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CATALYST, APPLICATION THEREOF, AND METHOD FOR PREPARING 2,5-FURANEDICARBOXYLIC ACID BY CATALYZING 5-HYDROMETHYLFURFURAL IN BASE-FREE CONDITION

20240228453 ยท 2024-07-11

    Inventors

    Cpc classification

    International classification

    Abstract

    A catalyst, an application, and a method for preparing 2,5-furanedicarboxylic acid by catalyzing 5-hydroxymethylfurfural in a base-free condition, which include a catalyst having the formula A/Mn.sub.aB.sub.bO.sub.x-yVC, wherein A is Pt, Ru, Pd, or Au, B is Co, Ce, Cu, or Ni, a mole ratio of a and b is 1.5-14, and y=0.0-0.4.

    Claims

    1. A method for preparing 2,5-furanedicarboxylic acid by catalyzing 5-hydroxymethylfurfural in a base-free condition, comprising: synthesizing the 2,5-furanedicarboxylic acid by catalyzing the 5-hydroxymethylfurfural using a catalyst in the base-free condition with a solvent of water using air or oxygen as an oxygen source, and a reaction time is 0.5-21 hours; and the catalyst is a metal catalyst supported by an Mn-based bimetallic oxide enriched with oxygen vacancies, a formula of the catalyst is A/Mn.sub.aB.sub.bO.sub.x-yVC, wherein: A is at least one of Pt, Ru, Pd, or Au, B is at least one of Co, Ce, Cu, or Ni, a mole ratio of a and b is 1.5-14, and y=0.0-0.4.

    2. The method according to claim 1, wherein: a reaction pressure is 0.2-4.0 MPa, a temperature of a reaction autoclave for the method is 80-130? C., and the reaction time is 1-21 hours.

    3. The method according to claim 1, wherein preparing the catalyst comprises the following steps: 1) mixing and grinding a precursor manganese nitrate, metal nitrate, and ascorbic acid, then calcining at 200-500? C. for 2 hours to obtain a carrier with the Mn-based bimetallic oxide enriched with oxygen vacancies, wherein the metal nitrate is at least one of cobalt nitrate, cerium nitrate, copper nitrate, or nickel nitrate, a molar ratio of the precursor manganese nitrate and the metal nitrate is 1.5-14:1, and a molar ratio of the ascorbic acid and a sum of the precursor manganese nitrate and the metal nitrate is 0-0.4:1; and 2) adding at least one of hexahydrate chloroplatinic acid, trihydrate ruthenium chloride, palladium chloride, trihydrate chloroauric acid and the carrier with the Mn-based bimetallic oxide enriched with oxygen vacancies to deionized water, stirring to be dispersed to even, and reducing to obtain the catalyst.

    4. The method according to claim 3, wherein: in the step 2), the reducing to obtain the catalyst comprises adding a sodium borohydride solution, continually stirring for 2 hours, then filtering, and drying the catalyst.

    5. The method according to claim 3, wherein: the reducing to obtain the catalyst in the step 2) comprises: drying by evaporating water, then calcinating at 500? C. for 4 hours, and then reducing at 500? C. in a hydrogen atmosphere for 1 hour.

    6. A metal catalyst supported by an Mn-based bimetallic oxide enriched with oxygen vacancies, wherein: a metal of the metal catalyst is A, and a formula of the metal catalyst is A/Mn.sub.aB.sub.bO.sub.x-yVC, wherein: A is at least one of Pt, Ru, Pd, or Au, B is at least one of Co, Ce, Cu, or Ni, a mole ratio of a and b is 1.5-14, and y=0.0-0.4.

    7. An application of the metal catalyst supported by the Mn-based bimetallic oxide enriched with the oxygen vacancies according to claim 6, comprising: preparing 2,5-furanedicarboxylic acid by catalyzing 5-hydroxymethylfurfural using the metal catalyst supported by the Mn-based bimetallic oxide enriched with the oxygen vacancies.

    8. The application according to claim 7, wherein: the preparing 2,5-furanedicarboxylic acid by catalyzing 5-hydroxymethylfurfural using the metal catalyst supported by the Mn-based bimetallic oxide enriched with the oxygen vacancies comprises: mixing the 5-hydroxymethylfurfural and water solvent and placing in a reaction kettle; adding the metal catalyst under a base-free condition; and sealing the reaction kettle, and filling with air or oxygen, wherein a pressure is 0.2-4.0 MPa, a temperature of the reaction kettle is 80-130? C., and a reaction time is 0.5-21 hours.

    9. The application according to claim 8, wherein the pressure is 0.5-2.5 MPa, and the reaction time 0.5-2 hours.

    10. The method according to claim 1, wherein the reaction time is 0.5-2 hours.

    11. The method according to claim 1, wherein y is 0.1-0.4.

    12. The method according to claim 1, wherein a loading amount of A is 1-5 wt %.

    13. The metal catalyst supported by the Mn-based bimetallic oxide enriched with the oxygen vacancies according to claim 6, wherein a loading amount of A is 1-5 wt %.

    14. The metal catalyst supported by the Mn-based bimetallic oxide enriched with the oxygen vacancies according to claim 6, wherein y is 0.1-0.4.

    Description

    BRIEF DESCRIPTION OF THE DRAWING

    [0032] The present disclosure will be further described in combination with the accompanying drawings and embodiments.

    [0033] FIGS. 1A and 1B show an electron paramagnetic resonance (EPR) spectrum of oxygen vacancy (O.sub.v) of a catalyst.

