AgNO3 (0.20 mmol) and BTYE (0.05 mmol) are added, stirring at room temperature for 30 min, adjusting the pH to 3.0 with dilute nitric acid, continuing to stir at room temperature for 30 min, transferring the mixed solution into a 20 ml polytetrafluoroethylene reactor, heating in an oven at 180℃ for about 5 days, and slowly cooling to room temperature to obtain green strip-shaped metal-organic framework material 1 of polyacid;

[0057] (3) H4[SiMo 12 O 40 ]·xH2O (0.05 mmol) is dissolved in a mixed solution of 6 ml of water and 4 mL of ethanol, then CuCl2 (0.30 mmol) and BTYE (0.05 mmol) are added, stirring at room temperature for 30 min, adjusting the pH to 3.0 with dilute nitric acid, continuing to stir at room temperature for 30 min, transferring the mixed solution into a 20 ml polytetrafluoroethylene reactor, heating in an oven at 120℃ for about 5 days, and slowly cooling to room temperature to obtain blue block-shaped metal-organic framework material 3 of polyacid;

[0058] (4) The implementation steps of supercapacitor performance testing: a mixture of the metal-organic framework material 1 of polyacid, acetylene black and polyvinylidene fluoride of a weight ratio of 1:1:1 is ground in a mortar and the slurry is dispersed with a mixture of ethanol and water. Then the slurry is dispersed on the surface of carbon cloth and dried at room temperature for 2 h to form a uniform film, and then fully dried in a vacuum oven at 80℃ for 12 h.

[0059] (5) The implementation steps of selective catalytic oxidation of sulfide: 0.25 mmol of benzyl sulfide is added to a 5 ml glass reaction bottle, 0.0025 mmol of the catalyst synthesized in step 2 is added to 2 ml of methanol solvent, heated to 50℃, stirred for a period of time, then 0.25 mmol of oxidant hydrogen peroxide is added, and after a period of reaction, quantitative analysis by gas chromatography shows that the conversion rate and selectivity can reach more than 99%, the catalyst is recovered by simple filtration, washed and dried, and can be reused;

[0060] In this example, when the silver salt in step 2 is replaced by copper salt, metal-organic framework material 2 of polyacid is obtained;

[0061] The polyoxometalate-based metal-organic framework material 3 is obtained by replacing the silver salt in step 2 with a cobalt salt in the embodiment;

[0062] The polyoxometalate-based metal-organic framework material 5 is obtained by replacing the copper salt in step 3 with a cobalt salt in the embodiment;

[0063] In the embodiment, the copper salt includes at least one of copper chloride, copper nitrate, copper acetate, and copper sulfate; and the cobalt salt includes at least one of cobalt chloride, cobalt nitrate, cobalt sulfate, and cobalt acetate.

[0064] In the embodiment, the benzyl sulfide can be replaced by p-methoxybenzyl sulfide, p-chlorobenzyl sulfide, diphenyl sulfide, dibenzyl sulfide, and the like, and the catalytic reaction effect is shown in the figure.

[0065] In the embodiment, the catalytic reaction solvent methanol can be replaced by acetonitrile or ethanol.

[0066] The polyoxometalate-based metal-organic framework material obtained in the above embodiment [{Co2(BTYE)4}{SiMo 12 O 40}](4), BTYE = 1,2-di(4H-1,2,4-triazole-4-yl)ethane, and the specific crystal structure is as shown in Figures 1-9 .

[0067] The polyoxometalate-based metal-organic framework material prepared in the embodiment is subjected to electrochemical performance test by using an electrochemical workstation, Figures 10-14 The cyclic voltammetry, constant current charge and discharge, and impedance spectrum of the electrode material are shown, indicating that the compound has a good capacitance, and when the current density is 1 A·g -1 , the capacitances are 447.5 F·g -1 , 278.6 F·g -1 , 204.2 F·g -1 , 391.9 F·g -1 , and 289.6 F·g -1 , respectively, and the capacitance retention rate of the polyoxometalate-based metal-organic framework material can be maintained above 90% after 1000 constant current charge and discharge cycles.

[0068] The selective catalytic oxidation results of the polyoxometalate-based metal-organic framework material prepared in the embodiment are detected by using gas chromatography, Figure 15 The corresponding catalytic results are summarized, and the conversion rate and selectivity of benzyl sulfide can reach above 99%, and the conversion rate and selectivity of p-methylbenzyl sulfide, p-methoxybenzyl sulfide, and p-chlorobenzyl sulfide are between 95% and 99%.

[0069] The polyoxometalate-based metal-organic framework materials prepared in the examples were subjected to multiple cycle catalysis experiments by gas chromatography, Figure 17 showing that the conversion rate and selectivity did not decrease significantly after 8 cycles.

[0070] The polyoxometalate-based metal-organic framework materials prepared in the examples were subjected to catalysis experiments for sulfide oxidation in different solvents by gas chromatography, Figure 16 showing the catalytic efficiency in different solvents, and the results show that the effect in methanol is best.

