Fluorine-containing organic chain grafted polymetallic oxygen clusters and their derivatives, preparation methods and applications

Abstract

The present invention provides fluorine-containing organic chain grafted polymetallic oxygen clusters and their derivatives, preparation methods and applications, and belongs to the technical field of polymetallic oxygen cluster hybrid materials. The present invention utilizes perfluoroalkyltrimethoxysilane under the action of acid, and the silicon-oxygen bond is hydrolyzed and broken, and is bonded with the W-O bond at the vacant position of the vacant polymetallic oxygen cluster to form a W-O-Si bond. Each vacant polymetallic oxygen cluster vacancy position is bonded to two silanes, and a Si-O-Si bond is formed between the two silanes, thereby achieving covalent grafting of fluorine-containing organic molecular chains on the polymetallic oxygen cluster. The present invention can obtain a structurally adjustable polymetallic oxygen cluster hybrid by changing the types of components such as polymetallic oxygen clusters, fluorine-containing organic chains and counterions. The hybrid combines the characteristics of polymetallic oxygen clusters and fluorine-containing organic chains, can enrich the structure and function of organic grafted polymetallic oxygen cluster hybrids, and has good compatibility with perfluorosulfonic acid polymers, and can be used in the field of perfluorosulfonic acid proton exchange membrane modification.

Description

Technical Field

[0001] The present invention relates to the technical field of polymetallic oxygen cluster hybrid materials, and in particular to fluorine-containing organic chain grafted polymetallic oxygen clusters and derivatives thereof, as well as preparation methods and applications. Background Art

[0002] Polyoxometalates are a class of nano-sized inorganic metal oxide clusters. Their rich surface chemical properties allow them to be functionalized by organic modification to produce organic-inorganic hybrids. Polyoxometalates have super strong Brønsted acidity, excellent catalytic activity, and high electrochemical stability. Polyoxometalate hybrids prepared by organic covalent grafting strategies can combine the physicochemical properties of polyoxometalates themselves with the additional characteristics of organic grafted components. Organic covalently grafted functionalized polyoxometalate hybrids have been applied in surfactants, electrolyte materials, liquid crystal materials, catalytic materials, and electrode materials.

[0003] However, the organic grafting chains for the synthesis of polyoxometalate hybrids are currently mainly concentrated on alkyl chains and their derivatives, which to some extent limits the structural and functional diversity of polyoxometalate hybrids. Summary of the invention

[0004] The purpose of the present invention is to provide fluorine-containing organic chain grafted polymetallic oxygen clusters and their derivatives, preparation methods and applications, which can enrich the structure and function of organic grafted polymetallic oxygen cluster hybrids.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a fluorine-containing organic chain grafted polyoxometalate cluster, comprising the following steps:

[0007] The perfluoroalkyltrimethoxysilane, the vacancy polyoxometalate, the acid solution and the organic solvent are mixed to carry out a substitution reaction to obtain the fluorine-containing organic chain grafted polyoxometalate.

[0008] Preferably, the vacancy polyoxometallic cluster includes a Keggin-type polyoxometallic cluster or a Dawson-type polyoxometallic cluster.

[0009] Preferably, the Keggin-type polyoxometallic cluster includes Keggin-type vacant silicotungstic acid or Keggin-type vacant phosphotungstic acid; and the Dawson-type polyoxometallic cluster includes Dawson-type vacant phosphotungstic acid.

[0010] Preferably, the Keggin type vacancy silicotungstic acid is K 8 [SiW 11 O 39 ]; the Keggin type vacancy phosphotungstic acid is K 7[PW 11 O 39 ]; the Dawson type vacancy phosphotungstic acid is K 10 [P 2 W 17 O 61 ].

[0011] Preferably, the molar ratio of the perfluoroalkyltrimethoxysilane to the vacant polyoxometalate is 2:(0.5-3); the acid solution is hydrochloric acid, and the concentration of the acid solution is 1 mol / L; the molar ratio of the vacant polyoxometalate to the acid in the acid solution is 1:(2-8).

[0012] Preferably, the temperature of the substitution reaction is room temperature, and the time is 5 to 10 hours.

[0013] The present invention provides a fluorine-containing organic chain grafted polyoxometallic cluster prepared by the preparation method described in the above technical scheme, comprising a vacancy polyoxometallic cluster and a fluorine-containing organic chain grafted on the vacancy polyoxometallic cluster.

[0014] The present invention provides a method for preparing a fluorine-containing organic chain grafted polyoxometalate derivative, comprising the following steps:

[0015] The fluorinated organic chain grafted polyoxometalate described in the above technical solution is mixed with a counter ion reagent to perform substitution to obtain a fluorinated organic chain grafted polyoxometalate derivative containing different counter ions;

[0016] The counter reagent includes hydrogen-type ion exchange resin, sodium-type ion exchange resin, tetrabutylammonium bromide or dioctadecyldimethylammonium bromide.

