CN111087371A

CN111087371A - Photocatalytic synthesis method of 2, 5-furan dicarbaldehyde

Info

Publication number: CN111087371A
Application number: CN201911303030.9A
Authority: CN
Inventors: 吕红金; 张默
Original assignee: Beijing Institute of Technology BIT
Current assignee: Beijing Institute of Technology BIT
Priority date: 2019-12-17
Filing date: 2019-12-17
Publication date: 2020-05-01

Abstract

The invention relates to a photocatalytic synthesis method of 2, 5-furan dicarbaldehyde, belonging to the technical field of photocatalytic organic chemical synthesis. In the air atmosphere at normal temperature, 5-hydroxymethylfurfural and MAPbBr are added₃Adding the mixture into an organic solvent, stirring the mixture under the irradiation of a light-emitting diode (LED) light source, and oxidizing 5-hydroxymethylfurfural to obtain 2, 5-furandicarboxaldehyde; the wavelength of the LED light source is 400-540 nm. In the method, the reaction raw materials and the solvent are cheap and easy to obtain, and the catalyst is easy to prepare. During the reaction, the HMF can be oxidized into DFF by photocatalysis only in the air at normal temperature.

Description

Photocatalytic synthesis method of 2, 5-furan dicarbaldehyde

Technical Field

The invention relates to a photocatalytic synthesis method of 2, 5-furan dicarbaldehyde, belonging to the technical field of photocatalytic organic chemical synthesis.

Background

In recent years, the production of value added chemicals from renewable feedstocks has attracted considerable attention. Efficient conversion and utilization of biomass or biomass-derived intermediates as an important renewable carbon feedstock will play a key role in addressing energy, ecological and environmental issues. A great deal of effort has focused on the selective oxidation of 5-Hydroxymethylfurfural (HMF), a widely produced compound by dehydration of the C6 carbohydrate, as a valuable platform chemical, with 2, 5-furandicarboxaldehyde (DFF), one of the oxidation products of HMF. Catalysts currently used in connection with the oxidation of 5-hydroxymethylfurfural include homogeneous manganese and cobalt salt catalysts (adv. synth. Catal.,2001,343,102-111), and gold (Au), platinum (Pt) and palladium (Pd) thermal catalysts supported on carbon or aluminum (ChemPlusChem,2012,77, 259-272; chem. Rev.,2016,116,1540-1599), but most of these catalysts require pressurized oxygen, high temperatures or the addition of noble metal co-catalysts. There is therefore a need to find a process for the catalytic oxidation of HMF with mild reaction conditions.

The perovskite is a nano material with high yield, high monodispersity, wide emission spectrum range and adjustable emission spectrum. Simultaneously, mixing organic-inorganic perovskites, especially MAPbBr₃Due to its excellent photovoltaic characteristics, such as high photon absorption efficiency, excellent carrier lifetime, etc., it is a promising material for high-performance photovoltaic devices. Selection of MAPbBr₃No relevant report exists at present when the photocatalyst is used for oxidizing HMF to generate DFF.

Disclosure of Invention

In view of the above, the present invention aims to provide a photocatalytic synthesis method of 2, 5-furandicarboxaldehyde, which adopts MAPbBr₃As a photocatalyst, 5-hydroxymethylfurfural was oxidized to 2, 5-furandicarboxaldehyde under irradiation of a Light Emitting Diode (LED) light source.

In order to achieve the above object, the technical solution of the present invention is as follows.

A method for photocatalytic synthesis of 2, 5-furandicarboxaldehyde, comprising the steps of:

in the air atmosphere at normal temperature, 5-hydroxymethylfurfural and MAPbBr are added₃Adding the mixture into an organic solvent, stirring the mixture under the irradiation of a light-emitting diode (LED) light source, and oxidizing 5-hydroxymethylfurfural to obtain 2, 5-furandicarboxaldehyde; the wavelength of the LED light source is 400-540 nm.

Preferably, the 5-hydroxymethylfurfural and MAPbBr are₃And the dosage ratio of the organic solvent is 0.1-1 mmol: 8-80 mg: 10 mL.

Preferably, the reaction temperature is 15-25 ℃, and the reaction time is 2-10 h.

Preferably, the organic solvent is acetonitrile.

Preferably, the LED light source is blue light.

Advantageous effects

In the method, the reaction raw materials and the solvent are cheap and easy to obtain, and the catalyst is easy to prepare. During the reaction, the HMF can be oxidized into DFF by photocatalysis only in the air at normal temperature. Furthermore, the conversion rate of 5-hydroxymethylfurfural is 100 percent, the selectivity of 2, 5-furan diformaldehyde is over 90 percent, and the total carbon yield is over 96 percent by optimizing reaction conditions.

Drawings

FIG. 1 is a graph of HMF conversion and product selectivity over time for example 1.