    [0034] FIG. 2 shows O1s in an X-ray photoelectron high-resolution spectroscopy (XPS) spectrum of the catalyst.

    [0035] FIGS. 3A and 3B show a H.sub.2 temperature-programmed reduction (H.sub.2-TPR) spectrum of the catalyst.

    DETAILED DESCRIPTION OF THE EMBODIMENTS

    [0036] In the following embodiments or comparison embodiments 1-48, a catalyst is described as Pt (z wt %)/Mn.sub.aCo.sub.bO.sub.x-yVC-w ? C., where z represents a loading amount of Pt (unless otherwise defined, a default value is 2.2 wt %); in which a and b represents a molar ratio of Mn and Co in the catalyst, y represents a molar ratio of the VC and a total metal content (i.e., a molar ratio of the VC and (Mn+Co)), and w represents a calcination temperature of Mn-based bimetallic oxide, which is 200? C.-500? C. (unless otherwise defined, a default value is 200? C.).

    [0037] The catalyst is used to prepare 2,5-furanedicarboxylic acid from the oxidation of 5-hydroxymethylfurfural under base-free conditions. A reaction path is as follows:

    ##STR00001##

    [0038] Note: 2,5-Diformylfuran (DFF); 5-hydroxymethyl-2-furancarboxylic acid (HMFCA); 5-formyl-2-furancarboxylic acid (FFCA).

    Embodiment 1

    [0039] A preparation of a catalyst with platinum nanoparticles supported by manganese oxide: first, 10.0116 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O) is manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide MnO.sub.x. Second, 1.0019 g of the MnO.sub.x, 0.0884 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.1762 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0645 g of sodium borohydride is dissolved in 15.0292 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 revolutions per minute (rpm)) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese oxide (called Pt/MnO.sub.x).

    [0040] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0309 g of the 5-hydroxymethyl furfural, 0.0403 g of the Pt/MnO.sub.x, and 3.0245 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 1.

    Embodiment 2

    [0041] A preparation of a catalyst with platinum nanoparticles supported by cobalt oxide: first, 10.0052 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O) is manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide CoO.sub.x. Second, 1.0036 g of the CoO.sub.x, 0.0889 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.0758 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0645 g of sodium borohydride is dissolved in 15.0588 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by cobalt oxide (called Pt/CoO.sub.x).

    [0042] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0323 g of the 5-hydroxymethyl furfural, 0.0408 g of the Pt/CoO.sub.x, and 3.0020 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 2.

    Embodiment 3

    [0043] A preparation of a catalyst with platinum nanoparticles supported by manganese oxide: first, 10.0273 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O) and 1.4042 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide MnO.sub.x-0.2VC. Second, 1.0032 g of the MnO.sub.x-0.2VC, 0.0885 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.0354 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0643 g of sodium borohydride is dissolved in 15.0300 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese oxide (called Pt/MnO.sub.x-0.2VC).

    [0044] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0322 g of the 5-hydroxymethyl furfural, 0.0400 g of the Pt/MnO.sub.x-0.2VC, and 3.0029 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 3.

    Embodiment 4

    [0045] A preparation of a catalyst with platinum nanoparticles supported by cobalt oxide: first, 10.0090 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O) and 1.2117 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide CoO.sub.x-0.2VC. Second, 1.0013 g of the CoO.sub.x-0.2VC, 0.0887 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.0795 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0648 g of sodium borohydride is dissolved in 15.1019 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by cobalt oxide (called Pt/CoO.sub.x-0.2VC).

    [0046] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0302 g of the 5-hydroxymethyl furfural, 0.0402 g of the Pt/CoO.sub.x-0.2VC, and 3.0289 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 4.

    Embodiment 5

    [0047] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 9.7416 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 0.8061 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 1.4629 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.14Co.sub.1O.sub.x-0.2VC. Second, 1.0027 g of the Mn.sub.14Co.sub.1O.sub.x-0.2VC, 0.0889 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.2250 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0640 g of sodium borohydride is dissolved in 15.3397 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.14Co.sub.1O.sub.x-0.2VC).

    [0048] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0300 g of the 5-hydroxymethyl furfural, 0.0406 g of the Pt/Mn.sub.14Co.sub.1O.sub.x-0.2VC, and 3.0221 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 5.

    Embodiment 6

    [0049] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 9.6077 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 0.9281 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 1.4629 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.12Co.sub.1O.sub.x-0.2VC. Second, 1.0005 g of the Mn.sub.12Co.sub.1O.sub.x-0.2VC, 0.0887 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.2085 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0645 g of sodium borohydride is dissolved in 15.1055 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.12Co.sub.1O.sub.x-0.2VC).

    [0050] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0300 g of the 5-hydroxymethyl furfural, 0.0405 g of the Pt/Mn.sub.12Co.sub.1O.sub.x-0.2VC, and 3.0472 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 6.

    Embodiment 7

    [0051] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 9.4762 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 1.0977 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 1.4620 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.10Co.sub.1O.sub.x-0.2VC. Second, 1.0015 g of the Mn.sub.10Co.sub.1O.sub.x-0.2VC, 0.0882 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.2923 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0640 g of sodium borohydride is dissolved in 15.2198 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC).

    [0052] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0309 g of the 5-hydroxymethyl furfural, 0.0410 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC, and 3.0559 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the reactor. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 7.