[0071] Example 2

[0072] Polyoxometalate-based metal-organic framework material

[0073] [{Co2(BTYE)4}{SiMo 12 O 40}](4), The preparation method is as follows:

[0074] (1) The precursor H4[SiMo 12 O 40 ]·xH2O (Inorg. Chem. 1983, 22, 207-216) is obtained by a conventional aqueous solution method;

[0075] (2) H4[SiMo 12 O 40 ]·xH2O (0.1 mmol) is dissolved in 10 ml of water, then AgNO3 (0.40 mmol) and BTYE (0.1 mmol) are added, stirring at room temperature for 30 min, adjusting the pH to 3.0 with dilute nitric acid, and continuing to stir at room temperature for 30 min. The mixed solution is transferred to a 20 ml polytetrafluoroethylene reactor, heated in an oven at 180°C for about 5 days, and then slowly cooled to room temperature to obtain green strip-shaped polyoxometalate-based metal-organic framework material 1;

[0076] (3) H4[SiMo 12 O 40 ]·xH2O (0.1 mmol) is dissolved in a mixed solution of 6 ml of water and 4 mL of ethanol, then CuCl2 (0.60 mmol) and BTYE (0.082 g, 0.1 mmol) are added, stirring at room temperature for 30 min, adjusting the pH to 3.0 with dilute nitric acid, and continuing to stir at room temperature for 30 min. The mixed solution is transferred to a 20 ml polytetrafluoroethylene reactor, heated in an oven at 120°C for about 5 days, and then slowly cooled to room temperature to obtain blue block-shaped polyoxometalate-based metal-organic framework material 3;

[0077] (4) The implementation steps of supercapacitor performance test: the mixture of the polyacid-based metal-organic framework material 1, acetylene black and polyvinylidene fluoride in a weight ratio of 1:1:1 is ground in a mortar and dispersed in a slurry with a mixture of ethanol and water. Then the slurry is dispersed on the surface of carbon cloth and dried at room temperature for 2h to form a uniform film, and then dried in a vacuum oven at 80℃ for 12h.

[0078] (5) The implementation steps of selective catalytic oxidation of sulfide: in a 5ml glass reaction bottle, add benzyl sulfide 0.25mmol, add the catalyst synthesized in step 2 0.0025mmol into 2ml methanol solvent, heat to 50℃, stir for a period of time, then add oxidant hydrogen peroxide 0.25mmol, after reaction for a period of time, quantitative analysis by gas chromatography, the conversion rate and selectivity can reach more than 99%, the catalyst is recovered by simple filtration, washed and dried, and can be reused.

[0079] Example 3

[0080] Polyacid-based metal-organic framework material

[0081] [{Co2(BTYE)4}{SiMo 12 O 40}](4), The preparation method is as follows:

[0082] (1) The precursor H4[SiMo 12 O 40 ]·xH2O(Inorg. Chem. 1983, 22, 207-216) is obtained by a conventional aqueous solution method;

[0083] (2) H4[SiMo 12 O 40 ]·xH2O (0.0.05mmol) is dissolved in 10ml water, then AgNO3 (0.40mmol) and BTYE (0.1mmol) are added, stirred at room temperature for 30min, the pH is adjusted to 3.0 with dilute nitric acid, and the stirring is continued at room temperature for 30min, the mixed solution is transferred to a 20ml polytetrafluoroethylene reaction kettle, heated in an oven at 180℃ for about 5 days, and then slowly cooled to room temperature to obtain a green strip-shaped polyacid-based metal-organic framework material 1;

[0084] (3) H4[SiMo 12 O 40]·xH2O (0.05 mmol) was dissolved in 6 ml water and 4 mL ethanol mixed solution, then CuCl2 (0.60 mmol) and BTYE (0.082 g, 0.1 mmol) were added, stirred at room temperature for 30 min, adjusted to pH 3.0 with dilute nitric acid, continued to stir at room temperature for 30 min, the mixed solution was transferred into a 20 ml polytetrafluoroethylene reactor, heated in an oven at 120℃ for about 5 days, then slowly cooled to room temperature to obtain blue block-shaped polyacid-based metal-organic framework material 3;

[0085] (4) The implementation steps of supercapacitor performance test: the mixture of polyacid-based metal-organic framework material 1, acetylene black and polyvinylidene fluoride with a weight ratio of 1:1:1 was ground in a mortar and the slurry was dispersed with a mixture of ethanol and water. Then the slurry was dispersed on the surface of carbon cloth and dried at room temperature for 2h to form a uniform film, and then dried in a vacuum oven at 80℃ for 12h.

