A photocatalyst and its application

Abstract

The present invention discloses a photocatalyst and its application. Using light as a driving force, a method for selectively oxidizing 5-hydroxymethylfurfural to generate 2,5-furandicarboxaldehyde under the promotion of a photocatalyst based on perylene imide supramolecule / indium zinc sulfide. The method described in the present invention is the first to use a perylene imide supramolecule / indium zinc sulfide composite material as a catalyst, an oxygen-containing gas as an oxidant, and acetonitrile as a solvent, and catalyze 5-hydroxymethylfurfural under the irradiation of sunlight or a xenon lamp without affecting the active aldehyde group, and the C-H bond and the O-H bond in the target hydroxymethyl group are oxidatively broken, respectively, to generate a method for generating a 2,5-furandicarboxaldehyde compound. The method of the present invention has the characteristics of simple operation, green and efficient, mild reaction conditions, easy separation of the catalyst and the reaction system, and can be applied for multiple cycles, and has broad application prospects.

Description

Technical Field

[0001] The present invention relates to the fields of chemistry and materials science, and in particular to a photocatalyst SA-PDI / ZnIn2S4 that catalyzes the oxidation of hydroxymethyl with high selectivity, a synthesis method thereof, and an application of the photocatalytic SA-PDI / ZnIn2S4 in the preparation of 2,5-furandicarboxaldehyde by rapid oxidation of 5-hydroxymethylfurfural. Background Art

[0002] High-end and green development are the inevitable trends in the development of the chemical industry. 5-Hydroxymethylfurfural (HMF) can be prepared by dehydration of renewable biomass carbohydrates. It is a bulk low-value chemical and biomass platform compound with serious overproduction worldwide. The high-value of HMF has become a hot topic of research and attention at home and abroad in recent years. As one of the important bio-based platform compounds, HMF can be catalytically converted to synthesize a series of important organic chemical intermediates. Among them, DFF (2,5-furandicarboxaldehyde) is an important product in the selective oxidation reaction of HMF. It can be used in many fields, such as the synthesis of Schiff bases, drugs, antifungal agents and organic conductor materials, etc., and has great economic value.

[0003] The selective oxidation of HMF to value-added chemicals DFF under mild conditions is a synthetic route with great industrial production value, and efficient photocatalytic catalysis is the key to the selective catalytic oxidation of HMF to prepare DFF. So far, there have been some reports on the use of different semiconductor photocatalysts to catalytically oxidize HMF to prepare DFF. However, the yield or selectivity usually obtained in the prior art is low and the average reaction rate is slow. This is mainly due to the slow reaction rate of the photocatalytic oxidation of HMF system due to the mild reaction conditions, making it impossible to produce efficiently and continuously. For example, in 2017, Krivtsov et al. studied the photocatalytic selective oxidation process of HMF under g-C3N4 catalysis. After 4 hours of reaction, the DFF selectivity was 40%, the HMF conversion rate was only 50%, and the average reaction rate was only 75μmol·g -1 ·h -1 (I. Krivtsov, EI García-López, G. Marcì, L. Palmisano, Z. Amghouz, JR García, S. E. Díaz, Applied Catalysis B: Environmental 2017, 204, 430-439.). Similarly, in 2019, Wu et al. used WO3 / g-C3N4 as a photocatalyst. Although the main product was DFF (DFF selectivity was 87%), the conversion rate could only reach 27% after 6 hours of reaction (H. Zhang, Z. Feng, Y. Zhu, Y. Wu, T. Wu, Journal of Photochemistry and Photobiology A: Chemistry 2019, 371, 1-9.). Later, Ayesh et al. used the reactants to form an in-situ complex on the TiO2 surface as a sensitizer to light-driven catalytic oxidation of HMF. Although the high DFF selectivity of 87% was maintained, the average reaction rate under light was still not ideal, only 148 μmol·g -1 ·h -1 (A. Khan, M. Goepel, A. Kubas, D. Lomot, W. Lisowski, D. Lisovytskiy, A. Nowicka, JC Colmenares, R. Glaser, ChemSusChem 2021, 14, 1351-1362.). Lu et al. obtained the photocatalyst Cd through a hydrothermal method in one step. x In y S (x+1.5y) It was applied to the photocatalytic oxidation of HMF to prepare DFF. Unfortunately, the yield of DFF was only 43.2% after 6 hours of reaction (M. Zhang, Z. Yu, J. Xiong, R. Zhang, X. Liu, X. Lu, Applied Catalysis B: Environmental 2022, 300). In addition, the prior art CN111905812A (D1), CN113952981A (D2), CN114073982A (D3) and the like disclose the technical content of preparing photocatalysts by compounding perylene and zinc-containing compounds, but the content related to the photocatalyst of the present application has not been reported yet. Summary of the invention