    Embodiment 8

    [0053] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 9.2440 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 1.3435 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 1.4624 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.8Co.sub.1O.sub.x-0.2VC. Second, 1.0008 g of the Mn.sub.8Co.sub.1O.sub.x-0.2VC, 0.0884 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.3245 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0647 g of sodium borohydride is dissolved in 15.2656 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.8Co.sub.1O.sub.x-0.2VC).

    [0054] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0313 g of the 5-hydroxymethyl furfural, 0.0408 g of the Pt/Mn.sub.8Co.sub.1O.sub.x-0.2VC, and 3.0020 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 8.

    Embodiment 9

    [0055] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 8.9339 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 1.7246 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 1.4626 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.6Co.sub.1O.sub.x-0.2VC. Second, 1.0021 g of the Mn.sub.6Co.sub.1O.sub.x-0.2VC, 0.0885 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.2499 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0644 g of sodium borohydride is dissolved in 15.2877 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.6Co.sub.1O.sub.x-0.2VC).

    [0056] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0298 g of the 5-hydroxymethyl furfural, 0.0405 g of the Pt/Mn.sub.6Co.sub.1O.sub.x-0.2VC, and 3.0302 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 9.

    Embodiment 10

    [0057] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 8.3404 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 2.4165 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 1.4631 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.4Co.sub.1O.sub.x-0.2VC. Second, 1.0018 g of the Mn.sub.4Co.sub.1O.sub.x-0.2VC, 0.0887 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.1669 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0643 g of sodium borohydride is dissolved in 15.1830 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.4Co.sub.1O.sub.x-0.2VC).

    [0058] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0302 g of the 5-hydroxymethyl furfural, 0.0398 g of the Pt/Mn.sub.4Co.sub.1O.sub.x-0.2VC, and 3.0141 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 10.

    Embodiment 11

    [0059] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 7.8125 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 3.0195 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 1.4621 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.3Co.sub.1O.sub.x-0.2VC. Second, 1.0020 g of the Mn.sub.3Co.sub.1O.sub.x-0.2VC, 0.0892 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.0968 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0649 g of sodium borohydride is dissolved in 15.1293 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.3Co.sub.1O.sub.x-0.2VC).

    [0060] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0329 g of the 5-hydroxymethyl furfural, 0.0406 g of the Pt/Mn.sub.3Co.sub.1O.sub.x-0.2VC, and 3.0138 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 11.

    Embodiment 12

    [0061] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC is the same as Embodiment 7.

    [0062] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0302 g of the 5-hydroxymethyl furfural, 0.0602 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC, and 3.0353 g of the deionized water are added into a 25 mL autoclave, and 1.5 MPa air is charged into the reactor. Afterward, the reaction mixture is stirred at 120? C. for 1.5 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 12.

    Embodiment 13

    [0063] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC is the same as Embodiment 7.

    [0064] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0302 g of the 5-hydroxymethyl furfural, 0.0602 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC, and 3.0353 g of the deionized water are added into a 25 mL autoclave, and 0.2 MPa oxygen is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 120? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 13.

    Embodiment 14

    [0065] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 270.08 g of an aqueous solution of manganese nitrate (Mn(NO.sub.3).sub.2, 50 wt %), 21.97 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 29.26 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS. Second, 21.0034 g of the Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, 1.8590 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 420.64 g of deionized water are added to a beaker (2000 mL) to obtain a first mixture, and the first mixture is stirred for 2 hours. 1.3531 g of sodium borohydride is dissolved in 315.0457 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 12 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS).

    [0066] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0305 g of the 5-hydroxymethyl furfural, 0.0611 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 3.0432 g of the deionized water are added into a 25 mL autoclave, and 1.5 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 120? C. for 1.5 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 14.

    Embodiment 15

    [0067] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC is the same as Embodiment 7.

    [0068] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0306 g of the 5-hydroxymethyl furfural, 0.0402 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC, and 3.0275 g of the deionized water are added into a 25 mL autoclave, and 1 MPa oxygen is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 15.

    Embodiments 16-19

    [0069] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 9.4762 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 1.0977 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 0 g, 0.7322 g, 2.1924 g, or 2.9237 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to sequentially obtain four oxides, Mn.sub.10Co.sub.1O.sub.x, Mn.sub.10Co.sub.1O.sub.x-0.1VC, Mn.sub.10Co.sub.1O.sub.x-0.3VC, or Mn.sub.10Co.sub.1O.sub.x-0.4VC. Second, a preparation of the catalyst with the platinum nanoparticles supported by the four oxides is as follows: 1.0000 g of the four oxides, 0.0889 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.0000 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0644 g of sodium borohydride is dissolved in 15.0000 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (sequentially called Pt/Mn.sub.10Co.sub.1O.sub.x, Pt/Mn.sub.10Co.sub.1O.sub.x-0.1VC, Pt/Mn.sub.10Co.sub.1O.sub.x-0.3VC, or Pt/Mn.sub.10Co.sub.1O.sub.x-0.4VC).

    [0070] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0300 g of the 5-hydroxymethyl furfural, 0.0400 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-(0-0.4)VC, and 3.0000 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are sequentially listed in Table 1 as Nos. 16-19.