[0017] The present invention provides a fluorine-containing organic chain grafted polyoxometalate derivative prepared by the preparation method described in the above technical scheme, wherein the cluster anion portion includes a vacant polyoxometalate and a fluorine-containing organic chain grafted on the vacant polyoxometalate, and the counter cation portion includes a potassium ion, a hydrogen ion, a sodium ion, a tetrabutylammonium bromide ion or a dioctadecyldimethylammonium bromide ion.

[0018] The present invention provides the use of the fluorinated organic chain grafted polyoxometalate described in the above technical solution or the fluorinated organic chain grafted polyoxometalate derivative described in the above technical solution in the field of proton exchange membranes or surfactants.

[0019] The present invention provides a method for preparing a fluorine-containing organic chain grafted polyoxometallic cluster. The present invention utilizes perfluoroalkyltrimethoxysilane to hydrolyze and break the silicon-oxygen bond under the action of acid, and bonds with the WO bond at the vacant position of the vacant polyoxometallic cluster to form a WO-Si bond. Each vacant position of the vacant polyoxometallic cluster bonds with two silanes, and a Si-O-Si bond is formed between the two silanes, thereby achieving covalent grafting of a fluorine-containing organic molecular chain on the polyoxometallic cluster.

[0020] Polyoxometallic clusters have properties such as high proton conduction, catalytic activity, photoelectric activity, and pharmaceutical activity. Fluorine-containing organic chains have excellent chemical stability, extremely low surface energy, and high hydrophobicity, which give them good applications in surfactants and show excellent dispersibility and surface activity. Fluorine atoms have strong electron-binding ability and high electronegativity, and have excellent electrochemical and optical properties. The present invention can obtain polyoxometallic cluster hybrids with different grafted fluorine-containing organic chains by changing the type of polyoxometallic clusters. The hybrid combines the unique advantages of polyoxometallic clusters and fluorine-containing organic chains, which can enrich the structure and function of organic-grafted polyoxometallic cluster hybrids and expand their applications in catalysis, proton conduction, surfactants, electrochemistry, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) n ) 2 O] molecular structure diagram;

[0022] Figure 2 K 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) n ) 2 O] molecular structure diagram;

[0023] Figure 3 K obtained in Example 4 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2O] Fourier transform infrared spectrum;

[0024] Figure 4 K obtained in Example 10 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O] Fourier transform infrared spectrum;

[0025] Figure 5 K obtained in Example 16 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O] Fourier transform infrared spectrum;

[0026] Figure 6 This is the MALDI-TOF mass spectrum of the fluorine-containing organic chain grafted polyoxometalate cluster prepared in Example 4;

[0027] Figure 7 This is the MALDI-TOF mass spectrum of the fluorine-containing organic chain grafted polyoxometalate cluster prepared in Example 10;

[0028] Figure 8 This is the MALDI-TOF mass spectrum of the fluorine-containing organic chain grafted polyoxometalate cluster prepared in Example 16. DETAILED DESCRIPTION

[0029] The present invention provides a method for preparing a fluorine-containing organic chain grafted polyoxometalate cluster, comprising the following steps:

[0030] The perfluoroalkyltrimethoxysilane, the vacancy polyoxometalate, the acid solution and the organic solvent are mixed to carry out a substitution reaction to obtain the fluorine-containing organic chain grafted polyoxometalate.

[0031] In the present invention, unless otherwise specified, the required raw materials or reagents are commercially available products well known to those skilled in the art.

[0032] In the present invention, the structural formula of the perfluoroalkyltrimethoxysilane is shown in Formula 1:

[0033]

[0034] In Formula 1, n=1-20, more preferably n=2-8, and even more preferably 4-6.

[0035] In the present invention, the vacancy polyoxometallic cluster preferably includes a Keggin-type polyoxometallic cluster or a Dawson-type polyoxometallic cluster.

[0036] In the present invention, the Keggin type polyoxometallic cluster preferably includes Keggin type vacant silicotungstic acid or Keggin type vacant phosphotungstic acid; the Keggin type vacant silicotungstic acid is K 8 [SiW 11 O 39 ]; the Keggin type vacancy phosphotungstic acid is K 7 [PW 11 O 39 ];

[0037] In the present invention, the Dawson type polyoxometallic cluster preferably includes Dawson type vacant phosphotungstic acid; the Dawson type vacant phosphotungstic acid is preferably K 10 [P 2 W 17 O 61 ].

[0038] The present invention has no particular limitation on the specific source of the vacancy polyoxometallic cluster, and it can be prepared according to methods well known in the art.

[0039] In the present invention, the molar ratio of the perfluoroalkyltrimethoxysilane to the vacancy polyoxometalate is preferably 2:(0.5-3), more preferably 2.1:1.

[0040] In the present invention, the acid solution is preferably hydrochloric acid, and the concentration of the acid solution is preferably 1 mol / L; the molar ratio of the vacant polyoxometallic cluster to the acid in the acid solution is preferably 1:(2-8), and more preferably 1:5. The present invention utilizes acid solution to hydrolyze silane, so that perfluoroalkyltrimethoxysilane and the vacant polyoxometallic cluster undergo a substitution reaction.