[0004] In order to solve the problems in the prior art, the present invention adopts a simple, mild and low-cost photocatalytic method. First, a perylene diimide supramolecule / indium zinc sulfide composite catalyst (SA-PDI / ZnIn2S4) is prepared as a recyclable heterogeneous photocatalyst, and oxygen is used as an oxidant and acetonitrile is used as a reaction medium to catalyze the selective oxidation of 5-hydroxymethylfurfural to prepare 2,5-furandicarboxaldehyde.

[0005] A photocatalyst is prepared by the following method:

[0006] Step 1: Perylene tetracarboxylic anhydride, β-alanine and imidazole are heated to react under inert gas conditions. After the reaction, the mixture is cooled and dispersed in ethanol, HCl solution is added, stirred overnight, filtered and washed until the pH of the washing liquid becomes neutral, and PDI is obtained after drying;

[0007] Step 2: Disperse the PDI in step 1 in water, add triethylamine, and then add HCl solution and stir. When the solution precipitates, filter and wash until the pH of the washing liquid becomes neutral, and dry to obtain SA-PDI;

[0008] Step 3: Dissolve the inorganic salt containing zinc and indium and TAA (thioacetamide) in water and stir, then add the SA-PDI obtained in step 2 and stir, centrifuge and wash after stirring until the pH of the washing liquid becomes neutral, and dry to obtain the SA-PDI / ZnIn2S4 photocatalyst.

[0009] There is no special requirement for the amount of perylenetetracarboxylic anhydride, β-alanine and imidazole in the above step 1, and the preferred molar ratio is 1:0.8-1.2:0.8-1.2; the inert gas is a commonly used inert gas in the art, such as nitrogen or helium; the heating reaction preferably has a reaction temperature of 100-130° C. and a reaction time of 3-6 hours.

[0010] In the above-mentioned step 2, the triethylamine consumption is 0.1-0.4% (volume ratio) of water consumption, and the HCl solution consumption is 8-12% (volume ratio) of water consumption.

[0011] The inorganic salt containing zinc and indium in the above step 3 is preferably zinc nitrate and indium nitrate, and Zn(NO3)2·6H2O and In(NO3)2·4.5H2O are further preferred. Among them, there is no special requirement for the amount of Zn(NO3)2·6H2O, In(NO3)2·4.5H2O and TAA, and the preferred molar ratio is 1:0.8-1.2:0.8-1.2; the stirring reaction time of the three is preferably 0.3-2 hours, the amount of SA-PDI (obtained in step 2) is 0.5-2% of the total mass of Zn(NO3)2·6H2O, In(NO3)2·4.5H2O and TAA, and the stirring time after adding SA-PDI is preferably 6-10 hours, and the temperature needs to be controlled at 40-80°C.

[0012] In addition, the present invention also includes an application of a photocatalyst, which can be used for the selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxaldehyde. The specific application method is:

[0013] Step 1: Add the photocatalyst SA-PDI / ZnIn2S4 to 5-hydroxymethylfurfural and acetonitrile, degas with oxygen, stir, and seal;

[0014] Step 2: The reaction system obtained in step 1 is reacted under sunlight or a xenon lamp to obtain 2,5-furandicarboxaldehyde.

[0015] In step 1 of the above application method, the mass ratio of the photocatalyst to 5-hydroxymethylfurfural is 8-12:1, the dosage ratio of the photocatalyst to acetonitrile is 2:0.5-1.5 (mg / ml), the stirring time should not be too long, preferably 0.3-1 hour; the reaction time in step 2 is preferably 0.3-1 hour.

[0016] Beneficial effects of the present invention:

[0017] 1. The polyperylene imide supramolecule / indium zinc sulfide composite catalyst prepared by the present invention is stable, the preparation method is simple, and the operability is strong. The obtained polyperylene imide supramolecule / indium zinc sulfide improves the interface structure of the catalyst, greatly improves the utilization efficiency of the photoinduced charge, and has higher photocatalytic activity than other types of non-precious metal modified composite photocatalysts.