    Embodiments 20-22

    [0071] A preparation of a catalyst with platinum nanoparticles supported by manganese-cobalt oxide: first, 9.4762 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 1.0977 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 1.4620 g of ascorbic acid (VC) are manually ground for 5 minutes, then respectively calcined at 300? C., 400? C., or 500? C. for 2 hours under air atmosphere (e.g., 1 atm) to sequentially obtain three oxides, Mn.sub.10Co.sub.1O.sub.x-0.2VC-300? C., Mn.sub.10Co.sub.1O.sub.x-0.2VC-400? C., or Mn.sub.10Co.sub.1O.sub.x-0.2VC-500? C. Second, a preparation of the catalyst with the platinum nanoparticles supported by the three oxides is as follows: 1.0000 g of the three oxides, 0.0889 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.0000 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0644 g of sodium borohydride is dissolved in 15.0000 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (sequentially called Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-300? C., Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-400? C., or Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-500? C.).

    [0072] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0300 g of the 5-hydroxymethyl furfural, 0.0400 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-(300-500? C.), and 3.0000 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are sequentially listed in Table 1 as Nos. 20-22.

    Embodiments 23-26

    [0073] A preparation method of the Mn.sub.10Co.sub.1O.sub.x-0.2VC is the same as Embodiment 7.

    [0074] A preparation of the catalyst with the platinum nanoparticles supported by the oxide Mn.sub.10Co.sub.1O.sub.x-0.2VC is as follows: 1.0000 g of the oxide, 0.0356 g, 0.0634 g, 0.1174 g, or 0.1430 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.0000 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0644 g of sodium borohydride is dissolved in 15.0000 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (sequentially called Pt (1.1 wt %)/Mn.sub.10Co.sub.1O.sub.x-0.2VC, Pt (1.8 wt %)/Mn.sub.10Co.sub.1O.sub.x-0.2VC, Pt (3.3 wt %)/Mn.sub.10Co.sub.1O.sub.x-0.2VC, or Pt (4.4 wt %)/Mn.sub.10Co.sub.1O.sub.x-0.2VC).

    [0075] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0300 g of the 5-hydroxymethyl furfural, 0.0400 g of the Pt (1.1-4.4 wt %)/Mn.sub.10Co.sub.1O.sub.x-0.2VC, and 3.0000 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as Nos. 23-26.

    Embodiment 27

    [0076] A preparation of a catalyst with ruthenium nanoparticles supported by manganese-cobalt oxide: first, 6.2775 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 4.8020 g of cobalt nitrate hexahydrate (Co(NO.sub.3).sub.2.Math.6H.sub.2O), and 1.4620 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC. Second, 0.5043 g of the Mn.sub.3Co.sub.2O.sub.x-0.2VC, 0.0445 g of ruthenium chloride trihydrate (RuCl.sub.3.Math.3H.sub.2O), and 20.1020 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0628 g of sodium borohydride is dissolved in 15.1459 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and RuCl.sub.3-3H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with ruthenium nanoparticles supported by manganese-cobalt oxide (called Ru/Mn.sub.3Co.sub.2O.sub.x-0.2VC).

    [0077] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0298 g of the 5-hydroxymethyl furfural, 0.0420 g of the Ru/Mn.sub.3Co.sub.2O.sub.x-0.2VC, and 3.0268 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 2 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 27.

    Embodiments 28

    [0078] A preparation method of the Mn.sub.3Co.sub.2O.sub.x-0.2VC is the same as Embodiment 27.

    [0079] A preparation of the catalyst with the noble-metal platinum nanoparticles supported by the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC is as follows: 1.0018 g of the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC, 0.0891 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.3243 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0656 g of sodium borohydride is dissolved in 15.0667 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.3Co.sub.2O.sub.x-0.2VC).

    [0080] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0303 g of the 5-hydroxymethyl furfural, 0.0415 g of the Pt/Mn.sub.3Co.sub.2O.sub.x-0.2VC, and 3.0394 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 2 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 28.

    Embodiments 29

    [0081] A preparation method of the Mn.sub.3Co.sub.2O.sub.x-0.2VC is the same as Embodiment 27.

    [0082] A preparation of the catalyst with the noble-metal platinum nanoparticles supported by the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC is as follows: 1.0083 g of the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC, 0.0423 g of trihydrate chloroauric acid (HAuCl.sub.4.Math.3H.sub.2O), and 20.0712 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0393 g of sodium borohydride is dissolved in 15.0784 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and HAuCl.sub.4.Math.3H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with gold nanoparticles supported by manganese-cobalt oxide (called Au/Mn.sub.3Co.sub.2O.sub.x-0.2VC).

    [0083] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0301 g of the 5-hydroxymethyl furfural, 0.0670 g of the Au/Mn.sub.3Co.sub.2O.sub.x-0.2VC, and 3.0559 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 2 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 29.

    Embodiments 30

    [0084] A preparation method of the Mn.sub.3Co.sub.2O.sub.x-0.2VC is the same as Embodiment 27.

    [0085] A preparation of the catalyst with the noble-metal palladium nanoparticles supported by the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC is as follows: 1.0079 g of the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC, 0.0346 g of palladium chloride (PdCl.sub.2), and 20.0254 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0718 g of sodium borohydride is dissolved in 15.3153 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and PdCl.sub.2 is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with palladium nanoparticles supported by manganese-cobalt oxide (called Pd/Mn.sub.3Co.sub.2O.sub.x-0.2VC).

    [0086] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0300 g of the 5-hydroxymethyl furfural, 0.0374 g of the Pd/Mn.sub.3Co.sub.2O.sub.x-0.2VC, and 3.0426 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 2 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 30.

    Embodiments 31

    [0087] A preparation method of the Mn.sub.3Co.sub.2O.sub.x-0.2VC is the same as Embodiment 27.