[0041] In the present invention, the organic solvent preferably includes acetonitrile, acetone, toluene, xylene, tetrahydrofuran or dichloroethane, and more preferably acetonitrile. The present invention has no particular limitation on the amount of the organic solvent, and it can be adjusted according to actual needs to ensure that the reaction proceeds smoothly.

[0042] The present invention has no particular limitation on the specific process of mixing the perfluoroalkyltrimethoxysilane, the vacancy polyoxometalate, the acid solution and the organic solvent. The materials can be uniformly mixed according to a process well known in the art.

[0043] In the present invention, the temperature of the substitution reaction is preferably room temperature, and the time is preferably 5 to 10 hours, more preferably 8 hours.

[0044] After the substitution reaction is completed, the present invention preferably filters the obtained product solution, and removes the organic solvent by rotary evaporation of the obtained clear solution to obtain a fluorine-containing organic chain grafted polymetallic oxygen cluster; the rotary evaporation is preferably performed under vacuum conditions, and the rotary evaporation temperature is preferably 50° C. The present invention has no special limitation on the filtration, and it can be performed according to a process well known in the art.

[0045] The present invention provides a fluorine-containing organic chain grafted polyoxometallic cluster prepared by the preparation method described in the above technical scheme, comprising a vacancy polyoxometallic cluster and a fluorine-containing organic chain grafted on the vacancy polyoxometallic cluster.

[0046] In the present invention, the fluorine-containing organic chain grafts the vacant Keggin-type polyoxometallic cluster K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) n ) 2 The molecular structure of O] is Figure 1 As shown: Figure 1 In the figure, green represents Si atoms, grayish white represents W atoms, red represents oxygen atoms, and purple represents oxygen atoms in the gaps.

[0047] In the present invention, the fluorine-containing organic chain grafts the vacant Dawson-type polyoxometallic cluster K 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) n ) 2 The molecular structure of O] is Figure 2 As shown: Figure 2 In the figure, green represents P atoms, gray represents W atoms, red represents oxygen atoms, and purple represents oxygen atoms in the gaps.

[0048] The present invention provides a method for preparing a fluorine-containing organic chain grafted polyoxometalate derivative, comprising the following steps:

[0049] The fluorinated organic chain grafted polyoxometalate described in the above technical solution is mixed with a counter ion reagent to perform substitution to obtain a fluorinated organic chain grafted polyoxometalate derivative containing different counter ions;

[0050] The counter reagent includes hydrogen-type ion exchange resin, sodium-type ion exchange resin, tetrabutylammonium bromide or dioctadecyldimethylammonium bromide.

[0051] In the present invention, when the counter reagent is a hydrogen-type ion exchange resin or a sodium-type ion exchange resin, it is preferred to use the hydrogen-type ion exchange resin or the sodium-type ion exchange resin as the stationary phase and acetonitrile, acetone or toluene as the mobile phase to replace the fluorinated organic chain grafted polymetallic oxoclusters to obtain hydrogen-type fluorinated organic chain grafted polymetallic oxoclusters or sodium-type fluorinated organic chain grafted polymetallic oxoclusters. In the replacement process, the counter ions of the fluorinated organic chain grafted polymetallic oxoclusters are K + Replace with H + Or Na + .

[0052] The present invention has no particular limitation on the source or type of the hydrogen-type ion exchange resin or the sodium-type ion exchange resin, and any corresponding resin known in the art may be used. In an embodiment of the present invention, the hydrogen-type ion exchange resin is of Amberlite IRC 120H (Aladdin), and the sodium-type ion exchange resin is of Amberlite IR-120Na (Aladdin).

[0053] In the present invention, the replacement is preferably carried out in a chromatographic column. The present invention has no special limitation on the chromatographic column, and any corresponding chromatographic column well known in the art can be used.

[0054] After the replacement is completed, the present invention preferably removes the mobile phase by rotary evaporation of the obtained clear solution at 50° C. under vacuum conditions to obtain hydrogen-type fluorine-containing organic chain grafted polymetallic oxoclusters or sodium-type fluorine-containing organic chain grafted polymetallic oxoclusters.

[0055] In the present invention, when the counter reagent is tetrabutylammonium bromide (TBA) or dioctadecyl dimethylammonium bromide (DODA) (the solubility of the entire molecule of the counter reagent is reduced and can be precipitated), the aqueous solution of TBA or DODA is added dropwise to the aqueous solution of the fluorinated organic chain grafted polyoxometalate, filtered, and a TBA-type fluorinated organic chain grafted polyoxometalate or a DODA-type fluorinated organic chain grafted polyoxometalate solid is obtained. The present invention has no special restrictions on the concentration of the aqueous solution of TBA or DODA and the aqueous solution of the fluorinated organic chain grafted polyoxometalate, which can be adjusted according to actual needs. The present invention has no special restrictions on the dripping and filtering, which can be carried out according to the process well known in the art.

