Supported porous organic polymer catalyst and application thereof in preparation of 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural
By using an amino-modified porous organic polymer catalyst supported with a gold-palladium alloy catalyzed with a catalytic oxidation of HMF under alkali-free conditions, the problems of high production cost and poor selectivity of FDCA in the prior art are solved, and efficient and environmentally friendly FDCA production is achieved.
Patent Information
- Application Number
- CN202311719601.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-14
- Publication Date
- 2025-06-17
AI Technical Summary
The prior art has the problem of additional alkali need and poor selectivity in the catalytic oxidation process from HMF to FDCA, which leads to high production costs of FDCA and insufficient market competitiveness.
The aniline polymer as a support is used to efficiently catalyze the oxidized HMF to FDCA under alkali-free conditions by using an amino-modified porous organic polymer catalyst supported by a gold-palladium alloy.
The yield of FDCA is achieved up to 82%, and the selectivity of FDCA reaches more than 87%, reducing production costs, improving market competitiveness, and being more environmentally friendly.
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Abstract
Description
Technical Field
[0001] The present application relates to a supported porous organic polymer catalyst and its application in the preparation of 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural, belonging to the field of chemical engineering. Background Art
[0002] 2,5-Furandicarboxylic acid (FDCA) has a conjugated carbon ring and a diacid structure similar to petroleum-based terephthalic acid (TPA), and can replace TPA for synthesizing bio-based furan polyesters with better thermal stability and gas barrier properties, greatly reducing the severe dependence of the polyester industry on fossil resources. In addition, FDCA also has wide applications in medicine, spices, and metal coordination chemistry, and is considered to be one of the 12 most promising bio-based platform compounds.
[0003] As a renewable biomass resource, the catalytic oxidation of HMF to FDCA under laboratory conditions has become the mainstream strategy for FDCA production. However, there are some obstacles in this method, such as the need to add extra alkali, poor selectivity, etc., resulting in a relatively high production cost of FDCA, insufficient market competitiveness, and being not conducive to large-scale industrialization. Summary of the Invention
[0004] Aiming at the above-mentioned route for preparing FDCA from biomass energy HMF as a raw material, the present invention provides a catalyst of an amino-modified porous organic polymer loaded with a gold-palladium alloy, which can efficiently catalyze the oxidation of HMF to FDCA under alkali-free conditions. This catalyst selects an aniline polymer as the carrier and loads the AuPd alloy. Under the action of this catalyst, the yield of FDCA is as high as 82%, and the selectivity of FDCA reaches more than 87%.
[0005] One aspect of the present application provides a supported porous organic polymer catalyst, and the supported porous organic polymer catalyst includes a carrier and an active component loaded on the carrier;
[0006] The carrier is an aniline polymer;
[0007] The active component is a gold-palladium alloy.
[0008] Optionally, in the supported porous organic polymer catalyst, the loading amount of the active component is 0.5 wt% - 5 wt%.
[0009] Optionally, in the supported porous organic polymer catalyst, the loading amount of the active component is 2 wt%.
[0010] Optionally, in the supported porous organic polymer catalyst, the loading amount of the active component is independently selected from any value of 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt% or any range value between any two of the above.
[0011] The catalyst provided by this application is a catalyst for efficiently catalytically oxidizing 5-hydroxymethylfurfural to prepare 2,5-furandicarboxylic acid. The catalyst uses an aniline polymer as a carrier, and an AuPd alloy is loaded on the polymer as a reaction site.
[0012] Another aspect of this application provides a preparation method of the above-mentioned supported porous organic polymer catalyst, and the preparation method includes:
[0013] Immerse the aniline polymer carrier in the AuPd alloy solution, impregnate, and dry to obtain the supported porous organic polymer catalyst.
[0014] Optionally, the mass ratio of the aniline polymer carrier to the AuPd alloy solution is 100:1 to 10:1.
[0015] Optionally, the mass-volume ratio of the aniline polymer carrier to the AuPd alloy solution is independently selected from any value of 100:1, 80:1, 50:1, 30:1, 10:1 or any range value between any two of the above.
[0016] Optionally, the AuPd alloy solution further includes Solvent I, and Solvent I is selected from at least one of water and ethanol.
[0017] Optionally, in the AuPd alloy solution, the concentration of the AuPd alloy is 0.5 to 10 mg / ml.