    [0088] A preparation of the catalyst with the noble-metal ruthenium nanoparticles supported by the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC is as follows: 1.0009 g of the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC, 0.0878 g of ruthenium chloride trihydrate (RuCl.sub.3.Math.3H.sub.2O), and 20.1596 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. Subsequently, the first mixture is dried by evaporating water at 80? C. for 12 hours, then calcined at 500? C. for 4 hours in air atmosphere, and subsequently reduced at 500? C. for 1 hour in 10% H.sub.2/N.sub.2 atmosphere to obtain a dark black catalyst with ruthenium nanoparticles supported by manganese-cobalt oxide (called Ru/Mn.sub.3Co.sub.2O.sub.x-0.2VC-H.sub.2).

    [0089] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0305 g of the 5-hydroxymethyl furfural, 0.0417 g of the Ru/Mn.sub.3Co.sub.2O.sub.x-0.2VC-H.sub.2, and 3.0576 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 2 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 31.

    Embodiments 32

    [0090] A preparation method of the Mn.sub.3Co.sub.2O.sub.x-0.2VC is the same as Embodiment 27.

    [0091] A preparation of the catalyst with the noble-metal platinum nanoparticles supported by the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC is as follows: 1.0016 g of the oxide Mn.sub.3Co.sub.2O.sub.x-0.2VC, 0.0861 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.3453 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. Subsequently, the first mixture is dried by evaporating water at 80? C. for 12 hours, then calcined at 500? C. for 4 hours in air atmosphere, and subsequently reduced at 500? C. for 1 hour in 10% H.sub.2/N.sub.2 atmosphere to obtain a dark black catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt/Mn.sub.3Co.sub.2O.sub.x-0.2VC-H.sub.2).

    [0092] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0314 g of the 5-hydroxymethyl furfural, 0.0414 g of Pt/Mn.sub.3Co.sub.2O.sub.x-0.2VC-H.sub.2, and 3.0186 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 2 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 32.

    Embodiments 33

    [0093] A preparation method of the Mn.sub.10Co.sub.1O.sub.x-0.2VC is the same as Embodiment 7.

    [0094] A preparation of the catalyst with the noble-metal platinum nanoparticles supported by the oxide Mn.sub.10Co.sub.1O.sub.x-0.2VC is as follows: 1.0030 g of the oxide Mn.sub.10Co.sub.1O.sub.x-0.2VC, 0.0888 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), 0.1717 g of polyvinyl pyrrolidone (PVP), and 60.0254 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0644 g of sodium borohydride is dissolved in 15.3153 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cobalt oxide (called Pt-PVP/Mn.sub.10Co.sub.1O.sub.x-0.2VC).

    [0095] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0304 g of the 5-hydroxymethyl furfural, 0.0407 g of the Pt-PVP/Mn.sub.10Co.sub.1O.sub.x-0.2VC, and 3.0566 g of the deionized water are added into a 25 mL autoclave, and 1 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 110? C. for 1 hour. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 33.

    Embodiment 34

    [0096] A preparation of a catalyst with platinum nanoparticles supported by manganese-cerium oxide: first, 1.8940 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 0.3276 g of cerium nitrate hexahydrate (Ce(NO.sub.3).sub.3.Math.6H.sub.2O), and 0.2924 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.10Ce.sub.1O.sub.x-0.2VC. Second, 1.0000 g of the Mn.sub.10Ce.sub.1O.sub.x-0.2VC, 0.0889 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.1020 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0644 g of sodium borohydride is dissolved in 15.1459 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-cerium oxide (called Pt/Mn.sub.10Ce.sub.1O.sub.x-0.2VC).

    [0097] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0305 g of the 5-hydroxymethyl furfural, 0.0611 g of the Pt/Mn.sub.10Ce.sub.1O.sub.x-0.2VC, and 3.0476 g of the deionized water are added into a 25 mL autoclave, and 1.5 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 120? C. for 1.5 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 34.

    Embodiment 35

    [0098] A preparation of a catalyst with platinum nanoparticles supported by manganese-copper oxide: first, 1.8940 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 0.1823 g of copper nitrate trihydrate (Cu(NO.sub.3).sub.2.Math.3H.sub.2O), and 0.2924 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.10Cu.sub.1O.sub.x-0.2VC. Second, 1.0000 g of the Mn.sub.10Cu.sub.1O.sub.x-0.2VC, 0.0881 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.1020 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0645 g of sodium borohydride is dissolved in 15.0000 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-copper oxide (called Pt/Mn.sub.10Cu.sub.1O.sub.x-0.2VC).

    [0099] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0304 g of the 5-hydroxymethyl furfural, 0.0600 g of the Pt/Mn.sub.10Cu.sub.1O.sub.x-0.2VC, and 3.0390 g of the deionized water are added into a 25 mL autoclave, and 1.5 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 120? C. for 1.5 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 35.