[0056] After the replacement is completed, the present invention preferably removes water from the obtained solid under vacuum conditions at 50° C. to obtain TBA-type fluorinated organic chain-grafted polyoxometallic clusters or DODA-type fluorinated organic chain-grafted polyoxometallic clusters.

[0057] The present invention provides a fluorine-containing organic chain grafted polyoxometalate derivative prepared by the preparation method described in the above technical scheme, wherein the cluster anion portion includes a vacant polyoxometalate and a fluorine-containing organic chain grafted on the vacant polyoxometalate, and the counter cation portion includes a potassium ion, a hydrogen ion, a sodium ion, a tetrabutylammonium bromide ion or a dioctadecyldimethylammonium bromide ion.

[0058] The present invention provides the use of the fluorinated organic chain grafted polyoxometalate described in the above technical solution or the fluorinated organic chain grafted polyoxometalate derivative described in the above technical solution in the field of proton exchange membrane or surfactant. The present invention has no special limitation on the method of the application, and the application can be carried out according to the method known in the art.

[0059] When the hydrogen-type fluorine-containing organic chain grafted polyoxometallic cluster is used for a proton exchange membrane, the present invention preferably mixes the hydrogen-type fluorine-containing organic chain grafted polyoxometallic cluster with a solution of a perfluorosulfonic acid membrane, and casts the resulting mixed solution into a membrane to obtain a hydrogen-type fluorine-containing organic chain grafted polyoxometallic cluster hybrid perfluorosulfonic acid membrane for use in a proton exchange membrane fuel cell.

[0060] In the present invention, the preparation process of the perfluorosulfonic acid membrane solution preferably includes: drying a Nafion solution (commercially available, 20%, w / w) at 60° C. in a forced air drying oven for 24 hours, stirring and dissolving the obtained perfluorosulfonic acid membrane in N,N-dimethylacetamide (DMAc) to obtain a perfluorosulfonic acid membrane solution.

[0061] In the present invention, the concentration of the perfluorosulfonic acid membrane solution is preferably 0.05 to 0.10 g / mL, and more preferably 0.06 to 0.08 g / mL.

[0062] The present invention has no special limitation on the process of mixing the hydrogen-type fluorine-containing organic chain grafted polyoxometalate with the solution of the perfluorosulfonic acid membrane, and the process can be carried out according to the process well known in the art.

[0063] In the present invention, the temperature of the film casting is preferably 25-180°C, more preferably 80°C.

[0064] After the casting and film formation is completed, the present invention preferably dries the obtained film to obtain a hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster hybrid perfluorosulfonic acid film; the drying temperature is preferably 60-80° C., and the drying time is preferably 12 hours.

[0065] In the present invention, based on the mass of the perfluorosulfonic acid membrane, the hybridization mass fraction of the hydrogen-type fluorinated organic chain grafted polyoxometallic clusters in the perfluorosulfonic acid membrane is preferably 1 to 20%, more preferably 1 to 15%, and further preferably 1 to 5%. In the present invention, the amount of the solution of the hydrogen-type fluorinated organic chain grafted polyoxometallic clusters and the perfluorosulfonic acid membrane is preferably controlled to reach the above range.

[0066] In the present invention, the thickness of the hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster hybrid perfluorosulfonic acid film is preferably 60 to 120 μm, more preferably 80 to 100 μm.

[0067] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0068] In the following examples, the vacant polyoxometallic clusters used refer to the prior art (Polyoxometallic Chemistry, edited by Chen Weilin and Wang Enbo, published in July 2013, ISBN code: 9787030379368. 8 [SiW 11 O 39 ] Synthesis see page 103, K 7 [PW 11 O 39 ] Synthesis see page 97, K 10 [P 2 W 17 O 61 ]Synthesis see page 178) method for preparation.

[0069] The model of the hydrogen-type ion exchange resin used is Amberlite IRC 120H (Aladdin), and the model of the sodium-type ion exchange resin used is Amberlite IR-120Na (Aladdin).

[0070] Example 1

[0071] 1mmol Keggin type vacant silicotungstate K 8 [SiW 11 O 39 ] was added to a round-bottom flask, and 5mmol hydrochloric acid (1mol / L), 50mL acetonitrile and 2.1mmol perfluoroalkyltrimethoxysilane with a polymerization degree n of 2 were added, and the reaction was carried out at room temperature for 8h. The obtained product was filtered, and the acetonitrile was removed by rotary evaporation at 50℃ under vacuum conditions to obtain fluorinated organic chain grafted Keggin-type silicotungstic acid K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O].

[0072] Example 2

[0073] According to the method of Example 1, fluorine-containing organic chain grafted Keggin type silicotungstic acid K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O];

[0074] The hydrogen-type ion exchange resin is added to the chromatographic column as the stationary phase, and acetonitrile is added as the mobile phase to replace the fluorinated organic chain grafted Keggin-type silicotungstic acid. The clarified solution after replacement is rotary evaporated at 50°C under vacuum conditions to remove the acetonitrile solvent, thereby obtaining a solid hydrogen-type fluorinated organic chain grafted Keggin-type silicotungstic acid H. 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O].