[0018] Optionally, in the AuPd alloy solution, the concentration of the AuPd alloy is independently selected from any value of 10 mg / ml, 8 mg / ml, 5 mg / ml, 3 mg / ml, 1 mg / ml, 0.5 mg / ml or any range value between any two of the above.
[0019] Optionally, the impregnation time is 120 to 240 min;
[0020] The drying temperature is 80 to 100 °C, and the drying time is 12 to 24 h.
[0021] Optionally, the impregnation time is independently selected from any value of 120 min, 180 min, 240 min or any range value between any two of the above.
[0022] Optionally, the drying temperature is independently selected from any value of 80 °C, 90 °C, 100 °C or any range value between any two of the above.
[0023] Optionally, the drying time is independently selected from any value among 12 h, 18 h, and 24 h or any range value between any two of the above.
[0024] Optionally, the method for preparing the aniline polymer carrier includes:
[0025] Mixing monomer aniline, a crosslinking agent, catalyst A, and solvent A, carrying out a polymerization reaction, and extracting to obtain the aniline polymer carrier.
[0026] Optionally, the crosslinking agent is selected from at least one of dimethoxymethane and chloromethyl methyl ether;
[0027] The catalyst A is selected from at least one of ferric chloride and aluminum chloride;
[0028] The solvent is selected from at least one of dichloromethane and dichloroethane.
[0029] Optionally, the molar ratio of the monomer aniline, the crosslinking agent, and catalyst A is 1:1:1 to 1:5:5.
[0030] Optionally, the molar ratio of the monomer aniline, the crosslinking agent, and catalyst A is 1:3:3.
[0031] Optionally, the molar ratio of the monomer aniline, the crosslinking agent, and catalyst A is independently selected from any value among 1:1:1, 1:2:2, 1:3:3, 1:4:4, and 1:5:5 or any range value between any two of the above.
[0032] Optionally, the molar volume ratio of the monomer aniline to the solvent is 1:10 to 1:20.
[0033] Optionally, the molar volume ratio of the monomer aniline to the solvent is independently selected from any value among 1:10, 1:15, and 1:20 or any range value between any two of the above.
[0034] Optionally, the temperature of the polymerization reaction is 80 to 110 °C;
[0035] The time of the polymerization reaction is 24 to 30 h;
[0036] The time of the extraction is 24 to 36 h.
[0037] Optionally, the temperature of the polymerization reaction is independently selected from any value among 80 °C, 90 °C, 100 °C, and 110 °C or any range value between any two of the above.
[0038] Optionally, the time of the polymerization reaction is independently selected from any value among 24 h, 26 h, 28 h, and 30 h or any range value between any two of the above.
[0039] Optionally, the extraction time is independently selected from any value among 24h, 30h, 36h or any range value between any two of the above.
[0040] Optionally, the method for preparing the gold-palladium alloy includes:
[0041] After adding a protective agent to a mixed solution containing a gold source and a palladium source, a reducing agent is added and stirred to obtain the gold-palladium alloy.
[0042] Optionally, the protective agent is selected from at least one of polyvinylpyrrolidone and polyvinyl alcohol.
[0043] Optionally, the gold source is selected from at least one of chloroauric acid and gold chloride;
[0044] The palladium source is selected from at least one of palladium chloride and palladium acetate.
[0045] Optionally, the molar ratio of the gold source to the palladium source is 1:1 to 1:10;
[0046] The mass ratio of the protective agent to the gold source is 1:2 to 1:4.
[0047] Optionally, the molar ratio of the gold source to the palladium source is 1:3.
[0048] Optionally, the molar ratio of the gold source to the palladium source is independently selected from any value among 1:1, 1:2, 1:3, 1:4, 1:6, 1:8, 1:10 or any range value between any two of the above.
[0049] Optionally, the mass ratio of the protective agent to the gold source is independently selected from any value among 1:2, 1:3, 1:4 or any range value between any two of the above.
[0050] Optionally, the reducing agent is selected from at least one of NaBH4 and KBH4.
[0051] Optionally, the molar ratio of the reducing agent to the gold source is 5:1 to 8:1.
[0052] Optionally, the molar ratio of the reducing agent to the gold source is independently selected from any value among 5:1, 6:1, 7:1, 8:1 or any range value between any two of the above.
