High-entropy organic small-molecule photocatalyst, preparation method and application thereof
The one-pot synthesis of high-entropy organic small molecule photocatalysts solves the problems of low light absorption efficiency and weak charge separation ability in existing technologies, achieving a high efficiency improvement in photocatalytic performance, especially in the field of photocatalytic hydrogen production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- TAIYUAN UNIVERSITY OF TECHNOLOGY
- Filing Date
- 2026-04-30
- Publication Date
- 2026-07-24
AI Technical Summary
Existing small organic molecule photocatalysts have low light absorption efficiency and weak charge separation ability, which limits their application in the field of photocatalysis.
A one-pot method was used to synthesize high-entropy organic small molecule photocatalysts, which consist of more than five kinds of organic small molecules with different chemical structures. Through the reaction of core unit monomers with peripheral unit monomers, multiple interfacial electric fields are formed, which improves light absorption rate and charge separation capability.
It significantly improves photocatalytic performance, enhances photocurrent response characteristics and charge transport capabilities, and is suitable for photocatalytic hydrogen production.
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Figure CN122444572A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic small molecule materials technology, and in particular to a high-entropy organic small molecule photocatalyst, its preparation method, and its application. Background Technology
[0002] With the escalating global energy crisis and environmental problems, the development of clean and renewable energy technologies has become an urgent need. Hydrogen energy, as a high-energy-density, zero-carbon-emission green energy source, has attracted widespread attention. Solar photocatalysis technology, due to its direct utilization of solar energy, simple equipment, and environmental friendliness, shows broad application prospects in hydrogen production, carbon dioxide reduction, and pollutant degradation. It is worth noting that the application areas of photocatalysis technology have far exceeded simple water splitting for hydrogen production, including oxygen production via the oxygen evolution reaction, synthesis of high-value-added hydrogen peroxide using a two-electron pathway, conversion of carbon dioxide into hydrocarbon fuels to achieve carbon cycling, and efficient degradation of environmental pollutants using photobiotic species. Therefore, developing efficient photocatalysts is not only key to improving the efficiency of photocatalytic hydrogen production, but also the core of promoting its widespread application in diverse fields such as energy conversion, chemical synthesis, and environmental governance.
[0003] Currently, organic small molecule photocatalysts have attracted attention due to their well-defined structure and ease of synthesis and modification, but their photocatalytic performance is still limited by problems such as low light absorption efficiency and weak charge separation ability.
[0004] High-entropy materials are a novel class of materials consisting of five or more components randomly and uniformly distributed in a single-phase structure, possessing tunable electronic structures, abundant active sites, and good thermal stability. Introducing the high-entropy concept into organic small molecule systems holds promise for enhancing the photoelectric properties of materials through multi-component synergistic effects, particularly in the field of photocatalysis. However, current research on high-entropy organic small molecule materials is still insufficient, especially regarding their controllable synthesis and performance optimization, which require further breakthroughs. Summary of the Invention
[0005] The purpose of this invention is to provide a high-entropy organic small molecule photocatalyst, its preparation method and application. The prepared high-entropy organic small molecule photocatalyst has excellent thermal stability, light absorption rate and multiple interfacial electric fields, thereby significantly improving photocatalytic performance and being widely used in the field of photocatalytic hydrogen production.
[0006] To achieve the above objectives, the present invention provides a high-entropy organic small molecule photocatalyst, which is composed of five or more organic small molecules with different chemical structures; the organic small molecules are prepared by one-pot reaction of at least one core unit monomer and at least two peripheral unit monomers.
[0007] Preferably, the core unit monomer is an organic compound having two or more reactive sites; the organic compound has a symmetrical or asymmetrical structure.
[0008] Preferably, the core unit monomer is a conjugated cyclic organic compound having two or more reactive sites.
[0009] Preferably, the reactive site is one of halogen, borate ester, tin alkyl, and diazonium salt groups.
[0010] Preferably, the core unit monomer has 2-4 reactive sites.
[0011] Preferably, the peripheral unit monomer is at least two of phenylboronic acid, aniline, phenol, thiophene and their derivatives.
[0012] Preferably, when the core unit monomer is one of a conjugated cyclic organic compound with four reactive sites and the conjugated cyclic organic compound has a symmetrical structure, there are two types of peripheral unit monomers.
[0013] This invention provides a method for preparing a high-entropy organic small molecule photocatalyst, comprising the following steps: At least one core unit monomer and at least two peripheral unit monomers are placed in a reaction vessel, and a catalyst and reaction solution are added. The reaction is carried out at 60℃-120℃ for 12h-48h under an inert atmosphere. After extraction and purification, a high-entropy organic small molecule photocatalyst is obtained.