[0018] 2. The perylene imide supramolecule / indium zinc sulfide composite photocatalyst of the present invention is low-cost, mild in conditions, plays a vital role in the selective oxidation of hydroxymethyl, and has high stability, and can be used for photocatalytic generation of corresponding diformaldehyde compounds from 5-hydroxymethylfurfural.

[0019] 3. The present invention uses acetonitrile as solvent and cheap raw materials to realize the process of photocatalytic heterogeneous oxidation of 5-hydroxymethylfurfural to generate corresponding diformaldehyde at room temperature.

[0020] 4. Compared with the prior art, the advantage of the present invention is that it avoids the use of difficult-to-recycle homogeneous catalysts and successfully provides a new, inexpensive, efficient, mild and rapid green method for selectively oxidizing 5-hydroxymethylfurfural to prepare the corresponding diformaldehyde by using organic molecules as co-catalysts for the first time.

[0021] 5. The photocatalyst prepared by the present invention can be used repeatedly and the effect remains basically unchanged.

[0022] Instruction Manual

[0023] Figure 1 This is the XRD pattern of the photocatalyst prepared in Example 1-1.

[0024] Figure 2 This is the IR spectrum of the photocatalyst prepared in Example 1-1.

[0025] Figure 3 is the X-ray photoelectron spectrum of the photocatalyst prepared in Example 1-1, wherein a is the Zn spectrum, b is the In spectrum, c is the S spectrum, d is the C spectrum, e is the N spectrum, and f is the O spectrum.

[0026] Figure 4 This is a test chart of the catalytic performance of the catalyst prepared in Example 1-1 in different solvents.

[0027] Figure 5 This is a test chart of the catalytic performance of the catalyst prepared in Example 1-1 in different atmospheres.

[0028] Figure 6 This is a test chart of the catalytic performance of the catalyst prepared in Example 1-1 at different reaction times.

[0029] Figure 7 This is a test chart of the cyclic stability of the catalyst prepared in Example 1-1. DETAILED DESCRIPTION

[0030] In order to facilitate further understanding of the present invention, the following examples are provided to illustrate it in more detail. However, these examples are only provided to provide a better understanding of the invention and are not intended to limit the scope or implementation principles of the present invention. The implementation methods of the present invention are not limited to the following contents.

[0031] Example 1-1 Preparation of photocatalyst SA-PDI / ZnIn2S4

[0032] Step 1: Place a certain amount of perylene tetracarboxylic anhydride, β-alanine, and imidazole in a three-necked flask and heat at 110°C for 4 hours under inert gas. After cooling the reaction mixture, disperse it in 100 mL of ethanol, then add 300 M of 2.0 M HCl solution, stir overnight, filter, wash until the pH of the washing liquid becomes neutral, and dry in an oven at 60°C.

[0033] Step 2: Take a certain amount of the above PDI and disperse it in 300 mL of water, add 850 μL of triethylamine and stir. Then add 28 mL of 4.0 M HCl and stir. When the solution precipitates, filter and wash until the pH of the washing liquid becomes neutral, and dry in an oven at 60°C.

[0034] Step 3: Dissolve a certain amount of Zn(NO3)2·6H2O, In(NO3)2·4.5H2O and TAA in 50mL water, stir for 0.5h, then add 1wt% of the above SA-PDI and stir evenly. Stir at 60℃ for 8h, centrifuge and wash until the pH of the washing liquid becomes neutral, and dry in an oven at 60℃.

[0035] Example 1

[0036] 20 mg SA-PDI / ZnIn2S4 was added to a round-bottom reaction bottle, and 2.6 mg 5-hydroxymethylfurfural and 10 mL acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp) for 0.5 h. HPLC detection of the reaction solution showed that the oxidation conversion rate of 5-hydroxymethylfurfural was 98%, and the selectivity of 2,5-furandicarboxaldehyde was about 89%.

[0037] Example 2

[0038] 20 mg SA-PDI / ZnIn2S4 was added to a round-bottom reaction bottle, and 2.6 mg 5-hydroxymethylfurfural and 10 mL water were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp) for 0.5 h. HPLC detection of the reaction solution showed that the oxidation conversion rate of 5-hydroxymethylfurfural was 65%, and the selectivity for 2,5-furandicarboxaldehyde was about 35%.

[0039] Example 3

[0040] 20 mg SA-PDI / ZnIn2S4 was added to a round-bottom reaction bottle, and 2.6 mg 5-hydroxymethylfurfural and 10 mL trifluorotoluene were added. The mixture was degassed with nitrogen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp) for 0.5 h. HPLC detection of the reaction solution showed that the oxidation conversion rate of 5-hydroxymethylfurfural was 42%, and the selectivity for 2,5-furandicarboxaldehyde was about 70%.