[0075] Example 3

[0076] According to the method of Example 1, fluorine-containing organic chain grafted Keggin type silicotungstic acid K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O];

[0077] 1mmol of fluorinated organic chain was grafted into Keggin-type silicotungstate K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O] was dissolved in 50 mL of water, and 7 mmol of tetrabutylammonium bromide was dissolved in 5 mL of water; the obtained aqueous solution containing tetrabutylammonium bromide was added dropwise into the aqueous solution of fluorine-containing organic chain grafted Keggin-type silicotungstic acid for replacement, and the solid obtained after filtration was dehydrated at 50°C under vacuum conditions to obtain TBA-type fluorine-containing organic chain grafted Keggin-type silicotungstic acid TBA 4 [SiW11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O].

[0078] Example 4

[0079] 1mmol Keggin type vacant silicotungstate K 8 [SiW 11 O 39 ] was added to a round-bottom flask, and 5mmol hydrochloric acid (1mol / L), 50mL acetonitrile and 2.1mmol perfluoroalkyltrimethoxysilane with a polymerization degree n of 4 were added, and the reaction was carried out at room temperature for 8h. The obtained product was filtered and the acetonitrile solvent was removed by rotary evaporation at 50℃ under vacuum conditions to obtain fluorinated organic chain grafted Keggin type silicotungstic acid K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O].

[0080] Example 5

[0081] According to the method of Example 4, the fluorine-containing organic chain grafted Keggin type silicotungstic acid K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O];

[0082] The hydrogen-type ion exchange resin is added to the chromatographic column as the stationary phase, and acetonitrile is added as the mobile phase to replace the fluorinated organic chain grafted Keggin-type silicotungstic acid. The clarified solution after replacement is rotary evaporated at 50°C under vacuum conditions to remove the acetonitrile solvent, thereby obtaining a solid hydrogen-type fluorinated organic chain grafted Keggin-type silicotungstic acid H. 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O].

[0083] Example 6

[0084] According to the method of Example 4, the fluorine-containing organic chain grafted Keggin type silicotungstic acid K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O];

[0085] 1mmol of fluorinated organic chain was grafted into Keggin-type silicotungstate K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O] was dissolved in 50 mL of water, 7 mmol of tetrabutylammonium bromide was dissolved in 5 mL of water, and the obtained aqueous solution containing tetrabutylammonium bromide was added dropwise into the aqueous solution of fluorine-containing organic chain grafted Keggin-type silicotungstic acid for replacement. The solid obtained after filtration was dehydrated at 50 ° C under vacuum conditions to obtain TBA-type fluorine-containing organic chain grafted Keggin-type silicotungstic acid TBA 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O].

[0086] Example 7

[0087] 1mmol Keggin type vacancy phosphotungstic acid (K 7 [PW 11 O 39 ]) was added to a round-bottom flask, and 5mmol hydrochloric acid (1mol / L), 50mL acetonitrile and 2.1mmol perfluoroalkyltrimethoxysilane with a polymerization degree n of 2 were added, and the reaction was carried out at room temperature for 8h. The obtained product was filtered, and the acetonitrile solvent was removed by rotary evaporation at 50°C under vacuum conditions to obtain a fluorinated organic chain grafted Keggin-type phosphotungstic acid K 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O].

[0088] Example 8

[0089] According to the method of Example 7, fluorine-containing organic chain grafted Keggin type phosphotungstic acid K 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O];

[0090] The hydrogen-type ion exchange resin is added to the chromatographic column as the stationary phase, and acetonitrile is added as the mobile phase to replace the fluorinated organic chain grafted Keggin-type phosphotungstic acid. The clarified solution after the replacement is rotary evaporated at 50° C. under vacuum conditions to remove the acetonitrile solvent, thereby obtaining a solid hydrogen-type fluorinated organic chain grafted Keggin-type phosphotungstic acid H 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O].

[0091] Example 9

[0092] According to the method of Example 7, fluorine-containing organic chain grafted Keggin type phosphotungstic acid K 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O];

[0093] 1mmol of fluorinated organic chain was grafted to Keggin type phosphotungstic acid K 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2O] was dissolved in 50 mL of water, 7 mmol of tetrabutylammonium bromide was dissolved in 5 mL of water, and the obtained aqueous solution containing tetrabutylammonium bromide was added dropwise into the aqueous solution of fluorine-containing organic chain grafted Keggin-type phosphotungstic acid for replacement. The solid obtained after filtration was dehydrated at 50 ° C under vacuum conditions to obtain TBA-type fluorine-containing organic chain grafted Keggin-type phosphotungstic acid TBA 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O].

[0094] Example 10

[0095] 1mmol Keggin type vacancy phosphotungstic acid (K 7 [PW 11 O 39 ]) was added to a round-bottom flask, and 5mmol hydrochloric acid (1mol / L), 50mL acetonitrile and 2.1mmol perfluoroalkyltrimethoxysilane with a polymerization degree n of 4 were added, and the reaction was carried out at room temperature for 8h. The obtained product was filtered, and the acetonitrile solvent was removed by rotary evaporation at 50°C under vacuum conditions to obtain a fluorinated organic chain grafted Keggin-type phosphotungstic acid K 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O].