FIG. 2 is a liquid chromatogram of the solutions obtained in example 1 at different reaction times.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

In the following examples, the liquid chromatography analysis method was: during the reaction, 1 ml of the resultant solution was collected every two hours, analyzed by Shimadzu LC-20A Liquid Chromatograph (LC) equipped with an Aminex HPX-87H 300mm × 7.8mm column (pH 2.0, aqueous sulfuric acid solution), and the compound was quantified from the peak area after calibration using a commercially available sample.

Example 1

0.5mmol of 5-hydroxymethylfurfural and 40mg of MAPbBr were added to the mixture at 15 ℃ in an air atmosphere₃Adding into a photocatalytic reaction bottle filled with 10mL of acetonitrile, and stirring for 10h under the irradiation of an LED (wavelength of 450nm) light source to obtain a final product.

The HMF conversion and product selectivity over time for different reaction times are shown in figure 1 and the results show that: HMF conversion increases gradually with increasing reaction time, while DFF yield increases and then decreases. After 2h of reaction, the highest selectivity for DFF reached 100%. The selectivity of DFF decreased slightly as the reaction proceeded, since a small fraction of DFF was converted to 2-formyl-furan-2-carboxylic acid (FFCA). When the reaction was carried out for 10h, the conversion of HMF reached 100%, the selectivity for DFF was 90. + -. 1.2%, and the selectivity for FFCA was 6.45. + -. 0.3%.

The liquid chromatography results of the solutions obtained at different reaction times are shown in FIG. 2 and show that: over time, the HMF content of the final product decreased and the DFF content increased, indicating conversion of HMF to DFF. After 10h of reaction, the signal for HMF disappeared, while the signal for DFF rose to a maximum, indicating complete conversion of HMF.

Example 2

Adding 0.1mmol of 5-hydroxymethylfurfural and 8mg of MAPbBr in an air atmosphere at 15 DEG C₃Adding into a photocatalytic reaction bottle filled with 10mL of acetonitrile, and stirring for 10h under the irradiation of an LED (wavelength of 400nm) light source to obtain a final product. The yield of DFF in the final product was 86.18%.

Example 3

1mmol of 5-hydroxymethylfurfural and 80mg of MAPbBr in an air atmosphere at 15 DEG C₃Adding into a photocatalytic reaction bottle filled with 10mL of acetonitrile, and stirring for 10h under the irradiation of an LED (wavelength of 540nm) light source to obtain a final product. The yield of DFF in the final product was 72%.

Example 4

In this example, the organic solvent was N-N dimethylformamide, as in example 2.

The final product was found to contain DFF by liquid chromatography.

Example 5

In this example, the organic solvent was methylene chloride, and the rest of the procedure was the same as in example 3.

The final product was found to contain DFF by liquid chromatography.

Comparative example 1

0.5mmol of 5-hydroxymethylfurfural and 40mg of MAPbBr were added to the mixture at 15 ℃ in an air atmosphere₃The mixture was added to a photocatalytic reaction flask containing 10mL of acetonitrile and stirred in the dark for 10 hours.

As can be seen from the liquid chromatography analysis, the conversion of HMF was 0 and the selectivity of DFF was 0.

Comparative example 2

Adding 0.5mmol of 5-hydroxymethylfurfural into a photocatalytic reaction bottle filled with 10mL of acetonitrile at 15 ℃ in an air atmosphere, and stirring for 10 hours under the irradiation of an LED (light emitting diode) (wavelength of 450nm) light source.

As a result of liquid chromatography analysis, the conversion of HMF was 0.05% and the selectivity of DFF was 36.6%.

In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.

Claims

1. A photocatalysis synthesis method of 2, 5-furan dicarbaldehyde is characterized in that: the method comprises the following steps:

in the air atmosphere at normal temperature, 5-hydroxymethylfurfural and MAPbBr are added₃Adding the mixture into an organic solvent, stirring the mixture under the irradiation of an LED light source, and oxidizing 5-hydroxymethylfurfural to obtain 2, 5-furandicarboxaldehyde; the wavelength of the LED light source is 400-540 nm.

2. The process of claim 1 for the photocatalytic synthesis of 2, 5-furandicarboxaldehyde, wherein: the 5-hydroxymethylfurfural and MAPbBr₃And the dosage ratio of the organic solvent is 0.1-1 mmol: 8-80 mg: 10 mL.

3. The process of claim 1 for the photocatalytic synthesis of 2, 5-furandicarboxaldehyde, wherein: the reaction temperature is 15-25 ℃, and the reaction time is 2-10 h.

4. The process of claim 1 for the photocatalytic synthesis of 2, 5-furandicarboxaldehyde, wherein: the organic solvent is acetonitrile.

5. The process of claim 1 for the photocatalytic synthesis of 2, 5-furandicarboxaldehyde, wherein: the LED light source is blue light.