[0086] (5) The implementation steps of selective catalytic oxidation of sulfide: 0.5 mmol of benzyl sulfide was added to a 5 ml glass reaction bottle, 0.005 mmol of the catalyst synthesized in step 2 was added to 2 ml of methanol solvent, heated to 50℃, stirred for a period of time, then 0.5 mmol of oxidant hydrogen peroxide was added, and after a period of reaction, quantitative analysis by gas chromatography showed that the conversion rate and selectivity could reach more than 99%, the catalyst was recovered by simple filtration, washed and dried, and could be reused.

[0087] The above shows and describes the basic principles and main features of the present application and the advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above examples, and the above examples and descriptions in the specification are only to illustrate the principles of the present application, and various changes and improvements can be made without departing from the spirit and scope of the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A bifunctional polyacid-based metal-organic framework material, characterized in that, having the following chemical formula: [{Co2(BTYE)4}{SiMo 12 O 40}](4), BTYE = 1,2-bis(4H-1,2,4-triazol-4-yl)ethane; The synthesis products include: metal-organic framework material 1, metal-organic framework material 2, metal-organic framework material 3, metal-organic framework material 4, and metal-organic framework material 5; The metal-organic framework material 1 belongs to monoclinic system, and the space group is P21 / c; the cell parameters are as follows β = 93.3590(14)°, The polyacidic metal-organic framework material 2 belongs to triclinic system, and the space group is P-1; the cell parameters thereof are c = 17.5598(4), a = 75.1010(10)°, β = 81.1600(10)°, γ = 73.5020(10)°, The polyacidic metal-organic framework material 3 is of triclinic system, and the space group is P1; the cell parameters thereof are α = 81.7942(17)°, β = 65.4177(16)°, γ = 77.2034(16)°, The metal-organic framework material 4 is monoclinic, and the space group is Pc; the cell parameters are β = 115.444(4)°, The polyacidic metal-organic framework material 5 is monoclinic, and the space group is P1; the cell parameters thereof are α = 70.994(5)°, β = 64.558(4)°, γ = 76.980(4)°, 2. The method for preparing a polyacid-based metal-organic framework material according to claim 1, characterized in that... ： A preparation method of a polyacid-based metal organic framework material is obtained by hydrothermal and solvothermal synthesis, and the preparation method comprises the following steps: dissolving H4[SiMo 12 O 40 ]·xH2O in water, then adding silver salt / copper salt / cobalt salt and ligand BTYE, stirring for 0.5h, adjusting the pH to be acidic by nitric acid, continuing to stir for 0.5h, then transferring to a polytetrafluoroethylene reaction kettle, slowly cooling to room temperature after heating in an oven until the reaction is completed, to obtain a polyacid-based metal organic framework material, and washing and drying the polyacid-based metal organic framework material to obtain polyacid-based metal organic framework materials 1, 2 and 4. H4[SiMo 12 O 40 ]·xH2O was dissolved in a mixed solution of water and ethanol, then copper / cobalt salt and ligand BTYE were added, stirred for 0.5 h, adjusted to acidic pH with nitric acid, and continued to stir for 0.5 h, then transferred to a polytetrafluoroethylene reactor, heated in an oven until the reaction was completed, slowly cooled to room temperature, and then polyacid-based metal-organic framework materials were obtained. After washing and drying, polyacid-based metal-organic framework materials 3 and 5 were obtained.

3. The method of claim 2, wherein the metal-organic framework material is a polyacidic metal-organic framework material. H4[SiMo 12 O 40 ] x H2O, silver / copper / cobalt salts and BTYE in a molar ratio of 1 :3-6:1 -3.

4. The method of claim 3, wherein the metal-organic framework material is a polyacidic metal-organic framework material. The copper salt includes at least one of copper chloride, copper nitrate, copper acetate, and copper sulfate; the cobalt salt includes at least one of cobalt chloride, cobalt nitrate, cobalt sulfate, and cobalt acetate.

5. The method for preparing a polyacid-based metal-organic framework material according to claim 2, characterized in that: The mixed solution is adjusted to a pH of 2-4; the hydrothermal reaction conditions are a temperature of 120-180 DEG C and a time of 2-5 days.

6. Use of the polyacidic metal-organic framework material according to claim 1, characterized in that: Electrochemical application as supercapacitor electrode material.

7. Use of a polyacid-based metal-organic framework material according to claim 6, characterized in that The metal-organic framework material has good electrochemical capacity and cycle stability as an electrode material.

8. Use of the polyacidic metal-organic framework material according to claim 1, characterized in that: Catalyst application for oxidizing conversion of a sulfide compound into a sulfoxide compound.

9. Use of a polyacid-based metal-organic framework material according to claim 8, characterized in that: The sulfide compound, the vase-shaped metal-organic framework material, and the oxidizing agent are mixed, heated to 40-60 DEG C, and then subjected to oxidation reaction to obtain a sulfoxide compound.

10. Use of a polyacid-based metal-organic framework material according to claim 9, characterized in that: The molar ratio of the sulfide compound, the metal-organic framework material, and the oxidizing agent is 100:1-1.5:100-150.

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