[0096] Embodiment 11

[0097] According to the method of Example 10, fluorine-containing organic chain grafted Keggin type phosphotungstic acid K 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O];

[0098] The hydrogen-type ion exchange resin is added to the chromatographic column as the stationary phase, and acetonitrile is added as the mobile phase to replace the fluorinated organic chain grafted Keggin-type phosphotungstic acid. The clarified solution after the replacement is rotary evaporated at 50° C. under vacuum conditions to remove the acetonitrile solvent, thereby obtaining a solid hydrogen-type fluorinated organic chain grafted Keggin-type phosphotungstic acid H 3 [PW11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O].

[0099] Example 12

[0100] According to the method of Example 10, fluorine-containing organic chain grafted Keggin type phosphotungstic acid K 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O];

[0101] 1mmol of fluorinated organic chain was grafted to Keggin type phosphotungstic acid K 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O] was dissolved in 50 mL of water, and 7 mmol of tetrabutylammonium bromide was dissolved in 5 mL of water; the obtained aqueous solution containing tetrabutylammonium bromide was added dropwise into the aqueous solution of fluorine-containing organic chain grafted Keggin-type phosphotungstic acid for replacement, and the solid obtained after filtration was dehydrated at 50°C under vacuum conditions to obtain TBA-type fluorine-containing organic chain grafted Keggin-type phosphotungstic acid TBA 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O].

[0102] Embodiment 13

[0103] 1 mmol Dawson type vacancy phosphotungstic acid (K 10 [P 2 W 17 O 61]) was added to a round-bottom flask, and 5mmol hydrochloric acid (1mol / L), 50mL acetonitrile and 2.1mmol perfluoroalkyltrimethoxysilane with a polymerization degree n of 2 were added, and the reaction was carried out at room temperature for 8h. The obtained product was filtered, and the acetonitrile solvent was removed by rotary evaporation at 50°C under vacuum conditions to obtain a fluorinated organic chain grafted Dawson type phosphotungstic acid K 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O].

[0104] Embodiment 14

[0105] According to the method of Example 13, Dawson type phosphotungstic acid K grafted with fluorine-containing organic chain was prepared 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O];

[0106] The hydrogen-type ion exchange resin is added to the chromatographic column as the stationary phase, and acetonitrile is added as the mobile phase to replace the fluorinated organic chain grafted Dawson-type phosphotungstic acid. The clarified solution after the replacement is rotary evaporated at 50°C under vacuum conditions to remove the acetonitrile solvent to obtain solid hydrogen-type fluorinated organic chain grafted Dawson-type phosphotungstic acid H 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O].

[0107] Embodiment 15

[0108] According to the method of Example 13, Dawson type phosphotungstic acid K grafted with fluorine-containing organic chain was prepared 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2O];

[0109] 1mmol of fluorinated organic chain was grafted into Dawson type phosphotungstic acid K 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O] was dissolved in 50 ml of water, 7 mmol of tetrabutylammonium bromide was dissolved in 5 ml of water, the obtained aqueous solution containing tetrabutylammonium bromide was added dropwise into the aqueous solution of Dawson type phosphotungstic acid grafted with fluorine-containing organic chain for replacement, and the solid obtained after filtration was dehydrated at 50°C under vacuum conditions to obtain TBA type fluorine-containing organic chain grafted Dawson type phosphotungstic acid TBA 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 2 ) 2 O].

[0110] Example 16

[0111] 1 mmol Dawson type vacancy phosphotungstic acid (K 10 [P 2 W 17 O 61 ]) was added to a round-bottom flask, and 5mmol hydrochloric acid (1mol / L), 50mL acetonitrile and 2.1mmol perfluoroalkyltrimethoxysilane with a polymerization degree n of 4 were added, and the reaction was carried out at room temperature for 8h. The obtained product was filtered, and the acetonitrile solvent was removed by rotary evaporation at 50°C under vacuum conditions to obtain a fluorinated organic chain grafted Dawson type phosphotungstic acid K 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O].

[0112] Embodiment 17

[0113] According to the method of Example 16, Dawson-type phosphotungstic acid K grafted with fluorine-containing organic chain was prepared 6 [P 2 W 17 O 61(SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O];

[0114] The hydrogen-type ion exchange resin is added to the chromatographic column as the stationary phase, and acetonitrile is added as the mobile phase to replace the fluorinated organic chain grafted Dawson-type phosphotungstic acid. The clarified solution after the replacement is rotary evaporated at 50°C under vacuum conditions to remove the acetonitrile solvent to obtain solid hydrogen-type fluorinated organic chain grafted Dawson-type phosphotungstic acid H 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O].