    Embodiment 36

    [0100] A preparation of a catalyst with platinum nanoparticles supported by manganese-nickel oxide: first, 1.8940 g of manganese nitrate tetrahydrate (Mn(NO.sub.3).sub.2.Math.4H.sub.2O), 0.2194 g of nickel nitrate hexahydrate (Ni(NO.sub.3).sub.2.Math.6H.sub.2O), and 0.2924 g of ascorbic acid (VC) are manually ground for 5 minutes, then calcined at 200? C. for 2 hours under air atmosphere (e.g., 1 atm) to obtain an oxide Mn.sub.10Ni.sub.1O.sub.x-0.2VC. Second, 1.0000 g of the Mn.sub.10Ni.sub.1O.sub.x-0.2VC, 0.0885 g of hexahydrate chloroplatinic acid (H.sub.2PtCl.sub.6.Math.6H.sub.2O), and 20.1890 g of deionized water are added to a beaker (100 mL) to obtain a first mixture, and the first mixture is stirred for 0.5 hours. 0.0649 g of sodium borohydride is dissolved in 15.0000 g of the deionized water to prepare a sodium borohydride solution (a molar ratio of NaBH.sub.4 and H.sub.2PtCl.sub.6.Math.6H.sub.2O is 10). The sodium borohydride solution is then added in drops under magnetic stirring (500 rpm) and continually stirred for 2 hours to obtain a second mixture. Finally, the second mixture is filtrated to separate the catalyst, washed with ethanol, dried under vacuum at 80? C. for 12 hours, and further ground to obtain the catalyst with platinum nanoparticles supported by manganese-nickel oxide (called Pt/Mn.sub.10Ni.sub.1O.sub.x-0.2VC).

    [0101] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0306 g of the 5-hydroxymethyl furfural, 0.0604 g of the Pt/Mn.sub.10Ni.sub.1O.sub.x-0.2VC, and 3.0608 g of the deionized water are added into a 25 mL autoclave, and 1.5 MPa air is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred at 120? C. for 1.5 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 36.

    Embodiment 37

    [0102] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0103] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.1585 g of the 5-hydroxymethyl furfural, 0.0606 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 2.8596 g of the deionized water are added into a 25 mL autoclave, and 0.5 MPa O.sub.2 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 7 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 0.2054 g of NaHCO.sub.3 is added into the reaction solution. Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 37.

    Embodiment 38

    [0104] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0105] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.3031 g of the 5-hydroxymethyl furfural, 0.1215 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 2.6992 g of the deionized water are added into a 25 mL autoclave, and 1.0 MPa O.sub.2 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 9 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 0.4019 g of NaHCO.sub.3 is added into the reaction solution. Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 38.

    Embodiment 39

    [0106] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0107] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.4540 g of the 5-hydroxymethyl furfural, 0.1814 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 2.5616 g of the deionized water are added into a 25 mL autoclave, and 1.5 MPa O.sub.2 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 11 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 0.6017 g of NaHCO.sub.3 is added into the reaction solution.

    [0108] Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 39.

    Embodiment 40

    [0109] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0110] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.6091 g of the 5-hydroxymethyl furfural, 0.2432 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 2.4173 g of the deionized water are added into a 25 mL autoclave, and 2.0 MPa O.sub.2 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 13 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 0.8083 g of NaHCO.sub.3 is added into the reaction solution.

    [0111] Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 40.

    Embodiment 41

    [0112] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0113] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.7665 g of the 5-hydroxymethyl furfural, 0.3047 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 2.2704 g of the deionized water are added into a 25 mL autoclave, and 2.5 MPa O.sub.2 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 15 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 1.0024 g of NaHCO.sub.3 is added into the reaction solution. Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 41.

    Embodiment 42

    [0114] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0115] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.9038 g of the 5-hydroxymethyl furfural, 0.3610 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 2.1031 g of the deionized water are added into a 25 mL autoclave, and 3.0 MPa O.sub.2 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 17 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 1.2005 g of NaHCO.sub.3 is added into the reaction solution. Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 42.

    Embodiment 43

    [0116] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0117] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 1.0556 g of the 5-hydroxymethyl furfural, 0.4211 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 1.9623 g of the deionized water are added into a 25 mL autoclave, and 3.5 MPa 02 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 19 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 1.4100 g of NaHCO.sub.3 is added into the reaction solution. Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 43.

    Embodiment 44

    [0118] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0119] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 1.2073 g of the 5-hydroxymethyl furfural, 0.4802 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 1.8112 g of the deionized water are added into a 25 mL autoclave, and 4.0 MPa 02 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 21 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 1.6000 g of NaHCO.sub.3 is added into the reaction solution. Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 44.

    Embodiment 45

    [0120] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0121] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.0492 g of the crude 5-hydroxymethyl furfural purchased from Zhongke Guosheng Technology Co., Ltd. (61 wt %, Hangzhou, China), 0.0253 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 3.0210 g of the deionized water are added into a 25 mL autoclave, and 0.5 MPa 02 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 6 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 0.0401 g of NaHCO.sub.3 is added into the reaction solution.

    [0122] Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 45.

    Embodiment 46

    [0123] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0124] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.2501 g of the crude 5-hydroxymethyl furfural purchased from Zhongke Guosheng Technology Co., Ltd. (61 wt %, Hangzhou, China), 0.1266 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 2.7831 g of the deionized water are added into a 25 mL autoclave, and 1.0 MPa O.sub.2 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 8 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 0.2001 g of NaHCO.sub.3 is added into the reaction solution. Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 46.

    Embodiment 47

    [0125] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0126] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.4968 g of the crude 5-hydroxymethyl furfural purchased from Zhongke Guosheng Technology Co., Ltd. (61 wt %, Hangzhou, China), 0.2405 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 2.5475 g of the deionized water are added into a 25 mL autoclave, and 1.5 MPa O.sub.2 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 10 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 0.4100 g of NaHCO.sub.3 is added into the reaction solution. Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 47.

    Embodiment 48

    [0127] A preparation method of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS is the same as Embodiment 14.