[0053] As a specific embodiment, the supported porous organic polymer catalyst can be prepared according to the following method:
[0054] Take the precursor chloroauric acid and palladium chloride solution in a certain proportion into a flask, and the proportion is 1:1 - 1:10; mix them evenly by magnetic stirring, add the prepared polyvinylpyrrolidone solution, stir until it becomes a sol state, then dropwise add the freshly prepared reducing agent NaBH4 solution, and stir for 30 min to obtain the reduced gold-palladium alloy.
[0055] Add the monomer aniline, the cross-linking agent dimethoxymethane, and the catalyst ferric chloride in a certain proportion to the dichloroethane solvent, and the proportion is 1:1:1 - 1:5:5; under the condition of vigorous stirring, heat to 80 °C to completely polymerize aniline, and the polymerization time is 24 h. Extract the obtained solid with methanol as the solvent by Soxhlet extraction for 24 h to obtain a porous organic polymer support.
[0056] Add the porous organic polymer support to the prepared gold-palladium alloy solution, impregnate and load for 120 min. Filter, wash with deionized water until neutral, and then dry in a vacuum oven at 80 °C. Obtain a catalyst containing a certain loading amount of gold-palladium alloy, and the loading amount is 0.5% - 5%.
[0057] Another aspect of the present application provides the use of the above-mentioned supported porous organic polymer catalyst in the oxidation of 5-hydroxymethylfurfural (HMF) to prepare 2,5-furandicarboxylic acid (FDCA), and the said use includes:
[0058] Under an oxygen atmosphere, mix 5-hydroxymethylfurfural, solvent B and the supported porous organic polymer catalyst, and react to obtain 2,5-furandicarboxylic acid.
[0059] Optionally, the reaction is carried out under alkali-free conditions.
[0060] Optionally, the reaction is carried out in a high-pressure reactor.
[0061] Optionally, the solvent B is selected from at least one of N,N-dimethylformamide (DMF) and chloromethyl methyl ether.
[0062] Optionally, the temperature of the reaction is 100 - 170 °C;
[0063] The pressure of the reaction is 0.1 - 2 MPa;
[0064] The time of the reaction is 0.5 - 6 h.
[0065] Optionally, the temperature of the reaction is 140 °C.
[0066] Optionally, the temperature of the reaction is independently selected from any value of 100 °C, 120 °C, 140 °C, 170 °C or any range value between any two of the above.
[0067] Optionally, the pressure of the reaction is 2 MPa.
[0068] Optionally, the pressure of the reaction is independently selected from any value of 0.1 MPa, 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa or any range value between any two of the above.
[0069] Optionally, the time of the reaction is 2 h.
[0070] Optionally, the time of the reaction is independently selected from any value of 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h or any range value between any two of the above.
[0071] Optionally, the mass ratio of the supported porous organic polymer catalyst to 5-hydroxymethylfurfural is 2:5 to 4:5;
[0072] The mass-volume ratio of the 5-hydroxymethylfurfural to the solvent B is 0.13:1 to 0.26:1.
[0073] Optionally, the mass ratio of the supported porous organic polymer catalyst to 5-hydroxymethylfurfural is independently selected from any value of 2:5, 3:5, 4:5 or any range value between any two of the above.
[0074] Optionally, the mass-volume ratio of the 5-hydroxymethylfurfural to the solvent B is independently selected from any value of 0.13:1, 0.15:1, 0.18:1, 0.2:1, 0.26:1 or any range value between any two of the above.
[0075] The beneficial effects that can be produced by this application include:
[0076] 1) Compared with the strong base system, the aldehyde group is prone to acetal reaction to produce by-products such as humin. This heterogeneous catalyst is modified with basic amino groups, without additional addition of alkali, the selectivity is improved, and the post-treatment of the solvent is avoided, which is more environmentally friendly.
[0077] 2) Compared with traditional petroleum substrates, the reaction substrates are derived from biomass, which conforms to the dual-carbon concept.
[0078] 3) Using a porous organic polymer loaded with an AuPd alloy as the catalyst, without additional addition of alkali, it has high conversion rate and selectivity, good stability, and is more green and environmentally friendly.
[0079] 4) Using an amino-modified porous organic polymer loaded with gold-palladium alloy as a catalyst, 5-hydroxymethylfurfural is efficiently catalytically oxidized to prepare 2,5-furandicarboxylic acid. Compared with the stoichiometric oxidation of HMF to obtain FDCA, which requires the use of strong oxidants such as KMnO4, this method uses oxygen as an oxidant, which is more green and efficient; compared with traditional heterogeneous catalysis that requires the addition of an alkali co-catalyst, this method can achieve catalytic oxidation under alkali-free conditions, with high conversion and high reaction selectivity while having a long catalyst service life. Description of the Drawings
[0080] Figure 1 This is the TEM of the gold-palladium alloy nanoparticles obtained in Example 2 of the present application, and the scale bar is 50 nm.