[0115] Embodiment 18

[0116] According to the method of Example 16, Dawson-type phosphotungstic acid K grafted with fluorine-containing organic chain was prepared 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O];

[0117] 1mmol of fluorinated organic chain was grafted into Dawson type phosphotungstic acid K 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O] was dissolved in 50 mL of water, 7 mmol of tetrabutylammonium bromide was dissolved in 5 mL of water, and the obtained aqueous solution containing tetrabutylammonium bromide was added dropwise into the aqueous solution of Dawson type phosphotungstic acid grafted with fluorine-containing organic chain for replacement. The solid obtained after filtration was dehydrated at 50 ° C under vacuum conditions to obtain TBA type fluorine-containing organic chain grafted Dawson type phosphotungstic acid TBA 6 [P 2 W 17 O 61 (SiC 2 H4 (C 2 F 4 ) 4 ) 2 O].

[0118] Application Example 1

[0119] 0.1 g of Nafion membrane was dissolved in 1.5 mL of DMAc solvent and stirred to dissolve, and then 5 mg of the hydrogen-type fluorine-containing organic chain grafted Keggin-type silicotungstic acid prepared in Example 5 was added and stirred to dissolve; the resulting mixed solution was cast into a membrane at 80° C. and dried at 80° C. for 12 hours to obtain a hydrogen-type fluorine-containing organic chain grafted Keggin-type silicotungstic acid hybrid perfluorosulfonic acid membrane with a membrane thickness of 80±3 μm, wherein the mass fraction of the hydrogen-type fluorine-containing organic chain grafted Keggin-type silicotungstic acid was 5%.

[0120] Application Example 2

[0121] 0.1 g of Nafion membrane was dissolved in 1.5 mL of DMAc solvent and stirred to dissolve, and then 5 mg of the hydrogen-type fluorinated organic chain grafted Keggin-type phosphotungstic acid prepared in Example 11 was added and stirred to dissolve; the resulting mixed solution was cast into a membrane at 80° C. and dried at 80° C. for 12 hours to obtain a hydrogen-type fluorinated organic chain grafted Keggin-type phosphotungstic acid hybrid perfluorosulfonic acid membrane with a membrane thickness of 80±3 μm, wherein the mass fraction of the hydrogen-type fluorinated organic chain grafted Keggin-type phosphotungstic acid was 5%.

[0122] Application Example 3

[0123] 0.1 g of Nafion membrane was dissolved in 1.5 mL of DMAc solvent and stirred to dissolve, and then 5 mg of the hydrogen-type fluorinated organic chain grafted Dawson-type phosphotungstic acid prepared in Example 17 was added and stirred to dissolve; the resulting mixed solution was cast into a film at 80°C and dried at 80°C for 12 hours to obtain a hydrogen-type fluorinated organic chain grafted Dawson-type phosphotungstic acid hybrid perfluorosulfonic acid membrane with a film thickness of 80±3 μm, wherein the mass fraction of the hydrogen-type fluorinated organic chain grafted Dawson-type phosphotungstic acid was 5%.

[0124] Comparative application example 1

[0125] 0.1 g of Nafion membrane was dissolved in 1.5 mL of DMAc solvent, stirred and dissolved, and the solution was cast into a membrane at 80° C. and dried at 80° C. for 12 hours to obtain a pure perfluorosulfonic acid membrane with a membrane thickness of 80±3 μm.

[0126] Characterization and performance testing

[0127] 1) Figure 3 K obtained in Example 4 4 [SiW 11 O39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O], from the spectrum we can see that the product also appeared at 1047cm -1 The Si-O-Si bond absorption peak is located at 1140 cm -1 The absorption peaks of the CF bond of the fluorinated organic chain at , and the absorption peaks of the Si-O bond and WO bond of the polyoxometalate cluster, prove that K 4 [SiW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O] was successfully synthesized.

[0128] Figure 4 K obtained in Example 10 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O], from the spectrum we can see that the product also appeared at 1110cm -1 The Si-O-Si bond absorption peak is located at 1150cm -1 The absorption peaks of the CF bond of the fluorinated organic chain at , and the absorption peaks of the PO bond and WO bond of the polyoxometalate cluster, prove that K 3 [PW 11 O 39 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O] was successfully synthesized.

[0129] Figure 5 K obtained in Example 16 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2O], from the spectrum we can see that the product also appeared at 1110cm -1 The Si-O-Si bond absorption peak is located at 1150cm -1 The absorption peaks of the CF bond of the fluorinated organic chain at , and the absorption peaks of the PO bond and WO bond of the polyoxometalate cluster, prove that K 6 [P 2 W 17 O 61 (SiC 2 H 4 (C 2 F 4 ) 4 ) 2 O] was successfully synthesized.

[0130] Figures 6 to 8 The MALDI-TOF mass spectra of the fluorinated organic chain grafted polyoxometalates prepared in Examples 4, 10 and 16 respectively show that the molecular weights of the fluorinated organic chain grafted polyoxometalates prepared in Examples 4, 10 and 16 are 3759, 3722 and 5326 respectively. The successful synthesis of the fluorinated organic chain grafted polyoxometalates molecules in Examples 4, 10 and 16 is demonstrated.