[0041] Example 4

[0042] 20 mg SA-PDI / ZnIn2S4 was added to a round-bottom reaction bottle, and 2.6 mg 5-hydroxymethylfurfural and 10 mL isopropanol were added. The mixture was degassed with nitrogen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp) for 0.5 h. HPLC detection of the reaction solution showed that the oxidation conversion rate of 5-hydroxymethylfurfural was 88%, and the selectivity for 2,5-furandicarboxaldehyde was about 67%.

[0043] Example 5

[0044] 20 mg SA-PDI / ZnIn2S4 was added to a round-bottom reaction bottle, and 2.6 mg 5-hydroxymethylfurfural and 10 mL acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp) for 3 hours. HPLC detection of the reaction solution showed that the oxidation conversion rate of 5-hydroxymethylfurfural was 98% and the selectivity of 2,5-furandicarboxaldehyde was about 90%.

[0045] Example 6

[0046] 20 mg SA-PDI / ZnIn2S4 was added to a round-bottom reaction bottle, and 2.6 mg 5-hydroxymethylfurfural and 10 mL acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp) for 10 hours. HPLC detection of the reaction solution showed that the oxidation conversion rate of 5-hydroxymethylfurfural was 99% and the selectivity of 2,5-furandicarboxaldehyde was about 90%.

[0047] Example 7

[0048] 20 mg SA-PDI / ZnIn2S4 was added to a round-bottom reaction bottle, and 2.6 mg 5-hydroxymethylfurfural and 10 mL acetonitrile were added. The mixture was degassed with air and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp) for 3 hours. HPLC detection of the reaction solution showed that the oxidation conversion rate of 5-hydroxymethylfurfural was 98% and the selectivity of 2,5-furandicarboxaldehyde was about 96%.

[0049] Example 8

[0050] 20 mg SA-PDI / ZnIn2S4 was added to a round-bottom reaction bottle, and 2.6 mg 5-hydroxymethylfurfural and 10 mL acetonitrile were added. The mixture was degassed with nitrogen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp) for 3 hours. HPLC detection of the reaction solution showed that the oxidation conversion rate of 5-hydroxymethylfurfural was 86%, and the selectivity for 2,5-furandicarboxaldehyde was about zero.

[0051] Comparative Example 1

[0052] Literature[1]M.Zhang,Z.Yu,J.Xiong,R.Zhang,X.Liu,X.Lu,Applied Catalysis B:Environmental 2022,300.Cd 1.5 In2S 4.5 catalyst.

[0053] Comparative Example 2

[0054] Reference [2] DAGiannakoudakis, V.Nair, A.Khan, EADeliyanni, JC Colmenares, KS Triantafyllidis, Applied Catalysis B: Environmental, 2019, 256. MnO2 catalyst.

[0055] Comparative Example 3

[0056] Literature [3] I.Krivtsov, EI García-López, G. Marcì, L. Palmisano, Z. Amghouz, JR García, S. E. Díaz, Applied Catalysis B: Environmental 2017, 204, 430-439. C3N4 catalyst.

[0057] Comparative Example 4

[0058] Reference [4] J.Xue, C.Huang, Y.Zong, J.Gu, M.Wang, S.Ma, Applied OrganometallicChemistry 2019, 33.Fe / Bi2MoO6 catalyst.

[0059] Comparative Example 5

[0060] Reference [5] A. Lolli, V. Maslova, D. Bonincontro, F. Basile, S. Ortelli, S. Albonetti, Molecules 2018, 23. Au-TiO2 catalyst.

[0061] Comparative Example 6

[0062] Reference [6] A. Akhundi, EI García-López, G. Marcì, A. Habibi-Yangjeh, L. Palmisano, Research on Chemical Intermediates 2017, 43, 5153-5168. C3N4 catalyst.

[0063] Comparative Example 7

[0064] Literature [7] C. Ayed, W. Huang, G. Kizilsavas, K. Landfester, KAIZhang, ChemPhotoChem 2020, 4, 571-576. CTF-Th@SBA-15 catalyst.

[0065] Comparative Example 8

[0066] Reference [8] L. Xiong, J. Tang, Advanced Energy Materials 2021, 11. SGH-TiO2 catalyst.