[0081] Figure 2 This is the TEM of the organic polymer catalyst loaded with gold-palladium alloy obtained in Example 2 of the present application, and the scale bar is 20 nm. Detailed Description of the Embodiments
[0082] The present application will be described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0083] Unless otherwise specified, the raw materials and catalysts in the embodiments of the present application are all purchased through commercial channels.
[0084] Preparation of Material A in Example 1
[0085] (1) Take 0.2 ml of 42 mg / ml precursor chloroauric acid and 0.2 ml of 42 mg / ml palladium chloride solution, pour them into a flask in a molar ratio of 1:1, stir magnetically to mix evenly, add 4 ml of the prepared 1 mg / ml polyvinylpyrrolidone solution, stir until it becomes a sol state, then dropwise add 4 ml of 2 mg / ml freshly prepared reducing agent NaBH4 solution, and stir for 30 min to obtain the reduced gold-palladium alloy.
[0086] (2) Add 1 mmol of monomer aniline, 1 mmol of cross-linking agent dimethoxymethane, and 1 mmol of catalyst ferric chloride to 10 ml of dichloroethane solvent in a ratio of 1:1:1. Under vigorous stirring, heat to 80 °C to completely polymerize aniline, and the polymerization time is 24 h. The obtained solid is subjected to Soxhlet extraction with methanol as the solvent for 24 h to obtain a porous organic polymer support.
[0087] (3) Add 200 mg of the porous organic polymer support obtained in step (2) to the prepared 8.4 ml of gold-palladium alloy solution (wherein the gold-palladium alloy is obtained in step (1) and the concentration of the gold-palladium alloy is 2.0 mg / ml), impregnate and load for 120 min, and the loading amount is 1 wt%. Filter, wash with deionized water until neutral, and then dry in a vacuum oven at 80 °C to obtain the catalyst A.
[0088] Preparation of Material B in Example 2
[0089] (1) Take 0.1 ml of 42 mg / ml precursor chloroauric acid and 0.3 ml of 42 mg / ml palladium chloride solution, pour them into a flask in a ratio of 1:3, stir magnetically to mix evenly, add 6 ml of prepared 0.3 mg / ml polyvinylpyrrolidone solution, stir until it becomes a sol state, then dropwise add 10 ml of freshly prepared 0.5 mg / ml reducing agent NaBH4 solution, and stir for 30 min to obtain the reduced gold-palladium alloy.
[0090] (2) Add 1 mmol of monomer aniline, 3 mmol of crosslinking agent dimethoxymethane, and 3 mmol of catalyst ferric chloride to 20 ml of dichloroethane solvent in a ratio of 1:3:3. Under the condition of vigorous stirring, heat to 80 °C to completely polymerize aniline, and the polymerization time is 24 h. Use methanol as the solvent to perform Soxhlet extraction on the obtained solid for 24 h to obtain a porous organic polymer support.
[0091] (3) Add 200 mg of the porous organic polymer support obtained in step (2) to the prepared 16.4 ml of gold-palladium alloy solution (wherein, the gold-palladium alloy is obtained in step (1) and the concentration of the gold-palladium alloy is 1.0 mg / ml), impregnate and load for 120 min, and the loading amount is 0.5%. Filter, wash with deionized water until neutral, and then dry in a vacuum oven at 80 °C to obtain the catalyst B.
[0092] Preparation of Material C in Example 3
[0093] (1) Take 0.2 ml of 42 mg / ml precursor chloroauric acid and 0.4 ml of 42 mg / ml palladium chloride solution, pour them into a flask in a ratio of 1:2, stir magnetically to mix evenly, add 3 ml of prepared 1 mg / ml polyvinylpyrrolidone solution, stir until it becomes a sol state, then dropwise add 3 ml of freshly prepared 2 mg / ml reducing agent NaBH4 solution, and stir for 30 min to obtain the reduced gold-palladium alloy.