[0131] 2) The conductivity of the hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster hybrid perfluorosulfonic acid membranes prepared in Examples 1 to 3 and the non-hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster hybrid perfluorosulfonic acid membrane prepared in Comparative Application Example 1 was tested. The test method was to use an AC impedance meter to measure. All membranes were immersed in deionized water at 30°C or 80°C for 24 hours, and then the conductivity was measured in a fully wet state in water. The results are shown in Table 1.

[0132] Table 1 Proton conductivity of sample membranes prepared in Application Examples 1 to 3 and Comparative Example 1

[0133]

[0134] As shown in Table 1, the proton conductivity of the hydrogen-type fluorinated organic chain grafted polymetallic oxygen cluster hybrid perfluorosulfonic acid membrane prepared in Application Examples 1 to 3 is higher than that of the pure perfluorosulfonic acid membrane, proving that the method provided by the present invention can obtain a hybrid proton exchange membrane with high proton conductivity and be applied to the field of proton exchange membrane fuel cells. The present invention utilizes the high polarity characteristics of the fluorinated organic chain to recombine with the fluorinated chain segment of the perfluorosulfonic acid membrane, so that the fluorinated organic chain covalently grafted with the polymetallic oxygen cluster is inserted into the fluorinated phase region of the perfluorosulfonic acid membrane, so that the prepared hybrid perfluorosulfonic acid membrane is immobilized with polymetallic oxygen clusters, and the oxygen-rich surface of the polymetallic oxygen clusters is used to form hydrogen bonds with the sulfonic acid groups of the perfluorosulfonic acid membrane, and at the same time, it is used as a proton hopping site to promote proton conduction, thereby obtaining a hybrid proton exchange membrane with high proton conductivity.

[0135] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. Application of a hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster in a proton exchange membrane, characterized in that: The proton exchange membrane is a hydrogen-type fluorinated organic chain grafted polymetallic oxygen cluster hybrid perfluorosulfonic acid membrane, and the preparation method of the hydrogen-type fluorinated organic chain grafted polymetallic oxygen cluster hybrid perfluorosulfonic acid membrane is: mixing the hydrogen-type fluorinated organic chain grafted polymetallic oxygen cluster and a solution of a perfluorosulfonic acid membrane, and casting the obtained mixed solution into a membrane to obtain a hydrogen-type fluorinated organic chain grafted polymetallic oxygen cluster hybrid perfluorosulfonic acid membrane; The hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster consists of a cluster anion part and a counter cation part; the cluster anion part is a vacancy polymetallic oxygen cluster and a fluorine-containing organic chain grafted on the vacancy polymetallic oxygen cluster, and the counter cation part is a hydrogen ion; The method for preparing the hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster comprises the following steps: The fluorine-containing organic chain grafted polyoxometalate is mixed with a counter reagent to perform substitution to obtain a hydrogen-type fluorine-containing organic chain grafted polyoxometalate; the counter reagent is a hydrogen-type ion exchange resin; The preparation method of the fluorine-containing organic chain grafted polymetallic oxygen cluster comprises the following steps: The perfluoroalkyltrimethoxysilane, the vacancy polyoxometalate, the acid solution and the organic solvent are mixed to carry out a substitution reaction to obtain the fluorine-containing organic chain grafted polyoxometalate; The temperature of the substitution reaction is room temperature and the time is 5 to 10 hours.

2. The use according to claim 1, characterized in that: The vacancy polyoxometallic cluster is a Keggin-type polyoxometallic cluster or a Dawson-type polyoxometallic cluster.

3. The use according to claim 2, characterized in that: The Keggin type polyoxometallic cluster is a Keggin type vacant silicotungstic acid or a Keggin type vacant phosphotungstic acid; and the Dawson type polyoxometallic cluster is a Dawson type vacant phosphotungstic acid.

4. The use according to claim 3, characterized in that: The Keggin type vacancy silicotungstic acid is K8[SiW 11 O 39 ]; the Keggin type vacancy phosphotungstic acid is K7[PW 11 O 39 ]; the Dawson type vacancy phosphotungstic acid is K 10 [P2W 17 O 61 ].

5. The use according to any one of claims 1 to 4, characterized in that: The molar ratio of the perfluoroalkyltrimethoxysilane to the vacant polyoxometallic cluster is 2:(0.5-3); the acid solution is hydrochloric acid, and the concentration of the acid solution is 1 mol / L; the molar ratio of the vacant polyoxometallic cluster to the acid in the acid solution is 1:(2-8).

6. A hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster hybrid perfluorosulfonic acid membrane, characterized in that: It comprises a perfluorosulfonic acid membrane and a hydrogen-type fluorine-containing organic chain covalently grafted polymetallic oxygen cluster inserted into a fluorine-containing phase region in the perfluorosulfonic acid membrane; The hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster is the hydrogen-type fluorine-containing organic chain grafted polymetallic oxygen cluster as claimed in claim 1.

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