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CN-121972231-A - COF-SO3H@N-MoOxComposite material, preparation method and application thereof

CN121972231ACN 121972231 ACN121972231 ACN 121972231ACN-121972231-A

Abstract

The invention provides a COF-SO 3 H@N-MoO x composite material and a preparation method and application thereof, wherein the preparation method comprises the steps of (1) dispersing melamine and ammonium molybdate tetrahydrate in water to obtain a suspension, evaporating the suspension to obtain a solid, calcining the solid, cooling to obtain N-doped molybdenum oxide, (2) dispersing the N-doped molybdenum oxide, 1,3, 5-trialdehyde-phloroglucinol and biphenyldiamine prepared in the step (1) in a first organic solvent, adding an acid catalyst, washing the obtained solid after reaction, drying to obtain the COF@N-MoO x , (3) dispersing the COF@N-MoO x in toluene, then adding 1, 3-propane sultone, reacting in a nitrogen atmosphere, washing the obtained solid, and drying to obtain the COF-SO 3 H@N-MoO x composite material. The COF-SO 3 H@N-MoO x composite material provided by the invention has the advantages of stable structure, easiness in separation and recovery and reusability as a bifunctional catalyst, and has higher catalyst utilization efficiency.

Inventors

  • SHEN ZHENLU
  • TIAN DAN
  • WU YOULIANG
  • LI MEICHAO

Assignees

  • 浙江工业大学

Dates

Publication Date
20260505
Application Date
20260122

Claims (10)

  1. 1. A method for preparing a COF-SO 3 H@N-MoO x composite material, comprising the steps of: (1) Dispersing melamine and ammonium molybdate tetrahydrate in water to obtain a suspension, evaporating the suspension to obtain a solid, calcining the solid, and cooling to obtain N-doped molybdenum oxide; (2) Dispersing the N-doped molybdenum oxide, 1,3, 5-trialdehyde-phloroglucinol and biphenyldiamine prepared in the step (1) in a first organic solvent, adding an acid catalyst, washing the obtained solid after reaction, and drying to obtain COF@N-MoO x ; (3) Dispersing the COF@N-MoOx in toluene, then adding 1, 3-propane sultone, reacting under nitrogen atmosphere, washing the obtained solid after the reaction, and drying to obtain the COF-SO 3 H@N-MoO x composite material.
  2. 2. The preparation method of the catalyst according to claim 1, wherein in the step (1), the molar ratio of the melamine to the ammonium molybdate tetrahydrate is 1 (18-30), the calcination temperature is 500-600 ℃, and the calcination time is 3-6 hours.
  3. 3. The preparation method of the metal oxide semiconductor material is characterized in that in the step (2), the molar ratio of the 1,3, 5-trialdehyde-phloroglucinol to the biphenyldiamine is 1 (1.5-2.1), and the mass ratio of the N-doped molybdenum oxide to the 1,3, 5-trialdehyde-phloroglucinol is 1 (1-10).
  4. 4. The preparation method of the composition according to claim 1, wherein in the step (2), the first organic solvent is selected from one or more of acetonitrile, methanol, dichloroethane, tetrahydrofuran and N, N-dimethylformamide, and the mass ratio of the first organic solvent to 1,3, 5-trialdehyde-phloroglucinol is (50-100): 1.
  5. 5. The preparation method of the catalyst according to claim 1, wherein in the step (2), the acid catalyst is acetic acid, the concentration of the acetic acid is 5-8 mol/L, the mass ratio of the acetic acid to the 1,3, 5-trialdehyde-phloroglucinol is (30-70): 1, the mixture is stirred at room temperature for 8-14 h after the acid catalyst is added, the drying temperature is 90-110 ℃, and the drying time is 8-12 h.
  6. 6. The preparation method of the catalyst according to claim 1, wherein in the step (3), the mass ratio of toluene to COF@N-MoO x is (100-300) 1, the mass ratio of 1, 3-propane sultone to COF@N-MoO x is (4-10) 1, the reaction temperature is 100-120 ℃, the reaction time is 6-10 h, the drying temperature is 90-110 ℃, and the drying time is 8-12 h.
  7. 7. A COF-SO 3 H@N-MoO x composite material produced by the production process according to any one of claims 1 to 6.
  8. 8. Use of a COF-SO 3 H@N-MoO x composite as claimed in claim 7 as a bifunctional catalyst for the direct preparation of 2, 5-diformylfuran from catalytic fructose.
  9. 9. The method according to claim 8, wherein the 2, 5-diformylfuran is prepared by heating and reacting fructose as a raw material and the COF-SO 3 H@N-MoO x composite material as a catalyst in a second organic solvent under normal pressure in an air atmosphere to dehydrate and oxidize.
  10. 10. The application of the compound film according to claim 9, wherein the second organic solvent is dimethyl sulfoxide, the mass ratio of the second organic solvent to fructose is (20-70): 1, the mass ratio of the COF-SO 3 H@N-MoO x composite material to fructose is (3-8), the reaction temperature is 100-160 ℃, the reaction time is 2-9 h, and after the reaction is finished, the COF-SO 3 H@N-MoO x composite material is filtered, separated and washed and then reused.