    [0128] Oxidation reaction of 5-hydroxymethyl furfural is as follows: 0.7377 g of the crude 5-hydroxymethyl furfural purchased from Zhongke Guosheng Technology Co., Ltd. (61 wt %, Hangzhou, China), 0.3601 g of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS, and 2.2885 g of the deionized water are added into a 25 mL autoclave, and 2.0 MPa O.sub.2 is charged into the 25 mL autoclave. Afterward, the reaction mixture is stirred (500 rpm) at 120? C. for 13 hours. Then the 25 mL autoclave is cooled to room temperature (e.g., 20-25? C.), and then 0.6094 g of NaHCO.sub.3 is added into the reaction solution. Subsequently, the reaction solution is analyzed quantitatively. The test results are listed in Table 1 as No. 48.

    TABLE-US-00001 TABLE 1 Test Results HMF conversion Yield (%) No. Catalyst rate (%) DFF FFCA FDCA 1 Pt/MnO.sub.x 94.9 13.5 58.1 14.6 2 Pt/CoO.sub.x 100 0.0 37.0 41.7 3 Pt/MnO.sub.x-0.2VC 100 0.0 14.1 64.5 4 Pt/CoO.sub.x-0.2VC 100 0.8 46.8 32.8 5 Pt/Mn.sub.14Co.sub.1O.sub.x-0.2VC 99.2 0.8 26.4 67.7 6 Pt/Mn.sub.12Co.sub.1O.sub.x-0.2VC 99.4 0.6 22.2 71.3 7 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC 100 0.0 11.9 83.1 8 Pt/Mn.sub.8Co.sub.1O.sub.x--0.2VC 99.2 0.6 23.2 67.5 9 Pt/Mn.sub.6Co.sub.1O.sub.x--0.2VC 99.3 0.9 24.3 64.1 10 Pt/Mn.sub.4Co.sub.1O.sub.x--0.2VC 99.3 0.5 26.4 62.5 11 Pt/Mn.sub.3Co.sub.1O.sub.x--0.2VC 99.3 0.9 33.6 55.1 12 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC 100 0.0 2.5 95.3 13 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC 100 0.0 3.3 95.8 14 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 12.1 84.9 15 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC 98.9 1.0 28.7 67.3 16 Pt/Mn.sub.10Co.sub.1O.sub.x 91.1 10.0 50.0 27.9 17 Pt/Mn.sub.10Co.sub.1O.sub.x-0.1VC 99.3 0.6 27.1 69.4 18 Pt/Mn.sub.10Co.sub.1O.sub.x-0.3VC 100 0.0 6.9 82.6 19 Pt/Mn.sub.10Co.sub.1O.sub.x-0.4VC 100 0.0 9.9 78.8 20 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC- 100 0.0 15.1 77.1 300? C. 21 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC- 100 0.0 17.9 71.3 400? C. 22 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC- 100 0.0 14.9 71.2 500? C. 23 Pt(1.1 wt %)/Mn.sub.10Co.sub.1O.sub.x- 99.5 0.0 20.1 71.8 0.2VC-200? C. 24 Pt(1.8 wt %)/Mn.sub.10Co.sub.1O.sub.x- 100 0.0 10.6 76.5 0.2VC-200? C. 25 Pt(3.3 wt %)/Mn.sub.10Co.sub.1O.sub.x- 89.1 8.1 47.4 30.0 0.2VC-200? C. 26 Pt(4.4 wt %)/Mn.sub.10Co.sub.1O.sub.x- 98.1 2.2 41.9 52.9 0.2VC-200? C. 27 Ru/Mn.sub.3Co.sub.2O.sub.x-0.2VC 100 6.3 14.6 53.7 28 Pt/Mn.sub.3Co.sub.2O.sub.x-0.2VC 100 7.2 16.9 72.3 29 Au/Mn.sub.3Co.sub.2O.sub.x-0.2VC 48.4 9.4 20.1 8.7 30 Pd/Mn.sub.3Co.sub.2O.sub.x-0.2VC 80.0 2.9 31.6 24.5 31 Ru/Mn.sub.3Co.sub.2O.sub.x-0.2VC-H.sub.2 100 21.4 43.3 12.4 32 Pt/Mn.sub.3Co.sub.2O.sub.x-0.2VC-H.sub.2 100 10.9 47.5 17.7 33 Pt-PVP/Mn.sub.10Co.sub.1O.sub.x-0.2VC 100 0.0 12.3 81.1 34 Pt/Mn.sub.10Ce.sub.1O.sub.x-0.2VC 100 0.0 6.3 87.7 35 Pt/Mn.sub.10Cu.sub.1O.sub.x-0.2VC 76.6 5.1 23.2 24.2 36 Pt/Mn.sub.10Ni.sub.1O.sub.x-0.2VC 100 0.0 7.2 87.1 37 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 93.5 38 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 92.9 39 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 93.6 40 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 95.2 41 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 94.5 42 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 94.9 43 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 91.7 44 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 83.2 45 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 93.7 46 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 92.6 47 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 0.0 91.8 48 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC-LS 100 0.0 21.9 73.0 Notes: 2,5-Diformylfuran (DFF); 5-formyl-2-furancarboxylic acid (FFCA)

    [0129] The catalytic system is compared with the existing catalytic systems, results are shown in Table 2:

    TABLE-US-00002 TABLE 2 Comparison between the catalytic system and other catalytic systems Generation HMF rate Conversion FDCA [mol.sub.FDCA Catalyst and Solvent, reaction rate Yield mol.sub.metal.sub.?1 NO. amount .sup.a alkali conditions (%) (%) h.sup.?1] .sup.c Embodiment Pt/Mn.sub.10Co.sub.1O.sub.x0.2VC, H.sub.2O, base- 1.5 hours, 100 95.3 24.8 12 39 free 120? C., 15 bar Air Embodiment Pt/Mn.sub.10Co.sub.1O.sub.x0.2VC, H.sub.2O, base- 1 hour, 100 95.8 37.4 13 39 free 120? C., 2 bar O.sub.2 [1] Ru(4%)/MnCo.sub.2O.sub.4, H.sub.2O, base- 10 hours, 100 99 3.4 34 free 120? C., 24 bar Air [2] Ru/CTF, 40 H.sub.2O, base- 3 hours, 100 78 10.4 free 140? C., 20 bar Air [3] Au/0.4MgF.sub.20.6MgO, H.sub.2O, base- 2 hours, 98 63 15.8 50 free 110? C., 26 bar Air [4] Ni.sub.0.5Pd.sub.0.5/Mg(OH).sub.2, H.sub.2O, base- 10 hours, 100 98 3.9 40 free 100? C., 1 bar Air [5] Ru/Mn.sub.6Ce.sub.1O.sub.Y, 80 H.sub.2O, base- 15 hours, 100 100 5.3 free 150? C., 10 bar O.sub.2 [6] Au.sub.1Pd.sub.1/pBNC-30% H.sub.2O, base- 48 hours, 99.8 93.9 1.1 HNO.sub.3, 55 free 100? C., 2.0 MPa O.sub.2 [7] Pt/HT, 100 H.sub.2O, base- 14 hours, 100 97 6.9 free 95? C., 5 bar O.sub.2 [8] Pt/COMg, 50 H.sub.2O, base- 12 hours, 100 97 4.1 free 110? C., 10 bar O.sub.2 [9] Pt/ZrO.sub.2-ALD, 73 H.sub.2O, base- 12 hours, 100 97 5.9 free 100? C., 4 bar O.sub.2 [10] Pt/C-EDA-4.1, 50 H.sub.2O, base- 12 hours, >99 96 4.0 free 110? C., 10 bar O.sub.2 Note: {circle around (1)} .sup.a the amount of the catalyst, refers to a molar ratio of the noble metal and HMF. .sup.b refers to an HMF concentration. .sup.c generation rate, refers to a molar amount of a target product obtained per mole amount of the noble metal per hour. {circle around (2)} The aforementioned other catalytic systems are disclosed in the following references: [1] Green Chem., 2017, 19, 1619-1623. [2] ChemSusChem, 2015, 8, 3832-3838. [3] ACS Sustainable Chem. Eng., 2018, 6, 16332-16340. [4] Inorg. Chem. Front., 2017, 4, 871-880. [5] Journal of Catalysis., 368, (2018) 53-68. [6] ChemSusChem, 2022, e202201041. [7] ChemCatChem, 7 (2015) 2853-2863. [8] Green Chem., 18 (2016) 1597-1604. [9] Appl. Catal., A 555 (2018) 98-107. [10] Appl. Catal., A 526 (2016) 1-8.

    [0130] Referring to the Table 2, it can be seen that other reported Pt-based catalysts usually require a reaction time of 9-14 hours to achieve similar catalytic effects under the base-free condition. The catalyst of the present disclosure is currently the most active Pt-based catalyst under the base-free condition.

    TABLE-US-00003 TABLE 3 A relative content of oxygen vacancies on a surface of the catalysts respectively obtained from EPR electron paramagnetic resonance spectrum.sup.b in FIGS. 1A and 1B and high-resolution XPS spectrum.sup.a in FIG. 2 Relative content Specific content of of oxygen oxygen vacancies No. Catalysts vacancies (%).sup.a ((spins .Math. g.sup.?1).sup.b 1 MnOx 46 1.567 * 10.sup.16 2 Pt/MnO.sub.x 51 2.098 * 10.sup.16 3 MnO.sub.x-0.2VC 54 2.140 * 10.sup.16 4 Mn.sub.10Co.sub.1O.sub.x-0.2VC 56 2.739 * 10.sup.16 5 Pt/MnO.sub.x-0.2VC 61 3.288 * 10.sup.16 6 Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC 64 4.476 * 10.sup.16

    [0131] Referring to Table 3, it can be seen that an addition of vitamin C additives can significantly increase the content of the oxygen vacancies on the surface of Mn-based oxide carriers.

    [0132] An H.sub.2-TPR spectrum in FIG. 3A indicates that an introduction of the vitamin C additives enables the Mn-based oxide carriers to be easily reduced, that is, lattice oxygen is more likely lost, and an activity of the lattice oxygen becomes higher. In addition, the H.sub.2-TPR spectrum in FIG. 3B indicates that a lower reduction peak appears after metal platinum is loaded on the Mn-based oxide carrier, indicating a formation of highly active lattice oxygen sites on surfaces of the Pt/Mn.sub.10Co.sub.1O.sub.x-0.2VC and the Pt/MnO.sub.x-0.2VC.

    [0133] The aforementioned embodiments are merely used to illustrate the technical solution of the present disclosure instead of a limitation of the technical solution of the present disclosure. Although the present disclosure has been described in detail in combination with the aforementioned embodiments, it should be understood for person of skill in the art, the technical solution described in the aforementioned embodiments can still be modified, or some or all of the technical features can still be equivalently replaced. These modifications or replacements are made without resulting in a substance of the corresponding technical solution departing from the scope of the various embodiments of the present disclosure.