[0067] Comparative Example 9

[0068] Reference [9] H. Zhang, Z. Feng, Y. Zhu, Y. Wu, T. Wu, Journal of Photochemistry and Photobiology A: Chemistry 2019, 371, 1-9. WO3 / g-C3N4 catalyst.

[0069] Comparative Example 10

[0070] Reference

[10] L. Cheng, D. Huang, Y. Zhang, Y. Wu, Applied Organometallic Chemistry 2021, 35. Bi2WO6 / mpg-C3N4 catalyst.

[0071] Table 1. Reaction results of light-driven catalytic oxidation of HMF in Examples 1-8 and Comparative Examples 1-10

[0072]

[0073]

[0074] Example 9

[0075] 20 mg SA-PDI / ZnIn2S4 was added to a round-bottom reaction bottle, and 2.6 mg 5-hydroxymethylfurfural and 10 mL acetonitrile were added. The mixture was degassed with air and stirred for 0.5 h in the dark and then sealed. After the reaction was completed for 0.5 h under illumination (300 W xenon lamp), the reaction solution was detected by HPLC, and the catalyst was washed and dried by centrifugation and the cycle was repeated 10 times under the same conditions.

[0076] The circulating reaction liquid was analyzed by HPLC. The results are shown in Figure 7 , showing that the HMF conversion rate of each reaction did not change much during the 10 cycles, indicating that the SA-PDI / ZnIn2S4 catalyst can be recycled.

Claims

1. Application of a photocatalyst in the photocatalytic selective oxidation of 5-hydroxymethylfurfural to prepare 2,5-furandicarboxaldehyde. It is characterized in that The specific application method is: Step 1: adding the photocatalyst SA-PDI / ZnIn2S4 to 5-hydroxymethylfurfural and acetonitrile, degassing with oxygen, stirring, and sealing; in step 1, the mass ratio of the photocatalyst to 5-hydroxymethylfurfural is 8-12:1, the mass volume ratio of the photocatalyst to acetonitrile is 2:0.5-1.5 mg / ml, and the stirring time is 0.3-1 hour; Step 2: reacting the reaction system obtained in step 1 under sunlight or a xenon lamp to obtain 2,5-furandicarboxaldehyde; the reaction time in step 2 is 0.3-0.5 hours; The photocatalyst is prepared by the following method: Step (1): heating perylene tetracarboxylic anhydride, β-alanine and imidazole under inert gas conditions for reaction, cooling the mixture after the reaction and dispersing it in ethanol, adding HCl solution, stirring overnight, filtering and washing until the pH of the washing liquid becomes neutral, and drying to obtain PDI; Step (2): dispersing the PDI in step (1) in water, adding triethylamine, and then adding HCl solution and stirring, until the solution precipitates, filtering and washing until the pH of the washing liquid becomes neutral, and drying to obtain SA-PDI; Step (3): dissolving an inorganic salt containing zinc and indium and TAA thioacetamide in water and stirring, then adding the SA-PDI obtained in step (2) and stirring, centrifuging and washing after stirring until the pH of the washing liquid becomes neutral, and drying to obtain the SA-PDI / ZnIn2S4 photocatalyst.

2. Use of the photocatalyst according to claim 1 in the photocatalytic selective oxidation of 5-hydroxymethylfurfural to prepare 2,5-furandicarboxaldehyde, characterized in that: In step (1), the molar ratio of perylene tetracarboxylic anhydride, β-alanine and imidazole is 1:0.8-1.2:0.8-1.2; the inert gas is nitrogen or helium; the heating reaction temperature is 100-130° C., and the reaction time is 3-6 hours.

3. Use of the photocatalyst according to claim 1 in the preparation of 2,5-furandicarboxaldehyde by photocatalytic selective oxidation of 5-hydroxymethylfurfural, characterized in that: In the above step (2), the volume ratio of triethylamine to water is 0.1-0.4%, and the volume ratio of HCl solution to water is 8-12%.

4. Use of the photocatalyst according to claim 1 in the photocatalytic selective oxidation of 5-hydroxymethylfurfural to prepare 2,5-furandicarboxaldehyde, characterized in that: In the above step (3), the inorganic salts containing zinc and indium are zinc nitrate and indium nitrate, and the molar ratio of zinc nitrate, indium nitrate and TAA is 1:0.8-1.2:0.8-1.2; the stirring reaction time of the three is 0.3-2 hours, the amount of SA-PDI is 0.5-2% of the total mass of zinc nitrate, indium nitrate and TAA, the stirring time after adding SA-PDI is 6-10 hours, and the temperature is controlled at 40-80°C.

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