[0094] (2) Add 1 mmol of monomer aniline, 3 mmol of crosslinking agent dimethoxymethane, and 3 mmol of catalyst ferric chloride to 20 ml of dichloroethane solvent in a ratio of 1:3:3. Under the condition of vigorous stirring, heat to 80 °C to completely polymerize aniline, and the polymerization time is 24 h. Use methanol as the solvent to perform Soxhlet extraction on the obtained solid for 24 h to obtain a porous organic polymer support.
[0095] (3) Add 200 mg of the porous organic polymer support obtained in step (2) to the prepared 6.6 ml of gold-palladium alloy solution (wherein the gold-palladium alloy is obtained in step (1) and the concentration of the gold-palladium alloy is 4.0 mg / ml), impregnate and load for 120 min, and the loading amount is 2%. Filter, wash with deionized water until neutral, and then dry in a vacuum oven at 80 °C to obtain the catalyst C.
[0096] Preparation of Material D in Example 4
[0097] (1) Take 0.1 ml of 42 mg / ml precursor chloroauric acid and 0.4 ml of 42 mg / ml palladium chloride solution, pour them into a flask in a ratio of 1:4, mix well by magnetic stirring, add 1 ml of the prepared 1.5 mg / ml polyvinylpyrrolidone solution, stir until it becomes a sol state, then dropwise add 1 ml of 6 mg / ml freshly prepared reducing agent NaBH4 solution, and stir for 30 min to obtain the reduced gold-palladium alloy.
[0098] (2) Add 1 mmol of monomer aniline, 5 mmol of crosslinking agent dimethoxymethane, and 5 mmol of catalyst ferric trichloride to 20 ml of dichloroethane solvent in a ratio of 1:5:5. Under the condition of vigorous stirring, heat to 80 °C to completely polymerize aniline, and the polymerization time is 24 h. Use methanol as the solvent to perform Soxhlet extraction on the obtained solid for 24 h to obtain the porous organic polymer support.
[0099] (3) Add 200 mg of the porous organic polymer support obtained in step (2) to the prepared 2.5 ml of gold-palladium alloy solution (wherein the gold-palladium alloy is obtained in step (1) and the concentration of the gold-palladium alloy is 8.0 mg / ml), impregnate and load for 120 min, and the loading amount is 4%. Filter, wash with deionized water until neutral, and then dry in a vacuum oven at 80 °C to obtain the catalyst D.
[0100] Example 5
[0101] Add 0.2 g of the synthesized catalyst A and 1 g of HMF to a high-pressure reactor equipped with 10 ml of DMF. After replacing the air, fill with oxygen to 0.1 MPa, heat to 100 °C in an oil bath, and react for 1 h. After the reaction, the conversion rate of HMF and the selectivity of FDCA are analyzed by GC. The conversion rate is 30%, and the FDCA selectivity is 82%.
[0102] Example 6
[0103] 0.2 g of the synthesized catalyst B and 1 g of HMF were added to a high-pressure reactor containing 10 ml of DMF. After displacing the air, oxygen was charged to 0.5 MPa, and the mixture was heated to 100 °C in an oil bath and reacted for 2 h. After the reaction, the conversion of HMF and the selectivity of FDCA were analyzed by GC. The conversion was 45%, and the FDCA selectivity was 85%.
[0104] Example 7
[0105] 0.2 g of the synthesized catalyst C and 1 g of HMF were added to a high-pressure reactor containing 10 ml of DMF. After displacing the air, oxygen was charged to 1 MPa, and the mixture was heated to 120 °C in an oil bath and reacted for 2 h. After the reaction, the conversion of HMF and the selectivity of FDCA were analyzed by GC. The conversion was 79%, and the FDCA selectivity was 85%.
[0106] Example 8
[0107] 0.2 g of the synthesized catalyst D and 1 g of HMF were added to a high-pressure reactor containing 10 ml of DMF. After displacing the air, oxygen was charged to 2 MPa, and the mixture was heated to 100 °C in an oil bath and reacted for 2 h. After the reaction, the conversion of HMF and the selectivity of FDCA were analyzed by GC. The conversion was 68%, and the FDCA selectivity was 87%.
[0108] Test Example 1
[0109] The obtained gold-palladium alloy nanoparticles in Example 2 were tested by TEM using a JEM-210 instrument. The test results are as Figure 1 shown. It can be seen from Figure 1 that the gold-palladium alloy particles are relatively uniform, and the particle size is about 5 - 10 nm.