[0014] Preferably, the catalyst is a palladium catalyst; the reaction solution is a mixture of tetrahydrofuran and an anhydrous potassium carbonate solution with a concentration of 2 mol / L; the volume ratio of the tetrahydrofuran to the anhydrous potassium carbonate solution is 3:1.
[0015] This invention provides an application of a high-entropy organic small molecule photocatalyst, such as the high-entropy organic small molecule photocatalyst described above for photocatalytic hydrogen production.
[0016] In summary, the high-entropy organic small molecule photocatalyst, its preparation method, and its application provided by this invention offer the following advantages compared to traditional technologies: (1) The high-entropy organic small molecule photocatalyst prepared in this invention exhibits high photocurrent response characteristics. Compared with traditional organic molecules, the high-entropy organic small molecule photocatalyst has a stronger response to light.
[0017] (2) The high-entropy organic small molecule photocatalyst prepared by the present invention forms an interfacial electric field through the synergistic effect of multiple components, which promotes the separation and transport of photogenerated charge carriers. In addition to enhancing the photocurrent response characteristics, it also improves the charge transport capability, which has a significant positive impact on the photocatalytic performance of organic small molecules. It can be widely used in the field of photocatalytic hydrogen production.
[0018] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description
[0019] Figure 1 This is a schematic diagram of the synthesis process of the high-entropy organic small molecule photocatalyst (HE-CF3) based on CF3 in Example 1 of the present invention; Figure 2 The image shown is a Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS) image of the high-entropy organic small molecule photocatalyst (HE-CF3) based on CF3 in Example 1 of this invention.
[0020] Figure 3 This is the 1H NMR spectrum of the high-entropy organic small molecule photocatalyst (HE-CF3) based on CF3 in Example 1 of the present invention; Figure 4 This is the Fourier transform infrared spectrum of the high-entropy organic small molecule photocatalyst (HE-CF3) based on CF3 in Example 1 of the present invention; Figure 5 This is a thermal stability diagram of the high-entropy organic small molecule photocatalyst (HE-CF3) based on CF3 in Example 1 of the present invention; Figure 6 This is a light absorption rate diagram of the high-entropy organic small molecule photocatalyst (HE-CF3) based on CF3 in Example 1 of the present invention; Figure 7 This is a graph showing the photocatalytic hydrogen production rate of the high-entropy organic small molecule photocatalyst (HE-CF3) based on CF3 in Example 1 of the present invention. Detailed Implementation
[0021] The technical method of the present invention will be further described below with reference to the accompanying drawings and embodiments. It should be noted that, unless otherwise specifically stated, the relative arrangement and numerical values of the steps in these embodiments do not limit the scope of this application. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the scope of this application or its application or use.
[0022] In the embodiments, all original reagent materials are commercially available. Experimental methods not specifically described are conventional methods and conditions well-known in the art, or are performed according to the conditions recommended by the instrument manufacturer. Unless otherwise defined, the technical or scientific terms used in this invention should be understood in their ordinary sense by one of ordinary skill in the art.
[0023] Example 1 A high-entropy organic small-molecule photocatalyst based on CF3 was prepared by a one-pot reaction of the core unit monomer 1,3,6,8-tetrabromopyrene with the peripheral unit monomers 2-trifluoromethylphenylboronic acid and 3,5-bis(trifluoromethyl)phenylboronic acid. Figure 1 As shown, the high-entropy organic small molecule agent based on CF3 is composed of seven organic small molecules with different chemical structures (component 1, component 2, component 3, component 4, component 5, component 6 and component 7).
[0024] A method for preparing a high-entropy organic small molecule photocatalyst based on CF3, comprising the following steps: First, in a two-necked flask, 517.84 mg of 1,3,6,8-tetrabromopyrene, 569.78 mg of 2-trifluoromethylphenylboronic acid, and 773.79 mg of 3,5-bis(trifluoromethyl)phenylboronic acid were mixed with 30 mL of tetrahydrofuran and 10 mL of 2 mol / L anhydrous potassium carbonate solution. After thorough stirring, 30 mg of tetra(triphenylphosphine)palladium was added to the flask under a nitrogen atmosphere. Nitrogen backfilling was then performed three times. The mixture was then heated to reflux at 80 °C for 24 h. After cooling to room temperature, the refluxed solution was quenched, extracted, and dried to obtain a crude product. The crude product was purified by column chromatography, washed, and dried to obtain a high-entropy organic small molecule photocatalyst, denoted as HE-CF3. HE-CF3 is a yellow powder.