Description

COF-SO 3H@N-MoOx composite material and preparation method and application thereof Technical Field The invention relates to the technical field of catalyst synthesis, in particular to a COF-SO 3H@N-MoOx composite material, a preparation method and application thereof. Background In recent years, with the increasing severity of shortage of fossil resources and environmental pollution, the traditional chemical production model faces challenges, which promote the chemical industry to use biomass as a sustainable development scheme for producing chemicals and biofuels. Biomass is used as the most abundant renewable carbon resource on the earth, has the advantages of wide sources, low cost, sustainable availability and the like, and can prepare high-added-value chemicals with rich types. Among the numerous biomass-derived platform compounds, 2, 5-Diformylfuran (DFF) is an important furans compound of excellent industrial value. DFF can be used for preparing chemicals such as 2, 5-furandicarboxylic acid (FDCA) by oxidation, and can also be used as fine chemicals such as intermediate synthetic drugs, fluorescent agents, antibacterial agents and the like. In addition, the DFF can be used for synthesizing various novel bio-based high polymer materials, such as bio-based polyester, fluorescent material, urea polyester and the like. Because the DFF compound has important application prospect, the synthesis method is also continuously abundant, and the synthesis of DFF by taking fructose as a raw material is one of the most important ways for preparing the DFF. There are two main schemes for preparing DFF from fructose. One is that fructose is dehydrated to produce 5-Hydroxymethylfurfural (HMF), and the separated and purified HMF is subjected to selective catalytic oxidation to obtain DFF. The other scheme is that the fructose is directly dehydrated and oxidized by a one-pot method to obtain the DFF, including a one-pot two-step method and a one-pot one-step method, and the method avoids the separation process of the HMF and simplifies the operation procedure. For example, halliday et al reported a "one-pot two-step process", using Dowex ion exchange resin as a catalyst, catalyzing dehydration of fructose to produce HMF, then supplementing vanadium-based catalyst to effect conversion of fructose to DFF [ org. Lett. 2003, 5 (11): 2003-2005 ], wei et al developed a magnetically separable catalytic system to effect conversion of fructose to DFF using two different catalysts of Fe 3O4@SiO2-SO3 H and ZnFeRu by O 2, [ J.Cold Interface Sci. 2021,602:146-158 ], yang et al reported Fe 3O4-RGO-SO3 H and ZnFe 1.65Ru0.35O4 catalysts to effect conversion of fructose to DFF [ ENERGY AND Fuels2016, 31 (1): 533-541 ] ], takagaki developed a "one-pot" catalytic system to effect direct conversion of fructose to DFF [ ACS. 2011 (11): 1562-1565 ] by combining Amberlyst with Ru/HT catalyst, and a two-catalyst to effect conversion of fructose to form a two-catalyst [ ACS. 2011, 1 (11): 1562-1565 ] ] two-carrier oxidation catalyst to effect conversion of DFF [ 35 ] and a two-carrier oxidation system to effect oxidation of DFF [ Z (35) by means of two-carrier, etc. ] A catalytic system, and so that a two-stage oxidation system was developed by two-stage oxidation catalyst, and so on, which was prepared by a two-stage oxidation system, and so on, a two-stage oxidation system, had been reported. Chinese patent CN120774871a discloses a dehydration and selective oxidation tandem reaction of fructose under the action of a nitrogen-doped carbon-supported Fe/Co bimetallic monoatomic catalyst to obtain DFF, FDCA or 5-formyl-2-furancarboxylic acid (FFCA). In the above synthesis method, when fructose is used for synthesizing DFF by a one-pot two-step method, a catalyst with an acidic site is required to exist in the process of dehydrating fructose to generate HMF, and a catalyst with oxidation performance is required for HMF oxidation, and the two different catalysts are often difficult to cooperatively perform under the same condition in two-step reaction. The fructose is synthesized into DFF by a one-pot one-step method, and the catalyst used can simultaneously realize dehydration of the fructose and oxidation of HMF. However, the catalyst has the problems of poor selectivity and stability, short service period and complex process of product separation and purification. Disclosure of Invention In view of the shortcomings of the prior art, the invention aims to provide a COF-SO 3H@N-MoOx composite material, a preparation method and application thereof, which are used for solving the problems that the existing catalyst for simultaneously realizing dehydration of fructose and oxidation of HMF has poor selectivity and stability, short service cycle and complex product separation and purification flow. To achieve the above and other related objects, the present invention provides a method for preparing a COF-SO 3H@N-MoOx composite material, which is c