[0110] The obtained organic polymer catalyst loaded with gold-palladium alloy in Example 2 was tested by TEM using a JEM-2100 instrument. The test results are shown in Figure 2 shown. It can be seen from Figure 2 that the gold-palladium alloy particles are successfully loaded on the polymer support and are uniformly dispersed, and the particle size is about 5 - 10 nm.
[0111] The above are only several embodiments of the present application, and do not impose any form of limitation on the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, making some changes or modifications using the disclosed technical content is equivalent to equivalent implementation cases and all belong to the scope of the technical solution.
Claims
1. A supported porous organic polymer catalyst, characterized in that, The supported porous organic polymer catalyst includes a support and an active component supported on the support; The support is an aniline polymer; The active component is a gold-palladium alloy.
2. The supported porous organic polymer catalyst according to claim 1, characterized in that, In the supported porous organic polymer catalyst, the loading amount of the active component alloy is 0.5 wt% to 5 wt%.
3. A method for preparing the supported porous organic polymer catalyst according to any one of claims 1 to 2, characterized in that, The preparation method includes: Immersing the aniline polymer support in a gold-palladium alloy solution, impregnating, and drying to obtain the supported porous organic polymer catalyst.
4. The preparation method according to claim 3, characterized in that, The mass ratio of the aniline polymer support to the gold-palladium alloy solution is 100:1 to 10:1; The gold-palladium alloy solution further includes a solvent I, and the solvent I is selected from at least one of water and ethanol; In the gold-palladium alloy solution, the concentration of the gold-palladium alloy is 0.5 to 10 mg / ml.
5. The preparation method according to claim 3, characterized in that, The impregnation time is 120 to 240 min; The drying temperature is 80 to 100 °C, and the drying time is 12 to 24 h.
6. The preparation method according to claim 3, characterized in that, The preparation method of the aniline polymer support includes: Mixing a monomer aniline, a crosslinking agent, a catalyst A and a solvent A, carrying out a polymerization reaction, and extracting to obtain the aniline polymer support.
7. The preparation method according to claim 6, characterized in that, The crosslinking agent is selected from at least one of dimethoxymethane and chloromethyl methyl ether; The catalyst A is selected from at least one of ferric chloride and aluminum chloride; The solvent is selected from at least one of dichloromethane and dichloroethane; Preferably, the molar ratio of the monomer aniline, the crosslinking agent, and the catalyst A is 1:1:1 to 1:5:5; The molar volume ratio of the monomer aniline to the solvent is 1:10 to 1:20; Preferably, the temperature of the polymerization reaction is 80 to 110 °C; The time of the polymerization reaction is 24 to 30 h; The extraction time is 24 to 36 h.
8. The preparation method according to claim 3, characterized in that, The preparation method of the gold-palladium alloy includes: Adding a protective agent to a mixed solution containing a gold source and a palladium source, and then adding a reducing agent and stirring to obtain the gold-palladium alloy; Preferably, the protective agent is selected from at least one of polyvinylpyrrolidone and polyvinyl alcohol; Preferably, the gold source is selected from at least one of chloroauric acid and gold chloride; The palladium source is selected from at least one of palladium chloride and palladium acetate; Preferably, the molar ratio of the gold source to the palladium source is 1:1 to 1:10; The mass ratio of the protective agent to the gold source is 1:2 to 1:4; Preferably, the reducing agent is selected from at least one of NaBH4 and KBH4; The molar ratio of the reducing agent to the gold source is 5:1 to 8:
1.
9. Use of the supported porous organic polymer catalyst according to any one of claims 1 to 2 in the oxidation of 5-hydroxymethylfurfural to prepare 2,5-furandicarboxylic acid, characterized in that, The application includes: In an oxygen atmosphere, mixing 5-hydroxymethylfurfural, a solvent B and the supported porous organic polymer catalyst, and reacting to obtain 2,5-furandicarboxylic acid.
10. The use according to claim 9, characterized in that, The solvent B is selected from at least one of N,N-dimethylformamide and chloromethyl methyl ether; The reaction temperature is 100 to 170 °C; The reaction pressure is 0.1 to 2 MPa; The reaction time is 0.5 to 6 h; Preferably, the mass ratio of the supported porous organic polymer catalyst to 5-hydroxymethylfurfural is 2:5 to 4:5; The mass volume ratio of 5-hydroxymethylfurfural to the solvent B is 0.13:1 to 0.26:1.