[0025] The high-entropy organic small molecule photocatalyst HE-CF3 was analyzed by FTICR-MS, proton nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy. Figure 2 It was confirmed that the high-entropy organic small molecule photocatalyst HE-CF3 exists in seven different organic small molecules with different chemical structures. Figure 3 The successful synthesis of the high-entropy organic small molecule photocatalyst HE-CF3 was verified by proton nuclear magnetic resonance spectroscopy. Figure 4 Fourier transform infrared spectroscopy verified the successful introduction of the cf bond.
[0026] Figure 5 and Figure 6 This demonstrates that the high-entropy organic small molecule photocatalyst HE-CF3 possesses excellent thermal stability and light absorption rate.
[0027] The high-entropy organic small molecule photocatalyst HE-CF3 was used for photocatalytic hydrogen production. The reaction was conducted in a closed, top-irradiated reaction vessel, with an external cryogenic bath maintaining the entire system at room temperature (25°C). A 420nm cutoff filter on a 300W xenon lamp was used to simulate visible light irradiation (visible light wavelength λ > 420nm). The photocatalytic hydrogen production process included: ultrasonically dispersing 2 mg of the high-entropy organic small molecule photocatalyst HE-CF3 in 6 mL of LDM via a 20-minute water bath sonication process, followed by the addition of 2.5 g of ascorbic acid as a sacrificial reagent and 30 mL of deionized water; before irradiation, dissolved air in the solution was removed by degassing; the concentration of evaporated hydrogen was detected online using an Agilent GC8860 gas chromatograph, with argon as the carrier gas. The results are as follows: Figure 7 As shown. According to Figure 7 It can be seen that HE-CF3 exhibits excellent hydrogen evolution reaction (HER) activity under visible light driving, with a maximum yield of 3.8 mmol / g. -1 ·h -1 .
[0028] The high-entropy organic small molecule photocatalyst in this invention has good long-term stability, and it promotes the formation and dissociation of excitons, which not only enhances the photocurrent response characteristics but also improves the charge transport capacity, thus having a significant positive impact on the photocatalytic performance of organic molecules.
[0029] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.
Claims
1. A high-entropy organic small molecule photocatalyst, characterized in that, The high-entropy organic small molecule photocatalyst is composed of five or more organic small molecules with different chemical structures; the organic small molecules are prepared by one-pot reaction of at least one core unit monomer and at least two peripheral unit monomers.
2. The high-entropy organic small molecule photocatalyst according to claim 1, characterized in that, The core unit monomer is an organic compound having two or more reactive sites; the organic compound has a symmetrical or asymmetrical structure.
3. The high-entropy organic small molecule photocatalyst according to claim 2, characterized in that, The core unit monomer is a conjugated cyclic organic compound with two or more reactive sites.
4. The high-entropy organic small molecule photocatalyst according to claim 3, characterized in that, The reactive sites are used to catalyze at least one of the following reactions: Suzuki coupling reaction, Sonogashira-Hagihara reaction, Stille coupling reaction, direct arylation reaction, Heck reaction, Schiff base reaction, Knoevenagel reaction, Horner-Wadsworth-Emmons reaction, Yamamoto coupling reaction, and oxidative coupling reaction.
5. The high-entropy organic small molecule photocatalyst according to claim 4, characterized in that, The number of reactive sites in the core unit monomer is greater than or equal to 2.
6. The high-entropy organic small molecule photocatalyst according to claim 1, characterized in that, The peripheral unit monomers are at least two of the following: phenylboronic acid, aniline, phenol, thiophene and their derivatives.
7. The high-entropy organic small molecule photocatalyst according to claim 6, characterized in that, When the core unit monomer is one of a conjugated cyclic organic compound with four reactive sites, and the conjugated cyclic organic compound has a symmetrical structure, there are two types of peripheral unit monomers.
8. A method for preparing a high-entropy organic small molecule photocatalyst, characterized in that, The preparation of a high-entropy organic small molecule photocatalyst as described in any one of claims 1-7 comprises the following steps: At least one core unit monomer and at least two peripheral unit monomers are placed in a reaction vessel, and a catalyst and reaction solution are added. The reaction is carried out at 60℃-120℃ for 12h-48h under an inert atmosphere. After extraction and purification, a high-entropy organic small molecule photocatalyst is obtained.
9. The method for preparing a high-entropy organic small molecule photocatalyst according to claim 8, characterized in that, The catalyst is a palladium catalyst; the reaction solution is a mixture of tetrahydrofuran and an anhydrous potassium carbonate solution with a concentration of 2 mol / L; the volume ratio of tetrahydrofuran to anhydrous potassium carbonate solution is 3:
1.
10. The application of a high-entropy organic small molecule photocatalyst, characterized in that, A high-entropy organic small molecule photocatalyst as described in any one of claims 1-7 is used for photocatalytic hydrogen production.